## DEVELOPMENT OF THE SAPRC **- 07 CHEMICAL**  **MECHANISM AND UPDATED OZONE REACTIVITY SCALES**  Report to the California Air Resources Board Contracts No. 03 - 318, 06 -408, and 07 - 730



### By William P. L. Carter Revised January 27, 2010

Center for Environmental Research and Technology

College of Engineering University of California Riverside, California 92521

### ii 

### ABSTRACT A completely updated version of the SAPRC - 99 chemical mechanism, designated SAPRC - 07, has been developed and is documented in this report. This includes a complete update of the rate constants and reactions based on current data and evaluations, reformulated and less parameterized aromatics mechanisms, a representation of chlorine chemistry, a reformulated method to represent peroxy reactions that is more appropriate for modeling secondary organic aerosol formation, and improved representations for many types of VOCs. This mechanism was evaluated against the result of ~2400 environmental chamber experiments carried out in 11 different environmental chambers, including experiments to test mechanisms for over 120 types of VOCs. The performance of the mechanism in simulating the chamber data was comparable to SAPRC - 99, with generally satisfactory results for most types of VOCs but some increases in biases in simulations of some mixture experiments. The mechanism was used to derive an update to the MIR and other ozone reactivity scales for over 1100 types of VOCs. T he average changes in relative MIR values was about 10%, with >90% of the VOCs having changes less than 30%, but with larger changes for some types of VOCs, including halogenated compounds. Recommendations are given for future mechanism development research. The mechanism documentation includes some large tabulations that are being provided only in electronic form. Links to downloading these tabulations are available at http://www.cert.ucr.edu/~carter /SAPRC. Note: This version of the report and the associ ated supplementary materials and files superceded those available previously at the above -referenced web site. The changes are summarized in Appendix E to this report.

### iii 

### ACKNOWLEDGEMENTS AND DISCLAIMERS This work was carried out at the College of Engineering Center for Environmental Research and Technology (CE - CERT) at the University of California at Riverside (UCR), with funding by the California Air Resources Board (CARB) primarily through contract number 03 - 318, with additional work carried out through Con

tracts 06 -408 and 07 - 730. However, the contents of this report reflect only the opinions and conclusions of the author, and not CE - CERT, UCR, or the CARB. The author wishes to thank Dr. Roger Atkinson of the Air Pollution Research Center at UCR for many he lpful discussions concerning available kinetic and mechanistic data and atmospheric chemistry in general, and for partial support during the period of this project. The author also appreciates the patience of the staff of the Research Division of the CARB, particularly Dr. Dongmin Luo, regarding the delays in completing this project and their continuing support. Experiments for this project that were used in this mechanism evaluation were carried out primarily by Ms. Irina Malkina with assistance from Mr. K urt Bumiller and other members of the CE - CERT Atmospheric Processes Laboratory staff, and their contributions are gratefully acknowledged. Finally, the author wishes to acknowledge the University of California Retirement System, which provided maj or support to the author during the completion of mechanism development and the preparation of this report. When discussing materials whose mechanisms were evaluated, this report makes references to "Texanol", which is a trademark of Eastman Chemical Company, and " Exxol" and "I sopar", which are trademarks of ExxonMobil Chemical Company. Mention of trade names and commercial products does not constitute endorsement or recommendation for use.

### iv 

### TABLE OF CONTENTS EXECUTIVE SUMMARY ................................ ................................ ................................ .......................... 1 Background ................................ ................................ ................................ ................................ ............ 1 Accomplishments ................................ ................................ ................................ ................................ ... 1 Results ................................ ................................ ................................ ................................ .................... 2 Recommendations ................................ ................................ ................................ ................................ .. 3 INTRODUCTION ................................ ................................ ................................ ................................ ........ 5 MECHANISM D OCUMENTATION ................................ ................................ ................................ .......... 8 Base Mechanism ................................ ................................ ................................ ................................ ..... 8 Listing of Standard Base Mechanism and Summary of Changes ................................ .................... 8 Representation of Peroxy Radical Operators ................................ ................................ ................. 13 Base Chlorine Mechanism ................................ ................................ ................................ ............. 15 Representation of Organic Products ................................ ................................ .............................. 16 Mechanisms for Individual VOCs ................................ ................................ ................................ ........ 17 Mechanism Generation and Estimation System ................................ ................................ ............ 17 Enhanced Capabilities for VOCs and Reactions ................................ ................................ ..... 18 Support for Chlorine Reactions ................................ ................................ ............................... 19 Updates to Rate Constants and Mechanisms ................................ ................................ ........... 26 Adjusted Product Mechanisms ................................ ................................ ................................ 28 Updated Aromatics Mechanisms ................................ ................................ ................................ ... 31 Reactions of Alkylbenzenes with O H ................................ ................................ ..................... 33 Representation of Unsaturated Dicarbonyl Products ................................ ............................... 42 Aromatic Ring Retaining Products ................................ ................................ .......................... 50 Non - Alkylbenzene Aromatics ................................ ................................ ................................ . 51 Reactions with Chlorine ................................ ................................ ................................ .......... 51 Mechanisms for Amines ................................ ................................ ................................ ................ 55 Miscellaneous Assigned Mechanisms ................................ ................................ ........................... 57 Lumped Molecule Representations ................................ ................................ ................................ 60 Lumped Mechanisms for Airshed Models ................................ ................................ ........................... 61 Adjustable Parameter Mechanisms ................................ ................................ ................................ 61 Fixed Parameter Mechanism ................................ ................................ ................................ .......... 61 Emissions Assignments ................................ ................................ ................................ ................. 65 MECHANISM EVALUATION ................................ ................................ ................................ ................. 67 Methods ................................ ................................ ................................ ................................ ................ 71 Data Presented ................................ ................................ ................................ ................................ ...... 77 Results ................................ ................................ ................................ ................................ .................. 79 Results for Chamber Characterization Experiments ................................ ................................ ...... 79 Results for Mechanism Evaluation Experiments ................................ ................................ ........... 79 Overall Performance in Simulating Entire Dataset ................................ ................................ . 79 Evaluation Experiments for Individual VOCs ................................ ................................ ........ 80 Evaluation Experiments for Mixtures ................................ ................................ ..................... 92 Mechanism Performance for Direct Reactivity Experiments ................................ ...................... 100 UPDATED REACTIVITY S CAL ES ................................ ................................ ................................ ....... 101 Methods ................................ ................................ ................................ ................................ .............. 101 Results ................................ ................................ ................................ ................................ ................ 103 Predicted Ozone Formation in the Scenarios ................................ ................................ ............... 103

### TABLE OF CONTENTS (continued)

v Updated Ozone Reactivity Scales ................................ ................................ ................................ 105 Updated Uncertainty Estimates ................................ ................................ ................................ .... 106 SUMMARY AND RECOMMENDATIONS ................................ ................................ ........................... 109 Summary of Project Accomplishments ................................ ................................ .............................. 109 Recommendations ................................ ................................ ................................ .............................. 114 REFERENCES ................................ ................................ ................................ ................................ ......... 121 APPENDIX A . GENERAL MECHANISM LI STING TABLES ................................ ............................ 135 APPENDIX B. MECHANIS M AND REACTIVITY LIS TI NGS FOR INDIVIDUAL VOCS .............. 176 APPENDIX C. MECHANIS M EVALUAT ION TABULATIONS AND PLOTS ................................ .. 270 APPENDIX D. SUPPLEMENTARY MATERIAL AVAILABLE ................................ ......................... 376 APPENDIX E. CHANGE L OG ................................ ................................ ................................ ................ 377

### vi 

### LIST OF TABLES Table 1. Reactions where the rate constants or photolysis rates changed by more than 5% or

that were added or removed in the standard base mechanism relative to SAPRC - 99. .......... 11 Table 2. Products formed in the reactions of the chemical operators used to represent peroxy

radical reactions in the SAPRC - 07 mechanism. ................................ ................................ .... 14 Table 3. Group additivity parameters used for estimating rate constants for abstraction

reactions by OH and NO 3 

### radicals and by Cl atoms. ................................ ............................. 20 Table 4. Rate constants for reactions with chlorine atoms for organic compounds used to

derive parameters for group - additivity estimates. ................................ ................................ .. 24 T able 5. Group additivity rate constants and factors used for estimating rates of addition of Cl

atoms to double bonds. ................................ ................................ ................................ ........... 26 Table 6. Branching ratio assignments for chlorine - substituted alkoxy radicals made to

generate mechanisms for the reactions of chlorine with representative alkenes. ................... 27 Table 7. Assigned mechanisms for Crigiee Biradicals used for deriving mechanisms for

reactions of O 3 

### with alkenes. ................................ ................................ ................................ .. 29 Table 8. Compounds whose Averaged Conditions MIR reactivities changed by more than

20% when adjustable product mechanisms were employed. ................................ ................. 31 Table 9. Measured or estimated yields of known products for benzene and methylbenzene

reactions that were incorporated in the SAPRC - 07 aromatics mechanisms .......................... 34 Table 10. Rate constants and assumptions used to estimate fractions of reaction of on and off

the aromatic ring for the reactions of OH with aromatic compounds or groups of compounds for which mechanistic parameters have been derived. ................................ ....... 40 Table 11. Model species use d to represent non -nitrate products from the reactions of OH

radicals at aromatic rings for various types of ring structures. Yields are normalized to OH ring addition only, excluding nitrate formation. ................................ .......................... 43 Table 12. Estimated yields for unsaturated dicarbonyl products in the OH reactions of the

methylbenzenes for which  - dicarbonyl yield data are available. ................................ ......... 44 Table 13. Mechanism estimation assignments made for representative unsaturated dicarbonyl

compounds for the purpose of generating mechanisms for the aromatic fragmentation product model speci es AFG1 - 3. ................................ ................................ ..... 46 Table 14. Discussion of mechanisms for the non - alkylbenzene aromatic compounds that for

which mechanistic assignments have been derived. The rate con stants and additional documentation are given in Table B -4 and the reactions are given in Table B - 2 in Appendix B. ................................ ................................ ................................ ........................... 51 Table 15. Assignments made for alkoxy radical intermediates predicted to be formed in the

photooxidation mechanisms of the amines. ................................ ................................ ........... 56 Table 16. Discussion of mechanisms for miscellaneous compounds that were not derived using

the procedures discussed previously in this report. The rate constants, reactions, and additional documentation are given in Table B - 2, and Table B -4 through Table B - 6 in Appendix B. ................................ ................................ ................................ ....................... 58

### LI ST OF TABLES (continued)

vii Table 17. List of model species used in the lumped mechanism for airshed models for

representing the various types of emitted VOCs. ................................ ................................ ... 62 Table 18. Compounds and weighting factors used to derive the parameters for the ALK and

ARO model species in the fixed parameter mechanism for airshed models .......................... 64 Table 19. Compounds and weighting factors used to derive the parameters for the OLE and

TERP model species in the fixed parameter mechanism for airshed models ........................ 65 Table 20. Summary of environmental chambers whose data were used for mechanism

evaluation ................................ ................................ ................................ ............................... 68 Table 21. Summary of types of experiments used for mechanism evaluation. ................................ ....... 70 Table 22. Chamber wall effect and background characterization parameters used in the

enviro nmental chamber model simulations for mechanism evaluation. ................................ 73 Table 23. Summary of mechanism evaluation results using chamber experiments for individual

compound s and mixtures. ................................ ................................ ................................ ...... 84 Table 24. Scenarios used for reactivity assessment, with updated calculated maximum O 3 

### ,

Integrated OH, and MIR, MOIR, and EBIR NO x 

### inputs. ................................ .................... 102 Table 25. List of compounds and mixtures whose reactivities in the MIR scale changed by

more than 30%. ................................ ................................ ................................ .................... 107 Table A - 1. List of model species used in the standard base SAPRC - 07 mechanism. The lumped

model species added for the fixed parameter lumped mechanism for airshed models are also listed. ................................ ................................ ................................ ....................... 135 Table A - 2. Listing of reactions and rate parameters in the base SAPRC - 07 mechanism. ..................... 139 Table A - 3. Absorption cross - sections and quantum yields for the all photolysis reactions in the

base mechanism. (Available in electronic form only) ................................ .......................... 162 Table A -4. List of model species used in the base chlorine SAPRC - 07 mechanism. ............................ 162 Table A - 5. Listing of reactions and rate parameters added to represent the reactions of chlorine

species in the SAPRC - 07 mechanism. ................................ ................................ ................. 163 Table A - 6. Absorption cross - sections and quantum yields for the all photolysis reactions added

for the chlorine chemistry mechanism. ................................ ................................ ................ 169 Table A - 7. Listing of reactions and rate parameters used for the lu mped model species in the fixed parameter version of the lumped SAPRC - 07 mechanism. ................................ ......... 172 Table B - 1. Listing of detailed model species, their representation in the model, and calculated

atmospheric reactivity values in various reactivity scales ................................ ................... 177 Table B - 2. Listing of mechanisms for all VOCs for which mechanism assignments have been

derived. (Available in electronic form only) ................................ ................................ ........ 209 Table B - 3. Listing of adjusted product mechanisms for all VOCs for which such mechanisms

have been derived . (Available in electronic form only) ................................ ....................... 209

### LI ST OF TABLES (continued)

viii Table B -4. Listing of compounds for which mechanisms have been derived. 1. OH radical rate

cons tants at 300 o

### K, mechanism types, and structures used for compounds with generated mechanisms. ................................ ................................ ................................ ........ 210 Table B - 5. Listing of compounds for which mechanisms have been derived. 2. Rate constants

for reactions with O 3 

### , NO 3 

### , and O 3 

### P at 300 o 

### K, where applicable. ................................ ....... 235 Table B - 6. Listing of compounds for which mechanisms have been derived. 3. Absorption

cross - sections, quantum yields, and mechanisms for photolysis reactions, where applicable. ................................ ................................ ................................ ............................ 241 Table B - 7. Listing of compounds for which mechani sms have been derived. 4. Rate constants

and mechanisms for reactions with chlorine atoms, where used. ................................ ........ 244 Table B - 8. Absorption cross sections used for the photo lysis reactions for represented

photoreactive VOCs that are not in the base mechanism. ................................ .................... 252 Table B - 9. Lumped molecule representations used in the SAPRC - 07 mechani sm. .............................. 256 Table B - 10. Listing of components of complex mixtures for which atmospheric reactivities have

been calculated. (Available in electronic form only) ................................ ........................... 269 Table B - 11. Assignments of explicitly represented compounds to lumped model species in the

fixed parameter mechanism. (Available in electronic form only) ................................ ........ 269 Table C - 1. List of environmental chamber experiments used in the mechanism evaluation. .

(Available in electronic form only) ................................ ................................ ...................... 270

### ix 

### LIST OF FIGURES Figure 1. Effect of using the adjustable product mechanisms vs. the standard fixed product

mechanisms on incremental reactivities in the "Averaged Conditions" MIR scale for those VOCs for which adjustable product mechanisms could be derived. ............................ 31 Figure 2. Reactions of the OH - aromatic ring adduct th at are assumed in the current

mechanism. The example shown is for benzene, but analogous reactions are assumed for the alkylbenzenes. ................................ ................................ .............................. 37 Figure 3. Nitrate yield f actors used for estimating aromatic oxidation mechanisms .............................. 39 Figure 4. Action spectra for photodecompositions of 2 -buene - 1,4 - dial, 4 - oxo - 2 -penteneal and

used for th e model species AFG1 and AFG2. ................................ ................................ ........ 50 Figure 5. Distribution of  ([O 3 

### ] - [NO]) model errors for the radical source characterization

experiments. ................................ ................................ ................................ ........................... 81 Figure 6. Distribution of O 3 

### model errors for the NO x 

### offgasing characterization experiments ............ 82 F igure 7. Distributions of  ([O 3 

### ] - [NO]) model errors for all of the single VOC - NO x 

### and

mixture - NO x 

### experiments used in the mechanism evaluation. ................................ ............ 83 Figure 8. Experimental and calculated effects of CO addition in representative toluene and

m - xylene NO x 

### experiments carried out in the UCR EPA chamber. ................................ ...... 91 Figure 9. Plots of model errors in simulations of miscellaneous mixture - NO x 

### experiments

carried out in various chambers. ................................ ................................ ............................ 94 Figure 10. Plots of model errors in simulations of miscellaneous surrogate - NO x 

### experiments

carried out in various UCR chambers and in the TVA chamber. ................................ .......... 95 Figure 11. Plots of model errors in simulations of surrog ate - NO x 

### experiments carried out in

the UNC chamber. ................................ ................................ ................................ .................. 96 Figure 12. Plots of model errors in simulations of the standard base case surrogate - NO x



### irradiations ca

rried out in conjunction with the incremental reactivity experiments in the ETC and DTC (blacklight), and CTC and XTC (arc light) chambers. ............................ 97 Figure 13. Plots of model errors in simulations of the surrogate - NO x 

### experiments carried out

in the UCR EPA chamber. ................................ ................................ ................................ ..... 98 Figure 14. Plots of model errors in simulations of 6 -hour  ([O 3 

### ] - [NO]) against initial ROG

surrogate /NO x 

### ratio. ................................ ................................ ................................ .............. 99 Figure 15. Model performance in simulating the direct reactivity data of Carter and Malkina

(2002). ................................ ................................ ................................ ................................ .. 100 Figure 16. Plots of maximum O 3 

### concentrations calculated for the various scenarios used for

reactivity assessment against the initial ROG levels in the scenarios. ................................ . 104 Figure 17. Change in maximum O 3 

### concentrations in the scenarios used for reactivity

assessment, calculated using SAPRC - 07 compared to SAPRC - 99. ................................ .... 105 Figure 18. Plots of incremental reactivities in the MIR scale computed using the updated

mechanism against those reported previously by Carter (2003a). ................................ ....... 106

### LI ST OF FIGURES (continued)

x Figure C - 1. Plots of experimental and calculated environmental chamber reactivity results for

carbon monoxide. ................................ ................................ ................................ ................. 271 Figure C - 2. Plots of experimental and calculated environmental chamber reactivity results for

ethane and propane ................................ ................................ ................................ ............... 272 Figure C - 3. Plots of experimental and calculated environmental chamber reactivity results for nbutane ................................ ................................ ................................ ................................ ... 273 Figure C -4. Plots of experimental and calculated environmental chamber reactivity results for nhexane and the Surg - 3 MIR1 experiments for n - octane. ................................ ..................... 274 Figure C - 5. Plots of experimental and calculate d environmental chamber reactivity results for n octane (excluding the Surg - 3 MIR1 experiments, which are on Figure C -4). ..................... 275 Figure C - 6. Plots of experimental and calculated environmental chamber reactivity results for ndodecane. ................................ ................................ ................................ .............................. 276 Figure C - 7. Plots of experimental and calculated environmental chamber reactivity results for ntetradecane ................................ ................................ ................................ ........................... 277 Figure C - 8. Plots of experimental and calculated environmental chamber reactivity results for npentadecane and n -hexadecane. ................................ ................................ ........................... 278 Figure C - 9. Plots of experimental and calculated environmental chamber reactivity results for

isobutane, 2,2,4 -trimethyl pentane, and 2,6 - dimethyl octane. ................................ ............. 279 Figure C - 10. Plots of experimental and calculated environmental chamber reactivity results for 2 -

methyl nonane and 3,4 - diethyl hexane. ................................ ................................ ................ 280 Figure C - 11. Plots of experimental and calculated environmental chamber reactivity results for

cyclohexane and hexyl cyclohexane. ................................ ................................ ................... 281 Figure C - 12. Plots of experimental and calculated environmental chamber reactivity results for

octyl cyclohexane. ................................ ................................ ................................ ................ 282 Figure C - 13. Plots of model errors in simulations of the ethene - NO x 

### environmental chamber

experiments. ................................ ................................ ................................ ......................... 283 Figure C - 14. Plots of experimental and calculated environmental chamber reactivity results for

ethene. ................................ ................................ ................................ ................................ .. 284 Figure C - 15. Plots of model errors in simulations of the propene - NO x 

### environmental chamber

experiments. ................................ ................................ ................................ ......................... 285 Figure C - 16. Plots of experimental and calculated environmental chamber reactivity results for

propene. ................................ ................................ ................................ ................................ 286 Figure C - 17. Plots of model errors in simulations of the 1 -buteme and 1 -hexene - NO x



### environmental chamber experiments. ................................ ................................ .................. 287 Figure C - 18. Plots of model errors in simulations of the trans - 2 -butene and isobutene - NO x



### environmental chamber experiments. ................................ ................................ .................. 288 Figure C - 19. Plots of experimental and calculated environmental chamber reactivity results for

isobutene and trans - 2 -butene. ................................ ................................ ............................... 289

### LI ST OF FIGURES (continued)

xi Figure C - 20. Plots of model errors in simulations of the isoprene - NO x 

### environmental chamber

experiments. ................................ ................................ ................................ ......................... 290 Figure C - 21. Plots of experimental and calculated environmental chamber reactivity results for

isoprene ................................ ................................ ................................ ................................ 291 Figure C - 22. Plots of model errors in simulations of the terpene - NO x 

### environmental chamber

experiments. ................................ ................................ ................................ ......................... 292 Figure C - 23. Plots of experimental and calculated environmental chamber reactivity results for  -

and  -pinene and d- limonene. ................................ ................................ .............................. 293 Figure C - 24. Plots of experimental and calculated environmental chamber reactivity results for

cyclohexene. ................................ ................................ ................................ ......................... 294 Figure C - 25. Plots of experimental and calculated environmental chamber reactivity results for

styrene. ................................ ................................ ................................ ................................ . 294 Figure C - 26. Plots of model errors in simulations of the benzene and benzene + CO - NO x



### environmental chamber experiments. ................................ ................................ .................. 295 Figure C - 27. Plots of experimental and calculated environmental chamber reactivity results for

benzene. ................................ ................................ ................................ ................................ 296 Figure C - 28. Plots of model errors in simulations of the toluene and toluene + CO - NO x



### environmental chamber experiments. ................................ ................................ .................. 297 Figure C - 29. Plots of model errors in simulations of the ethylbenzene - NO x 

### environmental

chamber experiments. ................................ ................................ ................................ .......... 298 Figure C - 30. Plots of experimental and calculated environmental chamber reactivity results for

toluene and ethylbenzene. ................................ ................................ ................................ .... 299 Figure C - 31. Plots of model errors in simulations of the m -xylene and m -xylene + CO - NO x



### environmental chamber experiments. ................................ ................................ .................. 300 Figure C - 32. Plots of model errors in simulations of the o -xylene - NO x 

### environmental chamb er

experiments. ................................ ................................ ................................ ......................... 301 Figure C - 33. Plots of model errors in simulations of the p -xylene - NO x 

### environmental chamber

experiments. ................................ ................................ ................................ ......................... 302 Figure C - 34. Plots of experimental and calculated environmental chamber reactivity results for mxylene (additional experiments shown on Figure C - 35). ................................ ..................... 303 Figure C - 35. Plots of experimental and calculated environmental chamber reactivity results for mxylene (with variable surrogate conditions), o -xylene, and p -xylene. ................................ . 304 Figure C - 36. Plots of model errors in simulations of the 1,2,3 -trimethylbenzene - NO x



### environmental chamber experiments. ................................ ................................ .................. 305 Figure C - 37. Plots of model errors in simulations of the 1,2,4 -trimethylbenzene - NO x



### environmental chamber experiments. ................................ ................................ .................. 306 Figure C - 38. Plots of model errors in simulations of the 1,3,5 -trimethylbenzene and 1,3,5 -

trimethylbenzene + CO - NO x 

### environmental chamber experiments. ................................ .. 307 Figure C - 39. Plots of experimental and calculated environmental chamber reactivity results for

1,2,3 - , 1,2,4 - and 1,3,4 -trimethylbenzenes. ................................ ................................ .......... 308

### LI ST OF FIGURES (continued)

xii Figure C -40. Plots of model errors in simulations of the naphthalene, 2,3 - dimethyln aphthalene,

and tetralin - NO x 

### environmental chamber experiments. ................................ ..................... 309 Figure C -41. Plots of model errors in simulations of the acetylene - NO x 

### environmental chamber

experiments. ................................ ................................ ................................ ......................... 310 Figure C -42. Plots of experimental and calculated environmental chamber reactivity results for

acetylene. ................................ ................................ ................................ .............................. 311 Figure C -43. Plots of experimental and calculated environmental chamber reactivity results for

methanol and ethanol. ................................ ................................ ................................ .......... 312 Figure C -44. Plots of experimental and calculated environmental chamber reactivity results for

isopropyl alcohol. ................................ ................................ ................................ ................. 313 Figure C -45. Plots of experimental and calculated environmental chamber reactivity results for tbutyl alcohol. ................................ ................................ ................................ ........................ 314 Figure C -46. Plots of exp erimental and calculated environmental chamber reactivity results for 1 - ,

2 - , and 3 - octanol. ................................ ................................ ................................ ................. 315 Figure C -47. Plots of experimental and calculated environmental chamber reactivity results for

ethylene glycol. ................................ ................................ ................................ .................... 316 Figure C -48. Plots of experimental and calculated environmental chamber reactivity results for

propylene glycol . ................................ ................................ ................................ .................. 317 Figure C -49. Plots of experimental and calculated environmental chamber reactivity results for

dimethyl ether and diethyl ether. ................................ ................................ .......................... 318 Figure C - 50. Plots of experimental and calculated environmental chamber reactivity results for

methyl t -butyl ether. ................................ ................................ ................................ ............. 319 Figure C - 51. Plots of experimental and calculated environmental chamber reactivity results for 1 -

methoxy - 2 -propanol. ................................ ................................ ................................ ............ 320 Figure C - 52. Plots of experimental and calculated environmental chamber reactivity results for 2 -

ethoxyethanol and 2 - (2 - ethoxyethoxy) ethanol (DGEE). ................................ .................... 321 Figure C - 53. Plots of experimental and calculated environmental chamber reactivity results for 2 -

butoxyethanol. ................................ ................................ ................................ ...................... 322 Figure C - 54. Plots of experimental and calculated environmental chamber reactivity results for 2 -

(2 -butoxyethoxy) - ethanol. ................................ ................................ ................................ .... 323 Figure C - 55. Plots of experimental and calculated environmental chamber reactivity results for

methyl acetate. ................................ ................................ ................................ ..................... 324 Figure C - 56. Plots of experimental and calculated environmental chamber reactivity results for

ethyl acetate. ................................ ................................ ................................ ......................... 325 Figure C - 57. Plots of experimental and calculated environmental chamber reactivity results for

isopropyl and t -butyl acetates. ................................ ................................ .............................. 326 Figure C - 58. Plots of experimental and calculated environmental chamber reactivity results for

methyl isobutyrate. ................................ ................................ ................................ ............... 327 Figure C - 59. Plots of experimental and calculated environmental chamber reactivity results for

methyl pival ate. ................................ ................................ ................................ .................... 328

### LI ST OF FIGURES (continued)

xiii Figure C - 60. Plots of experimental and calculated environmental chamber reactivity results for nbutyl acetate. ................................ ................................ ................................ ........................ 329 Figure C - 61. Plots of experimental and calculated environmental chamber reactivity results for

dimethyl carbonate and methyl isopropyl carbonate. ................................ ........................... 330 Figure C - 62. Plots of experimental and calculated environmental chamber reactivity results for

propylene carbonate. ................................ ................................ ................................ ............ 331 Figure C - 63. Plots of experimental and calculated environmental chamber reactivity results for 1 -

methoxy - 2 -propyl acetate. ................................ ................................ ................................ .... 332 Figure C - 64. Plots of exp erimental and calculated environmental chamber reactivity results for

dimethyl succinate and dimethyl glutarate. ................................ ................................ .......... 333 Figure C - 65. Plots of experimental and calcul ated environmental chamber reactivity results for

the Texanol® isomers. ................................ ................................ ................................ ......... 334 Figure C - 66. Plots of model errors in simulations of the furan - NO x 

### environmental chamber

experiments. ................................ ................................ ................................ ......................... 335 Figure C - 67. Plots of model errors in simulations of the methyl furan - NO x 

### environmental

chamber experiments. ................................ ................................ ................................ .......... 336 Figure C - 68. Plots of model errors in simulations of the benzyl alcohol and benzyl alcohol + CO -

NO x 

### environmental chamber experiments. ................................ ................................ .......... 337 Figure C - 69. Plots of experimental and calculated environmental chamber reactivity results for

benzyl alcohol. ................................ ................................ ................................ ..................... 338 Figure C - 70. Plots of model errors in simulations of the formaldehyde - NO x 

### environmental

chamber experiments. ................................ ................................ ................................ .......... 339 Figure C - 71. Plots of experimental and calculated environmental chamber reactivity results for

formaldehyde. ................................ ................................ ................................ ...................... 340 Figure C - 72. Plots of model errors in simulations of the acetaldehyde - NO x 

### environmental

chamber experiments. ................................ ................................ ................................ .......... 341 Figure C - 73. Plots of experimental and calculated environmental chamber reactivity results for

acetaldehyde. ................................ ................................ ................................ ........................ 342 Figure C - 74. Plots of model errors in simulations of the acrolein and methacrolein (MA) - NO x



### environmental chamber experiments. ................................ ................................ .................. 343 Figure C - 75. Plots of experimental and calculated environmental chamber reactivity results for

benzaldehyde. ................................ ................................ ................................ ....................... 344 Figure C - 76. Plots of model errors in simulations of the acetone - NO x 

### environmental chamber

experiments. ................................ ................................ ................................ ......................... 345 Figure C - 77. Plots of experimental and calculated environmental chamber reactivity results for

acetone. ................................ ................................ ................................ ................................ 346 Figure C - 78. Plots of model errors in simulations of the methyl ethyl ketone (MEK), 2 -pentanone

(MPK) and 2 -heptanone - NO x 

### environmental chamber experiments. ................................ 347 Figure C - 79. Plots of experimental and calculated environmental chamber reactivity results for

methyl ethyl ketone. ................................ ................................ ................................ ............. 348

### LI ST OF FIGURES (continued)

xiv Figure C - 80. Plots of experimental and calculated environmental chamber reactivity results for 2 -

pentanone. ................................ ................................ ................................ ............................ 349 Figure C - 81. Plots of experimental and calculated environmental chamber reactivity results for 4 -

methyl - 2 -pentanone and 2 - heptanone. ................................ ................................ ................. 350 Figure C - 82. Plots of experimental and calculated environmental chamber reactivity results for

cyclohexanone. ................................ ................................ ................................ ..................... 351 Figure C - 83. Plots of model errors in simulations of the methyl vinyl ketone - NO x 

### environmental

ch amber experiments. ................................ ................................ ................................ .......... 352 Figure C - 84. Plots of experimental and calculated  ([O 3 

### ] - [NO]), cresol, and PAN concentrations

in the cresol - NO x 

### environmental chamber experiments. ................................ .................... 353 Figure C - 85. Plots of experimental and calculated environmental chamber reactivity results for mcresol. ................................ ................................ ................................ ................................ ... 353 Figure C - 86. Plots of experimental and calculated environmental chamber reactivity results for

para toluene isocyanate. ................................ ................................ ................................ ....... 354 Figure C - 87. Plots of experimental and calculated environmental chamber reactivity results for

2,4 -toluene diisocyanate (TDI1) and 2,6 -toluene diisocyanate (TDI2). .............................. 355 Figure C - 88. Plots of experimental and calculated environmental chamber reactivity results for nmethyl - 2 -pyrrolidone. ................................ ................................ ................................ .......... 356 Figure C - 89. Plots of experimental and calculated environmental chamber reactivity results for npropyl bromide and n -butyl bromide. ................................ ................................ .................. 357 F igure C - 90. Plots of experimental and calculated environmental chamber reactivity results for

trichloroethylene. ................................ ................................ ................................ ................. 358 Figure C - 91. Plots of model errors in simulations of the 1,3 - dichloropropene and 1,3 -

dichloropropene + n -butane - NO x 

### environmental chamber experiments. ........................... 359 Figure C - 92. Plots of experimental and calculated environmental chamber reactivity results for

the 1,3 - dichloropropenes. ................................ ................................ ................................ ..... 360 Figure C - 93. Plots of experimental and calculated environmental chamber reactivity results for 2 -

(chloromethyl) - 3 - chloro -propene. ................................ ................................ ........................ 360 Figure C - 94 Plots of model errors in simulations of the chloropicrin (CP)

– alkane - NO x 

### and the

chlorine + alkane - NO x 

### experiments. ................................ ................................ .................. 361 Figure C - 95. Plots of experimental and calculated environmental chamber reactivity results for

chloropicrin. ................................ ................................ ................................ ......................... 362 Figure C - 96. Plots of experimental and calculated environmental chamber reactivity results for

chlorine. Note that chlorine was added to the "base case" experiment after four hours of irradiation. ................................ ................................ ................................ ........................ 362 Figure C - 97. Plots of experimental and calculated environmental chamber reactivity results for

hexamethyldisiloxane, d4 cyclosiloxane, and hydroxymethyldisiloxane. ........................... 363 Figure C - 98. Plots of experimental and calculated environmental chamber reactivity results for

carbon disulfide and methyl isothiocyanate. ................................ ................................ ........ 364

### LI ST OF FIGURES (continued)

xv Figure C - 99. Plots of experimental and calculated O 3 

### , NO, DMSO and formaldehyde in the

dimethyl sulfoxide - NO x 

### environmental chamber experiments. ................................ ......... 365 Figure C - 100. Plots of experimental and calculated environmental chamber reactivity results

for dimethyl sulfoxide. ................................ ................................ ................................ ......... 365 Figure C - 101. Plots of experimental and calculated environmental chamber reactivity results

for s - ethyl dipropylthiocarbamate (EPTC). ................................ ................................ .......... 366 Figure C - 102. Plots of experimental and calculated environmental chamber reactivity results

for the mineral spirits samples studied for Safety- Kleen (Carter et al, 1997e). ................... 367 Figure C - 103. Plots of experimental and calculated environmental chamber reactivity results

for Exxon Exxol® D95 Fluid and Exxon Isopar® M Fluid studied for ExxonMobil (Carter et al, 2000e). ................................ ................................ ................................ ............ 368 Figure C - 104. Plots of experimental and calculated environmental chamber reactivity results

for oxo - decyl Acetate fluid studied for ExxonMobil (Carter et al, 2000e). ......................... 369 Figure C - 105. Plots of experimental and calculated environmental chamber reactivity results

for VMP Naphtha sample studied by Carter and Malkina (2005) and the Kerosene sample studied by Carter and Malkina (2007). ................................ ................................ .... 370 Figure C - 106. Plots of experimental and calculated environmental chamber reactivity results

for the dearomatized alkanes mixed, predominately C 10 

### - C 12 

### (ASTM - 1C), synthetic isoparaffinic alkane mixture, predominately C 10 

### - C 12 

### (ASTM - 3C1), Reduced Aromatics Mineral Spirits (ASTM - 1B), and Regular mineral spirits (ASTM - 1A) solvents studied by Carter and Malkina (2005). ................................ ................................ .. 371 Figure C - 107. Plots of experimental and calculated environmental chamber reactivity results

for the aromatic - 100 solvent studied by Carter and Malkina (2005). ................................ .. 372 Figure C - 108. Plots of experimental and calculated environmental chamber reactivity results

for ethanolamine and isopropyl amine. In order to obtain the fits shown, the initial amine concentrations had to be adjusted to optimize the model fits to the reactivity data. ................................ ................................ ................................ ................................ ...... 372 Figure C - 109. Plots of experimental and calculated environmental chamber reactivity results

for t -butyl amine and 2 - amino - 2 - methyl - 1 -propanol. In order to obtain the fits shown, the initial amine concentrations had to be adjusted to optimize the model fits to the reactivity data. ................................ ................................ ................................ ............ 373 Figure C - 110. Plots of selected experimental and calculated concentration-time plots for the

methyl iodide - NO x 

### , methyl iodide - CO - NO x 

### , and methyl iodide - O 3 

### experiments. ...... 374 Figure C - 111. Plots of experimental and calculated environmental chamber reactivity results

for the methyl iodide experiments of Carter (2007). ................................ ............................ 375

### 1 

### EXECUTIVE SUMMARY **Background** Airshed models are essential for the development of effective control strategies for reducing photochemical air pollution because they provide the only available scientific basis for making quantitative estimates of changes in air quality resulting from changes in emissions. The chemical mechanism is an important component of the model that represents the processes by which emitted volatile organic compound (VOC) pollutants and oxides of nitrogen (NO x

### ) react to form secondary pollutants such as ozone (O 3 

### ) and other oxidants. If the mechanism is incorrect or incomplete in significant respects, then the model's predictions of se condary pollutant formation may also be incorrect, and its use might result in implementation of inappropriate or even counter-productive air pollution control strategies. One airshed model application where the accuracy of the chemical mechanism is important is the calculation of reactivity scales that measure relative impacts of different types of VOCs on ozone formation. VOCs differ significantly in their impacts on O 3 

### formation, and regulations that take this into account are potentially mu ch more cost - effective than those that regulate all VOCs equally. In view of this, several VOC regulations implemented (or being considered) in California take reactivity into account. The current California regulations use the Maximum Incremental Reactivity (MIR) scale calculated using the SAPRC - 99 chemical mechanism. The SAPRC - 99 mechanism includes representations of atmospheric reactions of almost 780 types of VOCs for reactivity assessment, and is widely used in other airshed modeling applications for research and regulatory applications. Although this represented the state of the art at the time it was developed, since then there has been continued progress in basic atmospheric chemistry, and new information has become available concerning the reactions and O 3 

### impacts of many individual VOCs. In addition, the California Air Resources Board (CARB) is obligated to update the reactivity scales used in its regulations approximately every three years so they reflect the current state of the science. Since the mechanism was developed in 1999, updates to the mechanism and the reactivity scale are now due. Another reason for updating the SAPRC mechanism is to make it more suitable for prediction of secondary particulate matter (PM), which is another air quality issue o f concern. SAPRC - 99, like most other mechanisms used in current airshed models, incorporates simplifications and approximations that may be appropriate for O 3 

### modeling, but that restricts its capability to represent how secondary organic aerosol (SOA) formation is affected by chemical conditions. This needs to be addressed. Inview of this, the CARB funded us to provide an update to the SAPRC - 99 mechanism used for modeling and VOC reactivity assessment, and to provide some needed improvements and enhancements. This report documents this mechanism, its evaluation against available environmental chamber data, and the updated reactivity scales that were developed. **Accomplishments** The maj or accomplishment of this project is the development of the SAPRC - 07 chemic al mechanism and its associated reactivity scales, which are documented in this report. Specific accomplishments are summarized as follows. Base mechanism updated . All the reactions and rate constants in the mechanism have been reviewed based on results of current evaluations, and updated as needed. Most of the rate constant changes were relatively small, but a few errors were found and corrected and some potentially significant changes occurred. These have been assessed in the evaluations against chamber data.

### 2

Aromatics mechanisms reformulated . The mechanisms for the aromatic ring fragmentation reactions were reformulated to be more consistent with estimated explicit mechanisms, and to give predictions that are somewhat more consistent with available data. However, although an improvement over that used in SAPRC - 99, the updated mechanism is still simplified in many respects, and is still not completely consistent with all of the available data Chlorine chemistry added . A representation of chlorine chemistry has been added to the mechanism as an optional capability. In addition to improving the ability of airshed models to simulate air quality in regions impacted by chlorine emissions, the representation of chlorine chemistry has resulted in reduced uncertainties in reactivity estimates for chlorinated VOCs. Capability for adaptation to SOA predictions improved . The method that the mechanism used to represent the reactions of peroxy radicals was reformulated so that effects of changes in NO x 

### conditions on organic product formation can be more accurately represented. Because development of SOA mechanisms was beyond the scope of this project, the current mechanism does not fully take advantage of this capability, but it provides a framework upon which improved SOA mechanisms can be developed. Mechanisms for many types of VOCs added or improved . The number of types of VOCs for which reactivity estimates have been made has been increased by over 20%, and the methods used to estimate mechanisms for a number of compounds were improved. This has involved enhancements of the capabilities of the mechanism estimation and generation system that is used to derive many of the mechanisms, and deriving estimated mechanisms for new classes of VOCs. A few errors found in the SAPRC - 99 mechanism for some VOCs were corrected. Updated mechanism evaluated against chamber experiments . The updated mechanism was comprehensively evaluated by comparing predictions with results of all environmental chamber experiments used for SAPRC - 99 evaluation, plus the results of more recent UCR experiments, and experiments in other chambers. The results are summarized below. Reactivity scales updated . The updated mechanism used to calculate MIR and other reactivity scales for all the ~1100 types of VOCs that are currently represented. Uncertainty classifications were also updated as part of this work. Iti s recommended that these be used to supercede the reactivity values distributed previously. The mechanism developed in this project was implemented for the box model calculations used for reactivity scale calculations, and the data files used in this implementation can serve as the basis for implementing in more comprehensive airshed models such as CMAQ or CAMx. The data files are being made available at the project web site at http://www.cert.ucr.edu/~carter/SAPRC. **Results** Evaluation Results . In ge neral, the performance of the updated mechanism in simulating the available environmental chamber data for individual compounds was comparable to SAPRC - 99, though there were some differences. Some uncertain parameters for some compounds that were adjusted to fit the data for SAPRC - 99 had to be re - adjusted for this mechanism. The updated aromatic mechanism simulated most of the experiments about as well as SAPRC - 9 9, but some discrepancies observed with the previous version were reduced. Model performance was improved in simulating data for some compounds whose mechanisms were not changed, but biases were slightly increased with others. This is attributed to changes in the base mechanism, but the specific causes have not been determined. One area of potential concern is that the mechanism update caused a slight increase in overall biases in model simulations of experiments with mixtures of VOCs. These changes are small compared to the  30% variability of the fits overall

– which is less than the average biases

– but because of the large number of such experiments (>1500 total) it may be statistically significant. The mechanism update also did not solve the problem, noted previously for other mechanisms, of underpredicting O 3 

### formation and

### 3

NO oxidation in ambient surrogate - NO x 

### experiments carried out at relatively low NO x 

### levels in the new UCR EPA cham

ber. These biases cannot be attributed to problems with individual VOCs, whose experiments are generally reasonably well simulated. Preliminary assessment of impacts of updates on predictions of ambient ozone . Results of box model simulations of 1 - day urban scenarios used for the reactivity scales indicate that the mechanism update caused changes in maximum ozone concentrations ranging from a ~10% decrease to a ~5% increase, with the predicted O 3 

### decreasing by about 5% on average. T he largest increase appears at the lower ROG/NO x 

### ratios, but other factors appear to be equally important. However, the scenarios used in the reactivity assessment calculations are highly simplified representations of ambient conditions, and comprehensive models are needed to fully assess the impacts of this update on ambient ozone and control strategy predictions. Reactivity Scale Update . F or most VOCs, the reactivity scale update did significantly affect the reactivity values, with the average change in relative MIR values for the VOCs on the previous scales, being on the order of 10%. However, the MIR value changed by more than 5% for 56% of the VOCs given in the previous tabulation. The MIR change was less than 30% for approximately 93% of these VOCs, but 35 VOCs had changes greater than 35% and 5 VOCs had changes greater than a factor of 2. The latter consisted of halogenated compounds and one compound where a rate constant error was corrected. **Recommendations** Although the accomplishments of this project were significant, there were some objectives of this project that could not be met within the available time and resource, and there are other areas where additional work is recommended. These are summarized below. Aromatics Mechanisms . Although the aromatics mechanisms developed in this work represent an improvement, problems remain and addi tional work is needed. Work was begun during this project in developing a more explicit aromatics mechanism, and new environmental chamber data useful for this effort was obtained. Work in this area needs to continue. Chlorine and Halogen Mechanisms . Uncertainties remain in the mechanisms of halogenated compounds. Estimation me thods need to be developed for reactions of halogen - containing radicals, and reactivities of halogenated oxidation products need to be assessed. Reactivity data are available for only a limited number of such compounds, and the available data indicates problems that need to be addressed. Mechanisms for bromine chemistry need to be developed. Mechanism Generation System . An important component of the current mechanism is the mechanism generation and estimation system that is used to derive the mechanisms for most of the non aromatic VOCs that are represented. However, because of time constraints we were unable to update most of the estimation methods incorporated in the system, except f or the initial VOC rate constants and those related to chlorine chemistry. This needs to be done. The capability of the system needs to be enhanced to more reliably estimate mechanisms for additional classes of VOCs and intermediates, such as halogenated radicals, aromatics, and aromatic products. This will make it valuable for future mechanism improvements and reactivity scale updates. Finally, the system needs to be undergo peer review and be documented in the peer-reviewed literature. Adaptation to SOA Predictions . Although the capability of the mechanism for improved SOA predictions has been enhanced, the potential of this capability has not been exploited. Recommendations in this regard include adding new species to the mechanism to represent low volatility products, implementing methods in the mechanism generation system to estimate volatility and incorporate them in the mechanisms so derived, and evaluating the predictions against SOA formation measured in chamber experiments.

### 4

Mechanism Performance I ssues . The reason that the mechanism has biases in simulations of mixture experiments, while simulating single compound experiments reasonably well, needs to be investigated. This is necessary to assess the implications on ambient simulations of the biases in the simulations of the mixture experiments that were found, and for developing methods to reduce these biases. The reason for the relatively poor performance of the mechanisms in simulating the University of North Carolina outdoor chamber database also needs to be investigated. Although existing tools involved in sensitivity, uncertainty, and process analysis may be useful, new analysis methods probably need to be developed. This is an area where original research is needed. Mechanism Evaluation Databas e . Although the database of chamber experiments useful for mechanism evaluation is very extensive and comprehensive in some respects, there are gaps and problems that need to be addressed. There are a number of classes of compounds where reactivity chamber data are needed to reduce mechanism uncertainties. Incremental reactivity experiments need to be developed that are more sensitive to reactions of organic oxidation products, which affect predicted reactivities in ambient scenarios much more than in chamb er experiments. The current chamber dataset is not adequate for evaluating effects of temperature on mechanism performance. Experiments are needed for testing mechanisms for predictions of SOA formation, particularly under lower pollutant conditions more representative of ambient conditions than are most PM chamber data. Mechanism Condensation . One of the objectives of this project that was not accomplished was to develop a condensed version of the mechanism to serve as an alternative to CB4/CB05 for modeling applications where computer speed is more important than chemical detail. This still needs to be done. Reactivity Scenarios . The scenarios used for deriving the reactivity scales developed in this work are poorly documented, oversimplified, and do not represent current ambient conditions. Evaluations carried out by the Reactivity Research Working Group (RRWG) indicate that this methodology could be improved in a number of respects, particularly the scenarios and modeling methods. This update is way overd ue, and may result in changes in relative reactivity values that are greater than those resulting from updates to the mechanism. Next Mechanism Update . The CARB is still committed to updating its regulatory reactivity scale on a periodic basis. This will obviously need to include updated reactivity scenarios, as indicated above. Another problem is that the developer of the SAPRC mechanisms and the MIR s cale is now semi -retired, and may be completely retired by the time the next update is needed, and it is unclear who will be carrying out this work in the future. Funding agencies need to show an interest in providing support for this type of mechanism development on a sufficiently consistent basis that it will attract younger researchers into this field. As it is now, support for mechanism development is relatively limited, and not of the type needed for the long -term commitment that this type or research requires.

### 5 

### INTRODUCTION Airshed models are essential for the development of effective control strategies for reducing photochemical air pollution because they provide the only available scientific basis for making quantitative estimates of changes in air quality resulting from changes in emissions. The chemical mechanism is the portion of the model that represents the processes by which emitted primary pollutants, such as volatile organic compounds (VOCs) and oxides of nitrogen (NO x

### ), interact in the gas pha se to form secondary pollutants such as ozone (O 3 

### ) and other oxidants. This is an important component of airshed models because if the mechanism is incorrect or incomplete in significant respects, then the model's predictions of secondary pollutant formati on may also be incorrect, and its use might result in implementation of inappropriate or even counter-productive air pollution control strategies. One airshed model application where the accuracy of the chemical mechanism is particularly important is the a ssessment or implementation of control strategies to encourage use of VOCs that have lower impacts on ozone or other secondary pollutant formation than VOCs that are currently emitted. Such strategies require a means to quantify the impacts, or "reactiviti es" of the VOCs with respect to O 3 

### or other measures of air quality. There are several examples of control strategies where accurate O 3 

### reactivity estimates are important. In the California Air Resources Board (CARB)’s "Low Emissions Vehicle/Clean Fuels" regulations, "reactivity adjustment factors" are used to place exhaust emissions standards for alternatively - fueled vehicles on an equal ozone impact basis as those for vehicles using conventional gasoline (CARB, 1993). More recently, the CARB implemented reactivity -based regulations for aerosol coatings (CARB, 2000), and is considering expanding such regulations to other types of stationary sources (e.g., CARB, 2006, 2007). In addition, the EPA has used O 3 

### impacts of VOCs calculated for various environments among the factors they consider when evaluating proposals to exempt various compounds from controls as ozone precursors (Dimitriades, 1999). The MIR scale initially adopted in the CARB vehicle regulation was calculated using the SAPRC - 90 chemical mechani sm (Carter, 1990), but it has since been recalculated using an updated version of this mechanism, designated SAPRC - 99 (Carter, 2000, 2003a). This mechanism has assigned or estimated mechanisms for over 500 types of VOCs. Although other state - of -the - art mec hanisms are available for airshed model applications (e.g., Stockwell et al, 1997; Yarwood et al, 2005, Jenkin et al, 2003; Saunders et al, 2003), the SAPRC mechanisms were used for this purpose because they are the only mechanisms that represent a large number of VOCs that was comprehensively evaluated against environmental chamber data. However, although the SAPRC - 99 mechanism represented the state of the art at the time it was developed, since then there has been continued progress in basic atmospheric c hemistry, and new information has become available concerning the reactions and O 3 

### impacts of many individual VOCs. In addition, the CARB is obligated to update the reactivity scales used in its regulations approximately every three years so they reflect the current state of the science. Since the last update was made in 2003 (Carter, 2003a), updates to the scale are now due. In addition to calculation of reactivity scales for regulatory applications, a condensed version of the SAPRC - 99 mechanism (Carter, 2 000b) is widely used in comprehensive airshed models for prediction of effects of emissions on secondary pollutant formation in regional and urban atmospheres. Such regional models are required for many research and regulatory applications, so they should represent the current state of the science. In the United States, the two alternative mechanisms most generally used in comprehensive airshed models are the Carbon Bond 4 (CB4) (Gery et al, 1988) and the SAPRC - 99 mechanism, and the two mechanisms have been found to give quite different predictions in some cases. The use of CB4 is preferred for many model applications because of it compact nature and because it is more computationally efficient, but SAPRC - 99 is preferred in applications where chemical accuracy is a priority because it is more chemically detailed and more comprehensively evaluated against available environmental chamber data. CB4 has recently been updated to "Carbon Bond 05" (CB05) (Yarwood et

### 6

al, 2005; Sarwar et al, 2008), and this is now being implemented in such models. Therefore, SAPRC - 99 needs to be updated so it can continue to be a viable alternative to the Carbon Bond mechanisms for applications where chemical accuracy is a priority. Another reason for updating the SAPRC mechanism is to make it more suitable for prediction of secondary particulate matter (PM). Fine particulate matter pollution an important issue because of the maj or health impacts it is believed to cause, and secondary PM is a maj or contribution to this problem. The formation of secondary PM is even more complex and incompletely understood than the formation of ozone. Models for prediction of secondary PM have appended aerosol models to gas -phase mechanisms such as SAPRC - 99 and CB4, but the treatment is necessarily parame terized and approximate because of the condensation approaches incorporated in these mechanisms. These approaches may be appropriate for ozone modeling, but are not necessarily appropriate for prediction of secondary organic aerosol. For example, such mech anism use lumped species to represent oxidation products based on their gas -phase reactivity, but without considerations of volatility, which is the maj or factor in secondary organic aerosol (SOA) formation. Inaddition, SAPRC - 99, like CB4 and CB05, uses a condensed method to represent the many peroxy + peroxy radical reactions that does not readily permit models to represent how organic product distributions may change under very low NO x 

### conditions where these reactions are important. Recent data (e.g., Song et al, 2005) indicate that, at least for aromatics, secondary PM formation may be much more dependent on NO x 

### conditions than represented in current models. The condensation methods used in current mechanisms need to be modified to be more suitably adapted for models for PM prediction Based on these considerations, the California Air Resources Board funded us to develop and document an updated version of the SAPRC mechanism, and use it to derive updated MIR and other VOC ozone reactivity scales. The speci fic objectives of the project were as follows:  Update rate constants and reactions to current state of science.  Improve mechanisms for aromatics to incorporate new data and improve performance in simulating available chamber data.  Conduct environmental cha mber experiments as appropriate to support this effort.  Add chlorine chemistry, to support modeling areas impacted by chlorine emissions and also calculating reactivities of chlorinated organics.  Update and enhance the mechanism generation system used to derive the mechanisms for most of the VOCs (Carter, 2000a). This includes updating the estimation methods and assignments as needed, and also enhancing the capabilities of the system, e.g., to support generating explicit mechanisms for aromatics and chlorin e atom reactions;  Improve capability of the mechanism to be adapted to secondary PM models  Increase the number of VOC mechanisms to include more compounds present in emissions inventories or otherwise of interest to the CARB.  Develop new condensed mechanis ms from the detailed version (including a highly condensed version as an alternative to CB4).  Make the mechanism available for implementation in airshed models  Calculate updated reactivity scales and update associated uncertainty classifications. The maj or accomplishments of this project are the development of a completely updated version of SAPRC - 99, which is designated SAPRC - 07 1 

### , and the update of the associated MIR and other reactivity

1 

### SAPRC stands for "Statewide Air Pollution Research Center", which is the unit at the University of California at Riverside where the SAPRC mechanisms were initially developed. Thi s unit has since been

### 7

scales, and their uncertainty classifications. The bulk of this repor t consists of the documentation of this mechanism and its evaluation, and the reactivity scales. The final section of this report includes a summary of the accomplishments of this project, the objectives that were not fully addressed, recommendations for f

uture research.

renamed to "Air Pollution Research Center" (APRC), so strictly speaking this acronym is no longer meaningful. However, this designation for these mechanisms is retained for continuity.

### 8 

### MECHANISM DOCUMENTAT **ION** The maj or components of the SAPRC mechanisms are the base mechanism used to represent the reactions of the inorganic reactants and the common organic oxidation products and radicals, the representation of the reactions of the individual VOCs , the lumped mechanism used for complex mixtures in airshed models, and the emissions assignments necessary for implementing the mechanism in airshed models. The general structure of this mechanism is essentially the same as that f or SAPRC - 99 mechanism documented by Carter (2000a), except that in this case chlorine chemistry is added and can be incorporated in the base and lumped mechanisms as an option, and is incorporated in representations and reactivity calculations for halogenated VOCs as needed. Each of these components, and their updates relative to SAPRC - 99 are discussed in this section of this report. Reference is made to the comprehensive documentation of the SAPRC - 99 mechanism (Carter, 2000a) for documentation of the featu res of the mechanism that were retained in this version, so that document must be considered an integral part of the documentation of this mechanism. Appendices to the report include the tabulations or data plots that are too large to include in the main b ody of the text, and additional information, such as complete listings of the mechanisms of the over 700 types of VOCs that are explicitly represented, is available in electronic form at the SAPRC mechanism website at http://www.cert.ucr.edu/~carter/SAPRC. **Base Mechanism** The base mechanism is the portion of the mechanism that represents the reactions of the inorganic species, the common organic products, and the intermediate radicals leading to these products, including those formed from the initial reactio ns of the represented VOCs not in the base mechanism. Most of the VOCs that can be separately represented are not in the base mechanism, but can be added to the mechanism, either as explicit reactions for individual VOCs or as lumped model species whose parameters are derived from the mixture of detailed model species they represent, as needed in the model application. However, a few VOCs are represented explicitly and incorporated in the base mechanism, either because they are also common organic oxidation products that are represented explicitly, or are sufficiently important in emissions inventories and have sufficiently different mechanisms than most other VOCs that representation with lumped model species is inappropriate. These include formaldehyde, ac etaldehyde, acetone, ethylene, isoprene, and (new to this version) benzene and acetylene. This portion of the mechanism is discussed in this section. **Listing of Standard Base Mechanism and Summary of Changes** The "Standard Base Mechanism" is the portion of the base mechanism excluding the optional additional reactions used to represent chlorine chemistry, and is the portion that is directly comparable to the SAPRC - 99 base mechanism. Table A - 1 in Appendix A gives the list of model species used in the standard base SAPRC - 07 mechanism. These include the inorganic reactants, common reactive organic product species, chemical operators used to represent peroxy radical reactions (discussed below), and explicitly represented primary organics. Except as discussed below, the species used are the same as in the base SAPRC - 99, though some model species have been renamed to be more compatible with some airshed model software systems. The changes, and additions, are as follows:  The set of lumped peroxy radical species and chemical operators was changed because as discussed in the "Project Summary" section, above, a different method was used to represent peroxy radical reactions. SAPRC - 99 used three active chemical operators (RO2 - R., RO2 -N., and R2O2.) to represent the effects of peroxy radical reactions on NO x 

### and organic nitrates. The updated mechanism uses two active chemical operators (RO2C and RO2XC) to represent the

### 9

effects of peroxy radical reactions on NO x 

### and 34 steady - state operators to represent the effects on formation of organic products (not counting the 3 used in the added chlorine mechanism). Two additional model species were added to represent the reactions of the higher hydroperoxides that were previously lumped with one generic hydroperoxide species in SAPRC - 99. These higher hydroperoxides are expected to have different reactivities and SOA formation potentials than propyl hydroperoxide, which was used as the basis for the single generic hydroperoxide in SAPRC - 99.  Although three active model species are still used to represent the reactions of the unsaturated aromatic ring fragmentation products, the types of compounds they represent have been changed. This is discussed in conjunction with the discussion of the revised aromatic mechanisms, below.  The reactions of formic acid, acetic acid, and the lumped higher organic acids were added to the mechanism. These species were in SAPRC - 99 as inert tracers, but their reactions wi th OH radicals were added to this mechanism because they may be non -negligible loss processes in some regional modeling applications.  Acetylene and benzene are now represented explicitly in this mechanism. This is because both compounds are relatively impo rtant in emissions inventories, their reactivities are quite different than the other compounds with which they previously w ere lum

ped (monoalkylbenzenes and low reactivity alkanes, respectively), and are not well represented by other species used in the lumped mechanism. In addition, explicit simulations of benzene are of interest for toxics modeling, and acetylene can provide a useful tracer for vehicle emissions. Although the objective of this update was to provide a mechanism with similar or, if appropriate, greater level of detail as SAPRC - 99, a few SAPRC - 99 model species were judged to be unnecessary and were removed from this version. These are as follows.  Phenol was removed from the mechanism because it is important only in the oxidation of benzene, and representing it by the lumped cresol species (CRES) did not significantly affect results of simulations of benzene, whose mechanism is very uncertain in any case.  The SAPRC - 99 model species BZNO2 - O, used in the mechanism for the reaction of NO 3 

### with lumped nitrophenols, was removed. Itw as found that representing it with the phenoxy model species used in the cresol mechanism gave model simulations that were essentially the same, especially considering the large uncertainty in the nitrophenol and cresol mechanisms.  The SAPRC - 99 model species CCO - OOH and RCO - OOH, used to represent various peroxy acids formed in the reactions of acyl peroxy radicals with HO 2 

### , were removed. These are represented by the reactions of the corresponding acid model species. Itw a s judged that separate representation of these species was not necessary, though this could be changed in future versions of the mechanism if desired. The reactions and rate parameters used in the base mechanism are given in Table A - 2 in Appendix A, and Table A - 3 gives the absorption cross sections and quantum yields used for the p hotolysis reactions listed in this table. Footnotes to Table A - 2 indicate the source of the rate constants and mechanisms used. As indicated there, most of the update d rate constants are based on results of the IUPAC (2006) and NASA (2006) evaluations, though a number of other sources were also used as the basis for the updates. The maj or changes to the inorganic and common organic radical and product mechanisms are di scussed further below. The changes to the mechanisms for the explicitly represented species are discussed later in conjunction with the mechanisms for the other individual VOCs. Table 1 shows the changes in rate constants or atmospheric photolysis rates for this version of the base mechanism compared to SAPRC - 99, for the cases where the rate constants or photolysis rates were changed by more than 5%. Reactions used to represent unsaturated aromatic ring fragmentation products, or reactions of chemical operators used to represent peroxy radical reactions are not shown because the

### 10

representations are not comparable on a reaction -by - reaction basis; these are discussed below or later in this report. Specific changes of potential interest are as follows.  The most important single change to the base mechanism may be the ~19% increase in the rate constant for the OH + NO 2 

### reaction, based on the results of the recent NASA (2006) evaluation. This affected the mechanism evaluation against the chamber experiments because it required re deriving some chamber effects parameters and also some uncertain mechanistic parameters derived to fit chamber data. Iti s also expected to result in somewhat lower O 3 

### predictions in ambient simulations, though this may be offset somewhat by the changes in the parameters adjusted to fit chamber data.  The ~7% increase in the NO 2 

### photolysis rate under atmospheric conditions has no effect on NO 2 

### photolysis rates used in chamber simulations because all photolysis rates are normalized to measured NO 2 

### photolysis rates. However, rates of other photolysis reactions in chamber simulations will decrease accordingly.  There was a relatively large increase in the cal culated atmospheric photolysis rates for the  - dicarbonyl aromatic ring fragmentation products. However, this will not result in increases in calculated reactivities of aromatics because of changes that were made to the representation of the other reactive aromatic fragmentation products, discussed later in this report.  The ~30% increase in the calculated photolysis rates for methacrolein and the model species used to represent C 5 

### aldehyde products formed from isoprene did not seem to have a significant effect on simulations of isoprene chamber experiments or calculations of the atmospheric reactivity of this important biogenic compound. Despite the relatively large decrease in the peroxy + HO 2 

### rate constant, this reaction is still calculated to be the maj or loss process for peroxy radicals competing with reaction with NO under low NO x 

### conditions.  The photolysis of PAN was added to the mechanism at the request of Deborah Luecken of the EPA . Although not important in urban simulations, this reaction may be important under low temperature conditions such as occur at higher altitudes.  New information available concerning the reactions of nitrophenols indicates that the maj or atmospheric loss p rocesses are photolysis and reactions with OH (see footnotes for these reactions on Table A - 2 ). The speculative reaction of nitrophenols with NO 3 

### was deleted, though it may still occur to some extent.  As discussed below, the mechanism for PROD2 is based on mechanism for various C 5 

### - C 9 

### ketones. The updated mechanism gives better simulations of incremental reactivity environmental chamber experiments for higher ketones if lower photolysis rates for higher ketones are assumed (see discussion of mechanisms of individual VOCs and the evaluation against chamber experiments later in this report). The overall quantum yield for photolyses of C 7+ 

### ketones are set to a sufficiently l ow value that photolysis is unimportant. This is reflected in the average overall quantum yield used for PROD2.  As indicated above, several model species were removed and the base mechanism now explicitly represents the reactions of some additional compounds. These changes should have relatively small effects on most simulations except that atmospheric simulations will now simulate these species explicitly, rather than ignoring their reactions (as with the acids) or lumping them with other compounds. Note that this change does not, by itself, affect reactivity calculations for these compounds because the compound of interest (or the compound used to represent them if the "lumped molecule" approach is used) is always represented explicitly in reactivity calculations.

### 11

Table 1 . Reactions where the rate constants or photolysis rates changed by more than 5% or that

were added or removed in the standard base mechanism relative to SAPRC - 99 . Rate constant or photolysis rate [a] Reaction [b] Notes [c] SAPRC - 07 SAPRC - 99 Change 7.23e - 1 6.69e - 1 8% NO2 + HV = NO + O3P 1 1.64e - 12 2.45e - 12 - 33% O3P + NO = NO2 1.03e - 11 9.70e - 12 6% O3P + NO2 = NO + O2 3.24e - 12 1.79e - 12 81% O3P + NO2 = NO3 2 2.02e - 14 1.87e - 14 8% O3 + NO = NO2 + O2 1.24e - 12 1.53e - 12 - 19% NO2 + NO3 = N2O5 5.69e - 2 6.74e - 2 - 16% N2O5 = NO2 + NO3 1.80e - 39 N2O5 + H2O + H2O = #2 HNO3 + H2O 3 1.91e+0 1.59e+0 20% NO3 + HV = NO + O2 1.99e - 10 2.20e - 10 - 10% O1D + H2O = #2 OH 3.28e - 11 2.87e - 11 14% O1D + M = O3P + M 1.14e - 1 1.27e - 1 - 10% HONO + HV = OH + NO

- 1.60e - 2 HONO + HV = HO2 + NO2 5.95e - 12 6.42e - 12 - 7% OH + HONO = H2O + NO2 1.05e - 11 8.81e - 12 19% OH + NO2 = HNO3 1 2.28e - 13 2.08e - 13 10% OH + CO = HO2 + CO2 7.41e - 14 6.78e - 14 9% OH + O3 = HO2 + O2 8.85e - 12 8.36e - 12 6% HO2 + NO = OH + NO2 1.12e - 12 1.36e - 12 - 18% HO2 + NO2 = HNO4 1.07e - 1 9.61e - 2 11% HNO4 = HO2 + NO2 5.42e -4 4.69e -4 16% HNO4 + HV = Products 4.61e - 12 4.98e - 12 - 7% HNO4 + OH = H2O + NO2 + O2 1.69e - 15 1.89e - 15 - 11% HO2 + O3 = OH + #2 O2 1.80e - 12 1.70e - 12 6% HO2H + OH = HO2 + H2O 4.65e - 12 5.12e - 12 - 9% MEO2 + HO2 = COOH + O2 4.50e - 13 MEO2 + HO2 = HCHO + O2 + H2O 2.16e - 13 2.61e - 13 - 17% MEO2 + MEO2 = MEOH + HCHO + O2 1.31e - 13 1.08e - 13 21% MEO2 + MEO2 = #2 {HCHO + HO2} 7.63e - 12 1.45e - 11 -47% Peroxy + HO2 = Products 4 9.37e - 12 1.04e - 11 - 10% MECO3 + NO2 = PAN 6.27e -4 7.04e -4 - 11% PAN = MECO3 + NO2 6.12e - 5 PAN + HV = Products 1 

### 1.97e - 11 2.12e - 11 - 7% MECO3 + NO = MEO2 + CO2 + NO2 2.30e - 12 4.00e - 12 -43% MECO3 + NO3 = Products 2,5 1.06e - 11 9.53e - 12 11% MECO3 + MEO2 = Products 5 1.56e - 11 7.50e - 12 108% MECO3 + Peroxy = Products 2,4,5 5.48e -4 5.90e -4 - 7% PAN2 = RCO3 + NO2 2.08e - 11 2.78e - 11 - 25% RCO3 + NO = Products 7.63e - 12 1.45e - 11 -47% BZO + HO2 = CRES

3.80e - 11 BZNO2 - O. + NO2 = inert products 6 1.49e - 11 BZNO2 - O. + HO2 = NPHE 6 1.00e - 3 BZNO2 - O. = NPHE 6 2.76e - 3 2.32e - 3 19% HCHO + HV = #2 HO2 + CO 8.47e - 12 9.19e - 12 - 8% HCHO + OH = HO2 + CO + H2O

### Table 1 (continued)

12

Rate constant or photolysis rate [a] Reaction [b] Notes [c] SAPRC - 07 SAPRC - 99 Change 1.49e - 11 1.57e - 11 - 6% CCHO + OH = MECO3 + H2O 6.74e - 15 3.82e - 15 76% RCHO + NO3 = HNO3 + RCO3 3.24e - 5 4.16e - 5 - 22% ACET + HV = Products 1.69e -4 1.42e -4 19% MEK + HV = Products 6.78e - 12 1.10e - 11 - 38% ROOH + OH = Products 3.18e - 3 1.08e - 3 193% GLY + HV = HCHO + CO 1.56e - 2 1.10e - 2 42% MGLY + HV = HO2 + CO + MECO3 2.67e - 2 1.90e - 2 41% BACL + HV = #2 MECO3

2.63e - 11 PHEN + OH = products 6 

### 3.78e - 12 PHEN + NO3 = products 6 

### 3.50e - 12 - NPHE + OH = BZO + XN 1



### 3.78e - 12 NPHE + NO3 = products 1 

### 1.08e - 3 NPHE + HV = HONO + #6 XC 1 

### 1.08e - 2 NPHE + HV = #6 XC + XN 1 

### 1.20e - 11 1.29e - 11 - 7% BALD + OH = BZCO3 2.84e - 11 3.35e - 11 - 15% MACR + OH = Products 1.28e - 18 1.19e - 18 8% MACR + O3 = Products 3.54e - 15 4.76e - 15 - 26% MACR + NO3 = Products 1.97e -4 1.36e -4 45% MACR + HV = Products 1.99e - 11 1.87e - 11 6% MVK + OH = Products 5.36e - 18 4.74e - 18 13% MVK + O3 = Products 7.50e - 5 6.97e - 5 8% MVK + HV = Products 1.97e -4 1.36e -4 45% IPRD + HV = Products 4.69e - 6 1.90e - 5 - 75% PROD2 + HV = Products 1 

### 7.20e - 12 7.80e - 12 - 8% RNO3 + OH = Products 4.50e - 13 HCOOH + OH = HO2 + CO2 7 7.26e - 13 CCOOH + OH =products 7 1.20e - 12 RCOOH + OH = products 7 1.64e - 11 - R6OOH + OH = products 7 3.94e -4 - R6OOH + HV = products 7 1.08e - 10 - RAOOH + OH = products 7 3.94e -4 RAOOH + HV = products 7 7.56e - 13 ACETYLEN + OH = products 7 1.16e - 20 ACETYLEN + O3 = products 7 1.22e - 12 BENZENE + OH = products 7 [a] Rate constants are for T=300 o 

### K and are in molecule, cm3 

### sec - 1 

### units. Photolysis rates are calculated for direct overhead sunlight based on the actinic fluxes used in the reactivity scale calculations (Carter, 1994a,b). [b] Reactions used to represent unsaturated aromatic ring fragmentation products, and reactions of chemical operators used to represent peroxy radical reactions, are not directly comparable in the two mechanisms. They are discussed separately later in this report. [c] Notes concerning changes for reaction. See also text and footnotes to Table A - 2 1 See text for a discussion of this change. 2 This is a relatively minor process under most conditions of interest, so the change should not have a significant effect on most model predictions.

### Table 1 (continued)

13

3 This reaction is added to represent the expected humidity dependence of this process. 4 "Peroxy" refers to the various model species used to represent various types of peroxy radicals or peroxy radical operators. 5 The same rate constants are used for all the higher acyl peroxy radical model species. 6 This model species was deleted. See text. 7 The reactions of these compounds were added to the base mechanism. See text. Note that the discussion given above of expected effects of these changes on model simulations is based on expectations that have not, in most cases, been verified by actual model sensitivity calculations. Such sensitivity calculations would be useful to assess the effects of various changes, and help focus on areas where basic research may be useful. **Representation of Peroxy Radical Operators** Because of the large number of peroxy radicals that a re involved even in condensed atmospheric chemistry mechanisms, it is generally not practical to represent the many possible peroxy + peroxy reactions explicitly, especially considering that under most conditions, especially conditions favorable for O 3 

### formation, most of these reactions are relatively unimportant. Even highly explicit mechanisms such as the MCM (Jenkin et al, 2003; Saunders et al, 2003) use an approximate method to represent the many peroxy + peroxy cross reactions involving a chemical operator representing the total peroxy radical concentration. The RADM - 2 and RACM mechanisms (Stockwell et al, 1990, 1997) have separate peroxy radical species for each VOC or VOC product model species whose reactions form peroxy radicals, but neglect peroxy + peroxy reactions except for those involving HO 2 

### and methyl peroxy radicals. Because of the large number of reactions and model species involved even with the more approximate RADM - 2 representation, SAPRC - 99 represents methyl peroxy radicals explicitly, but uses a limited number of "chemical operators" to represent effects of peroxy radical reactions on NO x 

### and radicals, and represents the organic products formed when higher peroxy radicals react with other peroxy radicals by those formed when they react with NO x 

### . The CB4/05 mechanisms use a similar, though somewhat more condensed approach. Use of these condensed representations of peroxy radical reactions has been shown to have relatively little effects on predictions of O 3 

### formation and overall gas -phase reactivity because they involve no approximation when the major fate of peroxy radicals is reaction with NO , 

### as is the case when O 3 

### formation occurs, and because they gi ve reasonably good representations of how NO to NO 2 

### conversions, organic nitrate formation, and regeneration of radicals change when NO x 

### levels are reduced to the point where the competing peroxy + peroxy become non -negligible. However the representations incorporated in SAPRC - 99 and CB4/05 do not represent the changes in organic oxidation products that occur when these peroxy + peroxy reactions become non -negligible, since they use the set of products formed in the peroxy + NO reaction as the surrogate for the generally different products formed in the competing reactions. The inability of this representation to represent the formation of hydroperoxides formed in the peroxy + HO 2 

### reaction is o f particular concern, because these are predicted to be the maj or competing products formed under low NO x 

### conditions (e.g., see Carter, 2004), and as discussed above are believed to be important precursors to secondary organic aerosol (SOA) formation. Therefore, the peroxy radical representation used in SAPRC - 99 is not satisfactory for use of the mechanism for prediction of SOA formation, and for this reason was changed as part of this update. The peroxy radical operator method implemented in SAPRC - 99 is de scribed in the SAPRC - 99 documentation (Carter, 2000a). Briefly, it involves the operator RO2 - R. to represent the reactions converting NO to NO 2 

### forming HO 2 

### , RO2 -N. to represent reactions with NO forming organic nitrates, and R2O2. to represent extra NO to NO 2 

### conversions involved in multi - step peroxy radical reactions. Since it uses the set of

### 14

products formed in the NO reaction to represent the products in the competing peroxy + peroxy reactions, it uses no additional model species for this purpose except f or the inclusion of a g eneric "ROOH" species to represent reactions at the hydroperoxide group formed in the peroxy + HO 2 

### reaction (with the set of products formed in the NO reaction also being formed in the HO 2 

### reaction.) The SAPRC - 07 representation is similar in that operators are also used to represent the effects of peroxy radicals on NO x 

### , with "RO2C" representing NO to NO 2 

### conversions and "RO2XC" representing NO consumption that occurs in conjunction with nitrate formation, but uses separate chemical operator model species to represent the formation of radicals and oxidation products, and how they depend on which peroxy radical reactions are occurring. Three sets of chemical operators are used for this purpose: "xPROD" species are used to represent the formation of the alkoxy radical products resulting when the peroxy radical react with NO, NO 3 

### , and (in part) RO 2 

### ; "yPROD" species are used to represent the formation of hydroperoxides formed when peroxy radicals react with HO 2 

### or H - shift disproportion prod ucts formed when peroxy radicals react with acyl peroxy radicals or (in part) with RO 2 

### ; and "zRNO3" species are used to represent the formation of organic nitrates when peroxy radicals react with NO or the alkoxy radical formed (in part) in RO 2 

### + RO 2 

### reactions. The products formed in the reactions of these operators are summarized on Table 2 . Table A - 2 and footnotes to Table A - 2 indicate how they are implemented in the model.

Table 2 . Products formed in the reactions of the chemical operators used to represent peroxy

radical reactions in the SAPRC - 07 mechanism. Reaction RO2C RO2XC xPROD yROOH zRNO3 NO - NO + NO 2 

### [a] - NO [a] PROD RNO3 NO 3 

### - NO 3 

### + NO 2 

### [a] PROD PROD2 + HO2 [b] HO 2 

### ROOH RO 2 

### ·  RO·. PROD PROD2 + HO2 [b] H - Shift MEK or PROD2 [c] RC(O)O 2 

### · PROD PROD2 + HO2 [b] [a] " -NO" or " -NO 3 

### " means that the reaction consumes these reactions. If this is not shown, it me ans that the reaction should not consume any reactant other than the peroxy radical operator. For example, the reaction of RO2C with HO2 would be simulated as "RO2C + HO2  HO2". [b] This represents products formed from alkoxy radicals formed in the absenc e of NO x 

### that are not represented by xPROD model species because they are not used for the portions of the reactions that form organic nitrates in the presence of NO x 

### . The present version of the mechanism has only a single zRNO3 species, and uses PROD2 for this purpose. HO 2 

### is used to represent the radicals formed. [c] The model species used to represents the H - shift disproportion products depends on the size of molecules being represented by yROOH. For the operators forming the ROOH model species used for 4 or fewer carbons, MEK is used for these processes. For operators forming larger hydroperoxides (R6OOH or RAOOH), PROD2 is used.

### 15

Note that in this representation the total yield of RO2C or RO2C + RO2XC may be greater than unity in multi - step processes involving formation of secondary peroxy radicals that cause additional NO to NO 2 

### conversions or nitrate formation. However, radical conservation requires that the sum of RO2XC and all xPROD operators where PROD is a radical be equal to 1 in VOC + radical (e.g ., VOC + OH) reactions, and the sum of all yROOH species must be equal to the total yield of all peroxy radicals formed in the initial reaction. The main approximation involved in this representation concerns the treatment of the cases of multi - step mechanisms where the peroxy radicals undergo reactions to form other peroxy radicals, which can react with NO or other peroxy radicals, etc. This would result in different (generally intermediate) branching ratios in the competitions of the peroxy radical reacti ons in terms of the overall products. In this representation it is assumed that the overall branching ratios, e.g., the extent to which hydroperoxides are formed from peroxy + HO 2 

### reactions, are the same in multi - step as in single step mechanism. Removing this approximation would require a much more complex mechanism, with more operators or model species, than is appropriate given its level of importance. Note that this approximation is incorporated in all mechanisms that use the more approximate peroxy radical representations, such as SAPRC - 99 or CB4/05. Although this representation can otherwise potentially give the same predictions as fully explicit mechanisms, it is not particularly intuitive from a chemical perspective. Itinvolves using separate model species for each type of product that is formed, and its "reactions" do not have a straightforward correspondence to explicit reactions. An alternative method, that is more straightforward to understand in terms of actual chemical processes (and gives the same predictions), is to use separate model species for each group of peroxy radicals formed from the reactions of each of the various VOCs, and represent the competing overall reactions of these lumped groups of peroxy radicals with NO, NO 3 

### , HO 2 

### , RCO 3 

### , and other peroxy radicals. Chemical operators would still be needed to represent NO to NO 2 

### conversions in multi - step processes and to determine a total RO 2 

### concentration for calculating peroxy + peroxy rates, but the result would be closer to the actual chemical processes that occur. This is the approach used in the RADM2/RACM mechanisms (Stockwell et al, 1990, 1997), with the problem of representing peroxy + peroxy reactions dealt with by ignoring all but reactions with methyl peroxy; which is not a bad app roximation (Carter and Lurmann, 1990). Although we considered use of the RADM2 approach for this mechanism, we had to abandon it because it was incompatible with the "lumped parameter" approach incorporated in the SAPRC mechanisms for flexible representati on of the hundreds of individual VOCs or deriving parameters for lumped model species based on the specific compounds they represent. This representation involves having a numerical parameter represent each of the product or radical model species involved in their overall reactions, including NO to NO 2 

### conversions and NO consumptions. This is not readily adaptable to the RADM2 peroxy radical representation because the overall products are not associated directly with the reacting VOCs but with their peroxy radicals, and the yield of peroxy radicals from VOCs can vary. On the other hand, it is readily adaptable to the peroxy radical representation incorporated in SAPRC - 07, where each overall product is still directly related to each reacting VOC. **Base Chlorin e Mechanism**  The model species added to the base mechanism to represent the atmospheric reactions of chlorine species are listed on Table A -4 in Appendix A. These include 8 model species to represent active inorganic reactants and radicals, 2 to represent chlorine - containing oxidation products, 3 steady state chemical operators to represent formation of chlorine species in peroxy radical reactions, and 2 chlorine containing inert tracer species. Table A - 5 gives the reactions and rate parameters used in the base chlorine mechanism, and Table A - 6 gives the absorption cross sections and quantum yields for the photolysis reactions listed in this table. Footnotes to Table A - 5 and indicate the source of the rate constants and

### 16

mechanisms used. As indicated there, most of the rate constants are based on results of the IUPAC (2006) and NASA (2006) evaluations, though several other sources were also used in some cases. Except for the updated rate constants and photolysis data, the base inorganic chlorine mechanism is very similar to that developed previously by Carter et al (1996a, 1997b). The maj or difference is the addition of separate model species to represent the re actions of chlorinated aldehydes and ketones that may be formed in the reactions of chlorinated VOCs. Carter and Malkina (2007) found that the reactivities of the 1,3 - dichloropropenes are significantly underpredicted if the standard aldehyde model species are used to represent the reactions of the chloroacetaldehyde predicted to be formed, but satisfactory simulations are obtained if a separate model species is used, using the NASA (2006) - recommended absorption cross sections and quantum yields for this com pound. This is because this compound is calculated to photolyze ~15 times faster than acetaldehyde and ~4.5 times faster than the lumped higher aldehyde model species used in the standard base mechanism. This model species (CLCCHO) is also used to represent the reactions of other  - chloroaldehydes, which are assumed to be similarly photoreactive. Because chloroacetone is calculated to photolyze ~7 times faster than MEK and even more for higher ketones, a chloroacetone (CLACET) model species is added to represent the reactions of  - chloroketones. However,  - chloro - aldehydes and ketones and other chlorinated aldehydes are still represented by the generic higher aldehyde or ketone species (RCHO, MEK, or PROD2) in the standard mechanism. Chlorine atoms react rapidly with most reactive VOCs and any complete chlorine mechanism must include a representation of their reactions, at least for the VOCs present in the chamber experiments with chlorine - containing species, and for the explicit and lumped VOC species used in atmospheric models. The mechanisms for these reactions are discussed in conj unction with the mechanisms for individual VOCs and lumped mechanisms for airshed models, below. **Representation of Organic Products** The set of model species to represent the reactions of the organic oxidation products are given in Table A - 1 in Appendix A. Some of these are compounds represented explicitly (e.g. formaldehyde) and some are lump ed species whose mechanisms are derived based on that for a compound or group of compounds chosen as representative. In the latter case, the compound or compounds used to derive the mechanisms for the lumped species are given in Table A - 1 and in applicable footnotes to Table A - 2 . Except for the additional species added to represent higher hydroperoxides and the removal of phenol and the organic peroxyacids (now lumped with cresols or organic acids, respectively), this mechanism uses essentially the same set of model species to represent the organic products, and the same set of comp ounds to derive their mechanisms in the case of lumped species, as does SAPRC - 99. Therefore the discussion of these species, and the choice of representative compounds used to derive the mechanisms of the lum ped species, given in the SAPRC - 99 documentation (Carter, 2000a) are still applicable. However, the rate constants and in some cases the products used for the reactions of these species or representative compounds were updated, and the reactions of these species with chlorine atoms were added and incorp orated in the base chlorine mechanism discussed above. The optional added chlorine mechanism gi ven in Table A - 5 includes the reactions of Cl atoms with most of the model species used reactive organic products in the base mechanism. Although reactions of Cl with some organic product species have been omitted 1 

### , the processes represented should be sufficient for most ambient and chamber simulations, where the maj or sinks for the chlorine atoms or the product species are other reactions. As indicated above the added chlorine mechanism also includes model sp ecies for chlorinated aldehydes and ketones that may be formed from the reactions of chlorinated VOCs. The mechanism also includes the reactions of chlorine atoms with these compounds. 1 

### The reactions of Cl atoms with the following mo del species have been omitted: HCOOH, CCOOH, RCOOH, COOH, BACL, NPHE, AFG1, AFG2, and AFG3.

### 17

**Mechanisms for Individual VOCs** An important distinguishing feature of the current SAPRC mechanisms is their ability to optionally include separate representations of the atmospheric reactions of many hundreds of different types of VOCs. Generally these are not all included in the airshed model at the same time, but selected individual compounds can be represented explicitly for the purpose of calculating reactivity scales or for toxics modeling, or mechanisms for groups of compounds can be used for deriving parameters for lumped model species used for representing complex mixt ures such as ambient emissions. The current mechanism has separate explicit representations for 734 types of VOCs, making it the most comprehensive in terms of types of VOCs than any current gas -phase atmospheric mechanism. In addition, for deriving reactivity scales or representations of complex mixtures, 304 additional types of VOCs are represented using the "lumped molecule approach", where their impacts are estimated by assuming they are the same, on a per molecule basis, of an explicitly represented VO C. This yields a total of 1038 types of VOCs that are represented by a "detailed model species" in the mechanism. A listing of all of the detailed model species in the SAPRC - 07 in the mechanism, their molecular weights and general representation method (explicit or lumped molecule) is given in Table B - 1 in Appendix B. That table also gives codes for availability of mechanism evaluation data, calculated ozone reactivity values, and reactivity uncertainty classifications. Table B - 2 and Table B -4 through Table B - 6 give the reactions and rate parameters for all the explicitly represented VOCs, Table B - 3 gives the mechanisms for those VOCs where "adjusted product" mechanisms (discussed below) were used in the reactivity calculations, Table B - 7 gives the mechanisms for the reactions of chlorine with the VOCs that were used in developing the fixed parameter lumped mechanism discussed in the following section. In addition to giving the OH radical rate constants and references for all VOCs that are explicitly represented in the mechanism, Table B -4 gi ves codes indicating the general type of mechanism used for each, and gives the structures used for compounds whose mechanisms were derived using the mechanism generation system. Footnotes to Table B - 2 and Table B -4 through Table B - 7 document the sources of the rate constants used, and Table B - 8 gives the absorption cross sections and quantum yields for those that are photoreactive and have different absorption cross sections and quantum yields than those used in the base mechani sm. Table B - 9 gives the lumped molecule assignments used for the types of VOCs that are represented using this approximation. The derivations of these mechanisms are discussed further in the remainder of this section. **Mechanism Generation and Estimation System** A maj or tool used in the derivation of the SAPRC - 99 mechanisms for individual VOCs was the automated mechanism generation and estimation software system that is described in the SAPRC - 99 documentation (Carter, 2000a). Given the structure of the molecule, available information concerning applicable rate constants and branching ratios, and various estimation methods, this system can derive fully explicit mechanisms f or the atmospheric reactions of many classes of VOCs in the presence of NO x 

### , and then use these mechanisms to derive the appropriate representations of the VOCs in terms of the model species in the base mechanism. This was used to derive the SAPRC - 99 mechanisms for the acyclic and monocyclic alkanes, acyclic and monocyclic mo noalkenes, many classes of oxygenates including alcohols, ethers, glycols, esters, aldehydes, ketones, glycol ethers, carbonates, etc, and the organic nitrates. Although many of the estimated rate constants and rate constant ratios are highly uncertain, this procedure provided a consistent basis for deriving "best estimate" mechanisms for chemical systems which are too complex to be examined in detail in a reasonable amount of time. The system allows for assigning or adjusting rate constants or branching ratios in cases where data are available, or where adjustments are necessary for model simulations to fit chamber data. Therefore, it could be used for deriving fully detailed mechanisms for VOCs that fully incorporate whatever relevant data are available, relying on various estimation methods only when information is not otherwise available. The program also outputs documentation for the generated mechanism, indicating the source of the e stimates or assumptions or explicit assignments that were used.

### 18

This SAPRC - 99 mechanism generation system, with some enhancements and updates as described below, was also used for deriving mechanisms for many of the VOCs in the SAPRC - 07 mechanism. Since this system is comprehensively documented by Carter (2000a) and most of the estimation methods were not updated as part of this project, in this section we will restrict our discussion to the changes, updates, and enhancements that were made as part of this project and utilized when deriving the updated mechanisms for the individual VOCs. These are described below

**Enhanced Capabilities for VOCs and Reactions** During the period of this project, the capabilities of the mechanism generation system were enhanced to support generating mechanisms for VOCs and radicals that could not previously be processed. These are briefly summarized below. These enhancements, and the associated estimates and branching ratio assignments, will be described in more detail in a future report when the current system is more comprehensively documented.  Reactions of VOCs with chlorine atoms can now be generated. This is discussed in the following subsection.  The ability to represent compounds with more than one ring has been added. This required revising the way structures were identified. Because of this, mechanisms for terpenes can now be generated. This is also useful in generating estimated mechanisms for aromatics, discussed below.  The ability to represent compounds with more than one double bond has been added. This also required revising the way structures were identified. However, estimation methods for reactions of compounds with conjugated or cumulated double bonds were not developed, and automatically generated rate constants and branching ratios for OH and NO 3 

### reactions of such compounds are not necessarily chemically reasonable, and reactions of O 3 

### with compounds with more than one double bond are still not supported. Explicit assignments have to be made for such reactions, as w as the case with, for example, isoprene and 1,3 -butadiene.  The ability to estimate reactions of unsaturated radicals has been added. The system recognizes allylic resonance and the probability of reaction at various positions of alkyl radicals with allylic resonance is estimated by assuming that the probability of reaction at a particular structure is proportional to exp(H f



### /RT), where H f 

### is the estimated heat of formation of the structure, R is the gas constant, and T is the temperature. If the heat of formation cannot be estimated, equal probability for reaction at all positions (or the positions with the most conjugated double bonds if there are more than one double bond) is assumed.  Reactions involving H - atom abstractions are now considered when generating mechanisms for reactions of OH, NO 3 

### , and Cl with alkenes. These previously had to be assumed to be negligible because of lack of support for generating mechanisms for unsaturated radicals. These are still neglected if they are estimated to occur less th an 1% of the time, as is generally the case in OH and NO 3 

### reactions. However, abstraction reactions are generally not negligible in chlorine + alkene reactions, as discussed below.  The ability to generate mechanisms for amines (compounds with >N - , -NH - , o r -NH 2 

### groups) was added. The new amine mechanisms, and their evaluation against chamber data, are documented by Carter (2008a). The available kinetic data indicates that reaction with OH occurs by H - atom abstraction from the amino group and that the rate of H - atom abstraction from the carbon next to the amino group is significantly enhanced, and group - additivity estimates for rates of reaction at these positions were derived. The data of Aschmann and Atkinson (1998) on N - methyl pyrrolidinone (NMP) indicate that reaction of amines with NO 3 

### radicals may also occur to a non negligible extent, and estimates (albeit highly uncertain) of NO 3 

### reactions for amines in general were derived. Methods for estimating rate constants and mechanisms for reactions of amines with O 3 

### were also developed. A more complete discussion and documentation of the amine mechanisms are given by Carter (2008a).

### 19

 The ability to represent alkynes was added. The mechanisms for OH reactions were assumed to be analogous to that derived for acetylene (Carter et al, 1997c, Carter, 2000a).  The ability to represent alkylbenzenes and their initial reactions has also been added. However, our ability to estimate these reactions has not evolved to the point where this can be used to generate reliable mechanisms useful for modeling, and this has been used primarily as a research tool in working towards eventually developing more explicit mechanisms for aromatics. This work, which is still underway, was useful in deriving the updated condensed mechanisms for aromatics discussed later in this section. The enhanced capabilities required group additivity estimates deriving rate constants for additional types of abstraction reactions that were not previously supported, such as abstractions from compounds with double bonds, abstractions from aromatics, and abstraction reactions by NO 3 

### radicals and Cl atoms. As discussed previously (e.g., see Kwok and Atkinson, 1995 or Carter, 2000a), rate constants for abstraction processes can be estimated using 

# 

   Group on ts Substituen Groups 

### Factor Correction Constant Rate Group Constant Rate Total 

### where "group" refers to various parts of the molecule for which group additivity assignments are made. Group additivity parameters used for estimating abstraction reactions are given in Table 3 . The assignments for abstractions by OH are the same as used previously (Carter, 2000a), with assignments for reactions of aromatics or amines added as indicated by footnotes to the table. The assignments for the NO 3 

### re actions are primarily from Atkinson (1991). The assignments for abstractions by chlorine atoms are discussed in the following section.

**Support for Chlorine Reactions** As indicated above, in order to support the extension of the mechanism to represent chlorine chemistry, the mechanism generation system was enhanced to generate mechanisms for chlorine + VOC reactions. Since the reactions of Cl radicals with VOCs are similar to those of OH. This general procedure can be readily adapted to generate mechanisms fo r Cl + VOC reactions. This requires (1) making group - additivity estimates for all the possible initial reactions of Cl with VOCs, (2) generating mechanisms for the Cl - containing radicals that can be formed when Cl adds to double bonds, and (3) generating mechanisms for the radicals formed. The general procedures are discussed in detail by Carter (2000a). The specific adaptations to chlorine atom reactions are discussed below.

Chlorine can react with VOCs either by abstracting a hydrogen atom to form HCl and the corresponding alkyl radical, or by adding to a double bond. For abstraction reactions, the rate constants can be estimated using group additivity methods, with the rate constant being determined by the sum of the abstraction rate constant assigned to the group, multiplied by substituent correction factors for each non -hydrogen substituent on the group, summed over all groups with hydrogen atoms (e.g., see Kwok and Atkinson, 1995 or Carter, 2000a). Note that the correction factor for methyl substitution is arbitrarily set at unity, with the factors for the other substituents being determined based on differences in rate constants at groups that are only methyl substituted.

### 20

Table 3 . Group additivity parameters used for estimating rate constants for abstraction reactions

by OH and NO 3 

### radicals and by Cl atoms . Table 3 a. Abstraction rate constants assigned to groups Group OH [a] NO 3 

### Cl

k(300) A B D Notes [b] k(300) Notes k(300) Notes CH 3 

### 1.39e - 13 4.49e - 18 2 320 1,2 7.00e - 19 9 3.43e - 11 13 CH 2 

### 9.41e - 13 4.50e - 18 2 - 253 1,2 1.50e - 17 9 6.77e - 11 13 CH 1.94e - 12 2.12e - 18 2 - 696 1,2 8.20e - 17 9 4.46e - 11 13 OH 1.42e - 13 2.10e - 18 2 85 1,2 0 10 0 10 CHO 1.56e - 11 5.55e - 12 0 - 311 1,3 2.84e - 15 [c] 11 6.64e - 11 13 HCO(O) 0 1,4 0 10 0 12 OH(O) 5.30e - 12 7.82e - 17 2 85 5 0 10 0 10 CH 3 

### (Bz) [d] 4.92e - 13 6 7.00e - 19 12 3.43e - 11 12 CH 2 

### (Bz) [d] 1.88e - 12 7 1.50e - 17 12 6.77e - 11 12 CH(Bz) [d] 1.33e - 12 8 8.20e - 17 12 4.46e - 11 12 CH 3 

### (NH x

### ) [e] 1.67e - 11 22 ~6.2e - 14 24 [f] CH 2 

### (NH x

### ) [e] 1.84e - 11 22 ~4.4e - 14 24 [f] CH(NHx

### ) [e] 2.01e - 11 23 ~9.9e - 14 24 [f] NH 2 

### 1.41e - 11 22 ~5.2e - 14 24 [f] NH 3.17e - 11 22 ~5.7e - 14 24 [f] [a] Tem perature dependences for OH rate constants given by k(T) = A B T 

### exp( - D/T), where T is in o

### K. [b] Notes for derivations of the group rate constants and substituent correction factors are given below (Note [a] with Table 3 b). [c] The temperature dependence o f this group rate constant is given by 1.40e - 12 x exp( - 1860/T). [d] "Bz" refers to any aromatic carbon. [e] Applicable for x=0,1,2. [f] Group rate constants for reactions of chlorine with amines were not derived

Table 3 b. Group correction factors for abstraction reactions Group Substituent Correction Factor OH NO 3 

### Cl Factor Note [a] Factor Note Factor Note CH 3 

### 1 1,2,14 1 17 0 14 CH x 

### (x<3) 1.23 1,2 1.34 11 0.95 13 CH x

### (CO) 3.90 1,2 1.34 17 0.95 17 CH x

### (CO - O) 1.23 1,2 1.34 17 0.95 17 CH x

### (Cl) 0.36 1,2 1.34 17 0.19 19 CH x

### (Br) 0.46 1,2 1.34 17 0.95 17 CH x

### (F) 0.61 1,2 1.34 17 0.95 17 OH 3.50 1,2 0 18 1.07 13 CHO 0.75 1,2 0.18 11 0.40 13 CO 0.75 1,2 0.89 11 0.04 13 CO(O) 0.31 15 0 12 0.04 17

### Table 3 (continued) Table 3 b. Substituent Correction Factors (continued)

21 Group Substituent Correction Factor OH NO 3 

### Cl Factor Note [a] Factor Note Factor Note CO(OH) 0.74 1,2 0 12 0.04 17 O 8.40 1,2 0 18 1.07 20 O(CO) 1.60 1,2 0 18 1.07 17 O(HCO) 0.90 1,15 0 18 1.07 17 O(NO2) 0.04 1,2 0 18 1.07 17 O(OH) 16.26 5 1 18 1.07 17 NO2 0.00 1,2 0 12 n/a F 0.09 1,2 0 12 0.01 21 Cl 0.38 1,2 0 12 0.01 13 Br 0.28 1,2 0 12 n/a I 0.53 1,2 0 12 n/a C=C 1.00 1,2 1 17 0.95 13 ONO 2 

### 0.04 1,2 0 12 0.12 Bz 1 14 1 17 2.03 13 NH 2 

### , NH, N 1 14 1 14 [b] [a] Notes for derivations of the group rate constants and group correction factors are as follows: 1 Same as used in SAPRC - 99 2 Kwok and Atkinson (1995) 3 Based on IUPAC (1997) recommendations for acetaldehyde and propionaldehyde 4 Reaction at formate group assumed to be negligible based on tabulated formate rate constants. 5 Derived to fit the NASA (2006) recommended rate constant and branching ratio for reaction of OH with methyl hydroperoxide. This results in an unusually large group substituent factor. 6 Average of estimated rate constants per methyl group for the alkylbenzenes for which aromatic aldehyde yields have been derived. Reacti on at the methyl group is estimated based on the aromatic aldehyde yield and the total rate constant. 7 Derived from the difference for the total rate constants for ethylbenzene and toluene, assuming the same rate constant for addition to the aromatic ring and the estimated rate constant at the methyl group in ethylbenzene. 8 Derived from the difference for the total rate constants for isopropyl benzene and toluene, and p cymene and p -xylene, assuming the same rate constant for addition to the aromatic ring and the estimated rate constants for reactions at the methyl groups in isopropyl benzene and p - cymene. 9 From Atkinson (1991). Derived from the correlation between NO 3 

### and OH radical rate constants. 10 Assumed to be negligible. 11 Derived from the IUPAC ( 1997) recommended rate constant for acetaldehyde. 12 No explicit assignment ma de. By default, the system uses the same assignment as for standard CH 3 

### , CH 2 

### , or CH groups. 13 Derived in this work from measured chlorine + VOC rate constants. See text and Table 4 14 Assigned. 15 From Kwok et al (1996). 16 Adjusted to fit OH + ethyl and propyl formate rate constants (Wallington et al, 1988b)

### 22

17 No assignment made. This is th e default value used by the mechanism generation system, and may not be appropriate. 18 This is the assignment incorporated into the current system. Itmay not be appropriate. Iti s not used as the basis for estimating NO 3 

### rate constants for any detailed model species. 19 Based on chloroacetaldehyde only 20 Estimated to be approximately the same as the factor for OH. 21 Estimated to be approximately the same as the factor for Cl. 22 Derived to give the best fits to the available kinetic data for simple amin es and alcohol amines for which kinetic data are available, as indicated in Table 3 c. In order to fit the data for tertiary amines, it is necessary to assume that OH reacts with an enhanced rate at groups next to the amino group, and in order to fit the data for amines, such as AMP and t -butyl amine, that do not have abstractable hydrogens next to the amino group it is necessary to assume that reaction also occurs at a significant rate at the NH or NH 2 

### groups. 23 No data are available for which to derive group - additivity estimates for this type of group. The group rate constant is estimated by linear interpolation from those used for CH 3 

### (NH x

### ) and CH 2 

### (NH x

### ). 24 The only kinetic data concerning the reactions of NO 3 

### radicals with amines is for N - methyl - 2 - pyrrolidinone (NMP), where a relatively high rate constant of 1.26 x 10 - 13 

### cm3 

### molec - 1 

### s - 1 

### is measured (Aschmann and Atkinson, 1999). This suggests that this reaction is also rapid for other amines. We assume that this is an H - atom abstraction reaction, forming HNO 3 

### . For lack of other data, use the rate constant for NMP as the basis for estimating the group rate constants for reaction at the - CH 2 

### (N) or CH 3 

### (N) groups. The group rate constants for reactions at other amine groups, including NH and NH 2 

### , are estimated assuming that the ratios of rate constants for reactions at the various groups are the same for the NO 3 

### reaction as derived for the OH reaction. This is highly uncertain. [b] Group rate constants for reactions of chlorine with amines were not derived Table 3 c. Experimental and best fit estimated rate constants for the reactions of OH radicals with

amines that were used as the basis for deriving structure -reactivity estimates Compound OH Rate Constant (10 - 11 

### cm3 

### molec - 1 

### s - 1 

### ) Measured value, reference Avg Calc Diff Methyl amine 1.73 1 2.20 2 1.97 3.08 36% Dimethyl amine 6.49 1 6.54 3 6.52 6.51 0% Trimethyl amine 3.58 1 6.09 3 4.84 5.01 4% Ethyl amine 2.38 1 2.77 3 2.58 3.59 28% N,N - Dimethylethanolamine (DMAE) 9.00 4 4.70 5 6.85 6.02 - 14% t - Butyl amine 1.18 6 1.18 1.79 34% 2 - Amino - 2 - methyl - 1 -propanol (AMP) 2.80 5 2.80 2.19 - 28% References for measured rate constants: 1 Carl and Crowley (1998) 4 Anderson and Stephens (1988) 2 Atkinson et al. (1977) 5 Harris and Pitts (1983) 3 Atkinson et al. (1978) 6 Koch et al (1996)

### 23 For addition to double bonds, we assume that the rate constant is determined only by the number of non -hydrogen substituents about the double bond, with correction factors used for some non alkyl substituents such as halogens. Although this doesn't affect the rate constant, for the purpose of estimating mechanisms it is also necessary to assign factors for the fractions that react at each position around the double bond. This has to be estimated be cause we are aware of no data available concerning this. The organic + Cl atom rate constants that were used as the basis for deriving group - additivity estimates for the mechanism generation system are given in Table 4 , with footnotes indicating the sources of the rate constants used. (Note that the rate constants in Table 4 are restricted to those used for deriving the group - additivity methods, and does not include compounds for which the estimation method was not developed to support. See Table B - 7 for the chlorine atom rate constants for all the VOCs in the mechanism.) Group additivity parameters found to give the best fits to the data on Table 4 are shown on Table 3 , above, for the abstraction reactions, and on Table 5 for reactions at double bonds. The "Est'n error" column on Table 4 shows the extent to which the estimated rate constant agrees with the measured value, with positive numbers indicating overprediction, and vise - versa. If there is no entry in this column it means that the current estimation method is not applicable to those compounds. The group additivity parameters were determined by minimizing the sum - of - square relative errors in for the compounds listed on Table 4 . In most cases the estimated rate constants agree with th e measured values to better than 25%. However, cases with prefect agreement usually indicate that a parameter was determined only by the data for a single compound, so perfect agreement is not always evidence for the success of the method.

The Cl abstracti on reactions form the same radicals as the corresponding reactions with OH, so the procedures for generating the subsequent reactions of those radicals formed have already been developed and described (Carter, 2000a). Therefore, for VOCs for which only the abstraction reaction is important, which include all saturated VOCs and also simple aldehydes, ketones, and esters, the derived mechanisms for the chlorine reactions are the same as those for the reaction with OH, except for the different branching ratios for the initial reactions because of the differences in the group additivity parameters, discussed above.

Although in principle the system could also derive mechanisms for the reactions of chlorine atoms with alkenes, in practice this proved difficult bec ause at present the system does not contain the necessary thermochemical or kinetic assignments to estimate reaction rates for many of the chlorine - substituted alkoxy radicals predicted to be formed. The only way to deal with this is to make explicit assignments of branching ratios for the Cl - substituted radicals that cannot presently be handled by the system, which can be time consuming for large molecules because of the number of radicals that can be formed. For that reason, assignments were made only to permit the generation of mechanisms for the explicitly represented alkenes (ethylene and isoprene), those chosen as representative of the lumped model species used in airshed models (discussed later in this report), or those present in the chamber experiments relevant to evaluating mechanisms for the chlorine - containing compounds for which chamber data are available. The alkoxy radical branching ratio assignments used to generate the chlorine + alkene mechanisms that were derived for this project are summarized on Table 6 , with footnotes giving a brief indication of the basis of the assignments. In addition, except as indicated on Table 6 , it is assumed that  - chloro - alkoxy radicals predominantly decompose to form chlorine atoms, e.g., ClCH 2 

### O·  HCHO + Cl· RCH(Cl)O·  RCHO + Cl· RC(R')(Cl)O·  RC(O)R' + Cl·

### 24

Table 4 . Rate constants for reactions with chlorine atoms for organic compounds used to derive

parameters for group - additivity estimates . Com pound Rate Constant Assignment [a] Note [b] Est'n Error [c] k(298) A Ea (deg K) Methane 1.03e - 13 6.60e - 12 1240 1 Ethane 5.93e - 11 8.30e - 11 100 1 15% Propane 1.37e - 10 1.20e - 10 - 40 2 - 3% n - Butane 2.05e - 10 2.05e - 10 0 1 - 5% n - Pentane 2.80e - 10 2 - 8% n - Hexane 3.40e - 10 2 - 6% n - Heptane 3.90e - 10 2 - 3% n - Octane 4.60e - 10 2 - 4% n -Nonane 4.80e - 10 2 5% n - Decane 5.50e - 10 2 3% Isobutane 1.43e - 10 2 0% Neopentane 1.11e - 10 1.11e - 10 0 2 18% Iso - Pentane 2.20e - 10 2 - 7% 2,3 - Dimethyl Butane 2.30e - 10 2 - 6% 2 - Methyl Pentane 2.90e - 10 2 - 8% 3 - Methylpentane 2.80e - 10 2 - 4% 2,2,3 - Trimethyl Butane 2.90e - 10 2 - 29% 2,4 - Dimethyl Pentane 2.90e - 10 2 - 4% 2 - Methyl Hexane 3.50e - 10 2 - 6% 2,2,3,3 - Tetramethyl Butane 1.75e - 10 2 12% 2,2,4 - Trimethyl Pentane 2.60e - 10 2 3% Cyclohexane 3.50e - 10 2 6% Methylcyclohexane 3.90e - 10 2 - 2% Propene 2.67e - 10 4 - 1% 1 - Butene 3.39e - 10 5 - 3% 1 - Pentene 4.05e - 10 5 - 4% 3 - Methyl - 1 - Butene 3.52e - 10 6 - 4% 3 - Methyl - 1 - Pentene 3.78e - 10 6 6% Isobutene 3.25e - 10 6 9% 2 - Methyl - 1 - Butene 3.82e - 10 6 10% cis - 2 - Butene 3.88e - 10 6 - 15% trans - 2 - Butene 3.55e - 10 4 - 7% 2 - Methyl - 2 - Butene 3.23e - 10 6 7% Cis 4 - Methyl - 2 - Pentene 4.04e - 10 6 0% Toluene 6.20e - 11 7 12% m - Xylene 1.35e - 10 7 3% o - Xylene 1.40e - 10 7 - 1% p - Xylene 1.44e - 10 7 - 4% 1,3,5 - Trimethyl Benzene 2.42e - 10 8 - 14% Methanol 5.50e - 11 5.50e - 11 0 1 - 34% Ethanol 1.00e - 10 8.60e - 11 - 45 1 5% Isopropyl Alcohol 8.60e - 11 1 31% n - Propyl Alcohol 1.62e - 10 2.50e - 10 130 1 3% Acetic Acid 2.65e - 14 1 0% Acetaldehyde 8.00e - 11 8.00e - 11 0 1 0% Propionaldehyde 1.23e - 10 9 0% Acetone 2.69e - 12 7.70e - 11 1000 10 0% Methyl Ethyl Ketone 3.60e - 11 1 2% Methyl Chloride 4.89e - 13 2.17e - 11 1130 10 - 7% Dichloromethane 3.49e - 13 7.40e - 12 910 10 11%

### Table 4 (continued)

25 Com pound Rate Constant Assignment [a] Note [b] Est'n Error [c] k(298) A Ea (deg K) Chloroform 1.19e - 13 3.30e - 12 990 10 - 7% Vinyl Chloride 1.27e - 10 11 4% 1,1 - Dichloroethene 1.40e - 10 11 - 19% Trans - 1,2 - Dichloroethene 9.58e - 11 11 8% Cis - 1,2 - Dichloroethene 9.65e - 11 11 7% Trichloroethylene 8.08e - 11 11 - 18% Perchloroethylene 4.13e - 11 11 9% 3 - Chloropropene 1.30e - 10 12 0% Chloroacetaldehyde 1.29e - 11 13 0% [a] Rate constants and A factors in units of cm 3 mo lec - 1 s - 1 . If no A factor or activation energy is given, rate constant is given only for 298K. Otherwise, 298K rate constant is calculated from A factor and activation energy. [b] Notes: 1 IUPAC (2006) recommendation. 2 Atkinson (1997) recommendation. 3 This reaction is in the pressure falloff region under atmospheric conditions. 4 Average of values tabulated by Wang et al (2002). Value of Wang et al (2002) placed on an absolute basis using the Atkinson (1997) -recommended rate constant for n - heptane. 5 Average of value of Coquet et al (2000), placed on an absolute basis using the Atkinson (1997) -recommended n - hexane rate constant, and the value of Wang et al (2002), placed on an absolute basis using the Atkinson (1997) -recommended rate constant for n -heptane. 6 Value of Wang et al (2002), placed on an absolute basis using the Atkinson (1997) -recommended rate constant for n -heptane. 7 Average of values tabulated by Wang et al (2005). 8 Wang et al (2005). 9 Average of values listed by Le Crane et al (2005) 10 NASA (2006) recommendation. 11 From rate constants relative to n -butane from Atkinson and Aschmann (1987), placed on an absolute basis using the n -butane rate constant recommended by IUPAC (2006). 12 Average of values tabulated by Albaladejo et al (2003). 13 Average of values tabulated by Scollard et al (1993) [c] (Estimated rate constant - measured rate constant) / measured rate constant.

### 26

Table 5 . Group additivity rate constants and factors used for estimating rates of addition of Cl

atoms to double bonds . Group k(add) Add'n to most substituted end Note Group Substituent Correction Note CH2=CH - 2.30e - 10 35% 1,2 Alkyl 1 3 CH2=C< 2.89e - 10 25% 1,4 - Cl 0.58 1

- CH=CH - 2.63e - 10 50% 1,5 2 - Cl' s 0.68 1

- CH=C< 2.47e - 10 25% 1,4 - CH 2 

### Cl 0.56 1,6 >C=C< 2.47e - 10 50% 1,5 1 Addition rate constant and substituent correction factor derived to minimize sum of squares error in predictions of Cl + alkene rate constants. (Optimization for group additivity parameters for abstraction reaction carried out at the same time.) 2 Assume same terminal bond addition fraction as used for the reaction of OH with propene (Carter, 2000a). 3 All alkyl substituents assumed to have the same factor. Unit factor assigned. 4 No information available concerning relative addition rates at the different positions. Assume addition at terminal position occurs about 25% of the time 5 Assume equal probability of addition, regardless of substituents. 6. Based on rate constant for 3 - chloropropene. These assignments, and therefore the mechanisms derived for the chlorine + alkene reactions that are based on them, are uncertain. However, reactions of alkenes with chlorine atoms are generally not major sinks either for chlorine or alkenes under most conditions, so these assumptions are probably not major sources of uncertainty in terms of overall model predictions.

**Updates to Rate Constants and Mechanisms** Because of time and resource limitations, we were not able to update most of the estimation methods incorporated in the SAPRC - 99 me chanism generation system used for this project, so most of the various estimation assignments given by Carter (2000a) are still applicable for this version. However, we did update the assignments for the rate constants for the initial reactions of the individual VOCs in those cases where rate constant measurement data are available, and these were used when generating the mechanisms for the applicable VOCs. Table B - 2 , and Table B -4 through Table B - 6 and their footnotes indicate the rate constants used and the sources of those rate constants, where applicable.

Based on results of recent evaluations and also results the evaluation against chamber data, some updates were also made to assigned reactions of excited Criegee radicals involved in the ozone + alkene reactions. The current assignments for Criegee biradical reactions are summarized on Table 7 . Note that the amount of radical formation in the decomposition of the primary biradicals, which was adjusted based on simulations of chamber data, is somewhat higher than used in the S APRC - 99 mechanism, but still lower than currently recommended radical yields for these reactions. This inconsistency, which is also seen in evaluations of the MCM, is discussed further by Pinho et al (2006).

Additional updates or modifications were made for mechanisms of some individual VOCs, based primarily on results of model simulations of chamber experiments. For example, the mechanism for the reaction of O 3 

### P with ethene was updated based on the Calvert et al. (2000)

### 27

Table 6 . Branching ratio assignments for chlorine - substituted alkoxy radicals made to generate

mechanisms for the reactions of chlorine with representative alkenes. Used for Reaction Fract. Notes Propene CH 3 

### CH(O·)CH 2 

### Cl + O 2 

###  CH 3 

### C(O)CH 2 

### Cl + HO 2 

### · 100% 1

CH 3 

### CH(CH 2 

### O·)Cl + O 2 

###  CH 3 

### CH(CHO)Cl + HO 2 

### · 100% 2 2 - Butenes CH 3 

### CH(O·)CH(CH 3 

### )Cl + O 2 

###  CH 3 

### C(O)CH(CH 3 

### )Cl + HO 2 

### · 100% 3 1 - Pentene CH 3 

### CH 2 

### CH 2 

### CH(O·)CH 2 

### Cl  ·CH 2 

### CH 2 

### CH 2 

### CH(OH)CH 2 

### Cl 100% 4

CH 3 

### CH 2 

### CH 2 

### CH(CH 2 

### O·)Cl  CH 3 

### CH(·)CH 2 

### CH(Cl)CH 2 

### OH 100% 4 CH 3 

### CH(O·)CH 2 

### CH(Cl)CH 2 

### OH  CH 3 

### CH(OH)CH 2 

### CH(Cl)CH(·)OH 100% 4 2 - Pentenes CH 3 

### CH 2 

### CH(O·)CH(CH 3 

### )Cl  CH 3 

### CH 2 

### CHO + CH 3 

### CH(·)Cl 100% 5

CH 3 

### CH 2 

### CH(Cl)CH(O·)CH 3 

###  CH 3 

### CHO + CH 3 

### CH 2 

### CH(·)Cl 100% 5 Isoprene CH 2 

### =C(CH 3 

### )CH(·)CH 2 

### Cl + O 2 

###  CH 2 

### =C(CH 3 

### )CH(OO·)CH 2 

### Cl 60% 6  CH 3 

### C(CH 2 

### OO·)=CHCH 2 

### Cl 41% CH 2 

### =CH - C(·)(CH 3 

### )CH 2 

### Cl + O 2 

###  CH 2 

### =CH - C(OO·)(CH 3 

### )CH 2 

### Cl 44% 6  CH 3 

### C(=CH - CH 2 

### OO·)CH 2 

### Cl 56% CH 2 

### =C(CH 3 

### )CH(O·)CH 2 

### Cl + O 2 

###  CH 2 

### =C(CH 3 

### )C(O)CH 2 

### Cl + HO 2 

### · 100% 7 CH 3 

### C(=CH - CH 2 

### O·)CH 2 

### Cl + O 2 

###  CH 3 

### C(CH 2 

### Cl )=CHCHO + HO 2 

### · 100% 8 CH 3 

### C(CH 2 

### O·)=CH - CH 2 

### Cl + O 2 

###  CH 3 

### C(CHO)=CHCH 2 

### Cl + HO 2 

### · 50% 9  CH 3 

### C(CH 2 

### OH)=CH - CH(·)Cl 50% CH 2 

### =CH - C(O·)(CH 3 

### )CH 2 

### Cl  CH 2 

### =CHC(O)CH 3 

### + .CH 2 

### Cl 100% 5 CH 2 

### =C(CHO)CH 2 

### O· + O 2 

###  CH 2 

### =C(CHO)CHO + HO 2 

### · 100% 10 CH 2 

### =C(CH 3 

### )CH(CH 2 

### O·)Cl + O 2 

###  CH 2 

### =C(CH 3 

### )CH(CHO)Cl + HO 2 

### · 50% 9  CH 2 

### =C(CH 2 

### ·)CH(Cl)CH 2 

### OH 50% CH 2 

### =C(CH 2 

### O·)CH(Cl)CH 2 

### OH  CH 2 

### =C(CH 2 

### OH)CH(Cl)CH(·)OH 50% 9 + O 2 

###  CH 2 

### =C(CHO)CH(Cl)CH 2 

### OH + HO 2 

### · 50% CH 2 

### =CH - C(CH 3 

### )(CH 2 

### O·)Cl + O 2 

###  CH 2 

### =CH - C(CH 3 

### )(CHO)Cl + HO 2 

### · 100% 10  - Pinene CH 3 

### C(O·)* 1 

### CH(Cl)CH 2 

### CH* 2 

### CH 2 

### CH* 1 

### C* 2 

### (CH 3 

### )CH 3 

###  CH 3 

### C(O)CH(Cl) -

CH 2 

### CH* 1 

### CH 2 

### CH(·)C* 1 

### (CH 3 

### )CH 3 

### 100% 4,11 CH 3 

### C(O)CH(Cl)CH 2 

### CH(O·)CH 2 

### CHO  HCOCH 2 

### CHO + CH 3 

### C(O) - CH(CH 2 

### ·)Cl 100% 5 CH 3 

### C(O)CH(CH 2 

### O·)Cl  ·CH 2 

### C(O)CH(Cl)CH 2 

### OH 100% 4 .OCH 2 

### C(O)CH(Cl)CH 2 

### OH  HOCH 2 

### C(O)CH(Cl)CH(·)OH 100% 4 CH 3 

### C* 1 

### (Cl)CH(O·)CH 2 

### CH* 2 

### CH 2 

### CH* 1 

### C* 2 

### (CH 3 

### )CH 3 

###  CH 3 

### C(·)(Cl)CH* 1



### - CH 2 

### CH(CH 2 

### CHO)C* 1 

### (CH 3 

### )CH 3 

### 100% 4,11 2 - (Chloromethyl) - 3 - chlororopene

ClCH 2 

### C(O·)(CH 2 

### Cl)CH 2 

### Cl  ClCH 2 

### C(O)CH 2 

### Cl + .CH 2 

### Cl 100% 12 ·OCH 2 

### C(Cl)(CH 2 

### Cl)CH 2 

### Cl + O 2 

###  HCOC(Cl)(CH 2 

### Cl)CH 2 

### Cl + HO 2 

### · 100% 10 1,3 - Dichloropropenes

ClCH 2 

### CH(O·)CH(Cl)Cl + O 2 

###  Cl - CH 2 

### C(O)CH(Cl)Cl + HO 2 

### · 100% 13 1 Assumed to be favored over decomposition on the basis of estimates for CH 3 

### C(O·)CH 3 

### and the expectation that Cl - substitution makes radicals less stable 2 Assumed to be favored over decomposition on the basis of estimates for CH 3 

### CH 2 

### CH 2 

### O· and the expectation that Cl - substitution makes radicals less stable 3 Assumed to be favored over decomposition on the basis of estimates for the radical where H - replaces Cl - and the expectation that Cl - substitution makes radicals less stable 4. Isomerization is assumed to dominate over competing processes for this radical.

### Table 6 (continued)

28

5 This decomposition is assumed to dominate based on estimates for similar radicals. 6 Branching ratios based on the mechanism of Fan and Zhang (2004) 7 Assumed to be fast on the basis of observation of this compound as a product in the isoprene - chlorine reactions. 8 Although isomerizations might be expected to be more important than O2 reaction, this is assumed to dominate to account for the observed formation of CMBA as a product in the isoprene + chlorine reactions. 9 Reaction with O 2 

### is assumed to be the dominant product when the radical is in the trans configuration, and isomerization is assumed to be the dominant process when it is in the cis configuration. Equal possibility of cis and trans configuration is assumed. 10 Itis expected that the competing decomposition isn't favorable, so the reaction with O 2 

### is assumed to dominate. However, this is uncertain. 11 The "* 1 

### " and "* 2 

### " symbols indicate join points for these cyclic radicals. 12 This appears to be the only available reaction. 13 Assumed to be favored over decomposition on the basis of estimates for CH 3 

### C(O·)CH 3 

### and the expectation that Cl - substitution makes radicals less stable recommendation, but it was still necessary to assume lower fragmentation yields than recommended in order to simulate the chamber data, as was the case for the reactions of O 3 

### P with other alkenes (Carter, 2000a; Pinho et al, 2006). Overall nitrate yields that were derived based on simulations of chamber data had to be readjusted for a number of compounds because changes to the base mechanism apparently caused the values of the nitrate yields that best fit the data to change somewhat. Assignments are made to the mechanism generation system to implement these adjustments where applicable.

**Adjusted Product Mechanisms** Although the mechanism generation system derives fully explicit mechanisms, by default it lumps all the reactive products predicted to be formed into the set of organic product model species in the base mechanism, as indicated on Table A - 1 in Appendix A. The mechanisms so derived are given in Table B - 3 in Appendix B. Because the mechanisms used for the product species are fixed regardless of what VOC is being represented, these are referred to as "fixed product" mechanisms in the subsequent discussion. However, lumping the many types of reactive products into a few model species is an approximation, and some V OCs may form products that are not particularly well represented by any of the generic product model species. This could introduce inaccuracies to calculations of atmospheric reactivity scales. For this reason the mechanism generation system is also capabl e of deriving mechanisms for the maj or reactive products of the VOCs that could be used "adjustable product" mechanisms where the more reactive product species are represented by lumped (or explicit) product species whose mechanisms were derived based on t he distribution of products they are being used to represent. Note that these adjustable mechanism products are only used on the mechanism for the particular VOC in the reactivity calculations, not for mechanisms of other VOCs in the base mechanism. The derivation and implementation of these adjustable product mechanisms is discussed by Carter et al (2000a). Since the same procedures were used for deriving the adjustable product mechanisms in this work, they are not discussed further here.

### 29

Table 7 . Assigned mechanisms for Crigiee Biradicals used for deriving mechanisms for reactions

of O 3 

### with alkenes. Reaction Fraction Discussion H 2 

### COO[excited]  Branching ratios based on recommendations by Atkinson (1997), modified to be consistent with the OH yield in the IUPAC (2006) recommendations H 2 

### COO[stab] 37% HCO + OH 16% CO 2 

### + H 2 

### 12% CO + H 2 

### O 35% CH 3 

### CHOO[excited]  Atkinson (1997) recommendation.

CH 3 

### CHOO[stab] 15% CH 3 

### · + CO + OH 54% CH 3 

### · + CO 2 

### + H 17% CH 4 

### + CO 2 

### 14% RCX(X')CXOO[excited]  (R=Alkyl other than CH3; X, X' = H or alkyl): Available data concerning stabilization and decompositions of RCHOO Criegee biradicals are limited and inconsistent. In order to fit chamber data to fit results of 1 -butene and 1 -hexene experiments, it is necessary to assume that stabilization occurs ~85% of the time for 4+ - carbon Criegee biradicals. RCX(X')CXOO[stab] 85% RCX(X')· + CO + OH 9.5% RCX(X')· + CO 2 

### + H 3.0% RCHXX' + CO 2 

### 2.5% XCX'H - COO[excited] - R  (X, X'= H or alkyl; R = alkyl): OH formation after hydroperoxide rearrangement assumed to be dominant process for disubstituted Criegee biradicals based on high OH yields, as discussed by Atkinson (1997). Relative importance of competing rearrangements estimated to be approximately proportional to estimated OH abstracting rate constant from H donating group. (Unchanged from SAPRC - 99) ·CXX' - CO - R + OH 100%

Rt - COO[excited] - Rt'  (Rt = tertiary alkyl): Most reasonable decomposition mode is formation of CO2 and radicals. No information about reactions of disubstituted Criegee biradicals that cannot undergo the hydroperoxide rearrangement. Roughly estimate that most is stabilized. The decomposition fraction is a guess. It probably depends on size of the molecul e, but this is not taken into account. (Unchanged from SAPRC - 99) Rt - COO[stab] - Rt' 90% Rt· + Rt' + CO 2 

### 10%

### 30

Adjustable product mechanisms were derived for all VOCs whose reactions and product reactions could be completely generated using the mechanis m generation system. To assess the effects of using adjustable product mechanisms on calculated atmospheric incremental reactivities, Figure 1 shows a comparison of incremental reactivities calculated for the "averaged conditions MIR scale" calculated using the two methods for all VOCs for which adj ustable product mechanisms could be derived. [Incremental reactivity scales are discussed in the "Updated Reactivity Scale s" section, below. Briefly, the Averaged Conditions MIR scale gives a good approximation of the MIR scale used in CARB regulations (CARB 1993, 2000) using a single scenario rather than the average of 39 MIR scenarios.] Itc an be seen that for most VOCs the adjustable mechanism reactivities are very close to the fixed mechanism values, with the average bias being - 1% and the average error being 6% 1



### . However, there were a number of compounds with non -negligible differences where use of the adjustable product mechanisms for reactivity calculations is appropriate. The com pounds where the ma gnitude of the change was greater than 20% are listed in Table 8 , with the reasons for the differences indicated for the top three compounds. For the purpose of calculating reactivity scales, we used the adjustable product mechanism if the calculated reactivity difference in the averaged conditions MIR scale was greater than 8%, and the fixed product mechanism otherwise. The use of 8% is somewhat arbitrary, but given the uncertainties in mechanisms in general, and product mechanisms derived using the mechanism generation system in particular, we did not consider the added complexity to be appropriate if the effect of less than approximately this amount. Table B - 3 in Appendix B gives the adjustable product mechanisms that were employed in the reactivity scale calculations as determined by this criterion. Note that the primary VOC rate constants and methods for deriving the mechanisms are the same as indicated in Table B - 2 for the fixed parameter mechanism, so this documentation is not duplicated on this table. If the mechanism for a

1 

### The average bias is calculated as the average relative difference, while the average error is the average of the absolute magnitude of the relative difference.

### 31

Figure 1 . Effect of using the adjustable product mechanisms vs. the standard fixed product

mechanisms on incremental reactivities in the "Averaged Conditions" MIR scale for those VOCs for which adjustable product mechanisms could be derived . Table 8 . Compounds whose Averaged Conditions MIR reactivities changed by more than 20%

when adjustable product mechanisms were employed. Compound Averaged Conditions MIR (gm O3 / gm VOC) Discussion Fixed Adj'd Diff 2,3 - Butanediol 2.51 4.41 75% High yield product reacts to form biacetyl 1,2 - Dihydroxy hexane 2.01 2.54 26% Products react to form methyl glyoxal Dimethoxy methane 1.25 0.93 - 26% Product represented by PROD2 has a relatively low rate constant for this group cis - 5 - Decene 2.96 3.73 26% Glycerol 2.53 3.17 25% 4 - Methyl - 2 -pentanol 2.15 2.61 21% cis -4 - Octene 3.94 4.79 22% VOC is not given in Table B - 3 , the mechanism used in Table B - 2 was used to calculate its reactivity. The reactivity listings on Table B - 1 in Appendix B indicate those cases where adjustable products mechanisms were used. **Updated Aromatics Me chanisms**  Although significant progress has been made in recent years concerning the atmospheric reactions of aromatics and their reactive products (e.g., Calvert et al, 2002, Barnes, 2006, and references therein), the aromatics continue to represent the ma jor class of compounds for which insufficient information exists for deriving predictive and explicit mechanisms based on mechanistic considerations alone. The most important uncertainties concern the reactions of the aromatic ring fragmentation products, which 0.1 1 10

0.1 1 10

Fixed Product Reactivity (gm O3 / gm VOC)Adjustabeproductreactivity Com pounds 1:1 Line

0 50 100 150 200<-25%-25%--15%-15%--5%-5%-5%5%-15%15%-25%>25%

Range of DifferenceNumberofVOCs

### 32

include highly photoreactive compounds that make significant contributions to overall aromatic reactivity. SAPRC - 99 mechanism incorporates a highly simplified and parameterized set of model species to represent these products, whose yields and photolysis rates are adjusted to fit chamber data. In addition, the mechanisms for the reactions of ring -retaining products such as phenols, cresols, and nitrophenols are also highly uncertain, and SAPRC - 99 uses simplified and parameterized representations for these reactions as well. Other mechanisms currently used in airshed models (Gery et al, 1988, Yarwood et al, 2005; Stockwell et al, 1990, 1997) also incorporate simplified and parameterized representations of aromatics, and although the MCM incorporates an attempt at a more explicit aromatics representation, its performance in simulating available environmental chamber data is so poor that it is not suitable for airshed modeling (Bloss et al, 2005). The uncertain parameters in the SAPRC - 99 aromatics mechanis ms were optimized to give reasonably good simulations of results of aromatics - NO x 

### and environmental chamber experiments, and the mechanisms so derived also gave generally satisfactory results of incremental reactivity experiments with aromatics (Carter, 2000a), including some experiments carried out after the SAPRC - 99 mechanism was developed at lower NO x 

### concentrations in the new UCR EPA chamber (Carter, 2004). However, Carter (2004) also found that the SAPRC - 99 mechanism consistently underpredicts the extent of ozone enhancement caused by adding CO to aromatics - NO x 

### irradiations, Carter and Malkina (2002) found that the mechanism overpredicts "direct reactivity" in experiments designed to be sensitive to the direct effects of the primary reactions of aro matics on NO to NO 2 

### conversions. This suggests that there may be compensating errors in the SAPRC - 99 aromatics mechanisms. In addition Carter (2004) found that SAPRC - 99 (and also CB4) tends to underpredict ozone formation in at low ROG/NO x 

### ratios and low N O x 

### concentrations in Surrogate - NO x 

### experiments when the surrogate contains aromatics, but this is not seen in surrogates where the aromatics have been removed (unpublished results from this laboratory

– also see "Mechanism Evaluation" section, below). Be cause of these problems, updating and improving the aromatics mechanisms was an important priority for this project. The approach that was initially attempted to derive updated aromatics mechanisms was to derive fully (or at least nearly) explicit mechanis ms for representative aromatic hydrocarbons and their oxidation products, and use these as a basis for deriving more condensed mechanisms that can be used for representing aromatics in general. However, this turned out to be unworkable in practice, at leas t within the time and resource constraints for this project. Developing fully explicit mechanisms that are entirely consistent with available data as given by Calvert et al (2002) is not possible because the low and inconsistent measured product yields can not account for complete reaction pathways, and mechanisms based on some of the data could not be made to give predictions that were consistent with the available environmental chamber reactivity data. This was found to be the case both for the initial aromatic ring opening reactions, where yields of the expected unsaturated dicarbonyl ring - opening products were found to be low, and the photolysis reactions of the unsaturated dicarbonyl products, where assuming relatively high yields of non -radical product s gave mechanisms that significantly underpredicted aromatic reactivities in chamber experiments. Also, mechanism incorporating new product data for phenols and cresols (Barnes, 2006; Berndt and Boge, 2003, Olariu et al, 2002) gave predictions that were inconsistent with the limited chamber data and therefore could not be used. The approach that was therefore adopted for this version of the mechanism is to use a simplified but consistent and chemically reasonable model for the initial ring fragmentation reactions that give improved simulations of the direct reactivity data of Carter and Malkina (2002), and derive new mechanisms for the model species used to represent the unknown or uncertain aromatic ring fragmentation products based on estimated mechanisms for representatives of the unsaturated 1,4 - and 1,6 - dicarbonyls expected to be formed. The only adjustable parameters employed concerned the ratio of photoreactive to un -photoreactive model species representing the unsaturated 1,4 - dicarbonyls, which were adj usted to fit the data for the aromatics - NO x 

### experiments for the individual compounds. This yielded mechanisms that performed as well as SAPRC - 99 in simulating aromatics - NO x 

### and aromatics

### 33

incremental reactivity experiments, and that performed somewhat better in simulating the direct reactivity results of Carter and Malkina (2002). However, the problem of underpredicting the effects of adding CO to aromatics - NO x 

### irradiations and underpredicting O 3 

### formation in surrogate - NO x 

### experiments at low NO x 

### and low ROG/NO x 

### conditions remained. Therefore, although the updated mechanisms are probably more chemically reasonable and consistent with somewhat more of the available data than was the case previously, not all of the problems could be resolved.

**Reactions of Alkylbenzenes with OH**  The major initial atmospheric reaction of aromatics is with OH radicals. Table 9 gives the measured or estimated product yields for the known products for the OH radical reaction that are used as the bases for the aromatics mechanisms developed in this work, with footnotes indicating the sources of these yields. The initial reactions can either be abstraction of H from side groups off the ring , or OH addition to the aromatic ring. The fractions reacted at the various positions, and their subsequent mechanisms, are derived as described below.

Reactions off the Aromatic Ring . The reactions following abstraction from the groups off the ring are ex actly analogous to those in the alkane photo - oxidation system, and are assumed to proceed as shown below for toluene

### 34

Table 9 . Measured or estimated yields of known products for benzene and methylbenzene

reactions that were incorporated in the SAPRC - 07 aromatics mechanisms Compound Yields and Notes [a]

Aromatic Aldehyde Phenol or

Cresol Glyoxal Methyl Glyoxal Biacetyl Nitrate yi eld [b] Benzene 57% [1] 29% [2] 7.7% [3 ] Toluene 6.5% [4] 18% [5] 24% [6] 15% [7] 10.6% [8] Xylenes 13.6% [3 ] o - 4.7% [9] 16% [10] 8.4% [11] 24% [11] 19% [12] m - 4.1% [13] 16% [14] 10% [15] 38% [16] p - 8.8% [17] 16% [18] 29% [19] 11% [20] Trimethylbenzenes 16.2% [3 ] 1,2,3 - 4.5% [21

] 3.1% [22

] 7.2% [23] 18% [23] 45% [24] 1,2,4 - 3.6% [25] 2.2% [26] 7.4% [27] 41% [28] 11% [29] 1,3,5 - 3.0% [30] 4.0% [31] 64% [34] [a] Footnotes giving the sources of the assignments are as follows. Italic indicates estimated values. 1 Average of values of Berndt and Boge (2006) and Volkamer et al (2002). 2 The yields of Berndt and Boge (2006), which are reasonably consistent with previou s studies (Calvert et al, 2002), are used. 3 Estimated based on carbon number and the nitrate yield derived for toluene as discussed in the text and shown on Figure 3 . 4 Yields tabulated by Calvert et al (2002) range from 5 - 12%. Value used is average of data from studies published since 1989, which tend to be reasonably consistent as a group. This is lower than the 8.5% used in SAPRC - 99 5 Total of yields for individual isomers from Calvert et al (2002) 6 Data tabulated by Calvert et al (2002) indicate a range of yields, from 4 - 24%, with Volkamer and co -workers (Volkamer, personal communication) reporting 35%. We tentatively use the value of Smith et al (1998), which is the highest tabulated by Calvert et al (2002) but still lower than the Volkamer value. The methyl glyoxal yield reported by Smith et al (1998) are in good agreement with the value used, which tends to support use of their data. Also, the mechanism estimati on system estimates higher yields of glyoxal than methyl glyoxal will be formed from toluene. 7 Data tabulated by Calvert et al (2002) indicate a range of yields, but a number of recent studies are reasonably consistent in indicating yields of ~15%. The average of the data from the studies with the higher yields is used. 8 Derived from the ratio of the benzyl nitrate to the benzaldehyde yield as discussed in the text. Assumed that the same ratio is applicable to the other peroxy radicals in the toluene photo oxidation system. 9 Most of the recent o -tolualdehyde yield data tabulated by Calvert et al (2002) are around 5%, and the value used is the average of those studies. A few studies indicate higher yields, but these are not used in computing the average. 10 The total dimethylphenol yields of Atkinson et al (1991) are used because they were conducted at the lowest NOx levels. 11 The data of Bandow and Washida (1985a) and Tuazon et al (1986) are in good agreement, and the average is used. The low value of S hepson et al (1984) is not used. 12 The low NO x 

### limit value of Atkinson and Aschmann (1994) is used. It is reasonably consistent with data from other studies at lower NO x 

### levels tabulated by Calvert et al (2002).

### Table 9 (continued)

35

13 Most of the recent o -tolualdehyde yield data tabulated by Calvert et al (2002) are around 5%, and the value used is the average of those studies. A few studies indicate higher yields, but these are not used in computing the average. 14 Average of the total dimethylphenol data reported by Atkinson et al (1991) and Smith et al (1999). However, these two studies are not in particularly good agreement on yields for the individual isomers. The total is consistent with the value used for o -xylene. 15 Average of the data tabulated by Calvert et al (2002 ). There is not particularly agreement among the studies, but there are no obvious outliers. 16 Average of the data tabulated by Calvert et al (2002), excluding the low value of Tuazon and co workers which is superceded by a more recent measurement from the same group. 17 Average of the various measurements tabulated by Calvert et al (2002). There is not particularly good agreement, but no obvious outliers to exclude from the average. 18 Average of 2,5 - dimethylphenol yields of Atkinson et al (1991) and Smith et al (1999). Yields reported by Becker et al (1997) are lower and not used. 19 Average of yields reported by Bandow and Washida (1985a), Tuazon et al (1986) and Smith et al (1999). 20 The data tabulated by Calvert et al (2002) show some variation, but three studies give good agreement and indicate yields of about 10%. The value used is the average from those studies. 21 No data available. Estimated from the average rate constant per methyl group for the other methylbenzenes and the total OH rate constan t. 22 No data available. The average of the assigned phenolic product yield for the other trimethylbenzenes is used. 23 The yields determined by Bandow and Washida (1985b) are used for consistency with assignment for biacetyl. 24 Average of Bandow and Washida (1985b) and Atkinson and Aschmann (1994). The slightly lower yield of Tuazon et al (1986) not used but may not be outside of range of uncertainty. 25 Sum of yields of 2,4 - , 2,5 - , and 3,4 - dimethylbenzaldehyde from Smith et al (1999) 26 Sum of 2,4,5 - , 2, 3,5 - , and 2,3,6 -trimethylphenol from Smith et al (1999) 27 Average of glyoxal yields of Bandow and Washida (1985b) and Smith et al (1999) and 3 - methyl 3 -hexene - 2,5 - dione of Smith et al (1999). The lower value of Tuazon et al (1986) is not used. Yields of glyoxal and 3 -me thyl - 3 -hexene - 2,5 - dione are assumed to be equal. 28 Average of Bandow and Washida (1985b) and Smith et al (1999). The value of Tuazon et al (1986) is not used because of the higher NO x 

### levels and for consistency with other assignments. 29 Average of Bandow and Washida (1985b) and Atkinson and Aschmann (1994). The lower yield of Tuazon et al (1986) is not used but may not be outside of range of uncertainty. 30 The 3,5 - dimethylbenzaldehyde yield from Smith et al (1999) is used. 31 The 2,4,6 -trimethylphenol yield from Smith et al (1999) is used. 34 The yield from Bandow and Washida (1985b) is used. The data of Smith et al (1999) appear to be high and the data from Tuazon et al (1986) was not used for consistency with assignments for the other trimethylbenzenes. [b] Nitrate yield for each peroxy reaction. Total nitrate yield is less because not all pathways involve peroxy reactions.

### 36 BzCH 3 

### + OH  H 2 

### O + BzCH 2 

### · BzCH 2 

### · + O 2 

###  BzCH 2 

### OO· BzCH 2 

### OO· + NO  NO 2 

### + BzCH 2 

### O· (Fraction = n7)

 BzCH 2 

### ONO 2 

### (Fraction = 1 -n7) BzCH 2 

### O· + O 2 

###  BzCHO + HO 2 

### or ethylbenzene BzCH 2 

### CH 3 

### + OH  H 2 

### O + BzCH(·)CH 3 

### BzCH(·)CH 3 

### + O 2 

###  BzCH(OO·)CH 3 

### BzCH(OO·)CH 3 

### + NO  NO 2 

### + BzCH(O·)CH 3 

### (Fraction = n8)

 BzCH(ONO 2 

### )CH 3 

### (Fraction = 1 -n8) BzCH(O·)CH 3 

### + O 2 

###  BzC(O)CH 3 

### + HO 2 

### Here, "Bz" refers to the aromatic ring, and n7 and n8 refer to the nitrate yields assumed for aromatics with 7 or 8 carbons, which are derived as discussed below. In terms of SAPRC - 07 model species, these overall processes are represented as

TOLUENE + OH  ( 1 -n7) {RO2C + xBALD} + (n7) zRNO3 + yR6OOH C2 - BENZ + OH  (1 -n8) {RO2C + PROD2} + (n8) Zrno3 + yR6OOH Ing eneral, the model species "BALD" is used to represent aromatic aldehydes such as benzaldehyde and tolualdehyde, PROD2 is used to represent aromatic ketones such as methyl phenyl ketone and methyl benzyl ketone, RNO3 is used to represent the organic nitrates formed from peroxy + NO reactions in the aromatic and other systems, and R6OOH is used to represent the hydroperoxides formed in the reactions off the aromatic ring.

Reactions on the Aromatic Ring. The maj or uncertainty concerning the reactions of aromatics with OH radicals concern the subsequent reactions after OH adds to the aromatic ring. Information and data concerning what is known about these processes is discussed by Calvert et al (2002), and that discussion is not duplicated here. The general model we assume for these reactions, which is probably an oversimplification of what really happens, is shown on Figure 2 , using benzene as an example. The processes are assumed to be analogous for the substituted benzenes such as toluene, xylenes, etc., except that the number of reactions and products are much greater because of various possible positions of the substituents on the intermediates and the products.

The products that are known to be formed and whose yields have been quantified include the phenols and cresols, and the  - dicarbonyls (phenol and glyoxal in the case or benzene). The formation of phenols is generally assumed to occur by OH abstraction of the initial OH - aromatic adduct, as shown on Figure 2 as "A". The observed yields of these phenolic products are then used to derive the branching ratio (a)/(1 - a) as shown on the figure. The co -product is HO 2 

### , formed without the intermediacy of any peroxy radicals and without any NO to NO 2 

### conversions.

The processes forming the  - dicarbonyls are more uncertain, but the most chemically reasonably process involves O 2 

### addition to form a peroxy radical that then internally adds to the double bonds to form an allylic - stabilized bicyc lic radical, which subsequently reacts to form the  - dicarbonyl(s) as shown on Figure 2 as the processes leading to product set "B". The predicted co -products are the monounsaturated 1,4 - dicarbonyls, such as the 2 -butene 1,4 - dial predicted for the benzene system. These products are indeed observed (Calvert et al, 2002, and references therein), though the total yields are generally much less than the total  - dicarbonyl yields. This could be due to other, unknown, processes leading to the  - dicarbonyls, or with problems with quantifying the unsaturated 1,4 - dicarbonyls, which are highly reactive. In any case, because of lack of available information and chemically reasonabl e

### 37 C H C H C H C H C H C H O O O C

H C H C H C H C H C H O O O H C H C H C H C H C H C H O H O O C H C H C H C H C H C H O H

C H C H C H C H C H C H O H O O C

H C H C H C H C H C H O H O O O

O C

H C H C H C H C H C H O H O O O C H

C H C H C H O O C

H C H O H O

C H C H C H C H O O C H C H O O O H

C H C H C H C H C H C H O H O O O N O

O C H C H C H C H C H C H O H O O O O H C H C H C H C H C H C H O H O

+ H O2

+ O2 NO NO2

+ + HO2 O2 O2

HO2 + (1-a) (a) (1-b) (b)

NO (n6) (1-n6)

HO2 O2 

### A

B C D E

(obs)

(obs) NO NO2 Other Products

(x)



### Figure 2 . Reactions of the OH - aromatic ring adduct that are assumed in the current mechanism.

The example shown is for benzene, but analogous reactions are assumed for the alkylbenzenes.

alternatives to explain the products that are observed, we assume that the processes leading to "B" as indicated on Figure 2 are the only processes in the forming the  - dicarbonyls in the primary OH + aromatic reactions, and that the unsaturated 1,4 - dicarbonyls are the corresponding co -products. The yields of the model species used to represent the unsaturated 1,4 - dicarbonyls (discussed below) are then set as the total yields of the measured  - dicarbonyl products. The total  - dicarbonyl and phenolic product yields are used to determine the branching ratio indicated as (b)/(1 -b) on Figure 2 .

Note that this process that are assumed to account for the  - dicarbonyl formation involve the intermediacy of a peroxy radical that converts NO to NO 2 

### in the processes of forming these products, but that can also react with NO to form an alkyl nitrate ("C" on Figure 2 ), react with HO 2 

### to form a highly oxygenated bicyclic hydroperoxide ("D" on Figure 2 ), or react with other peroxy radicals to form other products (not shown on the figure). The hydroperoxides formed in the HO 2 

### reaction (e.g., "D") are represented by a separate model species R AOOH because they are expected to have higher PM formation potential than other hydroperoxides, though they could be lumped with R6OOH if SOA predictions are not important. The general procedures used for representing products formed from peroxy reactions in this mechanism have been discussed previously, and these procedures are employed for these  - dicarbonyl and mono -unsaturated 1,4 - dicarbonyl products.

### 38 The sum of the measured yields of the phenolic and  - dicarbonyl products from the OH addition reactions , the aromatic aldehydes from the abstraction reactions off the aromatic ring, and estimated nitrate yields from the peroxy + NO reactions (discussed below) is not sufficient to account for all the processes involved in the OH reactions of toluene, xylene, and trimethylbenzenes (Calvert et al, 2002), so additional processes must also occur. The results of aromatic - NO x 

### environmental chamber experiments at various NO x 

### levels cannot be simulated by mechanisms that assume that yields of the photoreactive aromatic products such as  - dicarbonyls or the monounsaturated 1,4 - dicarbonyls are affected by total NO x 

### levels, and most of the available product data for the  - dicarbonyls from methylbenzenes do not indicate a NO x 

### - dependence on  - dicarbonyl yields at the NO x 

### levels relevant to the atmosphere and the chamber experiments used for mechanism evaluation. This rules out mechanisms involving competitions between unimolecular reactions of peroxy radicals and reactions of peroxy radicals with NO, such as between (b) and (x) shown on Figure 2 .

An additional consideration concerning potential competing processes is the fact that the direct reactivity experiments of Carter and Malkina (2002) indicate that the SAPRC - 99 mechanism has too many NO to NO 2 

### conversions in the reactions of aromatics with OH. We were unable to come up with chemically reasonable mechanisms for  - dicarbonyl, phenol or cresol, or aromatic aldehyde formation that involved fewer NO to NO 2 

### conversions, which leaves only the remaining process(es) forming the remaining products. Because of this, and also to avoid introducing com petitions between unimolecular and peroxy + NO reactions, we assume that the additional process involves a 6 - me mber ring H - shift of the aromatic - OH - O 2 

### adduct, giving rise to formation of a di -unsaturated 1,6 - dicarbonyl and OH radicals, shown as process (1 -b) and "E" on Figure 2 . This is a competition between two unimolecular reactions and thus the photoreactive product yields are predicted to be independent of NO x 

### , and the direct formation of OH radicals in this set of reactions involves two fewer NO to NO 2 

### conversions than assumed for these unknown processes in the SAPRC - 99 mechanism. Therefore, this is used in the current mechanism to represent all the processes that are not otherwise accounted for by the observed formation of aromatic aldehyde, phenol ic, and  - dicarbonyl products and the estimated formation of organic nitrates. The model species used to represent these di -unsaturated 1,6 - dicarbonyls is discussed below.

Estimation of Nitrate Formation Reactions . The mechanisms involving OH abstraction s off the aromatic ring, and also the mechanism involving the formation of the  - dicarbonyls and the monounsaturated 1,4 - dicarbonyls all involve the intermediacy of peroxy radicals that can react with NO to form the corresponding nitrate. The only data available concerning nitrate formation from peroxy + NO reactions in alkylbenzene systems concerns the observed formation of benzyl nitrate in the toluene system, for which the average of the yields tabulated by Calvert et al (2002) is ~0.8%. This is attributed to the reaction of benzyl peroxy radicals with NO (shown above), for which the competing process is formation of the alkoxy radical that reacts with O 2 

### to form benzaldehyde. Based on this and the benzaldehyde yield used in our toluene mechanism (discuss ed below), we derive an overall nitrate yield for the benzyl peroxy radical to be 10.6%. This can be compared with the 13.5% nitrate yield predicted by the mechanism generation system for 7 carbons for standard secondary alkylperoxy radicals formed in the alkane photooxidation system (Carter, 2000a). Based on this, we assume that nitrate yields for all peroxy radicals in aromatic systems, whether resulting from abstractions by OH off the ring or formation of  - dicarbonyls following OH + aromatic ring additi ons, are 78.5% those estimated for secondary alkyl peroxy radicals. Figure 3 shows the dependence of the nitrate yields on carbon number that is used when deriving aromatic mechanisms for SAPRC - 07. The nitrate yields are assumed to range from ~8% for benzene (n6) to ~21% for aromatics with carbon numbers greater than ~13 (n13+).

Assignments of Branching Ratios and Product Yields . Table 9 gives the measured or estimated yields from the known products from benzene, toluene, the xylenes , and the trimethylbenzenes that are used as the basis for the aromatic mechanisms derived for this work. Footnotes to the table

### 39

Figure 3 . Nitrate yield factors used for estimating aromatic oxidation mechanisms

indicate the ba sis for the assignments or estimates used. These were used, in conjunction with the nitrate yield estimates derived above, as the basis for deriving the branching ratios for all the reactions in the mechanisms for these aromatics. Note that, as discussed above, the total yields of the model species used for the mono -unsaturated 1,4 - dicarbonyls were set to the sum of the glyoxal, methyl glyoxal, and biacetyl yields shown on Table 9 , and the yields of the model species representing the di -unsaturated 1,6 - dicarbonyls was set at 1 - the sum of the aromatic aldehyde, phenol or cresol,  - dicarbonyl, and estimated nitrate yields. For the other alkylbenzenes or model species u sed to represent groups of alkylbenzenes with similar structures and carbon numbers, the mechanisms were derived based on estimates for reactions at various positions on the molecule and other estimates, as follows. The total rate constants for abstraction reactions off the aromatic ring were derived using structure -reactivity estimates, using the OH abstraction rate parameters given on Table 3 , above. These total non -ring rate constants are given for the various aromatic model species on Table 10 , along with the substituents assumed for the various model species used to represent groups of compounds. The total rates for additions to the aromatic ring were estimated by assuming they were the same as to those derived for the methylbenzene with the most similar structure, as indicated on Table 10 . The ring addition reactions for those compounds were derived from the total rate constant and the estimated extent of abstraction off the aromatic ring derived from the aromatic aldehyde and estimated off -ring abstraction rate constant derived from the aromatic aldehyde and estimated nitrate yield as indicated on Table 9 . The fractions of ring additions vs. off -ring abs tractions were derived from the ratio of the estimated rate constants for the two processes, and are shown on Table 10 . Note that for the compounds listed on Table 9 the mechanisms used the values derived based on the measured or estimated product yields shown on that table, not based on the estimated rate constants shown on Table 10 . Table 10 shows the differences between the off -ring abstraction fractions derived using these two methods for these compounds. 0% 5% 10% 15% 20% 25% 30%

6 7 8 9 10 11 12 13 14 15 16 Carbon num berNitrateyieldinPeroxy+NOreaction Nitrate y ield factor used for secondary

alky l radical estimates Derived from Benzy l Nitrate / Benzaldehyde y ield ratios from toluene Nitrate y ield factors used for arom atics m echanism estimates

### 40

Table 10 . Rate constants and assumptions used to estimate fractions of reaction of on and off the aromatic ring for the reactions of OH with

aromatic compounds or groups of compounds for which mechanistic parameters have been derived. Com pound or detailed model species group Rate Constant [a] Ring k Based on Non - Ring Rxn. Substituents [c] Total Non - Ring Ring Expt [b] Est'd Toluene 5.58e - 12 4.92e - 13 5.18e - 12 Toluene 7% 9% methyl o - Xylene 1.36e - 11 9.85e - 13 1.29e - 11 o - Xyl. 5% 7% dimethyl m - Xylene 2.31e - 11 9.85e - 13 2.20e - 11 m - Xyl. 5% 4% dimethyl p - Xylene 1.43e - 11 9.85e - 13 1.28e - 11 p - Xyl. 10% 7% dimethyl 1,2,3 - Trimethyl benzene 3.27e - 11 1.48e - 12 3.11e - 11 124 - TMB 5% trimethyl 1,2,4 - Trimethyl benzene 3.25e - 11 1.48e - 12 3.11e - 11 124 - TMB 4% 5% trimethyl 1,3,5 - Trimethyl benzene 5.67e - 11 1.48e - 12 5.47e - 11 135 - TMB 4% 3% trimethyl Ethylbenzene 7.00e - 12 2.05e - 12 5.18e - 12 Toluene 28% ethyl n - Propyl benzene 5.80e - 12 3.64e - 12 5.18e - 12 Toluene 41% 1 -propyl o - Ethyl toluene 1.19e - 11 2.54e - 12 1.29e - 11 o - Xyl. 16% methyl ethyl m - Ethyl toluene 1.86e - 11 2.54e - 12 2.20e - 11 m - Xyl. 10% methyl ethyl p - Ethyl toluene 1.18e - 11 2.54e - 12 1.28e - 11 p - Xyl. 17% methyl ethyl Isopropyl benzene 6.30e - 12 1.68e - 12 5.18e - 12 Toluene 24% 2 -propyl 1 - Methyl - 4 - isopropylbenzene 1.45e - 11 2.17e - 12 1.28e - 11 p - Xyl. 14% methyl 2 -propyl t - Butyl benzene 4.50e - 12 5.13e - 13 5.18e - 12 Toluene 9% t -butyl C10 monosubstituted benzenes 9.58e - 12 4.40e - 12 5.18e - 12 Toluene 46% 0.33 n -butyl + 0.33 2 - methyl - 1 -propyl + 0.34 1 - methyl - 1 -propyl C11 monosubstituted benzenes 1.10e - 11 5.82e - 12 5.18e - 12 Toluene 53% 0.33 n -pentyl + 0.33 3 - methyl - 1 -butyl + 0.34 1 - methyl - 1 -butyl C12 mo nosubstituted benzenes 1.24e - 11 7.25e - 12 5.18e - 12 Toluene 58% As above, but with - CH2 - added C13 monosubstituted benzenes 1.38e - 11 8.67e - 12 5.18e - 12 Toluene 63% C14 monosubstituted benzenes 1.53e - 11 1.01e - 11 5.18e - 12 Toluene 66% C15 mo nosubstituted benzenes 1.67e - 11 1.15e - 11 5.18e - 12 Toluene 69% C16 monosubstituted benzenes 1.81e - 11 1.29e - 11 5.18e - 12 Toluene 71% o - C10 disubstituted benzenes 1.64e - 11 3.51e - 12 1.29e - 11 o - Xyl. 21% 0.25 methyl n -propyl + 0.25 methyl isopropyl + 0.5 diethyl m - C10 disubstituted benzenes 2.55e - 11 2.20e - 11 m - Xyl. 14% p - C10 disubstituted benzenes 1.64e - 11 1.28e - 11 p - Xyl. 21% o - C11 disubstituted benzenes 1.82e - 11 5.40e - 12 1.29e - 11 o - Xyl. 30% 0.34 methyl (2 - metyl - 1 -propyl) + 0.33 ethyl isopropyl + 0.33 ethyl n -propyl m - C11 disubstituted benzenes 2.74e - 11 2.20e - 11 m - Xyl. 20% p - C11 disubstituted benzenes 1.82e - 11 1.28e - 11 p - Xyl. 30% o - C12 disubstituted benzenes 1.90e - 11 6.14e - 12 1.29e - 11 o - Xyl. 32% 0.25 methyl (3 - methyl - 1 -butyl) + 0.25 ethyl (1 - methyl - 1 -propyl) + 0.25 propyl isopropyl + 0.25 ethyl n -butyl m - C12 disubstituted benzenes 2.82e - 11 2.20e - 11 m - Xyl. 22% p - C12 disubstituted benzenes 1.90e - 11 1.28e - 11 p - Xyl. 32% o - C13 disubstituted benzenes 2.05e - 11 7.63e - 12 1.29e - 11 o - Xyl. 37% 0.25 ethyl (3 - methyl - 1 -butyl) + 0.25 propyl (1 - methyl - 1 -propyl) + 0.25 (2 - methyl - 1 -propyl) isopropyl + 0.25 ethyl n -pentyl m - C13 disubstituted benzenes 2.96e - 11 2.20e - 11 m - Xyl. 26% p - C13 disubstituted benzenes 2.05e - 11 1.28e - 11 p - Xyl. 37%

### Table 10 (continued)

41

Com pound or detailed model species group Rate Constant [a] Ring k Based on Non - Ring Rxn. Substituents [c] Total Non - Ring Ring Expt [b] Est'd o - C14 disubstituted benzenes 2.19e - 11 9.05e - 12 1.29e - 11 o - Xyl. 41% As above, but with - CH2 - added m - C14 disubstituted benzenes 3.11e - 11 2.20e - 11 m - Xyl. 29% p - C14 disubstituted benzenes 2.19e - 11 1.28e - 11 p - Xyl. 41% o - C15 disubstituted benzenes 2.33e - 11 1.05e - 11 1.29e - 11 o - Xyl. 45% m - C15 disubstituted benzenes 3.25e - 11 2.20e - 11 m - Xyl. 32% p - C15 disubstituted benzenes 2.33e - 11 1.28e - 11 p - Xyl. 45% o - C16 disubstituted benzenes 2.48e - 11 1.19e - 11 1.29e - 11 o - Xyl. 48% m - C16 disubstituted benzenes 3.39e - 11 2.20e - 11 m - Xyl. 35% p - C16 disubstituted benzenes 2.47e - 11 1.28e - 11 p - Xyl. 48% 1,2,3 - C10 trisubstituted benzenes 3.41e - 11 3.03e - 12 3.11e - 11 124 - TMB 9% Dimethyl ethyl 1,2,4 - C10 trisubstituted benzenes 3.41e - 11 3.11e - 11 124 - TMB 9% 1,3,5 - C10 trisubstituted benzenes 5.77e - 11 5.47e - 11 135 - TMB 5% 1,2,3 - C11 trisubstituted benzenes 3.57e - 11 4.60e - 12 3.11e - 11 124 - TMB 13% 0.5 dimethyl propyl + 0.5 methyl diethyl 1,2,4 - C11 trisubstituted benzenes 3.57e - 11 3.11e - 11 124 - TMB 13% 1,3,5 - C11 trisubstituted benzenes 5.93e - 11 5.47e - 11 135 - TMB 8% 1,2,3 - C12 trisubstituted benzenes 3.66e - 11 5.47e - 12 3.11e - 11 124 - TMB 15% 0.34 dimethyl 2 - methyl - 1 -propyl + 0.33 methyl ethyl isopropyl + 0.33 methyl ethyl n -propyl 1,2,4 - C12 trisubstituted benzenes 3.66e - 11 3.11e - 11 124 - TMB 15% 1,3,5 - C12 trisubstituted benzenes 6.01e - 11 5.47e - 11 135 - TMB 9% 1,2,3 - C13 trisubstituted benzenes 3.81e - 11 7.00e - 12 3.11e - 11 124 - TMB 18% 0.34 methyl ethyl 2 - methyl - 1 - propyl + 0.33 methyl ethyl n - butyl + 0.33 methyl propyl isobutyl 1,2,4 - C13 trisubstituted benzenes 3.81e - 11 3.11e - 11 124 - TMB 18% 1,3,5 - C13 trisubstituted benzenes 6.17e - 11 5.47e - 11 135 - TMB 11% 1,2,3 - C14 trisubstituted benzenes 3.93e - 11 8.16e - 12 3.11e - 11 124 - TMB 21% 0.25 methyl ethyl 3 - methyl - 1 - butyl + 0.25 methyl n -propyl n butyl + 0.25 ethyl isopropyl n - propyl 1,2,4 - C14 trisubstituted benzenes 3.93e - 11 3.11e - 11 124 - TMB 21% 1,3,5 - C14 trisubstituted benzenes 6.28e - 11 5.47e - 11 135 - TMB 13% 1,2,3 - C15 trisubstituted benzenes 4.04e - 11 9.31e - 12 3.11e - 11 124 - TMB 23% 0.25 methyl ethyl 4 - methyl - 1 - pentyl + 0.25 ethyl n -propyl 1 - methyl - 1 -propyl + methyl propyl 1 - methyl - 1 -butyl + ethyl isopropyl 2 - methyl - 1 -propyl 1,2,4 - C15 trisubstituted benzenes 4.04e - 11 3.11e - 11 124 - TMB 23% 1,3,5 - C15 trisubstituted benzenes 6.40e - 11 5.47e - 11 135 - TMB 15% 1,2,3 - C16 trisubstituted benzenes 4.17e - 11 1.06e - 11 3.11e - 11 124 - TMB 25% 0.25 ethyl propyl 3 - methyl - 1 - butyl + 0.25 ethyl propyl 1 - methyl 1 -butyl + methyl propyl 1,3 - dimethyl - 1 -butyl + 0.25 propyl isopropyl 2 - methyl - 1 -propyl 1,2,4 - C16 trisubstituted benzenes 4.17e - 11 3.11e - 11 124 - TMB 25% 1,3,5 - C16 trisubstituted benzenes 6.52e - 11 5.47e - 11 135 - TMB 16% [a] Rate constant in cm3 mo lec - 1 s - 1 . "Total" is total rate constant is rate constant used in the mechanism, either experimental or estimated. "Non- Ring" is total rate constant for abstraction at various positions off the aromatic ring, estimated using the group additivity factors shown in Table 4 . "Ring" is estimated rate constant for addition to the aromatic ring, derived by assuming the same aromatic ring addition rate constant as the indicate d compound. [b] Derived from the measured yields of the expected non -ring abstraction product, corrected for estimated nitrate formation, relative to the total rate constant. These can be compared with the estimated ratios of non -ring reaction, derived from the estimated ring and non -ring rate constants. [c] Substituents assumed when estimating rate constants for abstraction reactions off the aromatic ring.

### 42 The products formed from the off -ring abstraction reactions are represented by the organic nitrate model species RNO3 and either the aromatic aldehyde model species BALD or the reactive ketone model species PROD2, depending on the substituent. The RNO3 yield was derived from the carbon number as discussed above. If the substituent is a methyl group the reaction was expected to form an aromatic aldehyde and the product was represented by the benzaldehyde model species BALD. Otherwise, the pro ducts are assumed to be primarily ketones and are represented by PROD2.

The products used to represent those formed from the reactions following the addition to the aromatic ring were derived based on those derived for the corresponding reactions of ethylbenzene, a xylene, or a trimethylbenzene, depending on the structure of the compound or group of compounds being represented. The ring -reaction products for ethylbenzene were used for the ring reactions products for the monoalkylbenzenes, the ring -reaction products for o -xylene were used for all 1,2 - disubstituted benzenes, those for 1,2,3 -trimethylbenzene were used for all the 1,2,3 -trisubstituted benzenes, and similarly for the other isomers. The ring -reaction products for ethylbenzene were derived from those derived for toluene, taking into account estimated differences in off -ring reactions and nitrate yields, and with the ratio of the photoreactive and non -photoreactive model species used for the mono -unsaturated 1,4 - dicarbonyls adjusted to fit the chamber data for ethylbenzene (see discussion of these products, below). The ring reaction products for the xylene and trimethylbenzene isomers were derived from the product data for those compounds as shown on Table 9 , ratio of the photoreactive and non -photoreactive model species used for the monounsaturated 1,4 - dicarbonyls adjusted to fit the chamber data for those compounds. These are summarized on Table 11 .

The mechanistic assignments shown on Table 9 , Table 10 , Table 11 and Figure 3 were used to derive overall mechanisms for the individual aromatics or groups or aromatic s as listed on Table 10 . The resulting overall rate constants are given on Table B -4 and the mechanisms are given in Table B 2 in Appendix B. Footnotes to Table B -4 indicate the sources of the rate constants that were used.

**Representation of Unsaturated Dicarbonyl Products** As discussed above, the co -products assumed to be formed with the  - dicarbonyls in the ring opening products are the monounsaturated 1,4 - dicarbonyls, and the ring opening reactions not involving these products are assumed to be di -unsaturated 1,6 - dicarbonyls. For the benzene system, these consist of 2 -butene - 1,4 - dial and 2,4 -hexadienedial as shown on Figure 2 , while for the methylbenzenes various methyl substituted isomers can be formed, with relative yields depending on the position of OH addition to the double bond, and also where the O 2 

### adds to the O H - aromatic adduct. Estimated distributions of these products for the various methylbenzene isomers are shown on Table 12 . These estimates were derived based on estimated fractions of reaction of OH radicals at various positions of the molecules and estimated branching ratios for O 2 

### addition at the various positions of the OH + aromatic adducts, adjusted to be consistent with the observed yields of the  - dicarbonyl co -products 1



### .

This product distribution can serve as the basis for deriving explicit or semi - explicit mechanisms for the OH reactions of these aromatics. However, for airshed and reactivity simulations a more generalized mechanism, with a more limited number of model species, is needed. The model species used to represent these products in this version of the mechanism is indicated on Table 12 . The reasoning behind this representation, and the derivations of their mechanisms, are discussed below. Note that this is the same number of model species used to represent uncharacterized ring fragmentation products in SAPRC - 99, but in this case the mechanisms are derived based on estimations for actual compounds.

1 

### These estimates were made as part of the initial effort to derive explicit aromatics mechanisms, which is beyond the scope of the present report.

### 43

Table 11 . Model species used to represent non -nitrate products from the reactions of OH radicals at

aromatic rings for various types of ring structures. Yields are normalized to OH ring addition only, excluding nitrate formation. Ring structure A [a] B [b] B, C, D E CRES + HO2 xGLY xMGLY xBACL xAFG1+2 [c] AFG1/2

[d] xAFG3 [e] Peroxy Total [f] AFG3 +

OH [e] Benzene 12% 31% 31% 0.11 31% 31% Toluene 34% 29% 18% 47% 1.00 29% 29% Ethylbenzene [g] (based on toluene) 0.39 (same as toluene) o - Xylene 21% 10% 29% 23% 62% 1.00 10% 10% m - Xylene 25% 12% 46% 58% 2.33 12% 12% p - Xylene 31% 37% 14% 14% 0.67 37% 37% 37% 1,2,3 - Trimethylbenzene 9% 9% 23% 56% 88% 1.00 9% 9% 1,2,4 - Trimethylbenzene 24% 9% 50% 14% 55% 0.25 19% 9% 9% 1,3,5 - Trimethylbenzene 17% 79% 79% 1.00 [a] Pathway on Figure 2 that these model species are being used to represent. [b] Yields depend on nitrate yield in peroxy + NO reactions, and are shown for nitrate yields of zero. Actual yields are (tabulated yield s) x (1 - nx), where "nx" refers to the nitrate yield for carbon number "x", determined as shown on Figure 3 . The prefix "x" is used to indicate that they are formed following reactions of peroxy radicals with NO (see discussion of the base mechanism). [c] This is the total yield of monounsaturated 1,4 dialdehydes or aldehyde - ketones, represented by xAFG1 + xAFG2. [d] This is the ratio of the xAFG1 to xAF G2 yield, which is adjusted to aromatic - NO x chamber data for the indicated compound [e] AFG3 is the model species used to represent both monounsaturated 1,4 - diketones and di - unsaturated 1,6 - dicarbonyls. [f] This is the total level of peroxy radicals in the reaction, and also the total NO to NO 2 conversion + nitrate formation. The yield of RO2C, representing NO to NO 2 conversion, is given by the tabulated value x (1 - nx), and the nitrate yield, represented by RO2XC + zRNO3, is given by the tabulated value x (nx), where "nx" is the nitrate yield factor as indicated in Footnote [b]. The tabulated values also give the yields of yRAOOH, which is used to represent the [g] The yields are based on those derived for toluene, but are slightly different because of differences between the estimated and total rate constants. However, the AFG1/AFG2 yields (AFG1/2) were adjusted separately to fit the chamber experiments for ethylbenzene.



### Available data and theories concerning the atmospheric reactions of th ese unsaturated dicarbonyl ring - opening products are discussed by Calvert et al (2002). These compounds react at significant rates with OH radicals and O 3 

### and information is available concerning the rate constants for representative compounds. These compounds can also photolyze at significant rates under atmospheric conditions, and absorption cross - section data are also available for representative compounds. The quantum yields are more uncertain but measurements of photolysis consumption rates have been made in the Euphore outdoor chamber that can serve as a basis for estimating overall quantum yields for consumption by photolysis. The extent to which these photolysis reactions form radicals is a very important factor affecting the contribution of these pro ducts to the overall reactivity of the aromatic starting material. The limited product and environmental chamber reactivity data indicate that photolysis to form radicals is important for the mono -unsaturated 1,4 - dialdehydes and aldehyde - ketones, but that the photolysis of the mono -unsaturated 1,4 - diketones and the di -unsaturated 1,6 - dicarbonyls is much less

### 44

Table 12 . Estimated yields for unsaturated dicarbonyl products in the OH reactions of the

methylbenzenes for which  - dicarbonyl yield data are available. Ring fragmentation product compound or type of compound Methylbenzene Reactant Toluene Xylenes Trimethylbenzenes

o - m - p - 1,2,3 - 1,2,4 - 1,3,5 - Aldehydes and aldehyde - ketones (Represented by AFG1 and AFG2) 2 - Butene - 1,4 - dial 0.15 0.19 2 - Methyl - 2 -butene - 1,4 - dial 0.12 0.19 0.11 0.11 2,3 - Dimethyl - 2 -butene - 1,4 - dial 0.03 0.12 4 - Oxo - 2 -penteneal 0.11 0.24 0.19 0.45 2 - Methyl - 4 - oxo - 2 -penteneal 0.10 0.10 0.64 3 - Methyl - 4 - oxo - 2 -penteneal 0.05 0.18 0.11 2,3 - Dimethyl - 4 - oxo - 2 -penteneal 0.07 Diketones (Represented by AFG3) 3 - Methyl - 3 - hexene - 2,5 - dione 0.29 0.08 Diunsaturated dicarbonyls (Represented by AFG3) Methyl - substituted 1,4 - hexadienedials 0.22 0.09 0.09 0.12 0.03 0.05 6 - Oxo - 2,4 -hepadienedial and methyl substituted isomers 0.09 0.08 0.15 0.15 0.03 0.15 0.16 3,5 - Octadiene - 2,7 - dione and methyl substituted isomers 0.03 0.03 0.03 

### efficient, or forms primarily non -radical products. Calvert et al (2002), and references therein, should be consulted for details.

Based on this information, we use two model species, designated AFG1 and AFG2, to represent the highly photoreactive mono -unsaturated dialdehydes and aldehyde - ketones, and a separate model species, AFG3, to repres ent the less photoreactive unsaturated diketones and di -unsaturated dicarbonyls. Because the overall quantum yields for photolyses of the mono -unsaturated dialdehydes and aldehyde -ketones to form radicals are very important in affecting overall reactivity but are uncertain and may vary from compound to compound, these are treated as adjustable parameters in the mechanism. This is im plemented by using two model species for these compounds that have exactly the same mechanisms, except that one (AFG1) photolyz es to form radicals, while the other (AFG2) photolyzes at the same rate but forms non -radical products. The total yields of these model species are set at the total estimated monounsaturated aldehyde yield as indicated on Table 12 , while the yield of one relative to the other are adjusted to predict overall reactivities t hat are consistent with results of environmental chamber experiments with the various aromatics. This is equivalent to adjusting separately the overall quantum yields for formation of radical vs. non -radical products for photoreactive dicarbonyls for each compound without having to use a separate model species for each compound.

As indicated in footnotes to Table A - 2 in Appendix A, the mechanisms for AFG1 and AFG2 was derived based on those estimated for the representative dialdehydes and diketones 2 -butene 1,4 - dial 2 - methyl - 2 -butene - 1,4 - dial, 4 - oxo - 2 -petenal, and 2 - methyl -4 - oxo - 2 -pentenal, and the mechanism for AFG3 was derived based on those estimated for the represented di -unsaturated dicarbonyl products 3 - methyl 2,4 -hexene - 1,6 - dial, 6 - oxo - 2,4 -heptadienal, and 3,5 - octadien - 2,7 - dione. The relative contributions of each are based on relative yields of these and similar products from the methylbenzenes, as indicated on Table 12 . Use of a separate model species, based on mechanisms for 3 -methyl - 3 - hexene - 2,5 - dione, to represent the mono -unsaturated diketones was examined in an initial version of this mechanism. However, but it was found that lumping it with the model species used for the di -unsaturated dicarbonyls

### 45

gave essentially the same reactivity predictions for p -xylene and 1,2,4 -trimethylbenzene, the only compounds for which reactivity data are available where these products are predicted to be formed. Therefore, it was determined that use of a separate model species to represent these mono -unsaturated diketones was not necessary.

The mechanisms for the reactions of these model spec ies with OH and O 3 

### were derived using the enhanced mechanism generation system, using assignments for the specific compounds that are given on Table 13 . The reactions of these species with NO 3 

### and O 3 

### P were assumed to be negligible compared to the other processes and are not included in the mechanism. The mechanism for the photolysis of AFG1 to form radicals is based on the assignments for the initial reactions that are also given on Table 13 . Specific mechanisms were not generated for the photolyses of AFG2 to form stable products; the unspecified products formed are assumed to be moderately reactive and are represented by the model species PROD2. The overall mechanisms that were derived for these model species using this method are given with the listing of the base mechanism on Table A - 2 in Appendix A.

The absorption cross sections and quantum yields for the photolyses of AFG1 and AFG2 were derived from those for 2 -butene - 1,4 - dial and 4 - oxo - 2 -pentenal, assuming those for 2 -methyl - 2 - butene - 1,4 - di al and 2 - methyl -4 - oxo - 2 -pentenal are the same as those for 2 -butene - 1,4 - dial and 4 - oxo - 2 - pentenal, respectively. The derivations of the absorption cross sections and quantum yields used are indicated on Table 13 , and plots of the action spectra (absorption cross sections x overall quantum yields) for these two compounds are shown on Figure 4 , where they are compared with that derived for AFG1 and AFG2, which is the weighed average based on ratios of these compounds used to derive the rate constants and mechanisms for the other reactions (see footnotes to Table A - 2 in Appendix A). The action spectrum for AFG1,2 most closely resembles that for 4 - oxo - 2 -pentenal because of the higher absorption cross sections and quantum yields and also because of the higher weighting of the aldehyde -ketone products (68%) compared to the dialdehyde products (32%).

Note that although this representation uses the same number of model species as SAPRC 99 to represent the unspecified non -  - dicarbonyl aromatic ring op ening products, the meaning and the mechanisms of these species is different. In SAPRC - 99 the model species DCB1 is used to represent non photoreactive product species, DCB2 represents photoreactive products with action spectra like  - dicarbonyls, and DCB3 represents photoreactive products with action spectra like acrolein. The yields of DCB1 for various aromatics were set more or less arbitrarily, while those for DCB2 and DCB3 were adjusted to fit the aromatics - NO x 

### chamber data, with species with the dif ferent action spectra being needed to simulate experiments using differing light sources. In this mechanism, the total yields are set based on other product data or estimates that are independent of the chamber data, and only the AFG1/AFG2 yield ratio is adj usted to fit the chamber data. Note that the action spectra are derived independently of the chamber data, with no adjustments to account for reactivity differences using chambers with different light sources. This resulted in some cases in the SAPRC - 07 mechanism not performing as well as SAPRC - 99 in simulating blacklight chamber data, but in general model performance was satisfactory, indicating that the un - adjustable action spectra used in the model may be appropriate. This is discussed further in the " Mechanism Evaluation Results" section, below.

### 46

Table 13 . Mechanism estimation assignments made for representative unsaturated dicarbonyl

compounds for the purpose of generating mechanisms for the aromatic fragmentation product model species AFG1 - 3. Compound, reaction, and rate parameters Fraction 2 - Butene - 1,4 - dial OH Rate Constant = 5.29e - 11 cm3 

### molec - 1 

### s - 1 

### HCOCH=CHCHO + OH  HCOCH(·)CH(CHO)OH 44% HCOCH=CHCHO + OH  H 2 

### O + HCOCH=CHC(O)· 56% Rate constant from Bierbach et al (1994). Branching ratios estimated by assuming that abstraction from CHO has a rate constant per CHO group as estimated acrolein. O 3 

### Rate Constant = 1.60e - 18 cm3 

### molec - 1 

### s - 1 

### HCOCH=CHCHO + O 3 

###  HCOCHOO[excited] + HCOCHO Rate constant from Liu et al (1999). h Photolysis Set = BUTEDIAL, Quantum Yield = 0.723 HCOCH=CHCHO + h  HCOCH=CHC(O)· + H. 50% HCOCH=CHCHO + h  HCO· + HCOCH=CH. 50% The absorption coefficients are from Liu et al (1999) (file provided by Ken Sexton, University of North Carolina), normalized as discussed by Calvert et al (2002). The quantum yield is set to give the photolysis rate, relative to NO 2 

### , of 0.18, based on data of Sorensen and Barnes (1998). Only the radical formation pathways (us ed for AFG1) are shown on this table -- stable compounds formed by AFG2 are represented by PROD2 regardless of the compounds used to derive the mechanisms. The radical producing processes are uncertain, and the two shown are assumed to be most likely and to be equally important. 2 - Methyl - 2 -butene - 1,4 - dial OH Rate Constant = 9.63e - 11 cm3 

### molec - 1 

### s - 1 

### CH 3 

### C(CHO)=CHCHO + OH  CH 3 

### C(·)(CHO)CH(CHO)OH 52% CH 3 

### C(CHO)=CHCHO + OH  CH 3 

### C(CHO)(OH)CH(·)CHO 17% CH 3 

### C(CHO)=CHCHO + OH  H 2 

### O + CH 3 

### C(CHO)=CHC(O)· 31% The rate constant and branching ratios derived from estimated rate constants for reactions at various locations. Reaction by abstraction from CHO assumed to have same rate constant per CHO as assumed for acrolein. Addition to the double bond is calculated from OH addition rate constants for 1,4 -butanedial x methacrolein / acrolein. The relative rates of addition at the various positions are assumed to be the same as used by the mechanism generation system for alkenes with 3 substituents about the dou

ble bond. O 3 

### Rate Constant = 6.66e - 18 cm3 

### molec - 1 

### s - 1 

### CH 3 

### C(CHO)=CHCHO + O 3 

###  CH 3 

### COO[excited]CHO + HCOCHO 70% CH 3 

### C(CHO)=CHCHO + O 3 

###  HCOCHOO[excited] + CH 3 

### C(O)CHO 30% The rate constant is estimated from the O 3 

### rate constants for 1,4 -butanedial x methacrolein / acrolein. The branching ratios were derived by the mechanism generation system based on assignments for trisubstituted alkenes. h Photolysis Set = BUTEDIAL, Quantum Yield = 0.723 CH 3 

### C(CHO)=CHCHO + h  H. + CH 3 

### C(CHO)=CHC(O)· 25% CH 3 

### C(CHO)=CHCHO + h  H. + CH 3 

### CH=C(CHO)C(O)· 25% CH 3 

### C(CHO)=CHCHO + h  HCO· + CH 3 

### C(CHO)=CH. 25%

### Table 13 (continued)

47

Compound, reaction, and rate parameters Fraction

CH 3 

### C(CHO)=CHCHO + h  HCO· + CH 3 

### C(·)=CHCHO 25% The photolysis reaction is assumed to have the same absorption cross - section and overall quantum yield as used for 2 -butene - 1,4 - dial. The radical formation reactions shown above are assumed to have equal probability. 4 - Oxo - 2 -penteneal OH Rate Constant = 5.67e - 11 cm3 

### molec - 1 

### s - 1 

### CH 3 

### C(O)CH=CHCHO + OH  CH 3 

### C(O)CH(OH)CH(·)CHO 37% CH 3 

### C(O)CH=CHCHO + OH  CH 3 

### C(O)CH(·)CH(CHO)OH 37% CH 3 

### C(O)CH=CHCHO + OH  H 2 

### O + CH 3 

### C(O)CH=CHC(O)· 26% Rate constant from Bierbach et al (1994). Branching ratios estimated based on ratio of total rate constant relative to the rate constant for abstraction from CHO based on that derived for acrolein. Equal probability OH addition at the two positions about the bond is assumed. O 3 

### Rate Constant = 4.80e - 18 cm3 

### molec - 1 

### s - 1 

### CH 3 

### C(O)CH=CHCHO + O 3 

###  CH 3 

### C(O)CHOO[excited] + HCOCHO 50% CH 3 

### C(O)CH=CHCHO + O 3 

###  HCOCHOO[excited] + CH 3 

### C(O)CHO 50% Rate constant from Liu et al (1999). Equal probability of reaction assumed for the two possible routes. h Photolysis Set = 4OX2PEAL, Quantum yields = 1. CH 3 

### C(O)CH=CHCHO + h  HCOCH=CHC(O)· + CH 3 

### · 25% CH 3 

### C(O)CH=CHCHO + h  H. + CH 3 

### C(O)CH=CHC(O)· 25% CH 3 

### C(O)CH=CHCHO + h  HCOCH=CH. + CH 3 

### C(O)· 25% CH 3 

### C(O)CH=CHCHO + h  HCO· + CH 3 

### C(O)CH=CH. 25% Absorption cross - sections from Calvert et al (2002). A high quantum yield is indicated by the photolysis rate measurements made in the Euphore chamber by Sørensen and Barnes (1998), and a unit quantum yield is assumed. Equal probability of reaction is assumed for the various possible radical formation routes shown above. 2 - Methyl -4 - oxo - 2 -pentenal OH Rate Constant = 8.61e - 11 cm3 

### molec - 1 

### s - 1 

### CH 3 

### C(O)CH=C(CH 3 

### )CHO + OH  CH 3 

### C(O)CH(OH)C(·)(CH 3 

### )CHO 62% CH 3 

### C(O)CH=C(CH 3 

### )CHO + OH  CH 3 

### C(O)CH(·)C(CH 3 

### )(CHO)OH 21% Rate constant and branching ratios are derived from estimated rate constants for reactions at various locations. Reaction by abstraction from CHO assumed to have same rate constant as the analogous reaction of acrolein. Addition to double bond calculated from OH addition rate constants for 4 - oxo - 2 -pentenal x methacrolein / acrolein. The reaction shown is assumed to be the major addition process. O 3 

### Rate Constant = 2.00e - 17 cm3 

### molec - 1 

### s - 1 

### CH 3 

### C(O)CH=C(CH 3 

### )CHO + O 3 

###  CH 3 

### C(O)CHOO[excited] + CH 3 

### C(O)CHO 30% CH 3 

### C(O)CH=C(CH 3 

### )CHO + O 3 

###  CH 3 

### COO[excited]CHO + CH 3 

### C(O)CHO 70% The rate constant estimated from O 3 

### rate constants for 4 - oxo - 2 -pentenal x methacrolein / acrolein. The branching ratios were derived by the mechanism generation system based on assignments for trisubstituted alkenes. h Photolysis Set = 4OX2PEAL, Quantum yields = 1. CH 3 

### C(O)CH=C(CH 3 

### )CHO + h  CH 3 

### · + CH 3 

### C(CHO)=CHC(O)· 25%

### Table 13 (continued)

48

Compound, reaction, and rate parameters Fraction

CH 3 

### C(O)CH=C(CH 3 

### )CHO + h  H. + CH 3 

### C(O)CH=C(CH 3 

### )C(O)· 25% CH 3 

### C(O)CH=C(CH 3 

### )CHO + h  CH 3 

### C(O)· + CH 3 

### C(CHO)=CH. 25% CH 3 

### C(O)CH=C(CH 3 

### )CHO + h  HCO· + CH 3 

### C(·)=C(CH 3 

### )CHO 25% The photolysis reaction is assumed to have the same absorption cross - section and overall quantum yield as used for 4 - oxo - 2 -pentenal. The radical formation reactions shown above are assumed to have equal probability. 3 - methyl 2,4 -hexene - 1,6 - Dial OH Rate Constant = 1.20e - 10 cm3 

### molec - 1 

### s - 1 

### CH 3 

### C(=CHCHO)CH=CHCHO + OH  H 2 

### O + CH 3 

### C(=CHC(O)·)CH=CHCHO 12% CH 3 

### C(=CHCHO)CH=CHCHO + OH  H 2 

### O + CH 3 

### C(=CHCHO)CH=CHC(O)· 12% CH 3 

### C(=CHCHO)CH=CHCHO + OH  CH 3 

### C(=CHCHO)CH(·)CH(CHO)OH 75% Rate constant and branching ratios estimated from sum of estimated rate constants for reactions at various positions. Rate constant for abstraction from CHO assumed to be same as for analogous reaction of acrolein. Rate constant for addition to doub le bond estimated from addition rate constant estimated from addition rate constant for 2,4 - hexene - 1,6 - dial x rate constant for isoprene / rate constant for 1,3 -butadiene. The addition rate constant for 2,4 -hexene - 1,6 - dial is estimated from the total rate constant of 9.00e - 11cm3 

### molec - 1 

### s - 1 

### for that compound and the estimated rate constant for reaction at the CHO groups, based on the rate constant estimated for acrolein. The total rate constant for 2,4 -hexene - 1 - 6 - dial is representative of values reported by Klotz et al (1995, 1999) for the trans,trans and the cis,trans isomers. The addition reaction shown is assumed to be the major process. O 3 

### Rate Constant = 2.01e - 17 cm3 

### molec - 1 

### s - 1 

### CH 3 

### C(=CHCHO)CH=CHCHO + O 3 

###  CH 3 

### C(O)CH=CHCHO + HCOCHOO[excited] 25% CH 3 

### C(=CHCHO)CH=CHCHO + O 3 

###  HCOCHO + CH 3 

### COO[excited] - CH=CHCHO 25% CH 3 

### C(=CHCHO)CH=CHCHO + O 3 

###  HCOCHO + CH 3 

### C(CHOO[excited])=CHCHO 25% CH 3 

### C(=CHCHO)CH=CHCHO + O 3 

###  CH 3 

### C(CHO)=CHCHO + HCOCHOO[excited] 25% The rate constant is estimated from rate constants for 2,4 -hexene - 1,6 - dial x isoprene / 1,3 -butadiene. The rate constant used for 2,4 -hexene - 1,6 - dial is 1.00e - 17 cm3 

### molec - 1 

### s - 1 

### , based on the upper limit rate constant of Klotz et al (1995). Equal probability is assumed for reactions at the variou s positions, as shown above.

### Table 13 (continued)

49

Compound, reaction, and rate parameters Fraction 6 - oxo 2,4 -heptadienal OH Rate Constant = 7.51e - 11 cm3 

### molec - 1 

### s - 1 

### CH 3 

### C(O)CH=CH - CH=CHCHO + OH  H 2 

### O + CH 3 

### C(O)CH=CH - CH=CHC(O)· 20% CH 3 

### C(O)CH=CH - CH=CHCHO + OH  CH 3 

### C(O)CH=CH - CH(·)CH(CHO)OH 40% CH 3 

### C(O)CH=CH - CH=CHCHO + OH  CH 3 

### C(O)CH(OH)CH(·)CH=CHCHO 40% The rate constant and branching ratios estimated from estimated rate constants for reactions at various positions. Rate constant for abstraction from CHO assumed to be same as for analogous reacti on of acrolein. Rate constant for addition to double bond assumed to be the same as the analogous reaction of 1,4 -hexadiene - 1,6 - dial, derived as indicated above for 3 - methyl - 2 -4 -hexene - 1,6 - dial. The addition reactions shown are assumed to be the major proc esses, and equal probability for each is assumed. O 3 

### Rate Constant = 1.00e - 17 cm3 

### molec - 1 

### s - 1 

### CH 3 

### C(O)CH=CH - CH=CHCHO + O 3 

###  CH 3 

### C(O)CHO + HCOCH=CHCHOO[excited] 25% CH 3 

### C(O)CH=CH - CH=CHCHO + O 3 

###  HCOCH=CHCHO + CH 3 

### C(O)CHOO[excited] 25% CH 3 

### C(O)CH=CH - CH=CHCHO + O 3 

###  HCOCHO + CH 3 

### C(O)CH=CHCHOO[excited] 25% CH 3 

### C(O)CH=CH - CH=CHCHO + O 3 

###  CH 3 

### C(O)CH=CHCHO + HCOCHOO[excited] 25% The rate constant is assumed to be the same as that assigned for 3,4 -hexene - 1,6 - dial, based on the upper limit data of Klotz et al (1995). Equal probability of reaction at the various positions is assumed. 3,5 - octadien - 2,7 - dione OH Rate Constant = 6.02e - 11 cm3 

### molec - 1 

### s - 1 

### CH 3 

### C(O)CH=CH - CH=CHC(O)CH 3 

### + OH  CH 3 

### C(O)CH=CH CH(·)CH(OH)C(O)CH 3 

### 100% The rate constant for addition to the double bond is assumed to be the same as that derived for 2,4 -hexadiene - 1,6 - dial, as indicated above for 3 - methyl - 2,4 -hexene - 1,6 - dial. The reaction shown is assumed to be the major process. O 3 

### Rate Constant = 1.00e - 17 cm3 

### molec - 1 

### s - 1 

### CH 3 

### C(O)CH=CH - CH=CHC(O)CH 3 

### + O 3 

###  CH 3 

### C(O)CHO + CH 3 

### C(O)CH=CHCHOO[excited] 50% CH 3 

### C(O)CH=CH - CH=CHC(O)CH 3 

### + O 3 

###  CH 3 

### C(O)CH=CHCHO + CH 3 

### C(O)CHOO[excited] 50% The rate constant is assumed to be the same as that assigned for 3,4 -hexene - 1,6 - dial, based on the upper limit data of Klotz et al (1995). Equal probability of reaction at the various positions is assumed.

### 50

Figure 4 . Action spectra for photodecompositions of 2 -buene - 1,4 - dial, 4 - oxo - 2 -penteneal and used

for the model species AFG1 and AFG2 . **Aromatic Ring Retaining Products** In addition to ring fragmentation, aromatics also react to form products where the aromatic ring is retained, such as phenols, cresols, aromatic aldehydes, and nitrophenols. Mechanisms for these species are included in the base mechanism, and are given in Table A - 2 in Appendix A. The general methods used to represent these products are the same as employed in SAPRC - 99, though rate const ants and some mechanisms were updated. The various types of products that are represented, and changes relative to SAPRC - 99, are summarized briefly below. Footnotes to Table A - 2 document these reactions in more detail. Phenols and Cresols . Although SAPRC - 99 had a separate model species for phenol, in this mechanism the phenol and cresol model species are lumped together because representing phenol was found not to have a significant affect on model predictions for benzene, the only com pound that forms phenol as a primary product in its reactions. The ma jor atmospheric reactions of these compounds are with OH and NO 3 

### radicals, with the latter generally being the more impo rtant sink under most conditions. Because very little was known about the mechanisms of these reactions at the time SAPRC - 99 was developed, SAPRC - 99 had very sim plified and parameterized representations of these mechanisms, adjusted to fit results of a single o - cresol - NO x 

### environmental chamber experiment. However, recently Berndt and Boge (2003) and Olairu et al (2003) determined that the major products of the reactions of OH with these compounds were various dihydroxybenzenes, and Olariu et al (2000) ob tained rate constants for these compounds indicating that they were very reactive. However, if it was assumed that these were the major products of the OH + cresol reaction then the mechanism could not simulate the results of the o cresol - NO x 

### chamber exp eriment. Because of this it was decided to defer updating the mechanism used for these compounds until more information is available, and the general parameterization used in SAPRC - 99 for the reactions of the cresols was retained. T he rate constants were updated and the parameters in the mechanism were re - adjusted to fit the data for the current mechanism.

Nitrophenols . As with SAPRC - 99, the nitrophenol model species (NPHE) is used to represent the products formed in the NO 3 

### + cresol reactions. In SAPRC - 99 it was assumed that the maj or reactions of nitrophenols were with OH and NO 3 

### radicals, as was the case with cresols. However, recent Wa velength (nm)ActionSpectrum(cm-2)

1e-21 1e-20 1e-19 1e-18 1e-17

300 350 400 450 500 2-butene-1,4-dial 4-Oxo-2-penteneal AFG1 and AFG2

0.0e+0 5.0e-19 1.0e-18 1.5e-18 2.0e-18 2.5e-18

300 350 400 450 500

### 51

data presented by Barnes (2006) and Bejan et al (2006) indicate that photolysis is a major loss process for nitrophenols, with some of the photolysis resulting in the formation of HONO, but most forming unspecified products. Evidence was not given for significant reaction of nitrophenols with NO 3 

### radicals, though the possibility that it may occur at least to some extent cannot necessarily be ruled out. Based on this, the current mechanism includes photolysis as a maj or sink for nitrophenols, and assumes that its reaction with NO 3 

### radicals is not significant.

Aromatic Aldehydes . Benzaldehyde and similar aromatic aldehydes may b e formed when OH abstracts from methyl groups of methylbenzenes, and these continue to be represented using the benzaldehyde (BALD) model species. It s mechanism is the same as used in SAPRC - 99, though the rate constants were updated. The mechanism incorporates updated absorption cross sections for its photolysis to unspecified products, but the overall photodecomposition rate was not changed.

**Non -** **Alkylbenzene Aromatics** The alkylbenzenes are not the only types of aromatics for which mechanisms were derived. Mechanism assignments were also made for styrenes, naphthalenes, tetralin, various halo - and nitro -benzenes, phthalates, and other aromatic - containing compounds. The derivation of the mechanisms for these compounds is summarized on Table 14 , the rate constants are given in Table B - 2 and Table B -4 , and the mechanisms are given in Table B - 2 in Appendix B. As indicted on Table B -4 , some of these are based on the general procedures derived for the alkylbenzenes as discussed above, while others (e.g., styrenes, naphthalenes, tetralin, and the isocyanates) appear to have quite different mechanisms. In those cases mechanisms are derived based on considerations for the individual compounds (as with the styrenes), or parameterized mechanisms, that were adjusted to fit environmental chamber data, were used.

Other non - alkylbenzene aromatics are represented using the lumped molecule method based on mechanisms for aromatics for which mechanism assignments were made. These are discussed in the "Lumped Molecule Representation" section, below.

**Reactions with Chlorine** Alkylbenzenes . The low rate constant for the reaction of chlorine atoms with benzene (1.3 x 10 - 16 

### cm3 

### molec - 1 

### s - 1 

### , Sokolov et al, 1998), indicates that the only significant reactions of Cl with aromatics are abstractions off the aromatic ring. The rate constants for these reactions have been measured for some of the methylbenzenes (see Table 4 ) and can be estimated for other alkylbenzenes using the group - additivity parameters given on Table 3 . The products formed are expected to be aromati c aldehydes that are represented using the benzaldehyde (BALD) model species if the reaction is on a methyl group, or primarily various aromatic ketones that are represented by the lumped higher ketone model species (PROD2), plus organic nitrates formed in the peroxy + NO reaction or hydroperoxides formed in the peroxy + HO 2 

### reaction. These result from reactions of the same radicals formed when OH radicals react off the aromatic ring, and the mechanisms can be derived in the same way, except for the different branching ratios for the initial reactions at the various positions, where applicable.

Chlorine + alkylbenzene mechanisms were derived in this manner for all the alkylbenzenes that are used to derive parameters for the lumped model species ARO1 and ARO2, as discussed below. The rate constants and mechanisms so derived are given in Table B - 7 in Appendix B. Table 14 . Discussion of mechanisms for the non - alkylbenzene aromatic compounds that for which

mechanistic assignments have been derived. The rate constants and additional documentation are given in Table B -4 and the reactions are given in Table B - 2 in Appendix B. Compound Reacts With (reaction type)

### Table 14 (continued)

52

Styrene OH, O 3 

### , NO 3 

### , O 3 

### P (double bond reaction only) Mechanism as described by Carter et al (1999b) was used, except for some minor rate constants updates and the overall nitrate yield being increased from 13% to 18% to improve simulations of incremental reactivity data with styrene with the current mechanis m. Results of model simulations of the chamber experiments with this compound are summarized on Table 23 in the Mechanism Evaluation Results section.  -Methyl styrene OH, O 3 

### , NO 3 

### , O 3 

### P (double bond addition only) Assumed to react analogously to the mechanism derived for styrene. The nitrate yield in the OH reaction was increased to correspond to the additional carbon. Monochlorobenzene OH (100% ring addition) p - Dichlorobenzene OH (100% ring addition) Hexafluorobenzene OH (100% ring addition) Nitrobenzene OH (100% ring addition) The products formed in the reactions of these compounds are represented by those formed from in the reactions of OH with benzene. The appropriate measured rate constants for the compounds were used. Benzotrifluoride OH (100% ring addition) p - Trifluoromethyl - Cl -benzene OH (100% ring addition) The reaction is assumed to proceed only by addition of OH to the aromatic ring. The products formed are represented by those formed in the ring - addition reactions of toluene, as shown on Table 11 . The nitrate yields in the reactions of the peroxy radicals are also assumed to be the same as used for toluene. Benzyl Alcohol OH (70% ring addition) The mechanism and environmental chamber data for this compound are discussed by Carter et al (2005a). The measured concentrations of benzaldehyde in the chamber experiments are consistent with a fraction reacted by abstraction from the - CH 2 

### OH of 30%, which is assumed in the mechanism. This is formed by O 2 

### reacting with the BzCH(·)OH radical forming benzaldehyde + HO 2 

### without NO to NO 2 

### conversions or nitrate formation. The products formed following the addition to the aromatic ring are assumed to be the same as used for ethylbenzene, as shown on Table 11 . The nitrate yield factor derived f

or toluene is used for the peroxy reactions involved in the ring addition mechanism. Results of model simulations of the benzyl nitrate experiments are summarized on Table 23 in the Mechanism Evaluation Results section. Methoxybenzene; Anisole OH (93% ring addition) m -Nitrotoluene OH (60% ring addition) The fraction reacting by addition to the aromatic ring is estimated from the difference between the measured total OH rate constant and the rate constant for abstraction off the ring estimated using group - additivity methods as shown on Table 3 . The products formed following ring addition are represented by those formed from ring addition to toluene, as shown on Table 11 . The products formed from reaction off the ring are represented by the lumped higher oxygenated product PROD2 in the case of methoxybenzene and by the aromatic aldehyde species BALD in the case of m nitrotoluene. The nitrate yield factor of toluene was assumed. 2 - Phenoxyethanol; Ethylene glycol phenyl ether OH (54% ring addition) T he total rate constant was estimated by the sum of the estimated rate constants for addition to the aromatic ring and abstraction reactions off the aromatic ring. The latter was estimated using the group - additivity methods shown in Table 3 , and the products formed were derived using the estimates and procedures incorporated in the mechanism generation system. The rate constant and products for

### Table 14 (continued)

53

the ring addition reaction were assumed to be the same as derived for methoxybenzene, as discussed above. 1,2 - Diacetyl benzene OH (100% ring addition) 100% ring addition is assumed

– reaction on the methyl group is assumed to be relatively slow. The products formed are represented by those formed in the mechanism for OH ring addition to o -xylene, except that the nitrate yield factor for a C 10 

### compound, shown on Figure 3 , was used. Phthalic anhydride OH (100% ring addition) The rate constant was assumed to be the same as the measured rate constant for 1,2 - diacetyl benzene. The products formed are also represented by those formed in the mechanism for OH ring addition to o -xylene, except that the nitrate yield factor for a C 8 

### compound, shown on Figure 3 , was used. Diethyl phthalate OH (71% ring addition) Dibutyl phthalate OH (47% ring addition) The total rate constant was estimated by the sum of the estimated rate constants for addition to the aromatic ring and abstraction reactions off the aromatic ring. The latter was estimated using the group - additivity methods shown in Table 3 , and the products formed were derived using the estimates and procedures incorporated in the mechanism generation system. The rate constant and products for the ring addition reaction were assumed to be the same as derived for 1,2 - diacetylbenzene, as discussed above, except that the nitrate factors appropriate for the carbon numbers of the particulate compounds, shown on Figure 3 , were used. 2 - Ethylhexyl benzoate OH (20% ring addition) The rate constant for reaction at the aromatic ring estimated to be the same as the total rate constant for acetophenone (as tabulated by Atkinson, 1989), assuming that ring addition is the maj or reaction for that compound. The mechanism for reaction at aromatic ring based on that of toluene. The rate constant and mechanism for reaction at groups off the aromatic ring based on those estimated for 2 - ethyl hexyl acetate, since reaction at the acetate group is estimated to be negligible for that compound. Naphthal ene OH (parameterized) Tetralin OH (parameterized) 2,3 - Dimethyl naphthalene OH (parameterized) The details of the mechanisms for these compounds are still too uncertain to attempt to derive more explicit predictive mechanisms. The highly parameterized representations employed in SAPRC - 99 (Carter, 2000a) are retained, though the values of the parameters were re - adjusted to fit the chamber data with the current mechanism. As discussed by Calvert (2002), the mechanisms for the reactions of these compounds are expected to be affected by total NO 2 

### levels, since competitions apparently exist between reactions with O 2 

### and NO 2 

### for some of the intermediate radicals. In order to avoid introducing new model species into the mechanism to represent speculative and unc ertain processes, this NO x 

### dependence is in effect represented in SAPRC - 99 and SAPRC - 07 by using formation of lumped peroxyacetyl radicals (RCO3) in the parameterized mechanism. Results of adjusted model simulations of the chamber data with these compound s are summarized on Table 23 in the Mechanism Evaluation Results section. Methyl naphthalenes OH (parameterized) Estimated mechanism derived by averaging the paramet ers for naphthalene and 2,3 - dimethylnaphthalene, as was the procedure used when deriving the mechanism for this com pound for SAPRC - 99.

### Table 14 (continued)

54

Furan 2 - Methyl furan 3 - Methyl furan 2,5 - Dimethyl furan As discussed in the Introduction, chamber experiments were carried out for several furans as part of this project because their initial reactions are expected to form unsaturated 1,4 - dicarbonyls in high yield, which as discussed above are believed to be important photoreactive products formed in the oxidations of the aro matic hydrocarbons. The expected mechanism is as follows, using furan as the example: O C H C H C H C H O

C H C H C H C H O H O

C H C H C H C H O H O

C H C H C H C H O OH O2 HO2 

### Model simulations of experiments with these compounds could therefore serve as a means to evaluate mechanisms for the individual unsaturated 1,4 - dicarbonyls without the uncertainties involved with handling these highly reactive compounds directly. However, there was insufficient time and resources available to this project to complete the development of explicit mechanisms for aromatics and the ir ring - opening products, so the evaluation of mechanisms using experiments with these compounds will be completed in future projects. For this version of the mechanism, the unsaturated 1,4 - dicarbonyls expected to be formed from these furans were represented using the same approach as used for the aromatic hydrocarbons, i.e., by the AFG1 and AFG2 model species with their relative yields adj usted to fit the chamber data. Results of adjusted model simulations of the chamber data with this compound are summari zed on Table 23 in the Mechanism Evaluation Results section. 2,4 - Toluene Di - isocyanate (TDI) OH (parameterized) The details of the mechanism of this compound, which was found by Carter et al (1997d) to be a strong radical inhibitor, are unknown. The parameterized mechanism used by Carter et al (1997d) to fit the chamber data, which is retained in SAPRC - 99, is still retained for SAPRC - 07, though the parameters were re - adjusted to fit the data with the current base mechanism. Results of adjusted model simulations of the chamber data with this compound are summarized on Table 23 in the Mechanism Evaluation Results section. Para Toluene Isocyanate (PTI) OH (parameterized) This was experimentally studied by Carter et al (1999a) as a model compound from which to derive an estimated mechanism for MDI, which has too low a volatility to be studied experimentally. Like TDI, the mec hanism for this compound is unknown and Carter et al (1999a) derived a highly parameterized mechanism to fit the chamber data. This was used in SAPRC - 99 and is retained in SAPRC - 07, but with the parameters re - adjusted to fit the data for the current mechanism. Results of adjusted model simulations of the chamber data with this compound are summarized on Table 23 in the Mechanism Evaluation Results section. Methylene Diphenylene Diisocyanate (MDI) OH (parameterized) The mechanism for this compound was derived from the PTI mechanism as discussed by Carter et al (1999a). Based on structural considerations, the rate constant is assumed to be twice that for PTI, but the same set of products is assumed to be formed.

### 55 Aromatic Products . Reactions of chlorine atoms with the  - dicarbonyls and the aromatic ring -retaining products are included in the base chlorine mechanism, as shown in Table A - 5 in Appendix A. Footnotes to that table document the sources of the rate constants and mechanisms that were used. Although the unsaturated dicarbonyls represented by AFG1 - 3 undoubtedly react relatively rapidly with chlorine atoms, these reactions are ignored in the base chlorine mechanisms. This is because it is expected that the other reactions would be more important sinks for these products under most atmospheric conditions, and their high reactivity would result in low concentrations that would make them unimportant as sinks for chlorine atoms. This is probably true for the  - dic arbonyls as well, though their chlorine reactions are included. **Mechanisms for Amines** Amines react relatively rapidly with OH radicals, and are also expected to relatively rapidly with NO 3 

### , based on a relatively high rate constant for reaction of NO 3 

### with 1 - methyl - 2 -pyrrolidinone (Aschmann and Atkinson, 1999). Rate constant data of Tuazon et al (1994) suggests that the reaction with O 3 

### may also be non -negligible for some amines. Mechanisms for all three of these types of reactions were derived, as discussed by Carter (2008a) and summarized below. In the case of the OH and NO 3 

### reactions, the reaction is assumed to proceed by H - atom abstraction from the amino group or from the group next to the amino group, forming HNO 3 

### and the corresponding carbon - or nitrogen - centered radicals. Group - additivity parameters that can be used to estimate rates of these reactions are given in Table 3 , above, and footnotes to that table indicate how these parameters were derived. Table 3 c indicates that the group - additivity methods can estimate the rate constants to within  26% on the average. The subsequent reactions of the carbon - centered radicals formed in these reactions can be derived using the mechanism generation system as employed for other compounds, except that estimates need to be made for reactions of  - amino alkoxy radicals, e.g., RCH[O·] -NHR'. Although this is uncertain, to simplify the mechanism generation we assume that decompositions forming N - centered radicals, e.g., RCH[O·] -NHR'  RCHO + R'NH·, and estimate the relative rates of reactions for the competing routes based on estimates for other radicals considered to be similar. The applicable radicals and reactions assumed to dominate when generating mechanisms for amines in the current version of the mechanism are indicated on Table 15 These assumptions are uncertain, though alternative assumptions probably do not yield mechanisms with significantly different reactivities. The subsequent reactions of the nitrogen - cent ered radicals formed after H - abstraction from NH 2 

### or NH groups depends on whether there is an abstractable hydrogen in the  -position to the amine. If there is, then it is assumed that the dominant reaction is abstraction of this hydrogen by O 2 

### , forming HO 2 

### and the corresponding C=N compound, e.g., RCH 2

### NH· + O 2 

###  HO 2 

### + RCH=NH This is based on kinetic data obtained by Lindley et al (1979) for reactions of (CH 3 

### ) 2

### N· with O 2 

### , NO, and NO 2 

### , where the reaction with O 2 

### , forming HO 2 

### + CH 3 

### -N=CH 2 

### , is calculated to do minate under atmospheric conditions. The subsequent reactions of the C=N products formed in this reaction are unknown and therefore this is an additional source of uncertainty in the mechanism. These are expected to be reasonably reactive compounds. For the current mechanism, they are represented by the generic reactive non - aldehyde oxygenated species PROD2. The appropriateness of this representation is highly uncertain.

### 56

Table 15 . Assignments made for alkoxy radical intermediates predicted to be formed in the

photooxidation mechanisms of the amines. Radical Reaction Assumed to Dominate ·OCH 2 

### -NH 2 

### + O 2 

### HCO -NH 2 

### + HO 2 

### · CH 3 

### -NH - CH 2 

### O· + O 2 

### CH 3 

### -NH - CHO + HO 2 

### · .OCH 2 

### CH 2 

### -NH 2 

### HCHO + .CH 2 

### -NH 2 

### CH 3 

### CH(O·)NH 2 

### + O 2 

### CH 3 

### C(O)NH 2 

### + HO 2 

### · CH 3 

### -N(CH 3 

### )CH 2 

### O· + O 2 

### CH 3 

### -N(CH 3 

### )CHO + HO 2 

### · NH 2 

### CH(O·)CH 2 

### OH HCO -NH 2 

### + .CH 2 

### OH CH 3 

### C(O·)(CH 3 

### )NH 2 

### CH 3 

### C(O)NH 2 

### + CH 3 

### · CH 3 

### C(CH 3 

### )(CH 2 

### O·)NH 2 

### HCHO + CH 3 

### C(·)(CH 3 

### )NH 2 

### CH 3 

### -N(CH 2 

### O·)CH 2 

### CH 2 

### OH CH 3 

### -N(CH 2 

### OH)CH 2 

### CH(·)OH CH 3 

### C(CH 2 

### O·)(NH 2 

### )CH 2 

### OH + O 2 

### CH 3 

### C(CHO)(NH 2 

### )CH 2 

### OH + HO 2 

### · .OCH 2 

### CH 2 

### CH(NH 2 

### )CH 2 

### OH NH 2 

### CH(CH 2 

### CH 2 

### OH)CH(·)OH CH 3 

### -N(CH 3 

### )CH(O·)CH 2 

### OH CH 3 

### -N(CH 3 

### )CHO + .CH 2 

### OH CH 3 

### CH(O·)CH(NH 2 

### )CH 2 

### OH CH 3 

### CHO + NH 2 

### CH(·)CH 2 

### OH CH 3 

### CH 2 

### C(O·)(NH 2 

### )CH 2 

### OH CH 3 

### CH 2 

### C(O)NH 2 

### + .CH 2 

### OH HOCH 2 

### CH 2 

### -NH - CH(O·)CH 2 

### OH HCO -NH - CH 2 

### CH 2 

### OH + .CH 2 

### OH CH 3 

### CH 2 

### -N(CH 2 

### CH 3 

### )CH 2 

### CH 2 

### O· CH 3 

### CH 2 

### -N(CH 2 

### CH 2 

### OH)CH(·)CH 3 

### CH 3 

### CH 2 

### -N(CH 2 

### CH 3 

### )CH(O·)CH 3 

### CH 3 

### CH 2 

### -N(CH 2 

### CH 2 

### ·)CH(CH 3 

### )OH CH 3 

### CH 2 

### -N(CH 2 

### CH 2 

### O·)CH(CH 3 

### )OH CH 3 

### CH(·)N(CH 2 

### CH 2 

### OH)CH(CH 3 

### )OH CH 3 

### CH 2 

### -N(CH 2 

### CH 2 

### OH)CH(O·)CH 3 

### CH 3 

### CH 2 

### -N(CH 2 

### CH(·)OH)CH(CH 3 

### )OH CH 3 

### CH(O·)N(CH 2 

### CH 2 

### OH)CH(CH 3 

### )OH CH 3 

### CH(OH)N(CH 2 

### CH(·)OH)CH(CH 3 

### )OH HOCH 2 

### CH 2 

### -N(CH 2 

### CH 2 

### OH)CH(O·)CH 2 

### OH HCO -N(CH 2 

### CH 2 

### OH)CH 2 

### CH 2 

### OH + .CH 2 

### OH CH 3 

### CH(OH)CH 2 

### -N(CH 2 

### CH(CH 3 

### )OH)CH 2 

### - CH(CH 2 

### O·)OH HCHO + CH 3 

### CH(OH)CH 2 

### -N(CH 2 

### CH(·)OH)CH 2 

### CH - (CH 3 

### )OH CH 3 

### CH(OH)CH 2 

### -N(CH 2 

### CH(CH 3 

### )OH) - CH(O·)CH(CH 3 

### )OH CH 3 

### CH(OH)CH 2 

### -N(CHO)CH 2 

### CH(CH 3 

### )OH + CH 3 

### CH(·)OH The above type of reaction cannot occur if the nitrogen - centered radical lacks an abstractable hydrogen in the  -position, as is the case in radicals predicted to be formed in the reactions of t -butyl amine and 2 -Amino - 2 - Methyl - 1 - Propanol (AM P). In this case, the only expected reactions of the nitrogen - centered radical is reaction with NO, NO 2 

### , or HO 2 

### , e.g., (CH 3 

### ) 3 

### CNH· + NO  (CH 3 

### ) 3 

### CNHNO (a) (CH 3 

### ) 3 

### CNH· + NO 2 

###  (CH 3 

### ) 3 

### CNHNO 2 

### (b) (CH 3 

### ) 3 

### CNH· + HO 2 

###  O 2 

### + (CH 3 

### ) 3 

### CNH 2 

### (c) If NO x 

### is present, the major reaction is expected to be process (b), forming the nitramine, since the nitrosamine formed in process (a) is expected to undergo rapid photolysis back to NO and the radical, resulting in no net reaction. Since this is a radical inhibiting process, this mechanism predicts that t -butyl amine and AMP would be radical inhibitors, since reaction forming the N - centered radical is estimated to be the maj or initial reaction. This is consistent with the fact that these compounds are indeed found to be strong ozone and radical inhibitors in environmental chamber experiments (Carter, 2008a) For implementation in the mechanism, the model species "NRAD" is used to represent the reactions of the N - centered radicals that lack abstractable hydrogens in the  position. This species is

### 57

representing as reacting with NO 2 

### to form a nitramine, with a rate constant estimated by assuming that it is the same as for the reaction of NO 2 

### with the generic higher acyl peroxy radical species RCO3. The nitramine is approximately represented by PROD2 in the current mechanism, though the appropriateness of this representation is also highly uncertain. The reaction with NO, forming the nitrosoamine, is neglected because of the expected rapid photolysis of the nitrosoamin e to reverse the reaction. In the absence of NO x 

### , the NRAD is represented as reacting with HO 2 

### to re - form the amine, with a rate constant assumed to be the same as used for the reaction of RCO3 with HO 2 

### . Because of the way the mechanism is implemented it i s not practical to represent the amine formed in the reaction as the amine itself, so its subsequent reactions are therefore neglected. This is because the two amines represented to form NRAD are inhibitors, so representing them with reactive product model species such as PROD2 is inappropriate. Methods for estimating rate constants and mechanisms for the reactions of O 3 

### with amines were also derived. These are discussed in detail by Carter (2008a) and briefly summarized here. Based on the available rate co nstants of Tuazon et al (1994) and limited information concerning the products given by Tuazon et al (1994) and Murphy et al (2007), Carter (2008a) estimates that the initial reaction of O 3 

### with amines is at the group next to the amino group, ultimately re sulting in abstraction from  C - H bonds, forming OH radicals and the same types of radicals as formed in the OH reaction, e.g., CH 3 

### NH 2 

### + O 3 

###  [adduct?]  O 2 

### + OH + ·CH 2

### NH 2 

### The available kinetic data for the methylamines and DMAE are fit by K(group,O 3 

### ) = 10 -42.97 - {5.84 k(group,OH)} , where k(group) refers to net H - atom abstraction at a group adjacent to the amino group and the rate constants are in cm3 

### molec - 1 

### s - 1



### . This gives estimates for rate constants that agree with those of Tuazon et al (1994) to within a factor of two. This was also used as the basis for estimating relative rates of reaction at different positions secondary or tertiary amines that have non - equivalent substituents. The subsequent reactions of the radicals formed are derived as discussed above for the OH and NO 3 

### mechanisms. A significant uncertainty in terms of calculations of the atmospheric ozone impacts of the amines concerns the extent to which they react with gas -phase HNO 3 

### , forming the ami ne salt. If this reaction is sufficiently fast, and if most of the salt formed partitions to the vapor phase, then the amine would not be available to react in the gas phase and promote ozone formation. Although model simulations of the available environmental chamber experiments with amines are not sensitive to this reaction because the amount of HNO 3 

### formed in the experiments is small compared to the amount of amine added, the atmospheric incremental reactivity simulations are very sensitive to this because of the amount of amine added is relatively small compared to the amount of HNO 3 

### predicted to be formed (Carter, 2008a). The importance of this under atmospheric conditions is difficult to estimate because of uncertainties and variabilities concerning sources and sinks for HNO 3 

### in the atmosph ere. As discussed by Carter (2008a) in order to obtain upper limit ma gnitude estimates for the ozone impacts of the amines we assume that removal of the amines by reaction with HNO 3 

### is negligible, but this is likely not to be the case in actual atmospheres . **Miscellaneous Assigned Mechanisms** There are several compounds for which mechanisms have been derived where the procedures discussed above could be employed. In those cases, mechanisms were derived based on considerations of the relevant reactions of the particular compounds, or, if the details of the reactions for the particular compound are sufficiently uncertain, parameterized mechanisms were derived and adjusted to fit available environmental. These compounds are listed in Table 16 , along with a brief discussion of how

### 58

Table 16 . Discussion of mechanisms for miscellaneous compounds that were not derived using the

procedures discussed previously in this report. The rate constants, reactions, and additional documentation are given in Table B - 2 , and Table B -4 through Table B - 6 in Appendix B. Compound Reacts With N - Methyl - 2 - Pyrrolidone OH, NO 3 

### Mechanism based on that originally developed by Carter et al (1996b), using the kinetic data of Aschmann and Atkinson (1999). The SAPRC - 99 mechanism had an incorrect conversion of the original mechanism that did not incorporate all the NO to NO 2 

### conversions in the OH and NO 3 

### reactions, and compensated for this by reducing the overall nitrate yield to fit the chamber data. Once this was corrected, the chamber data are best fit using the nitrate yield originally derived by Carter et al (1996b). Note that the (presumably incorre ct) SAPRC - 99 mechanism fit some of the chamber data somewhat better than the original and the current updated mechanism, but is not as consistent with our current estimation of the chemistry. Results of model simulations of the chamber experiments with thi s compound are summarized on Table 23 in the Mechanism Evaluation Results section. Dimethyl Sulfoxide OH, NO 3 

### Environmental chamber experiments and possible mechanisms for DMSO reactions were discussed by Carter et al (2000d). No mechanism that was entirely consistent with the available data was found, but the best fit "Mechanism C", as adopted for the ambient reactivity calculations given by Carter et al (2000d) is re tained for this version of the mechanism. Results of model simulations of the chamber experiments with this compound are summarized on Table 23 in the Mechanism Evaluation Results section. 1,3 - Butadiyne OH, NO 3 

### Iti s assumed that the primary reaction is OH or NO 3 

### adding to terminal position, forming an allylic stabilized radical. In the case of the OH reaction, the 1,2 -unsaturated alpha -hydroxy radical reacts with O 2 

### to form HO 2 

### and 1,2 -butadien -4 - al, and in the case of the NO 3 

### reaction the analogous compound reacts unimolecularly to form NO 2 

### and the same aldehyde. The aldehyde is represented by RCHO, on the basis that this is probably not as bad an approximation as MAC R. Iti s assumed that the reaction with O 3 

### is slow. Methyl Bromide OH Ethyl Bromide OH 1,2 - Dibromoethane OH n - Propyl Bromide OH n - Butyl Bromide OH The mechanisms for these compounds are approximated by that of the corresponding chloride, but with the appropriate OH rate constant for the compound. This may somewhat overestimate the reactivity of the compounds, and may underestimate inhibition under low NO x 

### conditions. This can be considered to be useful for upper - limit mechanism estimates, but will need to be refined for "best estimate" reactivity estimates. Results of model simulations of the chamber experiments with n propyl bromide and n -butyl bromide, summarized on Table 23 in the Mechanism Evaluation Results section, are consistent with this assessment. Hexamethyldisiloxane OH D4 Cyclosiloxane OH Hydroxymethyldisiloxane OH Parameterized mechanisms adjusted to fit the incremental reactivity chamber data of Carter et al (1992) that were considered to be suitable for mechanism evaluation are employed. (Several runs had

### Table 16 (continued)

Compound Reacts With

59 no assigned initial NO 2 

### concentrations or non - standard run conditions, and were not used.) No chemically reasonable mechanism was found that was consistent with the data (Carter et al, 1992), so a highly simplified parameterized mechanism, which assumes an adjustable amount of radical loss and the remainder of the reaction forming HO 2 

### after an NO to NO 2 

### conversion, and assumes no reactive products formed, was used. Results of model simulations of the chamber experiments with these compounds are summarized on Table 23 in the Mechanism Evaluation Results section. D5 Cyclosiloxane OH Although reactivity chamber experiments were conducted for this compound (Carter et al, 1992), none of these runs were considered suitable for mechanism evaluation because of uncertainties concerning initial NO x 

### concentrations. Qualitative ly the results were similar to those for D4 cyclosiloxane in that large inhibition was assumed. The amount of inhibition used was assumed to be approximately the same as that derived for D4, since a similar mechanism is expected. Acrylonitrile OH The data of Hashimoto et al (1984) indicate that the products are formaldehyde and HCO - CN after an NO to NO 2 

### conversion. HCO - CN is assumed to be relatively unreactive, which is supported by the concentration -time profiles reported by Hashimoto et al (1984). Reactions with NO 3 

### and O 3 

### are assumed to be relatively slow, though no data are available concerning these reactions. Methyl nitrite OH, h The reaction with OH is assumed to proceed by abstraction from the methyl group, followed by decomposition to form NO and formaldehyde. The photolysis absorption cross sections are from Calvert and Pitts (1966). The maj or reaction pathway is photolysis, which is assumed to form methyl radicals and NO with unit quantum yields. Chloropicrin h Carbon disulfide OH, h Methyl isothiocyanate OH, h EPTC (S - Ethyl dipropylthiocarbamate) OH, NO 3 

### Molinate OH, NO 3 

### Pebulate OH, NO 3 

### Thiobencarb OH, NO 3 

### The mechanisms for these pesticide VOCs as given by Carter and Malkina (2007) are used without modifications other than adaptation to this version of the mechanism. Results of model simulations of the chamber experiments with these compounds are discussed in the Mechanism Evaluation Results section. trans 1,3,3,3 - Tetrafluoropropene OH 2,3,3,3 - Tetrafluoropropene OH The mechanisms derived for these compounds and evaluated against chamber data by Carter (2009a) and Carter (2009b), respectively, were used. Ethyl methyl ketone oxime OH An estimated mechanism was derived explicitly for this compound. About 24% of the reaction is assumed to occur at the methyl or CH2 groups, with the subsequent reactions estimated using the procedures in the mechanism generation system. The remainder of the reaction is assumed to be addition of OH to the C=N double bond, which is assumed to form primarily C 2 

### H 2 

### C(CH 3 

### ) (OH)N(.)OH, which is assumed to react with O 2 

### to form C 2 

### H 5 

### C(CH 3 

### )(OH)NO + HO 2 

### .

### Table 16 (continued)

Compound Reacts With

60 The rate constant is estimated by the rate constant for OH + isobutene x the average of the ratio of the rate constants for CH 2 

### =NOH / Ethene and CH 3 

### CH=NOH / Propene, with abstractions from the methyl group subtracted off. The CH 2 

### =NOH and CH 3 

### CH=NOH rate constants are from the tabulation of Atkinson (1989). The C 2 

### H 5 

### C(CH 3 

### )(OH)NO is assumed to photolyze rapidly, forming NO + an alpha -hydroxy radical that reacts with O 2 

### to form MEK and HO 2 

### . The absorption cross - sections and quantum yields are unknown, but photolysis is assumed to be relatively rapid, and estimated to be comparable to that of methyl nitrite. Methyl iodide OH, h The mechanism for this compound as given by Carter (2007) was used without modification. This mechanism, and the reactions of the inorganic iodine species formed in both the OH and photolysis reactions, are also included in Table B - 2 , with is available with the electronic version of this report. Results of model simulations of the chamber experiments with these compounds are discussed by Carter (2007) and summarized in the Mechanism Evaluation Results section. the mechanisms were derived. The initial rate constants are given in Table B -4 and their reactions are given in Table B - 2 in Appendix B, along with notes giving references for the rate constants and in some cases the mechanisms. The references cited can be consulted for additional information concerning the derivation of the mechanisms for these compounds. **Lumped Molecule Representations** A num ber of compounds or classes of compounds do not have explicit mechanistic assignments in the SAPRC - 99 or SAPRC - 07 mechanisms, but instead are represented by the "lumped molecule" approach for the purpose of estimating their reactivities or contributions to mixtures. In this approach, the impacts of a compound or class of compounds are assumed to be the same, on a per - molecule basis, as a compound or group of compounds for which a mechanism has b een derived. This is used for com pounds whose reactivities or impacts are of interest, but are either not considered to be sufficiently important to have an explicit mechanism derived, or whose mechanism is considered to be not significantly different from that for the compound representing it, or where the mechanistic difference with the representing compound is considered to be small compared to the uncertainty of the mechanism. Iti s also used for unspeciated mixtures of isomers, where a representative c ompound or group of compounds is used to estimate the impact of the mixture. The SAPRC - 07 lumped molecule representations are given in Table B - 9 in Appendix B. In mos t cases the same representations are used in SAPRC - 07 as im plemented in SAPRC - 99 (Carter, 2000a). The exceptions are primarily compounds or groups of compounds for which mechanisms have since been assigned, the representation of the higher alkylbenzenes, and the new detailed model species that have been added. The compounds or mixtures that were previously represented using the lumped molecule approach but now have mechanistic assignments are furan and lumped higher alkylbenzene species as discussed above in conjunction with the aromatics mechanisms. The new lumped aromatic model species is used to give a better lumped molecule representation for the higher aromatics that is more appropriate to their carbon numbers than by representing them using methylbenzenes or ethylbenzene, as was the case previously. In addition, a total of 31 new types of compounds that were not represented in SAPRC - 99 are now represented in SAPRC - 07 using the lumped molecule approach. The lumped molecule assignments shown on Table B - 9 are used to estimate the atmospheric reactivities of these compounds or mi xtures, and are also used where applicable to derive the mechanisms for the

### 61

lumped mechanisms in airshed models based on mixtures containing them, as discussed in the following section. **Lumped Mechanisms for Airshed Models** Airshed model applications require simulations of highly complex mixtures of large numbers of VOCs, and in most cases it is not necessary or practical to represent each of them separately. For such applications, models with lumped model species that represent reactions of a large number of species with similar reaction rates and mechanisms are generally employed. Even for VOC reactivity assessment it is only really necessary to separately represent the VOC whose reactivity is being assessed, with the reactions of most of the other VOCs present in the ambient simulation being represented using appropriate lumped model species. This is the approach used in the SAPRC - 99 mechanism, and is retained for SAPRC - 07. The lumping approach and recommended set of lumped model species is also unchanged in this version of the mechanism. **Adjustable Parameter Mechanisms** The SAPRC - 99 mechanism has the option to vary the lumping approach in terms of the number of model species used and how they are lumped, and also to vary the mixture of compounds used to derive the parameters for the lumped model species, based on the emissions in model scenario or other considerations (Carter, 2000a,b; Adleman et al, 2005). This is referred to as the "adjustable parameter" mechanism for airshed models. This feature is retained in this version of the mechanism, with the procedures and software for adjustable parameter SAPRC - 07 being the same as employed for SAPRC - 99, as discussed by Carter (2000a) and Adleman et al (2005). The data files implementing the variable parameter version of SAPRC - 07 will be made available at the Speciation Database website 1 

### and the SAPRC mech anism website 2



### . The files will have the same format as those currently used to implement SAPRC - 99. **Fixed Parameter Mechanism** Inp ractice most model applications have used the "fixed parameter" version of SAPRC - 99. This involves use of a fixed set of lumped model species, with the parameters for the adjustable parameter lumped species being derived using a pre - defined mixture. The updates to the fixed parameter mechanism for SAPRC - 07 are documented in the remainder of this section. The lumped model species and general lumping approach used in fixed parameter SAPRC - 99 is the retained in SAPRC - 99. The list of lumped and explicit model species used for representing various types of emitted VOCs is given in Table 17 , and lumped model species added to the base mechanism for the fixed parameter mechanism are included in Table A - 1 in Appendix A. These include the lumped model species that are added to the base mechanism whose parameter can be adjusted based on the emissions mixture being represented, the organic product model species already in the base mechanism that are also used to repres ent various types of primary emitted organics, and the model species for compounds that are explicitly represented. In all cases the lumped or explicit species represent the emitted compound on a mole - for - mole basis; there is no "reactivity weighting" in this version of the mechanism.

1 

### The Speciation Database website is at http://www.cert.ucr.edu/~carter/emitdb. 2 

### The SAPRC mechanism web site is at http://www.cert.ucr.edu/~carter/SAPRC.

### 62

Table 17 . List of model species used in the lumped mechanism for airshed models for representing

the various types of emitted VOCs. Name Description Amount in Base ROG [a] Lumped model species added to the base mechanism . Parameters can optionally be adjusted based on mixture being represented. ALK1 Alkanes and other non - aromatic compounds that react only with OH, and

have kOH (OH radical rate constant at 300 o

### K) between 1.36 and 3.41 x 10 - 13 

### cm 3 

### molec - 1 

### s - 1 

### . (Primarily ethane) 17.7 ALK2 Alkanes and other non - aromatic compounds that react only with OH, and

have kOH between 3.41 x 10 - 13 

### and 1.70 x 10 - 12 

### cm3 

### molec - 1 

### s - 1



### . (Primarily propane) 14.8 ALK3 Alkanes and other non - aromatic c ompounds that react only with OH, and

have kOH between 1.70 and 3.41 x 10 - 12 

### cm3 

### molec - 1 

### s - 1



### . 27.7 ALK4 Alkanes and other non - aromatic compounds that react only with OH, and

have kOH between 3.41 and 6.81 x 10 - 12 

### cm3 

### molec - 1 

### s - 1



### . 35.5 ALK5 Alkanes and other non - aromatic compounds that react only with OH, and

have kOH greater than 6.81 x 10 - 12 

### cm3 

### molec - 1 

### s - 1



### . 18.8 ARO1 Aromatics with kOH < 1.36 x 10 - 11 

### cm3 

### molec - 1 

### s - 1



### . 12.9 ARO2 Aromatics with kOH > 1.36 x 10 - 11 

### cm3 

### molec - 1 

### s - 1



### .. 17.2 OLE1 Alkenes (other than ethene) with kOH < 4.77 x 10 - 11 

### cm3 

### molec - 1 

### s - 1



### . 11.3 OLE2 Alkenes with kOH > 4.77 x 10 - 11 

### cm3 

### molec - 1 

### s - 1



### . 12.5 TERP Terpenes 0.7 Lumped organic product model species that are already in the base mechanism that are also used to represent certain types of primary emitted VOCs . (Mechanisms are not adjustable) RCHO C3+ saturated aldehydes 2.9 MEK Ketones and other non - aldehyde oxygenated compounds with kOH

between 5 x 10 - 13 

### and 5 x 10 - 12 

### cm3 

### molec - 2 

### sec - 1



### . 1.2 PROD2 Ketones and other non - aldehyde oxygenated compounds with greater than

5 x 10 - 12 

### cm3 

### molec - 2 

### sec - 1



### . RCOOH C3+ organic acids MGLY Methyl glyoxal and C3+  - dicarbonyl aldehydes BACL Biacetyl and other highly photoreactive compounds that are not otherwise

represented. CRES Phenols and cresols BALD Aromatic aldehydes 0.2 MACR Acrolein and methacrolein IPRD Other unsaturated aldehydes MVK Unsaturated ketones RNO3 Organic nitrates

### Table 17 (continued)

63

Name Description Amount in Base ROG [a] Model species for explicitly represented product compounds that can also be emitted HCHO Formaldehyde 8.3 CCHO Acetaldehyde 5.0 ACET Acetone 3.2 MEOH Methanol HCOOH Formic acid CCOOH Acetic acid GLY Glyoxal Model species for explicitly represented primary emitted VOCs. CH4 Methane ETHENE Ethene 14.1 ISOPRENE Isoprene 1.4 ACETYLEN Acetylene 10.2 BENZENE Benzene (also used for halo - and nitro -benzenes) 3.5 [a] Relative amount in the base ROG mixture used to represent emissions from all sources, in units of ppb model species per ppmC of mixture. This mixture was used to derive the parameters for the adjustable parameter lumped model species as discussed in this section, and was also used in the reactivity assessment calculations discussed in the "Updated Reactivity Scales" section, below.

The mechanisms for the model species already in the base mechanism have been discussed previously, and are given in Table A - 2 in Appendix A. The mechanisms for the lumped species added to the base mechanism fixed parameter SAPRC - 07 are derived using the same standard mixtures as used to derive their parame ters for parameter SAPRC - 99. For the model species ALKn, AROn, and OLEn, the mechanisms are derived based on the mixture of alkanes, aromatics, and alkenes in base reactive organic gas (ROG) mixture used to represent anthropogenic emissions from all source s u sed when calculating the Carter (1994) reactivity scales. This is based on an analysis by Je ffries et al. (1989) of urban ambient air measurements made by Lonneman (1986). For the model species TERP, the mechanisms are derived based on the top 5 terpene s in the North American Biogenic Inventory from the Guenther et al (2000) NARSTO assessment. The mixtures of compounds used to derive the parameters for the adjustable parameter model species for the fixed parameter mechanism are given in Table 18 and Table 19 , and Table A - 7 in Appendix A gives the mechanisms that were so derived. The latter includes the reactions that were added to the standard base mechanism and also the reactions of these model species with chlorine atoms that are included when the mechanism is used to represent chlorine chemistry. These are based on the mechanisms for the individual components given in Table B - 2 and Table B - 7 in Appendix B, with the weighting factors shown in Table 18 and Table 19 . Note that because of the difficulties in generating complete mechanisms for the Cl + alkene reactions (discussed above), the terpene + Cl mechanism is based entirely on that derived for  -pinene, and, as indicated in Table B - 7 the mechanisms and rate constants for many of the alkenes were assumed to be the same as structurally similar compounds. Note that the mixtures used to derive the parameters for the model species in the fixed parameter mechanism may be out of date and need to be updated. An update to the base ROG mixture used to derive

### 64

Table 18 . Compounds and weighting factors used to derive the parameters for the ALK and ARO model species in the fixed parameter

mechanism for airshed models Group and Compound Mole Fract. Group and Compound Mole Fract. Group and Compound Mole Fract. ALK1 ALK5 ARO2 Ethane 100% 2,4 - Dimethyl Hexane 12% m - Xylene 13% n - Decane 11% p - Xylene 13% ALK2 3 - Methyl Hexane 11% o - Xylene 11% Propane 100% 2,3 - Dimethyl Pentane 7% 1,2,3 - Trimethyl Benzene 9% 2 - Methyl Heptane 6% 1,3,5 - Trimethyl Benzene 9% ALK3 4 - Methyl Heptane 6% 1,2,4 - C10 trisubstituted benzenes 6% n - Butane 68% 2,4 - Dimethyl Heptane 5% m - Ethyl Toluene 5% Isobutane 30% 2,6 - Dimethyl Octane 5% o - Ethyl Toluene 5% 2,2 - Dimethyl Butane 2% Methylcyclohexane 4% p - Ethyl Toluene 5% n -Nonane 4% 1,2,4 - Trimethyl Benzene 5% ALK4 n - Octane 4% 1,2,3 - C10 trisubstituted benzenes 4% Isopentane 43% Cyclohexane 4% 1,3,5 - C10 trisubstituted benzenes 2% n - Pentane 17% 2 - Methyl Nonane 3% m - C10 disubstituted benzenes 2% 2 - Methyl Pentane 10% 2 - Methyl Hexane 3% o - C10 disubstituted benzenes 2% 3 - Methylpentane 7% 2 - Methyl Octane 3% p - C10 disubstituted benzenes 2% 2,4 - Dimethyl Pentane 5% 4 - Methyl Octane 3% 1 - methyl - 4 - isopropylbenzene 2% Methylcyclopentane 5% n - Dodecane 2% m - C11 disubstituted benzenes 0.4% n - Hexane 4% 4 - Methyl Nonane 1.4% 1,3,5 - C12 trisubstituted benzenes 0.3% n - Heptane 3% Ethylcyclohexane 1.1% m - C12 disubstituted benzenes 0.2% 2,3 - Dimethyl Butane 3% n - Undecane 1.0% p - C12 disubstituted benzenes 0.2% Cyclopentane 2% 3,6 - Dimethyl Decane 1.0% 1,2,4 - C11 trisubstituted benzenes 0.2% 1,1 - dimethylcyclopentane 0.1% 2,6 - Dimethyl Nonane 0.5% 1,2,3 - C11 trisubstituted benzenes 0.2% 3 - Methyl Undecane 0.5% 1,3,5 - C11 trisubstituted benzenes 0.2% ARO1 5 - Methyl Undecane 0.5% 1,2,4 - C12 trisubstituted benzenes 0.12% Toluene 75% 3 - Methyl Decane 0.2% 1,2,3 - C12 trisubstituted benzenes 0.12% Ethyl Benzene 10% 4 - Methyl Decane 0.2% o - C11 disubstituted benzenes 0.10% C11 Monosubstituted Benzenes 5% 1,2 - dimethylcyclopentane 0.12% p - C11 disubstituted benzenes 0.10% n - Propyl Benzene 4% Ethyl Cyclopentane 0.12% o - C12 disubstituted benzenes 0.06% C10 Monosubstituted Benzenes 3% n - Tridecane 0.09% Isopropyl Benzene (cumene) 2% 3,6 - Dimethyl Undecane 0.03% t - Butyl Benzene 0.7% 3 - Methyl Dodecane 0.02% C12 Monosubstituted Benzenes 0.2% 5 - Methyl Dodecane 0.02%

### 65

Table 19 . Compounds and weighting factors used to derive the parameters for the OLE and TERP

model species in the fixed parameter mechanism for airshed models Group and Compound Mole Fraction Group and Compound Mole Fraction] OLE1 OLE2 Propene 29% cis - 2 - Pentene 14% 1 - Hexene 24% trans - 2 - Pentene 14% 1 - Butene 12% trans - 2 - Butene 11% 1 - Pentene 11% Isobutene 10% 1 - Heptene 11% cis - 2 - Butene 9% 1 -Nonene 5% 2 - Methyl - 1 - Butene 8% 3 - Methyl - 1 - Butene 3% 1,3 - Butadiene 6% 1 - Octene 2% 2 - Methyl - 2 - Butene 5% 1 -Undecene 2% Cis - 2 - Hexene 5% 1 - Decene 0.9% Trans - 2 - Hexene 5% Trans - 3 - Heptene 4% TERP Trans - 4 -Nonene 2%  - Pinene 38% [a] Trans - 4 - Octene 2%  - Pinene 27% Trans - 5 -Undecene 2% 3 - Carene 17% Trans - 2 - Heptene 2% Sabinene 10% Cyclohexene 2% d- Limonene 9% Trans - 4 - Decene 0.7% 3,4 - Diethyl - 2 - Hexene 0.2% [a] The TERP + chlorine mechanism is assumed to be the same as that derived for  -pinene. 

### the ALK, ARO, and OLE parameters is almost certainly called for given changes in anthropogenic emissions since the mid 80's, and advances in analytical methods. However, deriving updated base ROG mixtures is beyond the scope of this project, and the CARB and the EPA were unable to provide recommendations for an updated mixture within the time frame of this project. Therefore, the same mixture is retained in this update for consistency with SAPRC - 99. However, the mechanisms for the individual compounds given in Table B - 2 in Appendix B could be used as the basis for deriving updated mechanisms for these lumped model species once updated base ROG or terpene compositions become available. **Emissions Assignments** An important part of implementing mechanisms into airshed models involves assigning individual chemical compounds and categories used in speciation profiles to lumped species in the mechanism. The general types of compounds assigned to the various model species in the fixed parameter version of SAPRC - 07 are indi cated in Table 17 , and the assignments of lumped model species to the individual compounds or types of compounds for which mechanistic assignments are made are shown in Table B - 1 1 in Appendix B. For compounds or groups of compounds that are represented using the lumped molecule method as shown on Table B - 9 , the lumped model assignments are derived from those that are assigned to the explicitly represented compounds that are used to represent them. Emissions speciation profiles use a variety of types of chemical categories, many of which do not refer to individual compounds or chemical categories used in the SAPRC mechanism. Because of this, we have previously developed an emissions speciation database for the purpose of assigning chemical

### 66

catego ries used in emissions profiles to model species in various mechanisms in a consistent manner. The mechanisms currently supported in the database include CB4, CB05, RADM2, as well as SAPRC - 99 (Adelman et al, 2005; Carter, 2008b). This speciation database h as been updated to support SAPRC - 07 and the files needed to process emissions for the fixed -parameter version of SAPRC - 07 are available at the speciation database project web site (Carter, 2008b). Note that emissions assignments are different than lumped molecule representations. Lumped molecule representations involve representing the compound or categories by a detailed model species, of which there are over 700, while emissions assignments involve representing id by one of the ~30 lum ped model species us ed in airshed models. Obviously lumped molecule assignments are less approximate and should be used for purposes of reactivity scale calculations or deriving optimum mechanistic parameters for mixtures, where maximum chemical detail is appropriate. Emissio ns assignments such shown on Table B - 1 1 and given in the speciation database (Carter, 2008b) should be reserved for applications where using the more limited number of lumped model species is necessary and appropriate.

### 67 

### MECHANISM EVALUATION The performance of the mechanism in simulating O 3 

### formation, rates of NO oxidation, and other measures of reactivity was evaluated by conducting model simulations of over 2500 environmental chamber experiments carried out in 11 different environmental chambers at 4 different laboratories 1



### . The experiments included 682 single VOC experiments, consisting primarily of VOC - NO x 

### or VOC - NO x 

### experiments with added CO or alkane, 591 incremental reactivity experiments, and 973 experiments with mixtures, though approximately 2/3 of the mixture runs were replicate base case reactivity experiments of various types. These include not only the experiments used when evaluating the SAPRC - 99 mechanis m (Carter, 2000a), but also the more recent experiments carried out at out at our laboratories at CE - CERT through June, 2006, experiments carried out in the Tennessee Valley Authority (TVA) chamber that were used in the low NO x 

### mechanism evaluation study o f Carter (2004), and also earlier University of North Carolina (UNC) chamber experiments used in the SAPRC - 90 and RADM - 2 mechanism evaluations of Carter and Lurmann (1990, 1991) and in the isoprene mechanism evaluation of Carter and Atkinson (1996). The c hambers whose data were used for mechanism evaluation are summarized on Table 20 , the types of experiments are summarized on Table 21 , and the individual experiments are listed in Table C - 1 in Appendix C. The input files, chamber data, and the computer programs used for the chamber simulations will be made available on the SAPRC mechanism web site 2



### . The results of the evaluation are given on Table C - 1 and in the numerous figures in Appendix C, and are summarized below. Note that the largest database of environmental chamber experiments used for mechanism evaluation for this project is from indoor chamber experiments carried out at the University of Californi a at Riverside (UCR). These experiments serve as the primary basis for mechanism evaluation and any adjustments made to mechanisms for individual VOCs are based on simulations of UCR indoor chamber runs. However, simulations of the available experiments from the Tennessee Valley Authority (TVA) chamber a subset of the experiments carried out in the University of North Carolina (UNC) outdoor chamber were also carried out, and results are also shown for information purposes. We believe that the TVA chamber is reasonably well characterized for modeling, and the results of these simulations provide useful supporting information for mechanism evaluation. However, because of time and resource constraints we were unable to obtain and process the most com plete and quality- assured set of UNC chamber data. The generally poor performance of the model in simulating the non - isoprene UNC experiments may reflect this. For this reason, the simulations of the UNC chamber experiments are shown for information only, and were not used as the primary basis for mechanism evaluation. A re - evaluation using an improved UNC chamber dataset may be appropriate, but was beyond the scope of this project. The performance of the mechanism is measured primarily in terms of its ability to simulate O 3 

### formation and NO oxidation. The effect of the compounds on overall OH radicals in the incremental reactivity experiments is also assessed. Although the model simulations of the experiments also give information on the ability of the mechani sm to predict other chemical transformations, such as rates of consumption of reactants other than NO and formation of various products besides O 3 

### that may have been measured, a comprehensive mechanism evaluation in this regard was beyond the scope of this project.

1 

### The experiments used to evaluate mechanisms for some of the compounds for which mechanisms and reactivity estimates are given were carried out after the experiment list for this report was finalized in March, 2009. In those cases, citations referencing the reports giving results of the evaluations for those compounds are given in footnotes to Table 23 . 2 

### The SAPRC mech anism web site is at http://www.cert.ucr .edu/~carter/SAPRC.

### 68

Table 20 . Summary of environmental chambers whose data were used for mechanism evaluation ID Brief description and references for additional information

Chambers at the Statewide Air Pollution Research Center (SAPRC) or the College of Engineering Center for Environmental Research and Technology (CE - CERT) at

the University of California at Riverside (UCR) EC A 5774 - liter evacuable chamber constructed of Teflon- coated aluminum with Quartz end windows. Located at SAPRC. Xenon arc solar simulator light source. Most experiments at ~50% RH and around 300 o

### K. Experiments carried out 1975 - 1984. See Carter et al (1995a) for description of chamber and experimental methods and Carter (2000a) for a discussion of the modeling methods used. This chamber is now primarily being used for mechanistic studies. IT C One semi - collapsible ~6400 - liter reactor constructed of 2 mil FTP Teflon film held in a framework. Blacklight light source. Located at SAPRC. Most experiments at ~50% RH and around 300 o

### K. Experiments carried out 1982 - 1986. See Carter et al (1995a) for description of chamber and experimental methods and Carter (2000a) for a discussion of the modeling methods used. This chamber is now primarily being used for mechanistic studi es. ETC One semi - collapsible ~3000 - liter reactor constructed of 2 mil FTP Teflon film held in a framework. Blacklight light source. Located at SAPRC. Most experiments used dry air and carried out around 300 o 

### K. Experiments carried out 1989 - 1993. See Cart er et al (1995a) for description of chamber and experimental methods and Carter (2000a) for a discussion of the modeling methods used. This chamber no longer exists. OTC Two completely collapsible ~20,000 - liter "pillow bag" reactors constructed of 2 mil F TP Teflon located outdoors. Located at the outdoor laboratory at SAPRC. Natural sunlight irradiation. Two irradiations carried out simultaneously, one in Side "A" and the other in Side "B". Experiments used dry air, with temperature varying with ambient conditions. Experiments carried out 1992 - 1993. See Carter et al (1995a,b) for description of chamber and experimental methods and Carter et al (1995b) and Carter (2000a) for a discussion of the modeling methods used. This chamber no longer exists. DTC Two semi - collapsible ~5000 - liter reactors constructed of 2 mil FTP Teflon film held in a framework. Initially located at the outdoor laboratory building at SAPRC, but subsequently re constructed at CE - CERT. Two irradiations carried out simultaneously, one in Side "A" and the other in Side "B". Blacklight light source. Most experiments used dry air at around 300 o 

### K. Experiments carried out 1993 - 1999. See Carter et al (1995a) for description of chamber and experimental methods and Carter (2000a) for a discussion of the modeling methods used. This chamber no longer exists. XTC One semi - collapsible ~5000 - liter reactor constructed of 2 mil FTP Teflon film held in a framework. Xenon arc light source. Located the outdoor laboratory building at SAPRC. Experiments use d dry air at around 300 o

### K. Experiments carried out in 1993. See Carter et al (1995a) for description of chamber and experimental methods and Carter (2000a) for a discussion of the modeling methods used. This chamber no longer exists. CTC (  82) Semi - collap sible ~5000 - liter reactor constructed of 2 mil FTP Teflon film held in a framework. Xenon arc light source. Located at CE - CERT. Experiments used dry air at around 300 o 

### K. Experiments carried out in 1994 - 1995. See Carter et al (1995a) for description of ch amber and experimental methods and Carter (2000a) for a discussion of the modeling methods used. This configuration is applicable to runs from 11 through 82.

### Table 20 (continued)

69

ID Brief description and references for additional information CTC (  83) Two semi - collapsible ~2500 - liter reactors constructed of 2 mil FTP Teflon film held in a framework. Xenon arc light source. Located at CE - CERT. Experiments used dry air at around 300 o 

### K. Experiments carried out in 1995 - 1999. This configuration is applicable to runs 83 and higher. See Carter et al (1995a) for description of chamber and experimental methods and Carter (2000a) for a discussion of the modeling methods used. This chamber no longer exists. EPA (Also referred to as the UCR EPA chamber.) Two ~90% collapsible ~100,000 - liter reactors constructed of 2 mil FEP Teflon film held on a framework with a moveable top for positive pressure control. Located in a temperature - controlled "clean room" clean room enclosure flushed with purified air. Located at CE - CERT. Can use either an argon arc solar simulator light source or blacklights. Two irradiations carried out simultaneously, one in Side "A" and the other in Side "B". Although the temperature and humidity can be varied, all experiments in this evaluation were carried out with dry air at around 300 o

### K. Experiments carried out from 2003 through present, but latest run in this evaluation was carried out in mid- 2006. See Carter (2004) and Carter et al (2005b) for a description of the chamber and experimental methods and Carter (2004) for a discussion of the modeling methods used. Note that mechanism evaluation experiments in this chamber can be carried out under lower NO x 

### conditions than the other chambers at UCR or the UNC outdoor chamber. This chamber is still in operation.

Chamber at the Tennessee Valley Authority (TVA). TVA One 28,300 - liter reactor constructed of 0.13 mm FEP Teflon film on a rigid frame located inside an enclosure flushed with purified air. Special procedures used to clean between experiments to permit experiments at lower concentrations. Light source consisted of blacklights and sunlamps. Experiments carried out at about 15% RH and the temperature varied from ~300 - 315 o 

### K. Experiments carried out in 1993 - 1995. See Simonaitis and Bailey (1995) and Bailey et al (1996) for a description of the chamber and experimental method s and Carter (2004) for a discussion of the modeling methods used. Note that mechanism evaluation experiments in this chamber were carried out under lower NO x 

### conditions than in the other chambers except for UCR EPA, but the chamber experience high background formaldehyde levels that needed to be taken into account when modeling the experiments (Carter, 2004). This chamber no longer exists.

Chamber at the University of North Carolina (UNC) UNC A very large dual reactor chamber consisting of 5 mil FEP Tefl on film held on a rigid A - frame structure located outdoors. Natural sunlight light source. Located in a rural site in North Carolina with filtered but otherwise unpurified air used for experiments that were conducted at ambient temperature. Two irradiation s carried out simultaneously, one in side "R" and the other in side "B". Experiments are designated by their run date and side (e.g., JN1279R). Most of the experiments used in this evaluation were carried out between 1978 and 1985, but a few isoprene experiments were carried out in 1992 and 1993. See Jeffries et al (1982, 1985a,b) for descriptions of the chamber and experimental methods and Carter and Lurmann (1990, 1991) for a discussion of the modeling methods used for the earlier experiments and Carter and Atkinson (1996) for the isoprene experiments. Note that this may not be a complete dataset or contain the best quality assured data from this chamber. This chamber has since been rebuilt and is probably not the primary chamber now used at UNC.

### 70

Table 21 . Summary of types of experiments used for mechanism evaluation. Designation Mixture irradiated or description Radical Source Characterization CO - NO x 

### CO - NO x 

### C4 - NO x 

### n - Butane - NO x 

### NO x 

### Offgasing characterization CO - Air CO - Air HCHO - CO - Air Formaldehyde - CO - Air ACETALD - Air Acetaldehyde - Air VOC Mechanism Evaluation VOC - NO x 

### VOC - NO x 

### VOC - CO - NO x 

### VOC - NO x 

### with added CO VOC - C4 - Air VOC - air with added n -butane VOC - C4 - NO x 

### VOC - NO x 

### with added n -butane VOC - C2 - NO x 

### VOC - NO x 

### with added ethane VOC - O3 VOC + O 3 

### (also includes control experiment in the other reactor without the VOC) IR Incremental reactivity experiment. Type of base case indicated Standard surrogate - NO x 

### experiments used in recent UCR experiments for mechanism evaluation Surg - 8 Standard 8 - component "full surrogate" consisting of n -butane, n - octane, ethene,

propene, trans - 2 -butene, toluene, m -xylene and formaldehyde (e.g., Carter et al, 1995c; Carter, 2002) Surg - 7 Standard 8 - component "full surrogate", above, but without formaldehyde (e. g. Carter

and Malkina, 2005, 2007, Carter et al, 2005a) Surg - 3 Standard mini - surrogate consisting of ethene, n -hexane, and m -xylene (e.g., Carter et

al, 1993, 1995c). Surg -NA Standard 8 - componene "full surrogate" but without aromatics and formaldehyde

(unpublished results from this laboratory). Surg - E Ethene surrogate consisting of ethene alone (e.g., Carter et al, 1995c). Surg -x Miscellaneous 3 - or 4 - componene surrogates (e.g., Carter et al, 1993, Carter and

Malkina, 2002) Types of surrogate or incremental reactivity base case experiments MIR1 Low ROG/NO x 

### , MIR - like conditions. NO x 

### 300 - 500 ppb (e.g., Carter et al, 1993,

1995c) MIR2 Low ROG/NO x 

### , MIR - like conditions, NO x 

### < 100 ppb (e.g., Carter, 2002; Carter and

Malkina, 2005, 2007, Carter et al, 2005a) LN1 Lower NO x 

### , e.g., MOIR/2. NO x 

### >100 ppb (e.g., Carter et al, 1993, 1995c) LN2 Lower NO x 

### ,, e.g. MOIR/2 conditions, NO x 

### < 50 ppb (e.g., Carter, 2002; Carter and

Malkina, 2005, 2007, Carter et al, 2005a) vary Non - standard ROG/NO x 

### . Conditions varied Older UCR and UNC and TVA surrogate and mixture - NO x 

### experiments IT Csrg -4 Experiments in the ITC chamber (primarily) using a 4 - component surrogate,

primarily for the early incremental reactivity study of Carter and Atkinson (1987). Surrogate consisted of propene, n -butane, trans - 2 -butene, and m-xylene. IT Csrg -4R Based on ITCsrg -4, but with propene removed. Used in the study of Carter and

Atkinson (1987).

### Table 21 (continued)

71

Designation Mixture irradiated or description ECsrg - 7 A surrogate mixture of seven hydrocarbons used in several runs in the SAPRC EC

(Pitts et al, 1979). Consisted of n -butane, 2,3 - dimethyl butane, ethene, propene, trans 2 -butene, toluene, m -xylene MDsrg - 8 A surrogate mixture of 8 hydrocarbons used in the "multi - day effects" study of Ca rter et al (1984). Consisted of n-butane, n -pentane, isooctane, ethene, propene, isobutene, toluene, and m-xylene TVAsrg - 1 A complex surrogate mixture of alkanes, alkenes, and aromatics used in the TVA

chamber (Simonaitis and Bailey, 1995; Bailey et al, 1996). TVAsrg - 2 A complex surrogate mixture of alkanes, alkenes, and aromatics used in the TVA

chamber (Simonaitis and Bailey, 1995; Bailey et al, 1996). UNCsrg - 3 A simple surrogate of propene, n -butane and an aromatic used in the UNC chamber

(Jeffries et al, 1982, 1985a). SynUrb A complex "synthetic urban" VOC mixture used in the UNC chamber (Jeffries et al,

1985a) SynAuto A synthetic auto exhaust VOC mixture used in the UNC chamber (Jeffries et al,

1985b) UNCsrg -x Miscellaneous surrogates used in the UNC chamber (Jeffries et al, 1982, 1985a). Simple mixtures (incomplete surrogates) Mix -A Mixture of alkanes Mix - E Mixture of alkenes Mix -AE Mixture of alkanes and alkenes Mix -AO Mixtures of alkanes and oxygenates (generally aldehydes) Mix - EO Mixture of alkenes and oxygenates Mix - RO Mixtures of aromatics and oxygenates (generally aldehydes) Mix -AR Mixtures of alkanes and aromatics Mix - ER Mixtures of alkenes and aromatics Light Source Designations used in run listing A Arc light (Xenon or Argon arc) solar simulator Bl Blacklights Bs Mixture of blacklights and sunlamps S Solar light This would be a maj or effort because of the considerable amount of variation from experiment to experiment in terms of measurements of other species that were made, and t he highly variable and uncertain quality of much of the measurements (e.g ., see Carter et al, 1995a for a discussion of the measurement data for the earlier UCR chamber experiments). However, evaluations of model performance in simulating individual oxidation products was often used when developing mechanisms for individual VOCs when relevant data were available, and in general the mechanisms for these compounds retain the product yield predictions so developed when updated for this version. **Methods** The pro cedures used when evaluating the mechanism against the chamber data were the same as employed in previous evaluations of the SAPRC - 90 (Carter and Lurmann, 1990, 1991) and SAPRC - 99 (Carter, 2000a, 2004; Carter and Malkina, 2007) mechanisms. Briefly, evaluations of mechanisms using

### 72

chamber data require an appropriate representation of the conditions of the chamber experiments that affect the simulation results. These include initial reactant concentrations, physical conditions such as temperature and dilution , light intensity and spectrum, and the maj or wall effects such as the chamber radical source, O 3 

### decays, NO x 

### offgasing, etc. These considerations are discussed in detail elsewhere (e.g., Carter et al, 1982; Carter and Lurmann, 1990, 1991; Carter et al, 1995a,b, 1997a; Carter, 2000a and references therein), and that discussion will not be duplicated here. The parameters in the chamber effects model used when modeling the experiments for this mechanism evaluation are given in Table 22 . Except for the parameters used to model the chamberdependent radical source and NO x 

### offgasing, which have to be adjusted for each mechanism, the input data used in modeling the chamber experiments were the same as used in previous studies. The reports describing the methods used to derive the input data, and giving the chamber effects characterization parameters employed, are given in footnotes to Table 20 . As indicated above, the input data files will be made available at the SAPRC mechanism web site. The most important and variable chamber background effect is the "cham ber radical source" first not ed by Carter et al (1982) and background NO x 

### offgasing. The former causes enhanced NO oxidation and O 3 

### formation experiments, such as CO - NO x 

### or alkane - NO x 

### irradiations with no significant radical sources in the gas -phase mechanism, while the latter cau ses O 3 

### formation in experiments where NO x 

### has not been added. Both of these effects are attributed to offgasing of HONO, which have been observed experimentally in the SAPHIR outdoor chamber in Germany (Brauers et al, 2003, Rohrer et al, 2004) to occur at rates similar to the radial source and NO x 

### offgasing rates derived for the UCR EPA chamber (Carter et al, 2005b). The ma gnitudes of the radical source and NO x 

### offgasing effects are larger in the older chambers (Carter and Lurmann, 1990, 1991; Carter et al, 1995a, 2005b; Carter, 2000a), but they are still generally comparable to each other, consistent with the assumption that both are due to the same process. This is represented in the chamber model by the parameter RN, which is the rate of HONO offgasing re lative to the light intensity as measured by the NO 2 

### photolysis rate. Since HONO has not been measured directly in any of the chambers used for mechanism evaluation for the conditions relevant to the experiments, the HONO offgasing rate parameter has to be determined by adjusting the parameter so the model calculations can simulate results of the appropriate characterization experiments. The most sensitive experiments are the CO - NO x 

### and alkane (primarily n butane) - NO x 

### experiments used for radical source characterization, and modeling these experiments is the primary method used to derive the RN parameters used when modeling the mechanism evaluation runs. The best fit parameters depend to some extent on the chemical mechanism used, particularly the rate c onstant for the OH + NO 2 

### reaction, which is the main radical terminating reaction in the characterization experiments. Since this rate constant changed in SAPRC - 07 com pared to SAPRC - 99, the set of RN parameters used in the mechanism evaluation also changed . The RN parameters that were used when modeling the chamber experiments for this mechanism evaluation are given on Table 22 . They were derived to minimize biases in simulations of the radical source characterization experiments, as indicated on Table 21 and Table C - 1 in Appendix C. For this purpose, experiments were grouped into "characterization sets" that were assumed to have similar chamber effects parameters. As discussed by Carter et al (1995a) and Carter (2002), for some chambers the co nditions affecting radical sources and NO x 

### offgasing appeared to change from time to time due to changes in reactors, exposure to reactants, etc., and assignments to characterization sets are used to take this into account. The characterization sets associ ated with the individual experiments are included with the run listing in Table C - 1 .

### 73

Table 22 . Chamber wall effect and background characterization parameters used in the

environmental chamber model simulations for mechanism evaluation. Cham. Set(s) Value Discussion RN - I (ppb) Ratio of the rate of wa ll + h - > HONO to the NO 2 photolysis rate. EPA 2 0.0075 Average of values that gave best fits to n -butane - NO x and CO - NO x , radical source characterization and CO - air NO x of fgasing characterization experiments carried out in this chamber. Note that for Set 3 the best fit RN - I values depended on the reactor. 3A 0.0165 3B 0.0115 4 0.0055 5 0.0110 6 0.0150 7 0.0100 ITC All 0.0475 Average of value of RS - I that gave best fits to n -butane - NO x radical source characterization chamber experiments carried out in this chamber. ETC 2 - 3 0.04 Same procedure as above DTC 1 0.058 Same procedure as above

3 0.210 4 0.300 10 0.055 11 0.092 12 0.310 13 0.170 14 0.095 15 0.063 16 0.240 17 0.083 18 0.074 XTC All 0.085 Same procedure as above CTC 1 0.06 Same procedure as above

2,3 0.10 4 - 8 0.095 9 0.115 10 0.08 OTC 7.2e+9 exp( - 9712/T)

0.063 @ 300K Based on Arrhenius plots of values of RS - I that give fits to n -butane - NO x

chamber experiments carried out in this chamber for the average tem peratures of the experiments. EC 1 0.235 Based on the NO 2 dependence radical source derived by Carter et al (1982), adjusted to reduce biases in simulations of n -butane - NO x experiments carried out in this chamber using this mechanism. The NO 2 - dependent radical source term, RS - S, was reduced b y an equal factor. TVA All 0.008 Estimated value. Could not be determined by modeling radical source characterization because of the large formaldehyde offgasing. See Carter (2004). UNC All 4.0e+14 exp( - 12581/T)

0.248 @ 300K Based on Arrhenius plots of v alues of RS - I that give fits to the few

available alkane - NOx chamber experiments carried out in this chamber for the average temperatures of the experiments. Older experiments mo deled by Carter and Lurmann (1990, 1991) were used. RS - S (unitless) Ratio of the rate of NO 2 + hv - > 0.5 HONO + 0.5 wall NO x to the NO 2 photolysis rate.

### Table 22 (continued)

74

Cham. Set(s) Value Discussion EC 1 0.0017 Based on the NO 2 dependence radical source derived by Carter et al (1982), adjusted downward by 20% to reduce biases in simulations of n butane - NO x experiments carried out in this chamber. The NO2 - independent radical source term, RN - I, was reduced by an equal factor. All others 0 Any dependence of apparent radical source on initial NOx levels in Teflon bag chambers wa s found to be much less than the run - to -run variability. HONO - I (ppb) Initial HONO in experiment, assumed to be independent of other reactants unless indicated. EPA All 0.05 Value that usually gives best fits to model simulations of results of n butane - NO x and CO - NO x experiment s in this chamber. ITC All 1.7 Average of initial HONO value that gave best fits to n -butane - NO x chamber experiments carried out in this chamber. The RN - I parameter was optimized at the same time. The best fit initial HONO values appear to be approximately independent of the initial NO 2 . ITC All 1.7 Similar procedure as above. TVA All 0.5 Similar procedure as above. DTC 1 0.001 x [NO 2 ]init Similar procedure as above, except for this chamber the best fit initial HONO appeared to be correlated with the initial NO 2 concentrations. 3,4 0.004 x [NO 2 ]init 10,18 0.008 x [NO 2 ]init 11,14 0.006 x [NO 2 ]init 12,16 0.005 x [NO 2 ]init 13 0.009 x [NO 2 ]init 15 0.007 x [NO 2 ]init 17 0.003 x [NO 2 ]init XTC All 0.012 x [NO 2 ]init Similar procedure as above CTC All 0.008 x [NO 2 ]init Similar procedure as above EC All 0.07 x [NO 2 ]init Similar procedure as above ETC, OTC, UNC 0 For most (though not all) characterization runs in these chambers the data are simulated best if the effect of any initial HONO is small compared to other chamber radical sources, o E -NO2/K1 (ppb) Ratio of rate of NO 2 offgasing from the wa lls to the NO 2 photolysis rate. EC 1 0.10 Adjusted to fit O 3 formation in acetaldehyde/air run EC - 253. All Teflon Film Chambers 0 The NO x offgasing caused by representing the radical source by HONO offgasing appears to be sufficient for accounting for NO x offgasing effects in most cases. RN - I parameters adjusted to fit experiments sensitive to the radical source are consistent with NOx offgasing rates adjusted to fit pure air or aldehyde - air runs, to within the uncertainty and variability. K(NO2W) (min - 1 ) Rate of unimolecular loss (or hydrolysis) of NO 2 to the walls. All Teflon Film Chambers 1.6e - 4 Based on dark NO 2 decay and HONO formation measured in the ETC by Pitts et al. (1984). Assumed to be the same in all Teflon bag chambers, regardless of volume. EC 1 2.8e - 4 Based on dark NO 2 decay and HONO formation measured in the EC by Pitts et al. (1984). UNC All 5.0e - 5 Value used by Carter and Lurmann (1990, 1991) was not updated.

### Table 22 (continued)

75

Cham. Set(s) Value Discussion YHONO Yield of HONO in the unimolecular reaction (hydrolysis) of NO 2 on the walls. All Teflon Film Chambers 0.2 Based on dark NO2 decay and HONO formation measured in the ETC by Pitts et al. (1984). Assumed to be the same in all Teflon bag chambers, regardless of volume. EC 1 0.5 Based on dark NO2 decay and HONO formation measured in the EC by Pitts et al. (1984). E - ALD/K1 (ppb) Ratio of rate of formaldehyde offgasing from the walls to the NO 2 photolysis rate. EPA All 0.01 Gives best fits to formaldehyde data in most pure air irradiations and other experiments where formaldehyde should not otherwise be present. TVA 0.045 + other sources

(see discussion) This chamber had significant wall offgasing of formaldehyde and

assuming a constant offgasing rate did not give best fits to the data. The additional process required to fit the data, derived by Simonaitis et al (1997) and used by Carter (2004), are as follows: Walls + h  WALLVOC; rate = NO 2 photolysis rate x 0.135 ppb WALLVOC + OH  HO2 + 0.2 HCHO; k = 2 x 10 4 ppm- 1 min- 1 All other chambers 0 Simulations of characterization experiments do not require assuming formaldehyde offgasing. Formaldehyde measurements not sufficiently sensitive to determine formaldehyde offgasing. K(O3W) (min - 1 ) Unimolecular loss rate of O 3 to the walls. EPA All 1.08e - 4 Based on results of O 3 decays carried out in this chamber ITC, ETC, DTC, XTC 1.5e - 4 Based on results of O 3 decay in Teflon bag chambers experiments as discussed by Carter et al (1995a). CTC All 8.5e - 5 Based on results of O 3 decay experiments in this chamber OTC All 1.67e - 4 Similar procedure as above EC All 1.1e - 3 Similar procedure as above TVA All 7.0e - 4 Similar procedure as above UNC All 1.43e - 4 Similar procedure as above k(N26I) (min - 1 ) Rate constant for N2O5 - > 2 Wall -NO x . This represents the humidity independent portion of the wall loss of N 2 O 5 , or the intercept of plots of rates of N 2 O 5 loss against humidity. All Teflon Bag Chambers 2.8e - 3 Based on N 2 O 5 decay rate measurements made by Tuazon et al (1983) for the ETC. Assumed to be independent of chamber size (Carter et al, 1995a). EC 1 4.7e - 3 Based on N 2 O 5 decay rate measurements made by Tuazon et al (1983) for the EC. See also Carter et al (1995a). k(N26S) (ppm- 1 min- 1 ) Rate constant for N2O5 + H2O - > 2 Wall -NOx **.** This represents the humidity dependent portion of the wall loss of N 2 O 5 , or the slope of plots of rates of N 2 O 5 loss against humidity. Note that this is in addition to the N 2 O 5 hydrolysis reaction in the gas -phase mechanism. All Teflon Bag Chambers 1.1e - 6 Based on N 2 O 5 decay rate measurements made by Tuazon et al (1983) for the ETC. Assumed to be independent of chamber size (Carter et al, 1995a). EC 1 1.8e - 6 Based on N 2 O 5 decay rate measurements made by Tuazon et al (1983) for the EC. See also Carter et al (1995a).

### Table 22 (continued)

76

Cham. Set(s) Value Discussion EPA All 0 Assumed to be negligible compared to the homogeneous process already in the base mechanism UNC All 2.0e - 8 Value used by Carter and Lurmann (1990, 1991) was not updated. k(XSHC) (min - 1 ) Rate constant for OH - > HO2 . This represents the effects of reaction of OH with reactive VOCs in the background air or of fgassed from the chamber walls. This parameter does not significantly affect model simulations of experiments other than pure air runs. All Teflon Bag Chambers 250 Estimated from modeling several pure air in the ITC (Carter et al, 1996d), and also consistent with simulations of pure air runs in the ETC (Carter et al, 1997a). EC 1 0 Assumed to be negligible because the EC is generally evacuated overnight between experiments (Carter et al, 1995a). EPA, TVA 0 Assumed to be negligible because steps are taken to reduce background effects for low

concentration experiments. UNC 750 Value used by Carter and Lurmann (1990, 1991) was not updated. H2O (ppm) Default water vapor concentration for runs where no humidity data are available. EPA All 3.4e+2 The EPA c hamber experiments used for mechanism evaluation to date were not humidified. This is the expected upper limit water concentration. ITC All 2.0e+4 This corresponds to ~50% RH at 303K, which is the condition for most experiments in this chamber. DTC 4 2.0 e+4 This corresponds to ~50% RH at 303K, which is the condition for experiments in this characterization set. (The other DTC experiments are not humidified) EC 1 2.0e+4 This corresponds to ~50% RH at 303K, which is the condition for most experiments in this chamber. Humidity data are available for most EC runs, so the default is usually not used. TVA, UNC (no default) The water concentration is specified in the input files for all experiments. All Other Chambers or char. sets. 1.0e+3 Experiments in these chambers were carried out using dried purified air. The limited humidity data for such runs indicate that the humidity was less than 5%, probably no more than ~2.5%, and possibly much less than that. The default value corresponds to ~2.5 - 3% RH for the c onditions of most experiments. Dilution rate (min- 1 ) Default rate of dilution in the experiment (used for most experiments if no dilution specified for the experiment) EPA All 0 Dilution expected to be small because of the design of the chamber ITC All 0 Dilution not well characterized but assumed to be small. ETC All 8.0e - 5 Based on CO dark decays or other dilution characterization data. DTC 1 5.3e - 5 Similar procedure as above

3,4 1.8e - 4 10 - 18 5.3e - 5 XTC All 2.7e - 5 Similar procedure as above C TC All 6.7e - 5 Similar procedure as above OTC All 6.7e - 5 Similar procedure as above EC All 2.0e - 4 Similar procedure as above

### Table 22 (continued)

77

Cham. Set(s) Value Discussion TVA (no default) Dilution specified in input files for each experiment UNC All 2.0e - 4 Value used by Carter and Lurmann (1990, 1 991) was not updated. 

### Note that, as discussed by Carter (2002) and Carter et al (2005b), the UCR EPA and the TVA chambers have much lower apparent NO x 

### offgasing rates than the older chambers, because these chambers were designed for conducting experiments at lower pollutant concentrations. Runs in these chambers were generally carried out at lower pollutant levels than in the other chambers, and the concentrations are generally more representative of ambient conditions. However, the TVA chamber had very high background levels of formaldehyde (Carter, 2002), so of these two chambers the UCR EPA chamber has the lowest overall background effects. Although most of the mechanism evaluation is based on simulations of environmental chamber experiments, we will also present results of simulations of the "direct reactivity" experiments developed by Carter and Malkina (2002). These consist of plug flow experiments where the effect of adding the VOC to HONO - air irradiations is determined. In the absence of added VOCs, the HONO - air plug flow irradiations results in the formation of NO, which is measured. If a VOC is added to the mixture, the OH radicals formed in the photolysis of HONO become peroxy radicals that convert the NO to NO 2 

### , and, if the amount of added VOC is sufficient to consume all the NO, causes O 3 

### to be formed. The change in NO consumption and O 3 

### formation, relative to the no -VOC case, for the limit of zero added VOC is the measure of direct re activity that is used. Model calculations carried out by Carter and Malkina (2002) show that this measurement is sensitive to the rate constant for the reactions of the VOC and the number of NO to NO 2 

### conversions caused when it reacts, but is not sensitive to indirect reactivity effects such as effects of VOCs on radical or NO x 

### levels. They showed that the results were generally consistent with the predictions of the SAPRC - 99 mechanism except for benzene and toluene, where the direct reactivities were signi ficantly overpredicted. The methods used to simulate the direct reactivity experiments for this evaluation were the same as described by Carter and Malkina (2002) for SAPRC - 99. **Data Presented** The results of the model simulations of the various types of exp eriments are given primarily in various plots and tables in Appendix C, and a few representative results are presented in conjunction with the discussion below. In most cases, results are given for SAPRC - 99 as well as this version of the mechanism, so the changes caused by the mechanism update can be assessed. As indicated above, the performance of the mechanism is measured primarily in terms of its ability to simulate O 3 

### formation and NO oxidation, though the effect of the compounds on overall OH radicals in the incremental reactivity experiments is also assessed. The amount of O 3 

### formed and NO oxidized in the experiments is measured by the quantity  ([O 3 

### ] - [NO]), which is calculated by [O 3 

### ] t 

### - [NO] t 

### - ([O 3 

### ] 0 

### - [NO] 0 

### ), where [O 3 

### ] 0 

### , [NO] 0 

### , [O 3 

### ] t 

### , and [NO] t 

### are the initial and time=t concentrations of ozone, and NO, respectively. As discussed previously (e.g., Carter and Atkinson, 1987; Carter and Lurmann, 1990, 1991), this gives a measure of the ability of the model to simulate the chemical processes that cau se ozone formation that gives a useful measure even where ozone is suppressed by the presence of excess NO. The ability of the mechanism to simulate this quantity in the experiments is measured by its "model error", which is calculated as  ([O 3 

### ] - [NO]) model error = {  ([O 3 

### ] - [NO]) mo del 

### -  ([O 3 

### ] - [NO]) experimental 

### } /  ([O 3 

### ] - [NO]) experimental 

### .

### 78

These values are calculated for each hour of the experiments, with the experimental values being derived by linear interpolation if no measurement were made exactly on the hour. Table C - 1 in Appendix C gives the model errors for the second hour and the sixth hour (or final hour if the experiment was less than 6 hours) for all the e xperiments, and distributions of these values are shown for various types of experiments as discussed below. Because of the very large number of VOC - NO x 

### and mixture - NO x 

### experiments used in the evaluation, in most cases experimental and calculated conc entration time plots are not shown for individual experiments, and only distributions of model errors are presented. The model error results for the different types of experiments are shown in various figures in Table C - 1 and in the discussion of the results below. These figures show how the average model errors vary with time during the experiments, which give information on the model performance in terms of simulating rates of NO oxidation and O 3 

### formation, as well as simulating final O 3 

### yields. These figures also show distribution plots of model errors for hour 2 and final  ([O 3 

### ] - [NO]). These show the degree of run -to -run variability of model performance in simulating these quantities. Results for comparable types of experiments are shown together, but because of the large number of types of experiments, a relatively large number of plots is needed. As indicated in Table 20 , a large number of mechanism evaluation experiments consisted of incremental reactivity experiments, and a different method was used to present the results for these experiments. Incremental reactivity experiments consist of simultaneous (or alternating) irradiations of a "base case" reactive organic gas (ROG) - NO x 

### mixture providing a simplified model of ambient chemical conditions, and irradiations of the same mixture with a test compound or mixture added. In this case the measures of model performance of interest concern the ability of the mechanism to predict the effects of the compound on the experiment. However, it is also important to see how well the model simulates the base case experiment as well, becaus e if it performs poorly it may introduce errors in the simulations of the effects of adding the test compound if the chemical conditions influencing these effects are not correctly simulated. Because of the relatively limited number of incremental reactivi ty experiments for any given compound combined with the additional considerations involved in assessing model performance for such experiments, the presentation of the evaluation results for the incremental reactivity experiments in Appendix C give plots f or each experiment. These include experimental and calculated time plots of  ([O 3 

### ] - [NO]) Base 

### ,  ([O 3 

### ] - [NO]) Test 

### , and IR  ([O 3 

### ] - [NO]), where  ([O 3 

### ] - [NO]) Base 

### and  ([O 3 

### ] - [NO]) Test 

### are the  ([O3] - [NO]) in the base case and the added test VOC experiments, respectively, and

IR  ([O 3 

### ] - [NO]) = {  ([O 3 

### ] - [NO]) Test 

### -  ([O 3 

### ] - [NO]) Base 

### } / amount of test VOC added where  ([O 3 

### ] - [NO]) Base 

### and  ([O 3 

### ] - [NO]) Test 

### are the  ([O3] - [NO]) in the base case and the added test VOC experiments, respectively. The IR  ([O 3 

### ] - [NO]) values are given in molar units (e.g., ppm  ([O 3 

### ] - [NO]) / ppm VOC added) if the test VOC is a single compound, or in mole carbon units if the test VOC is a com

plex mixture such as a petroleum distillate. Each figure includes plots for experiments with a single compound or group of similar compounds. Note that in the incremental reactivity experiments carried out in the ETC, the base case experiments were not carried out at the same time as the added test VOC experiments, but were carried out separately. This is because this is a single reactor chamber that does not permit simultaneous injections and irradiations of common reactants. For those experiments, the base case results for a given added test VOC experiment were interpolated or derived using cor relations between initial reactant concentrations and other characterization results in the base case experiment. Therefore, in the plots of the  ([O 3 

### ] - [NO]) data, the figures only show the model calculations for the base case experiment, not the experimental data. The figures with the evaluation results for the incremental reactivity experiments also show plots of the experimental and calculated effects of the VOC on the integrated OH radical levels. This is useful

### 79

for mechanism evaluation because an important factor affecting a VOC's incremental reactivity is its effect on overall radical levels, which affects O 3 

### formation caused by the reactions of other VOCs that are present. For radical inhibiting VOCs such as higher alkanes, the reduced O 3 

### formation caused by the effect of the VOCs on the reactions of the other compounds present counter- acts the direct O 3 

### formation caused by the compound's own reactions, resulting in a low net incremental reactivity for  ([O 3 

### ] - [NO]). However, for such compounds the effe cts on integrated OH levels, or IntOH are quite large, indicating that the compound indeed is having a large effect on the chemistry of the system. The IntOH levels in the experiments are calculated from the rates of consumption of the most reactive VOC in the base case mixture that reacts only with OH radicals (usually m- xylene but sometimes n - octane or 1,3,5 -trimethylbenzene) (Carter et al, 1993). The effect of the test VOC on this quantity is measured by IR IntOH = {IntOH Test 

### - InOH Base 

### } / amount of te st VOC added where IntOH Base 

### and IntOH Test 

### are the IntOH values derived from the base case and the added test VOC experiments, respectively. They are given in units of ppt - minute per ppm of test VOC added if the test VOC is a compound, or ppt- minute per pp mC of test VOC if it is a complex mixture. **Results Results for Chamber Characterization Experiments**  The results of the simulations of the radical source and NO x 

### offgasing characterization experiments are shown on Figure 5 and Figure 6 , respectively. These show distribution of model errors for both the SAPRC - 99 and SAPRC - 07 mechanisms as described above. Itc an be seen that there is relatively large variation from run to run, indicating the variability of the chamber effects related to radical source and NO x 

### offgasing. The average biases for the radical source characterizati on runs are generally small being within  25%, as would be expected since the radical source parameters were adjusted to minimize the biases. Except for the single CTC experiment, the biases for the NO x 

### offgasing characterization runs are also not large co mpared to the variability, despite the fact that, except for the TVA chamber where the large formaldehyde offgasing makes runs insensitive to the chamber radical source, the NO x 

### offgasing p arameters were adjusted based on the radical source characterization runs. This is consistent with the expectation that they are both due to the same effect. From the perspective of mechanism evaluation it is important to realize that these radical source and NO x 

### offgasing characterization experiments are, by design, particularly sensitive to these variable chamber effects. The experiments used for mechanisms evaluation, discussed in the following section, are much less sensitive to these effects, and variabilities in radical source or NO x 

### offgasing should not be important sources of variability in the simulations of these experiments. However, it is important that these chamber effects not be a source of bias in the simulations of the mechanism evaluation runs, so it is important that appropriate values of the parameters representing these effects be used. **Results for Mechanism Evaluation Experiments** The performance of the SAPRC - 07 mechanism in simulating NO oxidation and O 3 

### formation in the mechanism evaluation experiments is given in Table C - 1 and in the various figures in Appendix C. The ability of the mechanism to simulate effects of the added test compounds on integrated OH levels in the incremental reactivity experiments is also shown in the figures for those experiments. For comparison purposes, results for SAPRC - 99 are also shown on the figures, except for those few compounds that are not represented in SAPRC - 99. The results for various types of experiments are summarized below.

**Overall Performance in Simulating Entire Dataset** Figure 7 shows the distributions and averages of model errors in the SAPRC - 07 and SAPRC - 99 simulations of NO oxidize d and O 3 

### formation in the entire set of mechanism evaluation

### 80

chamber experiments modeled for this project. Itc an be seen that both mechanisms have essentially no bias in simulating  ([O 3 

### ] - [NO]) after the first hour of the experiment, though they both tend to slightly overpredict NO oxidation rates in the first hour. The same is true for the SAPRC - 99 simulations of the mixture experiments. On the other hand, the updated mechanism has a small positive average bias in simulating the mixture experiments, averaging about 20% for the first hour (only slightly greater than that for SAPRC - 99), going down to about 6% by the end of the run. However, this bias is small compared to the overall variability of the fits, which are within  30% for most experiments for both mechanisms. Therefore, this slight positive bias for the updated mechanism in simulating the mixture runs may not be significant. The reason for the slight positive bias in the simulations of  ([O3] - [NO]) in the mixture runs, if significant, is uncertain. The results for the single compounds or individual mixtures do not clearly indicate a cause in terms of particular compounds or types of compounds. It is considered unlikely that the slightly increased positive bias is due to problems with chamber characterization, since the most important chamber characterization parameters, regarding radical sources and NO x 

### offgasing, were re adjusted for this version of the mechanism, and the other parameters were the same as used for SAPRC 99. Indeed, if anything, Figure 5 and Figure 6 suggest that the parameters used with updated mechanism may be slightly biased towards being too unreactive in this regard. Of the rate constant updates made to the base mechanism, potentially the most important is the increase in the OH + NO 2 

### reaction, which is a maj or radical termination process that is im portant in essentially all experiments. But the increase, by itself, should cause slower NO oxidation and O 3 

### formation, which is opposite of the direction seen. On the other hand, if parameters in the mechanisms for the individual VOCs are adjusted to compensate for this change, it might cause increased reactivity in simulations of experiments that are more sensitive to these parameters than the OH + NO 2 

### rate constant. As indicated below, some uncertain mechanistic parameters (primarily nitrate yields in peroxy + NO reactions or yields of photoreactive aromatic products) had to be re - adjusted for the updated mechanism to fit results of reactivity and single VOC - NO x 

### experiments. This may need to be investigated.

**Evaluation Experiments for Individual VOCs** The maj or mechanism evaluation dataset consisted of the >1200 experiments carried out to evaluate mechanisms of almost 130 individual compounds and mixtures. These compounds or mixtures are liste d on Table 23 , along with an indication of the number and types of experiments for each, and references to the figure or figures in Appendix C where the results of the evaluation are presented. Table 23 also indicates whether any uncertain parameters were adjusted in the mechanisms as a result of this evaluation, and gives codes and comments concerning the overall quality of the fits, which are described

### 81

Figure 5 . Distribution of  ([O 3 

### ] - [NO]) model errors for the radical source characterization

experiments . Radical Source Characterization Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final EPA 48 6% 4% 5% 7% Indoor TC [a] 141 1% 0% -8% -3%

EC 7 9% 21% -19% -3% TVA 8 -20% -5% -21% -16% OTC 6 -6% -6% -8% -8% UNC 6 -1% 20% -14% 17% [a] ITC, ETC, DTC, XTC, and CTC

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Runs Chamber

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 UCR EPA Indoor TC EC TVA OTC UNC

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 82

Figure 6 . Distribution of O 3 

### model errors for the NO x 

### offgasing characterization experiments NOx Offgasing Characterization Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final UCR EPA 36 -17% -5% -13% 20% CTC 1 -11% 54% -19% 36% ITC 3 -31% -28% -33% -30% TVA 2 -6% 9% -10% 10% SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Chamber Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 UCR EPA CTC ITC TVA

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 83

Figure 7 . Distributions of  ([O 3 

### ] - [NO]) model errors for all of the single VOC - NO x 

### and mixture -

NO x 

### experiments used in the mechanism evaluation . All Experiments Group Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Avg Sdev Avg Sdev Avg Sdev Avg Sdev Single VOC 682 3% 34% 2% 19% 0% 34% 0% 26% Mixtures 1559 4% 32% 2% 20% 10% 40% 5% 23%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) -20% -10% 0% 10% 20%

1 2 3 4 5 6 -20% -10% 0% 10% 20%

1 2 3 4 5 6 Single VOC Mixtures

0% 10% 20% 30% 40% 50%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 10% 20% 30% 40% 50%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 10% 20% 30% 40% 50%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 10% 20% 30% 40% 50%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 84

Table 23 . Summary of mechanism evaluation results using chamber experiments for individual

compounds and mixtures . Compound or Mixture No. Runs [a] Fig. No. [b] O 3 

### -NO Fits [c] Adj [d] Note [e] Single Rct'y Single Rct'y Rate Max Single Compounds (or simple isomeric mixtures) Carbon monoxide 13 1 ok ok Ethane 7 2 ok ok Propane 3 2 ok N - Butane 10 3 ok ok N - Hexane 3 4 ok ok N - Octane 13 5 ok ok N - Dodecane 9 6 ok +1 N - Tetradecane 8 7 ok +1 N - Pentadecane 2 8 ok +1 N - C16 5 8 ok +1 Isobutane 4 9 ok 2,2,4 - Trimethyl pentane 2 9 ok 1 2,6 - Dimethyl octane 5 9 ok ok 2 - Methyl nonane 5 10 ok +1 3,4 - Diethyl hexane 6 10 ok +1 Cyclohexane 6 11 ok ok Hexyl cyclohexane 6 11 ok ok Octyl cyclohexane 7 12 ok ok Ethene 49 4 13 14 ok ok Or Propene 190 10 15 16 ok ok Or 1 - Butene 6 17 ok ok Or 1 - Hexene 3 17 - 2 - 2 Or Isobutene 2 3 18 19 ok Trans - 2 -butene 6 9 18 19 ok ok Isoprene 28 10 20 21 ok ok 3 - carene 4 22 - 1 - 1  - Pinene 6 4 22 23 ok ok Or, yN  - Pinene 6 2 22 23 ok note Or, yN 2 d - Limonene 7 3 [f] 22 23 ok ok Sabinene 3 22 ok ok Cyclohexene 1 24 ok ok Styrene 6 25 ok ok Benzene 9 4 25 27 note ok yP 3,4 Toluene 60 6 28 30 note ok yP 4,5,6 Ethyl benzene 8 3 29 30 ok ok yP m -Xylene 66 17 31 34,35 ok ok yP 6 o -Xylene 18 2 32 35 ok ok yP 7 p -Xylene 14 1 33 35 ok ok yP 6 1,2,3 - Trimethyl benzene 9 2 36 39 ok ok yP 1,2,4 - Trimethyl benzene 11 2 37 39 ok ok yP 1,3,5 - Trimethyl benzene 21 1 38 39 note note yP 8 Naphthalene 5 40 +1 ok Prm Tetralin 5 40 +1 ok Prm

### Table 23 (continued)

85

Compound or Mixture No. Runs [a] Fig. No. [b] O 3 

### -NO Fits [c] Adj [d] Note [e] Single Rct'y Single Rct'y Rate Max 2,3 - Dimethyl naphthalene 4 40 +1 +1 Prm Acetylene 4 7 41 42 - 1 - 1 9 Methanol 3 43 ok Ethanol 3 43 ok Isopropyl alcohol 10 44 ok ok t - Butyl alcohol 7 45 ok +1 yN 1 - Octanol 4 46 ok +1 2 - Octanol 3 46 ok +1 3 - Octanol 3 46 ok +1 Ethylene glycol 5 47 ok ok 10 Propylene glycol 12 48 ok ok 10 Dimethyl ether 4 49 ok Diethyl ether 6 49 ok ok yN Methyl t -butyl ether 4 50 ok 1 - Methoxy - 2 -propanol 6 51 ok +1 2 - Ethoxyethanol 3 52 ok 2 - (2 - Ethoxyethoxy) ethanol 3 52 ok 2 - Butoxyethanol 7 53 ok ok 2 - (2 - Butoxyethoxy) - ethanol 3 54 ok ok yN Methyl acetate 7 55 ok ok Ethyl acetate 9 56 ok ok 11 Isopropyl acetate 3 57 ok ok t - Butyl acetate 6 57 ok +1 yN Methyl isobutyrate 7 58 ok ok Methyl pivalate 6 59 ok ok n - Butyl acetate 8 60 ok +1 Dimethyl carbonate 6 61 ok ok yN Methyl isopropyl carbonate 5 61 ok ok yN Propylene carbonate 7 62 - 1 ok yN 1 - Methoxy - 2 -propyl acetate 6 63 ok +1 yN Dimethyl succinate 6 64 ok ok yN Dimethyl glutarate 6 64 ok ok yN Texanol® isomers 4 65 ok ok Furan 8 66 note note yP 12 2 - Methyl furan 2 67 ok ok yP 3 - Methyl furan 6 67 ok ok yP 2,5 - Dimethyl furan 2 67 ok ok yP Benzyl alcohol 6 3 68 69 ok ok yP Formaldehyde 33 8 70 71 ok ok Acetaldehyde 18 5 72 73 ok ok Acrolein 3 74 ok ok Methacrolein 12 74 ok ok Benzaldehyde 3 75 ok ok Acetone 7 10 76 77 note note QY 13,14 Methyl ethyl ketone 6 5 78 79 ok ok QY 13

### Table 23 (continued)

86

Compound or Mixture No. Runs [a] Fig. No. [b] O 3 

### -NO Fits [c] Adj [d] Note [e] Single Rct'y Single Rct'y Rate Max 2 - Pentanone 1 4 78 80 ok ok QY 2 - Heptanone 1 3 78 81 note note QY 15 4 - Methyl - 2 -pentanone 8 81 ok ok Cyclohexanone 9 82 ok ok Methyl vinyl ketone 6 83 ok ok o - Cresol 1 84 ok ok Prm 16 m - Cresol 1 1 84 85 - 2 ok? 16,17 p - Cresol 1 84 ok ok? 16,18 Para toluene isocyanate 6 86 ok ok Prm 2,4 - Toluene diisocyanate 7 87 ok ok Prm 2,6 - Toluene diisocyanate 2 87 ok ok Prm N - Methyl - 2 -pyrrolidone 6 88 ok ok yN N - Propyl bromide 6 89 - 1 +2 19 N - Butyl bromide 6 89 - 1 +2 19 Trichloroethylene 8 90 +2 +2 20 trans 1,3,3,3 - Tetrafluoropropene (See notes) ok ok yN 29,30 2,3,3,3 - Tetrafluoropropene (See notes) ok ok yN 29,31 1,3 - Dichloropropene mixture 6 3 91 92 ok ok 21 2 - (Chloromethyl) - 3 - chloropropene 1 93 - 1 ? 20 Chloropicrin 6 5 94 95 ok ok Chlorine 2 1 96 ok ok 22 Hexamethyldisiloxane 3 97 ok Prm Hydroxymethyldisiloxane 4 97 ok Prm D4 cyclosiloxane 3 97 ok Prm Carbon disulfide 4 98 ok ok Oth 21 Methyl isothiocyanate 4 98 ok ok Oth 21 Dimethyl sulfoxide 2 6 99 100 - 2 ok Oth 23 S - ethyl dipropylthiocarbamate (EPTC) 5 101 ok ok Oth 21 Ethanolamine 5 [f] 108 ok [g] Init 27 2 - Amino - 2 - methyl - 1 -propanol 7 [f] 109 ok [g] Init 28 Isopropyl amine 1 [f] 108 ok [g] +2 Init 27 t - Butyl amine 1 [f] 109 ok [g] +2 Init 28 Methyl Iodide 7 3 [f] 110 111 ok +1 Oth 26 Complex Mixtures Safety - Kleen mineral spirits "A" (type I -b, 91% alkanes) 3 102 ok +1 24 Safety - Kleen mineral spirits "B" (type II - c) 3 102 ok +1 24 Safety - Kleen mineral spirits "C" (type II - c) 3 102 ok +1 24 Safety - Kleen mineral spirits "D" (type II - c) 3 102 ok +1 24

### Table 23 (continued)

87

Compound or Mixture No. Runs [a] Fig. No. [b] O 3 

### -NO Fits [c] Adj [d] Note [e] Single Rct'y Single Rct'y Rate Max Exxon Exxol® D95 Fluid 6 103 ok ok 24 Exxon Isopar® M Fluid 5 103 ok ok 24 Oxo - decyl acetate 5 104 ok ok 24 VMP naphtha 4 105 ok ok 24 Kerosene 4 105 ok ok 24 Dearomatized Alkanes, mixed, predominately C10 - C12 (ASTM1C) 2 106 ok ok 24 Synthetic isoparaffinic alkane mixture, predominately C10 - C12 (ASTM3C1) 4 106 ok ok 24,25 Reduced aromatics mineral spirits (ASTM1B) 3 106 ok ok 24 Regular mineral spirits (ASTM1A) 3 106 ok ok 24 Aromatic 100 4 107 ok ok 24 [a] Number of chamber experiments. "Single" refers to single VOC - NOx or VOC + CO or alkane - NOx irradiation; "Rct'y" refers to incremental reactivity experiment. [b] Figure number in Appendix C where mechanism performance for single VOC or incremental reactivity experiments is shown. [c] Qualitative indication of ability of mechanism to fit initial rates of O3 formation and NO oxidation ("rate") and final ozone yields ("Max"). The former is more indicative of model performance under relatively high NOx, MIR - like conditions, and the latter is indicative of mo del performance in simulating O3 impacts under lower NOx conditions. If blank, then data are not available to evaluate this aspect of the mechanism. Codes used are as follows: ok Model simulates most of the data within the experimental variability, with low or no apparent biases. n Model tends to overpredict (+) or underpredict ( - ) O 3 

### yield or O 3 

### formation and NO oxidation rates.  1 = moderate but apparently consistent biases;  2 = potentially significant biases ? The data are insufficient to evaluate this aspect of the mechanism. note See note for a discussion of the model performance. [d] Indicates if mechanism was adjusted to fit the data in this evaluation. Codes indicate the type of adjustment, as follows: yN Nitrate yield in peroxy + NO reaction(s) adjusted yP Yield of photoreactive products(s)adjusted. For aromatics, this is the AFG1/AFG2 ratio. Or Radical yield in O 3 

### and O 3 

### P reaction adjusted. QY Quantum yield for photodecomposition adjusted Prm Parameterized mechanism used with various parameters adjusted. Oth Other adjustments were made. See references in notes. Init Initial reactant concentration injected. See Note [g]. [e] Notes and comments concerning the evaluation results of mechanism adjustment, as follows: 1 The model significantly overpredicts the direct reactivity measured by Carter and Malkina (2002) (see "Iso - Octane" on Figure 15 ) 2 The model tends to overpredict O 3 

### in the  -pinene - NO x 

### experiments but gives reasonably good simulations of the reactivity experiments.

### Table 23 (continued)

88

3 Model overpredicts O 3 

### formation rate in the arc light benzene - NO x 

### experiments but tends to underpredict it in the blacklight runs. Model gives reasonably good simulation of most of the incremental reactivity experiments. 4 The model underpredicts the direct reactivities measured by Carter and Malkina (2002), but not a s much as SAPRC - 99 (see Figure 15 ). 5 Model overpredicts initial NO oxidation and O 3 

### formation rates in the toluene - NO x 

### blacklight experiments but gives good simulatio ns to these experiments in the TVA chamber and in chambers using arc lights. Model gives good simulations of the incremental reactivity results. The model significantly overpredicts the reactivity seen in the toluene - NO x 

### experiments in the UNC outdoor ch amber, but this could be due to chamber characterization problems. The model underpredicts the direct reactivities measured by Carter and Malkina (2002), but not as much as SAPRC - 99 (see Figure 15 ). 6 The model underpredicts the effects of CO addition on O 3 

### formation, though to a lesser extent than SAPRC - 99 (see Figure 8 ). 7 The model somewhat overpredicts the reactivity seen in the o -xylene - NO x 

### experiments in the UNC outdoor chamber, but this could be due to chamber characterization problems. 8 The model tends to overpredict O 3 

### formation in experiments in the EC but gives good simulations to results of more recent experiments using both blacklights and arc lights. The model somewhat overpredicts the direct reactivities measured by Carter and Malkina (2002), but the discrepancy may be within the uncertainty of the measurement. 9 The model consistently underpredicts the reactivities in the acetylene - NO x 

### experiments, but the underprediction of the incremental reactivity results is relatively small. The SAPRC - 99 mec hanism, which uses a higher rate constant for OH + acetylene based on an earlier recommendation by Atkinson (1994), simulates the data with much less bias. This rate constant was changed to reflect the recommendation in the NASA (2006) evaluation. 10 Even th ough the mechanism was not changed, the model performs somewhat better than SAPRC 99 in simulating some experiments. 11 The model somewhat underpredicts the direct reactivity measured by Carter and Malkina (2002) (see Figure 15 ). 12 The model gives reasonably good simulations of earlier IT C experiments but tends to underpredict maximum O 3 

### in the new arc light and blacklight experiments carried out for this project. 13 See base mechanism documentation (footnotes to Table A - 2 ) for a discussion of the adjustments made for this compound. 14 The reactivity is somewhat underpredicted in the acetone - NO x 

### experiments with the arc lights and in the outdoor chamber but is well simulated in the blacklight chamber runs. The incremental reactivity results are reasonably well simulated. 15 The model evaluation results for this compound are highly variable. O 3 

### f ormation in the single heptanone - NO x 

### experiment is significantly underpredicted, but the reactivity in one of the two incremental reactivity experiments is overpredicted, while the other two incremental reactivity experiments are reasonably well simulate d. The latter were used as the basis for adjusting the photolysis rate, which was an important uncertain parameter in affecting the results. Note that the photolysis rate adjusted to fit this compound affects the base mechanism because the photolysis rate used for the lumped higher ketone product, PROD2, is based primarily on the photolysis rate derived for this compound.

### Table 23 (continued)

89

16 The parameterized mechanism used for all the cresol isomers was adj usted to fit the data for o cresol based on the model simulation of a single experiment. The  ([O 3 

### ] - [NO]), cresol and PAN data in that one experiment are simulated reasonably well. 17 The model underpredicts O 3 

### formation in the m - cresol - NO x 

### experiment and gives an incorrect prediction of the effect of o - cresol addition on th e initial NO oxidation and O 3 

### formation rate in the reactivity experiment, but simulates the effect on final O 3 

### reasonably well. 18 The one p - cresol - NO x 

### experiment is simulated reasonably well. 19 No attempt was made to adjust the approximate mechanisms to fit the chamber data. The performance indicates the performance of the approximation of using chlorine mechanisms to estimate mechanisms for Br- containing species. 20 No attempt was made to adjust this mechanism to improve simulations of the data. 21 See Carter and Malkina (2007) for a discussion of adjustments made to these mechanisms to fit the chamber data. 22 The effects of Cl 2 

### on n -butane - NO x 

### irradiations and the effects of multiple Cl 2 

### additions to a surrogate - NO x 

### experiment were reasonably well simulated. 23 The initial NO oxidation and O 3 

### formation rates are significantly underpredicted in the DMSO - NO x 

### experiments but are only slightly underpredicted in the MIR -ty pe incremental reactivity experiments. Except for one experiment where the model overpredicts D MSO reactivity, the effects of DMSO on final O 3 

### in the lower NO x 

### reactivity experiments are reasonably well simulated. 24 The mechanism evaluation with these complex mixtures primarily tests how well the mixtures are represented by the distribution of model species used to represent them. No mechanism adjustments can be made to improve simulations in these cases. 25 The model performance with this version of the mechanism is considerably better than SAPRC 99, which had a consistent bias in underpredicting the O 3 

### im pact (overpredicting the O 3 

### inhibition) of this mechanism. 26 See Carter (2007) for a discussion to the adjustments made to this mechanism to fit the chamber data. The mechanism tends to underpredict the amount of ozone inhibition caused by the addition of methyl iodide at the end of some of the experiments. 27 See Note [g] and Carter (2008a) for a discussion of the amine experiments. Although the amount of initial amine in the experiments are adjusted to fit the effects of the amine on the initial rates of NO oxidation and O 3 

### formation in the experiments (see Note [g]), the model does not predict the observed inhibition of ozone at the end of the lower NO x 

### experiments. 28 See Note [g] and Carter (2008a) for a discussion of the amine experiments. Because these co mpounds significantly inhibited the rates of O 3 

### formation, the ability of the mechanism to simulate the effects of the amine on final O 3 

### yields could not be determined. 29 See the report cited in the other note for the results of the evaluation experiments fo r these compounds, which were carried out after the list of experiments to be included in this report was finalized. 30 See Carter (2009a) for a discussion of the experiments used to evaluate the mechanism for this compound. Good simulations of MIR and MOIR/2 reactivity experiments were obtained after adjusting the overall nitrate yield. 31 See Carter (2009b) for a discussion of the experiments used to evaluate the mechanism for this compound. Good simulations of MIR and higher ROG/NO x 

### reactivity experiments were obtained after adjusting the overall nitrate yield.

### Table 23 (continued)

90

[f] These experiments that were not in the original (August, 2007) version of the report. [g] Amount of injected amine available for reaction is uncertain because initial concentration of the amine in th e gas phase could not be measured, and because of expected absorption of amines on the walls and other heterogeneous effects. The fits indicated on the table reflect the fits obtained after adjusting initial amount of amine to fit the initial rates of NO o xidation and O 3 

### formation in the experiments, and the adj usted initial amine concentrations were always lower than the calculated amount injected. See Carter (2008a). The figures show the fits with the amount of initial amine adjusted to best fit the data. in footnotes to the table. The figures in Appendix C show the model performance for both SAPRC - 99 and SAPRC - 07, but Table 23 only summarizes the results for SAPRC - 07, though cases where the mechanisms differ significantly are noted.

For the vast maj ority of the VOCs and mixtures, the performance for SAPRC - 07 was similar to that of SAPRC - 99, though as indicated on Table 23 , mechanism parameters had to be adjusted to obtain the comparable fits. This is expecte d, since for most VOCs the mechanisms were not significantly changed. Exceptions and other cases worth noting are as follows:

Alkylbenzenes . As discussed above, significant changes were made to the ring - opening mechanisms for the alkylbenzenes and the mode l species used to represent the non -  - dicarbonyl ring opening products. However, these changes did not result in significant changes in the ability of the model to simulate aromatic - NO x 

### experiments or incremental reactivity experiments with aromatics, presumably because portions of both mechanisms were optimized to simulate essentially the same database. Like SAPRC - 99, the updated mechanism also tended to underpredict the effects of adding CO to aromatics - NO x 

### irradiations, but to a lesser extent than SAPRC - 99. This is shown on Figure 8 , which shows results of selected toluene and m -xylene - NO x 

### exp eriments where CO was added. Likewise, as discussed below, the updated mechanisms also tended to overpredict direct reactivities of benzene and toluene, but again to a lesser extent than SAPRC - 99. Therefore, the overall performance of the updated mechanism is an improvement over SAPRC - 99 in some at least some respects, but problems in simulating all of the data still remain. Alkenes . As also indicated above, it was necessary to assume lower radical yields in the reactions of O 3 

### and O 3 

### P with alkenes than indicated by current laboratory data in order to obtain unbiased simulations of the data. This was the case for SAPRC - 99 and is also the case with this updated mechanism. However, the extent to which the yields had to be adjusted to lower values was somewhat less with this version of the mechanism, so at least in this respect the problem may be slightly reduced.

Acetylene . The current NASA (2006) evaluation recommends an OH + acetylene rate constant that is lower than that used in SAPRC - 99 by ~17% at ambient t emperature and pressure. This caused a negative bias in the model simulations of the acetylene experiments that was not the case for SAPRC - 99. However, this bias was not so large that it was considered appropriate to adjust the rate constant, and there were not other uncertain aspects of the mechanism considered to be appropriate to adjust to remove this bias.

Higher Ketones . The photolysis rate used in the base mechanism for the lumped model species used to represent the more reactive ketone pro ducts, PROD2, is based on overall quantum yields derived based on model simulations of the experiments with methyl propyl ketone, methyl isobutyl

### 91

Figure 8 . Experimental and calculated effects of CO addition in representative toluene and

m - xylene NO x 

### experiments carried out in the UCR EPA chamber . ketone and 2 -heptanone. The data indicate that the quantum yields decrease with carbon number, but the extent of the decrease with the higher ketones is somewhat greater with the updated mechanism than SAPRC - 99. This resulted in a lower overall photolysis rate for the PROD2 model species. However, the very limited and somewhat consistent data for 2 -heptanone provides the only information about ketones with greater than 7 carbons, which are used as the basis for the even larger ketones that are important in alkane and other photooxidations. More data are needed to place the estimates for photolysis rates of higher ketones on a firmer basis.

Alkyl Bromides . Since developing mechanisms for bromine species was beyond the scope of this project, the mechanisms for the few bromine - containing compounds that are represented are estimated based on mechanisms derived for the corresponding chlorine - containing compounds. The chamber data for n -p ropyl and n -butyl bromides, shown on Figure C - 89 , indicate that this may somewhat underestimate the rate of initial NO oxidation and O 3 

### formation but significantly overestimate the impact of the compound on final O 3 

### yields. The implication of this on predicted MIR values for these compounds is uncertain, but it is clear that low NO x 

### reactivities of these compounds are almost certainly overestimated. Isoparaffinic Alkan e Mixtures . Carter and Malkina (2005) noted that the SAPRC - 99 mechanism predicted much more O 3 

### inhibition in the incremental reactivity experiments with the synthetic isoparaffinic alkane mixture (designated ASTM3C1) than observed experimentally, and concluded that there is a problem either with the characterization of such mixtures or with branched alkane mechanisms in general. However, although neither the composition of the mixture nor the branched alkane mechanisms were changed, the updated mechani sm now gives much better simulations of these data, as shown on Figure C - 106 . This indicates that reactivities of compounds such as these, and presumably others, can be sensitive to changes in the base mechanism that has nothing directly to do with the mechanisms for the compounds themselves. 

### Toluene - NOx **m-Xylene - NOx EPA** **077 (~25 ppb NOx) EPA** **066 (~5 ppb NOx) EPA** **067 (~20 ppb NOx)**

Irradiation time (minutes)**( [** **O 3** **] -** **[ N** **O ]** **) (** **p p** **m )** **( [** **O 3** **] -** **[ N** **O ]** **) C** **h a** **n g** **e** 0.00 0.05 0.10 0.15 0.20 0.25 0.30

0 60 120 180 240 300 360

0.00 0.05 0.10 0.15

0 60 120 180 240 300 360 0.00 0.02 0.04 0.06 0.08

0 60 120 180 240 300 360

-0.01 0.00 0.01 0.02 0.03

0 60 120 180 240 300 360 0.00 0.03 0.06 0.09 0.12

0 60 120 180 240 300 360

0.00 0.02 0.04 0.06

0 60 120 180 240 300 360 Arom. - NOx + CO Experiment SAPRC-99 Model Aromatic - NOx Experiment SAPRC-07 Model

### 92 Amines . The mechanisms for amines were newly derived for this mechanism; SAPRC - 99 either has no mechanisms for these compounds or uses highly approximate "placeholder" mechanisms. The amine mechanisms derived for SAPRC - 07 are and are discussed above in the "Mechanisms for Individual VOCs" section and in more detail by Carter (2008a). A series of incremental reactivity environmental chamber experiments were carried out with 2 - amino - 2 - methyl - 1 -propanol (AMP) and ethanolamine and one experiment each was carried out for t -butyl amine and isopropyl amine (Carter, 2008a), and selected results are shown on Figure C - 108 and Figure C - 109 . As discussed by Carter (2008a), because of analytical problems no data were available concerning the amount of amines present in the gas phase at the start of the experiments, and if the amount of initial amine derived from the calculated amounts injected is assumed, then the effects of the amines on the results of the experiments are significantly overpredicted. This is even if it is assumed that the amines react rapidly with HNO 3 

### formed in the experiments to form the corresponding salt, which is also assumed to be removed from the gas -phase system. Therefore, the amount of amine initially present in the gas phase had to be treated as an adjustable parameter in the model simulations of the experiments, in order to obtain the fits shown on Figure C - 108 and Figure C - 109 . The amount of initial amine that best fit the reactivity data ranged from ~5% to ~60% of the calculated amount of amine inj ected, with no appa rent dependence on reaction conditions or type of experiment (Carter, 2008a). Because of this, the use of these experiments to evaluate amine mechanisms is highly uncertain. Nevertheless, the estimated mechanisms correctly predict that AMP and t -butyl amin e significantly inhibit NO oxidation O 3 

### formation, while they correctly predict that the other two amines have positive effects on initial NO oxidation and O 3 

### formation rates.

When the amounts of initially present amines are appropriately adjusted to simul ate the effects on initial NO oxidation rates, Figure C - 109 shows that the data for AMP and t -butyl amine are reasonably well sim

ulated throughout the experiments. On the other hand, as shown on Figure C - 108 , the chamber data indicated that the two reactive amines studied, aminoethanol and isopropyl amine, tended to inhibit O 3 

### formation under low NO x 

### conditions, which was not predicted by the mechanism. The reason for this inhibition is unknown, and this discrepancy could not be resolved by reasonable adjustments to the mechanisms for these compounds and the representations of the reactions of their maj or products (Carter, 2008a). Therefore, it must be concluded that the mechanisms for the positively reactive amines probably overpredict the reactivities of the compounds under low NO x 

### conditions, if the uncertainties regarding availab ility are not considered.

Methyl Iodide . Methyl iodide is another compound that was not represented in SAPRC - 99 but whose mechanism has been derived for SAPRC - 07. The mechanism for this compound, and its evaluation against chamber data, are described in detail by Carter (2007), and that discussion is not duplicated here. Figure C - 110 and F igure C - 111 show that the mechanism simulates most of the data of Carter (2007) reasonably well.

**Evaluation Experiments for Mixtures** Figure 9 through Figure 13 show distribution plots for the various types of mixture - NO x 

### experiments in the current evaluation set. For most type s of mixtures the model performance is generally satisfactory in terms of overall biases, but there are cases where the updated mechanism does not perform quite as well as SAPRC - 99. These are discussed below for the various types of experiments.

Simple mi xture experiments . These are runs with mixtures that are not considered to be complete surrogates because they do not contain at least one representative each of alkanes, alkenes, and aromatics. Figure 9 shows distributions of model errors for these runs, grouped by the chamber employed. Its hows that the average biases and distribution of errors are similar for both mechanisms. The mixture experiments in the TVA and UC R EC chamber are reasonably well simulated, while the reactivity experiments in the mixture experiments in the UNC chamber are overpredicted by about the same amount in both mechanisms. Given the good performance for the quite different EC and TVA chambers , the

### 93

poorer performance in simulating the UNC chamber data is considered to be likely due to characterization rather than mechanism problems.

Miscellaneous Surrogate Experiments . These are experiments with mixtures that contain at least one alkane, alkene and aromatic that are designed to represent, albeit in a simplified fashion, reactive organic gas mixtures that are emitted into ambient atmospheres. The more recent experiments in the UCR EPA chamber are considered separately because they were carried out at generally lower pollutant levels than the earlier chamber experiments, and conditions in that chamber are considered to be somewhat better characterized. Figure 10 shows the distribution of model errors in the earlier surrogate - NO x 

### experiments carried out in various UCR and the TVA chamber, and Figure 11 shows the results f or various surrogate mixtures in the UNC chamber. Because of the large number of the many standard surrogate experiments used as base cases in incremental reactivity studies in the UCR chambers, these are excluded from Figure 10 and are shown separately in Figure 12 . Overall the model performance for the updated mechanism is simil ar to SAPRC - 99 for these experiments, though the biases tend to be somewhat more (either positive or negative, depending on the type of experiment) for the miscellaneous mixtures shown on Figure 10 . The results with both mechanisms for the UNC or UCR standard surrogate runs, shown on Figure 11 and Figure 12 , respectively, are similar for both mechanisms, with the reactivity in the UNC experiments again being consistently overpredicted (though not as much so as for the simple mixture runs shown on Figure 9 ), and the earlier UCR standard base case surrogate runs being well simulated. New Surrogate Experiments in UCR EPA Chamber . A large number of surrogate - NO x 

### experiments have been carried out in the new UCR EPA chamber, most based on a similar 7 - or 8 - compound mixture designed to represent ambient VOC mixt ures (Carter et al, 1995c, Carter and Malkina, 2005) 1



### . As discussed by Carter (2004), a large number of such experiments were carried out at a variety of NO x 

### and ROG levels, including NO x 

### levels as low as 2 ppb, giving a large and reasonably well characterized database for testing model predictions of how O 3 

### changes with ROG and NO x 

### levels. The results indicated a bias in the SAPRC - 99 mechanism in underpredicting O 3 

### formation and NO oxidation at low ROG/NO x 

### levels, which have not been seen in simulating the earlier surrogate experiments carried out at higher NO x 

### levels (Carter, 2004; Carter et al, 2005b). Since then, a number of other experiments have been carried out in this chamber to further investigate this, including experiments using the blacklight light source and experiments using a "non - aromatic" surrogate with the aromatic constituents of the 7 - or 8 - compound surrogate mixture removed. The latter are useful to evaluate whether the bias at low ROG/NO x 

### is due to problems with the aromatics mechanisms , which are considered to be the most uncertain component of the overall mechanism for mixtures.

The performance of the mechanisms in simulating these experiments is shown in Figure 13 and Figure 14 . Figure 13 shows distribution plot s of model errors similar to those shown above for other mixtures, and shows that overall the updated mechanism simulates the full surrogate (i.e., the surrogates with the aromatics) approximately as well as SAPRC - 99, but that the updated mechanism has a s light positive bias in overpredicting O 3 

### formation and NO oxidation rates in the non - aromatic surrogate runs. Figure 14 shows plots of model errors against the ROG/NO x 

### ratio, similar to those shown previously (Carter, 2004; Carter et al, 2005b). This shows that the problem with the mo del underpredicting O 3 

### .

1 

### The 7 - compound surrogate was the same as the 8 - compound surrogate except that formaldehyde was removed because of experimental issues. Carter and Malkina (2005) showed that this removal should not significantly affect experimental or mechanism evaluation results.

### 94

Figure 9 . Plots of model errors in simulations of miscellaneous mixture - NO x 

### experiments carried

out in various chambers . Miscellaneous Simple Mixture Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final EC Chamber 25 0% 9% -14% 5% TVA chamber 6 -8% 3% -16% -6% UNC Chamber 32 74% 33% 63% 33%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50% 75%

1 2 3 4 5 6 -50% -25% 0% 25% 50% 75%

1 2 3 4 5 6 EC Chamber TVA chamber UNC Chamber

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 95

Figure 10 . Plots of model errors in simulations of miscellaneous surrogate - NO x 

### experiments

carried out in various UCR chambers and in the TVA chamber . Miscellaneous Surrogate Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final ETC, DTC Runs 35 24% 7% 47% 17% ITC 4 HC Mix 35 27% 12% 31% 15% ITC 8 HC Mix 14 -30% -13% -36% -20% EC 7 HC Mix 11 24% 27% 15% 21% TVA Surrogates 22 -16% -8% -23% -13% OTC 8 HC Mix 4 -10% -3% -13% -5%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 ETC, DTC Runs ITC 4 HC Mix ITC 8 HC Mix EC 7 HC Mix TVA Surrogates OTC 8 HC Mix

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 96

Figure 11 . Plots of model errors in simulations of surrogate - NO x 

### experiments carried out in the

UNC chamber . UNC Chamber Surrogate Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Simple Mix 9 18% 21% 7% 25% SynUrban 11 45% 39% 34% 27% SynAuto 14 12% 32% 8% 26%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 Sim ple Mix Sy nUrban Sy nAuto

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 97

Figure 12 . Plots of model errors in simulations of the standard base case surrogate - NO x 

### irradiations

carried out in conjunction with the incremental reactivity experiments in the ETC and DTC (blacklight), and CTC and XTC (arc light) chambers .

Earlier Chamber Standard Base Case Surrogate Runs

Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Arc, Surg-3 MIR1 40 21% 7% 6% -6% Arc, Surg-8 MIR1 40 2% 5% 0% 4% Arc, Surg-8 LN1 21 -1% 0% 4% 2% Black, Surg-3 MIR1 227 13% 3% 22% 7% Black, Surg-8 MIR1 114 -1% 2% 13% 7% Black, Surg-8 LN1 96 1% 3% 10% 7%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 Arc, Surg-3 MIR1 Arc, Surg-8 MIR1 Arc, Surg-8 LN1 Black, Surg-3 MIR1 Black, Surg-8 MIR1

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 98

Figure 13 . Plots of model errors in simulations of the surrogate - N O x 

### experiments carried out in the

UCR EPA chamber . Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Full Surg, Arc 111 -10% -10% -14% -14% Full Surg, Black 75 -19% -14% -8% -11% Non-Arom Surg, Arc 3 -1% 4% 15% 11% Non-Arom Surg, Black 23 -3% -2% 13% 8% SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 Full Surg, Arc Full Surg, Black Non-Arom Surg, Arc Non-Arom Surg, Black

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 99

Figure 14 . Plots of model errors in simulations of 6 -hour  ([O 3 

### ] - [NO]) against initial ROG surrogate

/NO x 

### ratio . formation and NO oxidation rates at the lower ROG/NO x 

### ratios has not been eliminated, and that the extent to which the bias is affected by ROG/NO x 

### ratios is essentially the same. This is observed in the blacklight as well as the arc light chamber experiments.

On the other hand, Figure 14 shows that if the aromatics are removed, the dependence of the bias on ROG/NO x 

### is in the opposite direction as seen with the full surrogate, with the model tending to overpredict reactivi ty more at lower ROG/NO x 

### ratios, and giving better predictions of the data at the higher ROG/NO x 

### conditions. This is true for both versions of the mechanism, but has been somewhat exacerbated as a result of the mechanism update

Overall, the evaluation with the experiments with mixtures indicate a slight degradation of model performance for the updated mechanism compared to SAPRC - 99, though this is not seen for all types of mixtures. Figure 7 , above shows a very slight (~5%) bias in the updated mechanism in simulating the mixture experiments when all are lumped together, with the bias being greater (~10%) in simulating initial NO oxidation and O 3 

### formation rates. However, when examining run types separately, one sees the biases vary with type of experiment, with some types of experiments having greater positive biases and some having greater negative biases, compared to SAPRC - 99.

The difference for the UCR EPA full surrog ate vs . non - aromatic surrogate at low ROG/NO x 

### conditions is suggestive, with the experiments with the aromatics having the distinct negative bias while those with aromatics removed having the bias in the opposite direction. But the evaluations of Full Surrogate (Surg-7 or Surg-8) Arc Lights Blacklights

Non-Aromatic Surrogate (Surg-NA), Blacklights

Surrogate /NOx Ratio (ppmC/ppm)([O3]-[NO])ModelError

-50% -25% 0% 25%

1 10 100 1000 SAPRC-99 SAPRC-07 -50%

-25% 0% 25%

1 10 100 1000

-25% 0% 25%

1 10 100 1000

### 100

the singl e compound or incremental reactivity experiments with the individual alkanes, alkenes, and aromatics, shown in figures in Appendix C and summarized on Table 23 above, do not indicate trends in biases with individual compounds that is consistent with this. The cause and significance of this problem is uncertain, and clearly this needs further study. Iti s important to note, however, the biases are not large compared to o verall run -to -run variability and characterization uncertainties in model simulations of environmental chamber experiments. **Mechanism Performance for Direct Reactivity Experiments** Figure 15 shows the model performance in simulating the direct reactivity experiments of Carter and Malkina (2002) for all the compounds for which useful direct reactivity data were obtained. The results for SAPRC - 99 are also shown. Except for benzene and toluene the results were very similar for the two mechanisms, with generally good fits being obtained for most compounds except for isooctane (2,2,4 -trimethylpentane) and ethyl acetate. This is as expected since the mechanisms for these compounds were not changed significantly. The reasons for the discrepancies for isooctane and ethyl acetate are unknown, and have not been resolved. Figure 15 shows that the new aromatics mechanisms do perform somewhat better in simulating the direct reactivities for benzene and toluene, though the direct reactivities of these compounds, and to a lesser extent 1,3,5 -trimethylbenzene, are still overpredicted. This can be attributed to the updated mechanism assuming direct OH formation, without NO to NO 2 

### conversions, in the ring opening pathways that do not involve  - dicarbonyl formation. However, the results suggest that actual total amount of NO to NO 2 

### conversion may still be less than assumed in this mechanism.

Figure 15 . Model performance in simulating the direct reactivity data of Carter and Malkina (2002 ).

0.0 0.5 1.0 1.5 2.0 2.5COEthanePropane(avg)n-Hexanen-Octane(avg.)n-Decanen-C12n-C13n-C14n-C16Iso-OctaneEthylAcetateMEKPropeneBenzeneToluene1,3,5-TM.BenzeneDirectReactivityMeasurement/kOH(RelativetoEthane) Experimental SAPRC-99 SAPRC-07

### 101 

### UPDATED REACTIVITY S **CALES** One of the major applications of the SAPRC mechanisms is calculation of ozone reactivity scales for V OCs, including the MIR scale that is used or being considered for use in regulatory applications (CARB 1993, 2000, 2006, 2007), and a maj or reason behind this mechanism update is to update these reactivity scales. The SAPRC - 99 mechanism was used to calculate MIR and other reactivity scales for many types of VOCs, with the latest update being that of Carter (2003a). That update includes reactivities for almost 780 types of VOCs, based on explicit or assigned mechanisms for ~560, and lumped molecule or mixture assignments for the rest. The listing included uncertainty codes for the reactivity estimates that may be potentially useful for regulatory applications or determining priorities for research. These scales, and their corresponding uncertainty classifications, have been updated as part of this project. **Methods** The methods, scenarios, and reactivity scales that were used in this reactivity scale update are the same as em

ployed previously for the SAPRC - 99 scales (Carter 2000a, 2003), and those references should be consulted for detail. Briefly this is based on the methods and scenarios originally developed by Carter (1994a,b), with slight modifications in the averaging methods as described by Carter (2000a). These are based on 39 single - day "base case" EKMA box model scenarios (EPA, 1984) derived by the EPA for assessing how various ROG and NO x 

### control strategies would affect ozone nonattainment in various areas of the country (Baugues, 1990). The conditions of these scenarios are summarized on Table 24 , and more details concerning the modeling inputs are given by Carter (1994b). The scenario conditions include specifications of initial concentrations and emissions sche dules for NO x 

### and total anthropogenic VOC emissions and also background O 3 

### , aloft VOCs, and initial and emitted biogenic VOCs (Bauges, 1990; Carter, 1994a,b). The scenarios as originally developed by Bauges (1990) do not specify the composition of the anthropogenic VOCs, and Carter (1994a) used a standard mixture of hydrocarbons derived by Je ffries (Jeffries et al (1989) from analysis of air quality data, with minor modifications as discussed by Carter (1994a,b). This is referred to as the "Base ROG mixture " in the subsequent discussion. This base ROG mixture was not modified for the SAPRC - 99 reactivity scale updates (Carter, 2000a, 2003a), and was also used in this update. Note that same base ROG mixture was used as the basis for deriving the "fixed paramet er" version of the SAPRC - 07 mechanism for airshed models, as discussed above. The composition of this mixture in terms of fixed parameter SAPRC - 07 lumped model species in given in Table 17 , above. The base case scenarios with the NO x 

### inputs as specified by Bauges (1990) were used to derive the updated "base case" reactivity scales, comparable to those given by Carter (1995a, 2000a) for SAPRC - 90 or SAPRC - 99. Because abs olute and even relative impacts of VOCs on O 3 

### formation are highly dependent on NO x 

### conditions that are highly variable in the base case scenarios, scenarios with adjusted NO x 

### inputs were derived to obtain scales that are more representative of standard conditions of conditions of NO x 

### availability. These are as follows:  The Maximum Incremental Reactivity (MIR) scale is derived from the scenarios where the NO x 

### inputs are adjusted to yield highest incremental reactivities (changes in O 3 

### caused by small VOC additions, divided by the amount of VOC added) of VOCs. Although the NO x 

### conditions yielding highest incremental reactivities tend to be the same for most VOCs, the sensitivity of O 3 

### formation to changes in total base ROG inputs was used to determine the NO x 

### levels corresponding to MIR conditions. T his represents relatively high NO x 

### conditions where, by definition, O 3 

### is most sensitive to changes in VOC emissions.

### 102

Table 24 . Scenarios used for reactivity assessment, with updated calculated maximum O 3 

### ,

Integrated OH, and MIR, MOIR, and EBIR NO x 

### inputs . Scenario Max O 3

(ppb) Max 8 - Hr Avg O 3 (ppb) ROG / NOx [a] Max Height (kM) ROG input [b] O 3 aloft (ppb) Int'd OH (ppt - mi n) Base MIR MOIR EBIR Averaged Conditions (Used for screening calculations and sensitivity studies) Max React (MIR) 179 117 3.70 1.8 15 70 121 Max O 3 (MOIR) 229 161 5.63 1.8 15 70 200 Eq. Benefit (EBIR) 213 166 8.86 1.8 15 70 200 Base Case (Used for MIR, MOIR, and EBIR scales) Atlanta, GA 173 127 7.25 3.54 5.37 7.66 2.1 12 63 198 Austin, TX 171 141 9.30 3.36 5.08 8.00 2.1 11 85 180 Baltimore, MD 318 196 5.15 3.90 5.92 10.04 1.2 17 84 171 Baton Rouge, LA 237 168 6.83 4.31 6.36 8.46 1.0 11 62 186 Birmingham, AL 239 198 6.94 2.71 4.09 6.26 1.8 13 81 204 Boston, MA 191 161 6.50 2.69 4.13 6.53 2.6 14 105 250 Charlotte, NC 139 123 7.79 1.80 2.78 3.86 3.0 7 92 207 Chicago, IL 286 230 11.63 4.29 6.39 9.75 1.4 25 40 176 Cincinnati, OH 196 145 6.38 3.29 5.05 9.01 2.8 17 70 208 Cleveland, OH 245 170 6.62 4.24 6.64 10.09 1.7 16 89 180 Dallas, TX 194 128 4.74 3.99 6.10 8.86 2.3 18 75 160 Denver, CO 197 132 6.33 4.88 7.37 11.37 3.4 29 57 140 Detroit, MI 237 168 6.82 3.64 5.55 9.85 1.8 17 68 224 El Paso, TX 178 130 6.59 4.49 6.96 9.70 2.0 12 65 136 Hartford, CT 167 140 8.39 2.74 4.26 7.09 2.3 11 78 213 Houston, TX 303 206 6.08 3.94 5.96 9.36 1.7 25 65 217 Indianapolis, IN 205 141 6.64 3.87 6.22 9.61 1.7 12 52 203 Jacksonville, FL 150 111 7.62 3.44 5.18 7.22 1.5 8 40 202 Kansas City, MO 152 120 7.09 2.95 4.59 8.34 2.2 9 65 221 Lake Charles, LA 289 211 7.42 3.46 5.01 6.91 0.5 7 40 235 Los Angeles, CA 566 401 7.59 5.11 7.75 11.08 0.5 23 100 136 Louisville, KY 204 148 5.53 3.10 4.77 7.17 2.5 14 75 248 Mem phis, TN 224 174 6.78 3.21 4.79 7.59 1.8 15 58 240 Miami, FL 129 108 9.63 2.71 4.19 6.09 2.7 9 57 178 Nashville, TN 162 134 8.05 2.46 3.74 5.79 1.6 7 50 224 New York, NY 371 293 8.09 4.59 6.41 9.54 1.5 39 103 161 Philadelphia, PA 237 157 6.18 3.98 6.00 9.44 1.8 19 53 213 Phoenix, AZ 271 189 7.58 4.87 7.61 12.98 3.3 40 60 155 Portland, OR 160 121 6.46 2.90 4.66 6.68 1.6 6 66 223 Richmond, VA 233 162 6.18 3.44 5.25 9.30 1.9 16 64 204 Sacramento, CA 198 136 6.59 3.73 5.75 8.89 1.1 7 60 200 St Louis, MO 311 194 6.08 4.55 6.93 11.51 1.6 26 82 167 Salt Lake City, UT 181 147 8.47 3.36 5.30 8.96 2.2 11 85 182 San Antonio, TX 124 90 3.92 2.85 4.42 6.11 2.3 6 60 173 San Diego, CA 188 142 7.09 4.54 6.86 9.63 0.9 8 90 141 San Francisco, CA 231 124 4.77 5.99 8.86 11.87 0.7 25 70 62 Tam pa, FL 219 141 4.36 3.32 4.93 6.71 1.0 8 68 192 Tulsa, OK 221 149 5.31 3.08 5.06 8.57 1.8 15 70 242 Washington, DC 274 198 5.32 3.06 4.59 7.22 1.4 13 99 225 [a] Ratio of initial + emitted anthropogenic reactive organic gas (ROG) input to initial + emitted NO x . Biogenic VOC input not included. [b] Initial + emitted anthropogenic VOC input, in units of millimoles m- 2

.

### 103

 The Maximum Ozone Incremental Reactivity (MOIR) scale is derived from the scenarios where NO x 

### inputs are adjusted to yield highest maximum O 3 

### concentrations. This represents NO x 

### conditions that are most favorable to O 3 

### formation. MOIR NO x 

### levels are generally about a factor of 1.5 lower than those yielding maximum incremental reactivities.  The Equal Benefits Incremental Reactivity (EBIR) scale is derived from scenarios where NO x 

### inputs are adjusted so that the reduction in O 3 

### caused by reducing base ROG inputs are the same as those caused by changing total NO x 

### inputs by the same percentage. This represents the lowest NO x 

### conditions where controls of VOCs are at least as effective as controlling NO x 

### ; since for lower NO x 

### levels NO x 

### controls are always more ef fective for reducing O 3 

### . EBIR NO x 

### levels are generally about a factor of 1.5 lower than those yielding maximum O 3 

### concentrations, or 2.3 times lower than MIR levels. Table 24 gives the NO x 

### levels that correspond to these various conditions of NO x 

### availability that were used to derive the MIR, MOIR, or EBIR scales. The incremental reactivities for those scales were averages of the incremental reactivities calculated for the 39 scenarios of the various types. The fixed parameter version of SAPRC - 07 with the base ROG mixture composition given in Table 17 was used to simulate the base c ases for the reactivity assessment scenarios used in this work. For the purpose of calculating incremental reactivities of individual compounds, model species were added to explicitly represent the compound, and also to represent the more reactive oxidation products if the "adjustable products" mechanisms were employed. For simulating reactivities of complex mixtures, lumped model species were added as indicated on Table 17 , above, with the mechanisms for the adjustable parameter species (ALKn, OLEn, and AROn) being derived based on the particular mixture being assessed. Note that as discussed by Carter (2008a) the impacts of the reactions of amines with HNO 3 

### under atmospheric conditions are very uncertain. This is because they are sensitive to atmospheric sources and other sinks of HNO 3 

### , which are highly variable and not determined for the reactivity assessment scenarios. For the purpose of deriving reactivity scales for regulatory applications, it is probably appropriate to use upper limit estimates of the ozone impacts of these compounds under conditions where they will have their highest impacts. For that reason, the atmospheric reactivities calculated for the amines are based on assuming that loss by reaction with HNO 3 

### is negligible. As discussed by Carter (2008a) if this reaction is important the magnitudes of the O 3 

### impacts of the amines could be lower by more than an order of magnitude. The incremental reactivity calculations were carried out by adding the amount of test compound or mixture such that the estimated amount reacted would be 0.05% the mole carbon of the base ROG input. The incremental reactivities were calculated change in final (i.e., maximum) O 3 

### concentrations in terms of total moles formed, divided by the moles of test compound or mixture added in the calculations. The incremental reactivities are then converted from mole to mass basis by using the molecular weights for O 3 

### and the test VOCs . **Results Predicted Ozone Formation in the Scenarios**  Before presenting the incremental reactivity results, it may be of interest to show the model predictions of O 3 

### formation in the various scenarios used for reactivity assessment. The maximum O 3 

### fo rmed in the base case (unadjusted NO x

### ) scenarios are tabulated in Table 24 , and Figure 16 shows predicted maximum O 3 

### levels for all scenarios used, plotted against total ROG inputs, which gives a

### 104

Figure 16 . Plots of maximum O 3 

### concentrations calculated for the various scenarios used for

reactivity assess ment against the initial ROG levels in the scenarios.

measure of the total amount of pollution in the scenario. As expected the O 3 

### levels correlate with the total amount of ROG input, though the correlation is not perfect, indicating the importance of other factors such as dilution, etc. As also expected (and by definition) the O 3 

### levels are highest for the MOIR scenarios, and in all cases are the lowest for the MIR scenarios. Note that some scenarios have O 3 

### levels as high as 500 ppb or more, which are m uch higher than now occurs in urban areas in the United States. This suggests that the scenarios should be updated to reflect present conditions. However, updating the scenarios for reactivity assessment was beyond the scope of this project. Figure 17 shows the changes in O 3 

### formation in the various scenarios predicted using this updated vers ion of the mechanism, compared to those calculated previously using SAPRC - 99. Figure 17 a shows the differences when the NO x 

### levels in the MIR, MOIR, and EBIR scenarios are adjusted separately for each mechanisms to yield the corresponding reactivity characteristics, while Figure 17 a shows the differences when the NO x 

### levels are not adjusted, i.e., when the SAPRC - 99 MIR, MOIR or EBIR NO x 

### levels are used in the SAPRC - 07 calculations. (The NO x 

### levels, and therefore the mechanisms differences, are the same in the base case calculations shown on both plots.) Itc an be seen that if the NO x 

### levels are adj usted to yield the same reactivity conditions, the changes in O 3 

### predictions resulting from the mechanism update varies from scenario to scenario, ranging from a ~10% increase to a ~5% increase, though for most scenarios the update causes a decrease in predicted O 3 

### , by about 5% on average. F or a given type of scenario the decrease tends to be correlated with the ROG/NO x 

### ratio, with the decrease being largest at the lowest ROG/NO x 

### ratios. However, the mechanism change caused a ~5 - ~1 5% decrease in the NO x 

### levels that yielded MIR, MOIR, or EBIR levels, so the results shown on Figure 17 a do not reflect the same NO x 

### levels. I f the NO x 

### levels are hel d constant, the changes caused by the update have a much more consistent dependence on ROG/NO x 

### ratio, and also larger changes for the MIR scenarios and smaller changes for the EBIR scenarios. This is consistent with the fact that O 3 

### sensitivities to mechanism differences are 0.0 0.1 0.2 0.3 0.4 0.5 0.6

0 10 20 30 40

ROG Input (millimoles C/m2)MaximumO3(ppm)(SAPRC-07) Base MIR MOIR EBIR Avg. Cond

### 105

Figure 17 . Change in maximum O 3 

### concentrations in the scenarios used for reactivity assessment,

calculated using SAPRC - 07 compared to SAPRC - 99 . greatest at the lowest ROG/NO x 

### ratios (e.g., MIR), and simulations become much less sensitive as the higher ROG/NO x 

### ratios (EBIR). O 3 

### reductions of up to ~20% are seen for the MIR scenarios with the lowest ROG/NO x 

### ratios, while the changes for most of the EBIR scenarios are less than 5 %. **Updated Ozone Reactivity Scales** Table B - 1 in Appendix B gi ves the results of the MIR, MOIR, EBIR, and average base case reactivity scale calculation for all the VOCs currently represented in this version of the mechanism. This includes a total of 1029 types of VOCs, of which 722 have explicit mechanism assignments and the remainder are represented using the "lumped molecule" approach, and a total of 52 complex mixtures. (The latter include the 32 complex mixtures used in previous reactivity tabulations, using the same compositions as employed previously [Carter, 2000a and references therein, Carter et al, 1997e, 2000a, 2000e; Carter and Malkina, 2005, 2007], plus n ew or revised unspeciated alkane and aromatic mixture categories. The Unspeciated alkane mixtures assuming equal amounts of normal, branched, and cyclic alkanes 1 

### , and unspeciated aromatic mixtures derived as discussed by Carter and Malkina [2005].) The tab le indicates whether the VOC is represented explicitly, and if so whether its reactivity was calculated using adjusted product mechanisms, whether the VOC was represented using the lumped molecule method, or whether the reactivities are given for complex mixtures. Molecular weights, carbon numbers, and (where applicable) CAS numbers are also given in the table. The incremental reactivities in the MIR scale are of greatest interest because this is the scale that is most often used or proposed for use in regulatory and other applications. Figure 18 shows a plot of the 1 

### This differs from previous tabulations where the unspeciated alkane mixtures had the normal alkanes excluded, on the theory that they could be identified in GC analyses. Therefore, th e new unspeciated categories are appropriate mainly for when no analytical data are available. If analytical data are available, the correspond BR - Cnn and CYC - Cnn should be used for the corresponding unspeciated and cyclic alkane constituents, with equal amounts being used if the cyclic vs. branched ratio is unknown.

(a) M IR, M OIR, EBIR NOx Adjusted (b) M IR, M OIR, EBIR NOx same as SAPRC-99

ROG / NOx Ratio

-20% -15% -10% -5% 0% 5%

0 4 8 12 Base MIR MOIR EBIR Avg. Cond -20% -15% -10% -5% 0% 5%

0 4 8 12ChangeinMaximumO3(SAPRC-07-SAPRC99)/SAPRC-99

### 106

incremental reactivities in the updated scale against those in the latest SAPRC - 99 scale provided by Cart er (2003a). The 1:1 and  30% lines are also shown. The average change (excluding the 13 outliers where the change was greater than 50%) in the MIR's was - 8%, and the average absolute magnitude of the change (again excluding the outliers) was 11%. The chang e was less than 30% for approximately 96% of these VOCs. The MIR for the base ROG mixture, which is used as the standard for relative reactivity scales, decreased by about 3%. If this is taken into account, the average change in relative MIR values would b e approximately - 5%, excluding the outliers. The compounds whose incremental reactivities in the MIR scale changed by more than 30% are listed in Table 25 . The tabl e also indicates the probable reasons for the changes for those with the greatest changes. Excluding 3 - methoxy - 1 -butanol, where the SAPRC - 99 mechanism had a factor of 10 error in the OH rate constant, the greatest changes were for halogenated compounds bec ause of the higher estimated photolysis rates for the chloroaldehyde and chloroketone products predicted to be formed, and for amines, for which new mechanisms were derived based on new chamber data by Carter (2008a). **Updated Uncertainty Estimates** The reac tivity tabulation in Table B - 1 in Appendix B gives updated uncertainty classifications for the various types of VOCs and other information that may be useful in this regard. This includes an indication of the availability of environmental chamber data to evaluate the mechanism for the compound, and the comprehensiveness of the data for this purpose, and also estimates of likely biases in the reactivity estimates, if known. The uncertainty and other codes that are used for this purpose are given and described in footnotes to Table B - 1 .

Figure 18 . Plots of incremental reactivities in the MIR scale computed using the updated mechanism

against those reported previously by Carter ( 2003a). -5 0 5 10 15 20

-5 0 5 10 15 20 SAPRC-99SAPRC-07 Represented Compounds 1:1 and +/- 30% lines Base ROG Mixture Incremental Reactivity in MIR Scale (gm O3 / gm VOC)

### 107

Table 25 . List of compounds and mixtures whose reactivities in the MIR scale c hanged by more

than 30% . Compound MIR (gm O 3 

### / gm VOC) Probable Reason [a] Old New Change 3 - Methoxy - 1 -butanol 0.97 3.87 300% 1 2 - (Chloromethyl) - 3 - chloropropene 3.13 7.00 123% 2 1,2 - Dibromoethane 0.046 0.102 119% 3 1,2 - Dichloroethane 0.098 0.21 119% 2 trans - 1,2 - Dichloroethene 0.81 1.70 110% 2 2 - Amino - 2 - methyl - 1 -propanol 4.75 0.25 - 95% 4 Dimethyl amine 9.37 3.17 - 66% 4 Mesityl oxide (2 - methyl - 2 -penten -4 - one) 17.37 6.51 - 63% 5 3,5,5 -trimethyl - 2 - cyclohexenone 10.58 4.63 - 56% 5 Propionic acid 0.79 1.22 55% Triethanolamine 2.75 4.21 53% 4 2,4 - Toluene diisocyanate - 0.133 - 0.065 - 52% Phenol 1.82 2.76 51% 6 1,1,2 - Trichloroethane 0.058 0.086 48% 4 Furan 16.54 9.15 -45% 7 2 - Methyl - 2,4 -pentanediol 1.03 1.45 41% CARB Hydrocarbon Bin 5 2.56 1.56 - 39% 8 Diethanol amine 4.05 2.47 - 39% 4 p -Xylene 4.24 5.84 38% Dichloromethane 0.066 0.041 - 37% Chloroform 0.034 0.022 - 37% Acetic acid 0.50 0.68 37% CARB Hydrocarbon Bin 20 1.49 0.95 - 37% 8 n -butyl bromide 0.60 0.82 36% 1,1,1 -trichloroethane 0.00 0.00 35% CARB Hydrocarbon Bin 3 2.52 1.63 - 35% 8 1,2 - Propylene glycol diacetate 0.94 0.61 - 35% CARB Hydrocarbon Bin 4 2.24 1.47 - 35% 8 p - diethyl benzene 3.36 4.43 32% CARB Hydrocarbon Bin 1 2.08 1.42 - 32% 8 1,1 - Dichloroethane 0.101 0.069 - 31% [a] Discussion of probable reasons for MIR change: 1 The OH radical rate constant used in SAPRC - 99 was found to be low by a factor of 10. 2 Chlorinated aldehyde and ketone products are now assumed to be much more photoreactive. 3 The approximate method used to represent bromine - containing compounds was changed. SAPRC - 99 used a highly approximate “placeholder” mechanism. SAPRC - 07 represents them using the mechanism for the corresponding Cl - containing compound. 4 New amine mechanisms developed. Note that amines without hydrogens on groups adjacent to amino groups are now estimated to be inhibitors, though their MIR values are still positive because of their NO x 

### removal characteristics. Note also that the ma gnitudes o f the amine MIRs could be significantly lower if loss of amines by reaction with HNO 3 

### is important. See Carter (2008a).

### Table 25 (continued)

108

5 These compounds are now represented by the model species used to represent the lumped C 5 

### isoprene product IPRD. The estimated mechanis ms used in SAPRC - 99, derived using the mechanism generation system, are now considered to be too uncertain to use. 6 Phenol is lumped with Cresols in SAPRC - 07 but was represented explicitly in SAPRC - 99. However, the change in MIR is well within the relatively large uncertainty of the mechanism. 7 Furan is now represented explicitly. Previously it was represented by m - xylene using the lumped molecule method. 8 The "old" value is from Kwok et al (2000), and were derived from correlations between MIR values and boiling points for various types of compounds. The "new" values are calculated using compositions derived from various compounds as discussed by Carter and Malkina (2005). Some of the differences may be due to the change in methodology, though for most b ins Carter and Malkina (2005) did not notice large differences between MIRs calculated using SAPRC - 99. Itis im portant to recognize that the uncertainty and bias estimates given on Table B - 1 are entirely subjective, and not based on any comprehensive sensitivity and unc ertainty analysis. This also does not take into the account that reactivities of some VOCs may be sensitive to environmental conditions or changes in the base mechanism, and may change if the base mechanism or scenarios are updated even if the mechanism fo r the VOC itself is unchanged. An analysis of such would clearly be useful.

### 109 

### SUMMARY AND RECOMMEN**DATIONS** This project was successful in accomplishing most of its objectives, particularly the primary objective of developing a complete update to the SAPRC - 99 mechanism that represents the current state of the science. However, some of the objectives of this project could not be accomplished or completed in the time frame for this project, and addressing these obj ectives need to be included among our recommendations for future research. In this section, we summarize the maj or accomplishments of this project and the results and conclusions that were obtained, followed by a summary of the obj ectives that could not be fully accomplished and our recommendations for future research. **Summary of Project Accomplishments** The maj or accomplishment of this project is the development of the SAPRC - 07 chemical mechanism and its associated reactivity scales that are documented in this report. Specific accomplishments, results, and conclusions of this project are summarized as follows. Rate constants updated . All the rate constants in the mechanism have been reviewed based on results of current evaluations, and updated as needed. This includes updates to the absorption cross sections and quantum yields for the photolysis reactions, where appropriate. The most recent IUPAC (2006) and NASA (2006) evaluations were used as the primary basis for updating the rate constants in the base mechanism and common organic products, the evaluations of Calvert et al (2000, 2002) were used for reactions relevant to alkenes (Calvert et al, 2002) and aromatics (Calvert et al, 2000), and the recent evaluations of Atkinson (1997), Atkinson and Arey (2003) and Calvert et al (2000, 2002) were use d for rate constants for individual VOCs. Other sources, including recent work in our laboratory on reactivity studies of specific compounds, were used as appropriate. Most of the rate constant changes were relatively small, but a few errors were found and corrected and some potentially significant changes occurred. Various uncertainty and sensitivity studies indicate that the rate constant for the OH + NO 2 

### reaction is particularly important, and based on the results of the recent NASA (2006) evaluation, th e rate constant for ground - level conditions increased by ~18%. This could result in somewhat lower O 3 

### predictions under some conditions (as indicated by results of box model simulations of ambient scenarios, discussed below), and probably contributed to the need to re - adjust uncertain parameters in mechanisms for some individual VOCs to be consistent with chamber data, as indicated below. Photolysis rates for some aromatic and isoprene oxidation products were increased by ~40% or more. The effects on the aromatics mechanism are compensated by other changes in the aromatics mechanisms, but the changes for i soprene may have an impact on airshed simulations, though the model performance in simulating available isoprene chamber data was not affected. However, the effects of the many changes that were made, taken as a whole, have not been fully assessed, other t han the limited number of box model simulations carried out in conjunction with updating the reactivity scale. Aromatics mechanisms reformulated . The mechanisms for the aromatic ring fragmentation reactions were reformulated to be more consistent with estimated explicit mechanisms that were derived as part of this project and to give predictions that are somewhat more consistent with "direct reactivity" results reported by Carter and Malkina (2002). These mechanisms incorporate much of the new information contained in the review of Calvert et al (2000), particularly in the representation of the ring opening products. However, although not as simplified and parameterized as the aromatic representation used in SAPRC - 99, the updated mechanisms are still highly simplified in many respects, and are not consistent with all of the available data given by Calvert et al (2000) and others, and some of the inconsistencies with available environmental chamber data still persist. The approach that was initially employed was to develop explicit versions of the mechanisms for representative aromatic hydrocarbons, and use these to derive more condensed, but chemically

### 110

reasonable, versions for airshed model calculations. Unfortunately, because of time constraints and other problems, the effort to develop explicit mechanisms that could account for reactivity differences among aromatic isomers could not be completed within the time frame available to this project. However, the explicit mechanisms were developed to the point where they did serve as the basis for the more condensed aromatics mechanism that is described in this report. The aromatic mechanism formulation developed for this project, though simplified in some respects, represents a much closer approximation to the expl icit mechanisms than SAPRC - 99, and serves a useful basis for future improvements in this area. As part of this effort, environmental chamber experiments were carried out with several furans, which were studied because these compounds are expected to form the same type of highly photoreactive fragmentation products as formed in the ring opening reactions of the alkylbenzenes, only in higher yields and without the complication of uncertain competing processes. Because the development of the explicit aromatics mechanisms based on these data could not be completed, the results of these experiments could not be incorporated in the final versions of the aromatics mechanisms developed for this work, other than in the mechanisms for the furans themselves. However, these data should be useful in future explicit aromatics mechanism development efforts. This explicit mechanism development effort, and the experiments carried out to support it, will be discussed in more detail in future reports. Chlorine chemistry added . The representation of chlorine chemistry has been added to the mechanism as an optional capability. The inorganic ClO x 

### and Cl atom reactions with common organic products have been added as an optional module of the base mechanism, and mechanisms for chlorine atom reactions were derived for all the explicit and lumped VOCs used in the version of the mechanism for ambient simulations and in the mechanisms used to calculate reactivities of individual chlorinated VOCs. The chlorine chemistry mechanisms were bas ed primarily on the recent IUPAC (2006) and NASA (2006) evaluations, various evaluations and studies of VOC + chlorine reactions, results obtained in our previous studies of chloropicrin (Carter et al, 1997a) and dichloropropenes (Carter and Malkina, 2007) , and also various estimation methods that were developed as part of this project. Inaddition to improving the ability of airshed models to simulate air quality in regions impacted by chlorine emissions, the representation of chlorine chemistry and associ ated updates has resulted in improved reactivity estimates for a number of VOCs of interest in California, including the pesticides chloropicrin and dichloropropenes (Carter and Malkina, 2007), and reduced uncertainties in reactivity estimates for chlorinated compounds in general. Mechanism generation system enhanced . The mechanism estimation and generation system is an important component of SAPRC - 99 that was used to generate fully explicit mechanisms for most of the non - aromatic VOCs, from which the more condensed mechanisms used in the model were derived. This system was enhanced in a number of respects for this project. Updated rate constants for the primary reactions of the individual VOCs with OH, O 3 

### , NO 3 

### , and O 3 

### P were incorporated in the system. The c apability of estimating and generating mechanisms for reactions of VOCs with chlorine atoms was added. The types of compounds and radicals whose reactions could be generated using the system was added to include to include species with more than one ring ( e.g., terpenes), species with more than one double bond, alkynes, and (to a limited extent) aromatics and unsaturated aromatic ring opening products. This was used to assist in the derivation of mechanisms for compounds that could not be processed previous ly, and was also useful in deriving portions of the updated aromatics and aromatic products mechanisms. Capability for adaptation to SOA predictions improved . Mechanisms for predictions of PM require an appropriate representation of the formation of the lo w volatility products that contribute to SOA, and how they depend on reactant conditions such as availability of NO x 

### . Recent environmental chamber studies (Odum et al, 1996, Hurley et al, 2001, Sato et al, 2004a, Presto et al, 2005, Doherty et al, 2005, So ng et al, 2005) indicate that SOA formation can change significantly with VOC/NO x 

### ratios. This is attributed to competing branching ratios in reactions of peroxy radicals with NO x 

### , HO 2 

### , and other

### 111

peroxy radicals. Hydroperoxides formed in the reactions of p eroxy radicals with HO 2 

### appear to be particularly important in this regard. Unfortunately, the SAPRC - 90 through SAPRC - 99 mechanisms, like CB4 and CB05, uses a chemical operator lumping approach to represent peroxy radical reactions that requires representing hydroperoxide formation in a highly condensed and approximate manner. This is because explicitly representing all the possible peroxy + peroxy reactions that may occur under low NO x 

### conditions requires an excessive number of reactions to represent proce sses that are unimportant to ozone formation, and the SAPRC - 90/CB4 chemical operator lumping approach results in a large reduction in mechanism size without significantly impacting predictions of O 3 

### and formation of organic product species that are important when ozone formation occurs. However, this is not as satisfactory an approximation when the model is being used to predict formation of secondary PM. Appropriately representing hydroperoxide formation under low NO x 

### conditions, and using separate species to represent low -volatility hydroperoxides, requires that a different method be used to represent peroxy radical reactions. An explicit approach, such as used in the MCM (Jenkin et al, 2003; Saunders et al, 2003), or a semi - explicit approach such as used in RADM - 2 (Stockwell et al, 1990) or RACM (Stockwell et al, 1997) mechanisms, would be satisfactory in this respect, but it requires adding a significant number of species and reactions to the mechanism, and is not compatible with the lumped parameter approach used in the SAPRC mechanisms to derived mechanisms for lumped species based on the mixtures of compounds they represent (Carter, 1990, 2000a, 2000b; Adleman et al, 2005). A more computationally efficient approach would be desirable for most comprehens ive modeling applications. The SAPRC - 07 mechanism developed for this project addresses these problems by implementing an alternative chemical operator approach for peroxy radicals reactions that involves adding a much smaller number of species and reaction s to the mechanism, and is compatible with the SAPRC lumped parameter methods and software that has already been developed. With this method, hydroperoxide formation can be represented more explicitly, with separate lumped species formed from different com pounds based on considerations such as reactivity and volatility. Italso permits separate representation of organic nitrates formed in peroxy + NO reactions based on reactivity and volatility considerations, which was also difficult under the formulation used in SAPRC - 99 and CB4/05. Because development and evaluating a mechanism for prediction of SOA precursors is a maj or project that was well beyond the scope of this project, the initial version of SAPRC - 07 does not fully take advantage of the enhanced capabilities of this mechanism to represent formation of SOA precursors. It does include a separate model species to represent the low volatility hydroperoxides formed from aromatics, primarily as a means to illustrate this capability, but its ability to pre dict SOA chamber experiments has not yet been evaluated. However, this version serves as a useful starting point in this regard, and can be used in a much more straightforward way to develop models that more accurately predict how SOA formation varies with conditions of NO x 

### availability. Mechanisms for many types of VOCs added or improved . A maj or feature of the SAPRC mechanisms is the ability to separately represent the many hundreds of types of VOCs for reactivity assessments, toxics modeling or other app lications, and for deriving condensed mechanisms tailored for the specific mixtures of compounds that are present. The rate constants and mechanisms for the VOCs represented in SAPRC - 99 were updated for this project, and in some cases improvements were made for VOCs previously represented using more approximate methods. The number of types of VOCs with distinct mechanisms was increased by 23% from 585 to approximately 720, and the total number of VOC classes for which reactivity estimates could be derived (whether by explicit representation or using the "lumped molecule" approach 1 

### ) was increased by 22% from 873 to over 1050. Most of the increases in distinct mechanisms are for alkanes, alkenes, and oxygenates found in emissions inventories, whose mechanisms could be readily derived using the me chanism generation system, but also an increased 1 

### In the lumped molecule approach, the compound is represented by assuming it has the same impact, on a per - molecule basis, as another compound or mixture of compounds assumed to have similar reactivities.

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number of mechanisms were derived for more appropriate representation of the higher alkylbenzenes 1



### . Improved mechanisms are incorporated for halogenated compounds incorpo rating chlorine chemistry as discussed above, though most of these need to be experimentally evaluated. A few errors were found in SAPRC - 99 mechanism assignments that were corrected, the most significant being a factor of 10 error in the rate constant for 3 - methoxy - 1 -butanol. Although mechanisms and representations were changed for a large number of the compounds, the number of compounds with significant MIR changes was relatively limited. The MIR changes were less than 25% for 95% of the chemical classes, and only 12 compounds had changes of more than 50%. However, some compounds whose MIRs were not previously listed have regulatory reactivities estimated using only "upper limit" methods (Appendix D in Carter, 2000a), so the addition of new compounds to the reactivity list may in some cases result in significantly different reactivities for regulatory applications. Updated mechanism evaluated against chamber experiments . The updated mechanism was comprehensively evaluated by comparing predictions with result s of all environmental chamber experiments used for SAPRC - 99 evaluation, plus the results of more recent UCR experiments, and also the TVA chamber experiments used by Carter (2004), the UNC experiments used in the RADM2, and SAPRC - 90 evaluations of Carter and Lurmann (1990, 1991). The results of this evaluation can be summarized as follows: For some compounds it was found that re - adjustments to some of the uncertain mechanistic parameters had to be made to obtain mechanism performance comparable to SAPRC - 99 . This is apparently because changes to the base mechanism resulted in changes in parameter values that gave best fits to the data. This included primarily re - adjustments to overall nitrate yields in peroxy + NO reactions for VOCs where these are uncertain , but also the radical yields in some ozone + alkene reactions could be increased to values that are somewhat more consistent with, but still lower than, results of laboratory studies of these reactions (e.g., see Carter, 2000a, Pinho et al, 2006). These adjustments were incorporated in the updated mechanism. In general, the model performance of the updated mechanism in simulating experiments for individual compounds or types of VOCs was comparable to that for SAPRC - 99, with the overall bias for all single compound experiments, taken as a whole, being very low. Although maj or changes were made to the aromatics mechanism, the model performance in simulating the single aromatic and aromatic reactivity experiments did not change significantly. This can be attributed to the fact that for both SAPRC - 99 and SAPRC - 07, the yields or (in the case of SAPRC - 07) effective quantum yields of photoreactive aromatic ring - fragmentation products were adjusted to optimize fits to the data. However, the updated mechanism did perform somewhat better in simulating direct reactivity data or effects of added CO (Carter and Malkina, 2002; Carter, 2004), though the results were still not completely satisfactory. The model performance for simulating data for some types of compounds changed even though no changes were made to their mechanisms. Biases that were previously seen in model simulations in propylene and ethylene glycol (Carter et al, 2005a) and synthetic isoparaffinic mixtures (Carter and Malkina, 2005) were significantly reduce d. On the other hand, slightly increased positive biases were seen in simulations of effects for some types of compounds, such as the larger n - alkanes, on maximum O 3 

### yields in lower NO x 

### conditions. These results indicate that O 3 

### reactivity predictions, at least for chamber

1 

### In SAPRC - 99, the higher alkylbenzenes are represented using mechanisms derived for the methylbenzenes. The updated mechanism has separate model species that incorporates the increased rate constants for reaction on the larger alkyl substituents of the aromatic ring, higher estimated nitrate yields, and reactivity differences for o - , m - , p - , and 1,2,3 - , 1,2,4 - , and 1,3,5 - isomers.

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experiments, can be sensitive to changes in the base mechanism even if the mechanism of the VOC is not changed. One area of potential concern is that the mechanism update caused a slight increase in overall biases in model simulations of experiments with mixtures of VOCs, including those designed to simulate ambient conditions. For all such experiments, the average bias in the sim ulations of the O 3 

### formation and NO oxidation rates in the second hour of the experiments increased from 5% to 12%, and the biases in simulations of final O 3 

### formed and NO oxidized increased from 3% to 6%. However, when examining run types separately, one sees the biases vary with type of experiment, with some ty pes of experiments having greater positive biases and some having greater negative biases, compared to SAPRC - 99. These changes are small compared to the  30% variability of the fits overall, but because of the large number of such experiments (>1500 total) it may be statistically significant. The mechanism update also did not solve the problem, noted by Carter (2004) and Carter et al (2005b) that SAPRC - 99 had a consistent bias in underpredicting rates of O 3 

### formation and NO oxidation in surrogate - NO x 

### experiments carried out at relatively low NO x 

### levels in the new UCR EPA cham ber, with the bias decreasing at higher ROG/NO x 

### ratios. This bias still exists with the updated mechanism, with the dependence of ROG/NO x 

### ratios being approximately the same. Iti s interesting to note that the dependence of the bias on ROG/NO x 

### in experiments in this chamber is in the opposite direction when the aromatics are removed from the surrogate, suggesting that the problem may be related to the aromatics mechanism, both for SAPRC - 99 and SAPRC - 07. Mechanism implementation . The mechanism developed in this project was implemented for the box model calculations used for reactivity scale calculations, and the data files used in this implementation can serve as the basis for implementing in more comprehensive airshed models such as C MAQ or CAMx. Although there was insufficient time and resources remaining in this project to adapt the updated mechanism into such a model, the necessary data files and associated implementation documentation are being made available at the project web sit e at http://www.cert.ucr.edu/~carter/ SAPRC. The types of data and files formats provided are similar to those used when distributing SAPRC 99, which has been successfully implemented into various models. However, we will continue to provide guidance to mo delers in implementing this mechanism, as needed. An important part of mechanism implementation is providing assignments of the many chemical categories used in speciation profiles for emissions inventories to the model species used in the mechanism. As part of this project, the emissions speciation database previously developed to provide a comprehensive and consistent speciation approach for the SAPRC - 99, RADM2, CB4, and CB05 were updated to include SAPRC - 07 as one of the optional mechanisms (Carter, 2008 b). At present, only the fixed -parameter version of SAPRC - 07 is implemented. Work on updating the system for the variable parameter version is planned, and when completed will be made available at the SAPRC mechanism web site noted above. Reactivity scales updated . The updated mechanism developed for this project was used to calculate MIR and other reactivity scales for all the ~780 types of VOCs for which reactivities values were provided on the most recent SAPRC - 99 update (Carter, 2003a), plus ~285 additi onal types of VOCs that have been added as part of this update. Uncertainty classifications were also updated as part of this work, and an additional code, indicating the estimated likely bias of the reactivity value (if known) was added. Although as indic ated above the number of VOCs for which large changes in MIR values is relatively limited, the MIR values changed by more than 5% for a maj ority (56%) of the VOCs whose MIRs were tabulated previously. Iti s recommended that these be used to supercede the reactivity values distributed previously (Carter, 2000a, 2003a). Preliminary assessment of impacts of updates on predictions of ambient ozone . Although this mechanism has not yet been implemented in comprehensive airshed models, the results of the box model simulations carried out in conjunction with the reactivity scale update provides some indication of how

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the mechanism update may affect predictions of ambient ozone. These are one - day of 39 simplified EKMA model scenarios designed to represent O 3 

### formatio n in 39 areas in the United States in the late '80's (Baugues, 1990), with NO x 

### levels adjusted to represent various conditions of relative NO x 

### availability that are relevant to VOC reactivity (Carter, 1994a). The results indicate that the mechanism update causes changes in maximum ozone concentrations ranging from a ~10% decrease to a ~5% increase, with the predicted O 3 

### decreasing by about 5% on average. F or a given type of scenario, the decrease tends to be correlated with the ROG/NO x 

### ratio, with the decrease being largest at the lowest ROG/NO x 

### ratios. However, this is not necessarily the case if the NO x 

### levels are varied with the other scenario conditions held constant, which means that the ROG/NO x 

### ratio is not the only factor determining how the mechanis m update changes predictions of O 3 

### formation in ambient scenarios. Overall, this suggests that it is more likely than not that the mechanism updates will cause slight decreases in predicted ambient O 3 

### , though this may not be true for all areas or scenario s. However, the box models used in the reactivity assessment calculations are highly simplified representations of ambient conditions, and comprehensive models are needed to fully assess the impacts of this update on ambient O 3 

### predictions, and also on pre dictions of effects of control strategies. **Recommendations** Although the accomplishments of this project were significant, there were some objectives of this project that could not be met within the time and resource constraints available for this project , and there areas where work is needed that were beyond the scope of the project as proposed. These objectives are still important, so the first recommendation resulting from this project is that work be carried out to address these objectives. These and other recommendations are summarized below. Aromatics Mechanisms . Although the reformulated aromatics mechanisms developed in this work represent an improvement over SAPRC - 99 in terms of representation of the actual chemistry expected to be involved, they s till contain significant simplifications and approximations, and are not fully consistent with all recent laboratory results. A considerable effort was expended in this project in an attempt to develop explicit or near - explicit mechanisms that could predic t reactivity differences in aromatic isomers (such as indicated in the chamber data of Carter et al, 1997a), but because of time constraints this could not be completed, and the preliminary explicit mechanisms were used as a basis for generalized mechanisms for aromatics that is incorporated in the current SAPRC - 07. This explicit mechanism development work, and the environmental chamber experiments with furan carried out to support this effort, will be described in more detail in future reports once more progress can be made in this area. As indicated above, the reformulated aromatics mechanisms gave somewhat improved performance in simulating the direct reactivity results of Carter and Malkina (2002), and also somewhat improved performance in simulating the effects of CO when added to aromatic - NO x 

### experiments (Carter, 2004). However, the performance, though improved, was still not entirely satisfactory in these regards, since direct reactivity was still somewhat overpredicted, and the effects of CO addition was still underpredicted. In addition, the problem of underpredicting O 3 

### at low ROG/NO x 

### ratios and low NO x 

### levels (as noted by Carter, 2004), which is attributed to problems with the aromatics mechanisms, has not been resolved. Therefore, although progre ss has been made, work on the aromatics mechanisms is still needed. Chlorine and Other Halogen Mechanisms . Significant progress was made in improving the representation of chlorine chemistry and chlorine - containing compounds, but more work is needed in thi s area. Because of limitations in the mechanism generation system's ability to estimate reactions of chlorine - containing alkoxy radicals, the system could not derive complete mechanisms for the reactions of chlorine atoms for the alkenes without having to make explicit assignments for these radicals as required. Because this is a time - consuming process, chlorine mechanisms could only be derived for the

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most important or representative alkenes, with the mechanisms for the others being approximated based on these results. This is probably not a major problem for most airshed and reactivity calculations, but is a limitation of the present system. A more significant problem is the fact that mechanism evaluation and reactivity data is available for only a limited number of chlorinated compounds, and the limited data that exist suggest that halogen containing oxygenated products of these compounds may be considerably more reactive than the model species used to represent the oxygenated products of the unhalogenated compounds (see, for example, Carter and Malkina, 2007). Although the data for chloropicrin and the 1,3 - dichloropropenes (Carter and Malkina, 2007) are reasonably well simulated by the current mechanism, the simulations of the experiments with trichloroethylene (Carter et al, 1996a) are not as satisfactory in some respects. Therefore, more data and mechanism development work is needed on individual chlorinated compounds and their oxidation products. A similar effort is needed for adding bromine chemistry and reducing uncertainties in reactivity estimated for bromine - or iodine - containing compounds, but this was beyond the scope of this project. Such compounds are also present in emissions inventories, and bromine or iodine chemistry may need to be represente d in some ambient scenarios. The few bromine - containing compounds representing in the current mechanism are approximately represented using the mechanisms for the corresponding chlorine containing compounds, but the biases introduced by this representation are highly uncertain, and iodine containing compounds are not currently represented in this mechanism. 1 

### Work in this area is needed if these compounds, or non - chlorine halogen chemistry, are determined to be important. Mechanisms for Amines. Although estimated mechanisms for amines were developed and to some extent evaluated as part of the study of Carter (2008a), significant uncertainties remain concerning their atmospheric ozone impacts. The largest uncertainty concerns the extent to which emitted amines are available for atmospheric reaction, and which is removed from the gas phase due to gas -phase reaction with HNO 3 

### or to heterogeneous processes. Atmospheric reactivity estimates vary by over an order of ma gnitude depending on what assumptions are made c oncerning removal by reaction with HNO 3 

### . The current reactivity values for amines are based on assuming that removal by reaction with HNO 3 

### is not important, in order to obtain upper limit ma gnitude ozone impact estimates. But use of these upper limit ma gni tude estimates may not be appropriate for all regulatory applications. The current mechanisms also do not correctly predict the effects of reactive amines on O 3 

### formation under low NO x 

### conditions, even if the amount present is adjusted to optimize model fi ts to initial rates of NO oxidation and O 3 

### formation. However, that uncertainty probably does not affect MIR predictions. Therefore, the amines mechanisms given here are much more uncertain than those given for most other VOCs, and more data, with improved analytical methods, and better characterization of sources and sinks of HNO 3 

### and amine salts in the atmosphere, are needed to reduce uncertainties for mechanisms and ozone impact estimates for amines. Mechanism Generation System . As discussed by Carter (2000a), the mechanism generation system incorporates a large number of estimation methods for alkoxy, peroxy, and other radical reactions that serve as the basis for the full oxidation mechanisms that are derived. These are based on various estimation methods and a large body of data for individual reactions that were available up to the time SAPRC - 99 was developed. Although an objective of this project was to update these radical reaction estimation methods based on any new data or theories that may have become available since then, because of time constraints we were unable to carry out these updates as part of this project. Although there is no indication that significant changes or updates to this system are needed, and in general the system has performed reasonably well for the types of compounds it is designed to represent, the predictions of the system is an integral part of the current SAPRC mechanisms, and updating its assignments should be included as part of the next comprehensive mechanism update effort. 1 

### Work on methyl iodide is being carried out under separate funding, and a mechanism for this compound and iodine species may be included in a future update.

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As indicated above, the lack of estimation assignments for reactions of halogenated radicals makes generation of most chlorine + alkene reactions difficult, and methods for estimating more of such reactions need to be implemented to permit full incorporation of chlorine chemistry for unsaturated VOCs. Estimation assignments, or heat of formation estimates needed to support the existing estimation methods, are also lacking or unreliable for many types of radicals formed in aromatic systems or other systems with multiple double bonds, limiting the utility of the system for development of explicit mechanisms for aromatics. Although progress was made in this project to adapt this system to be more useful in mechanism development for such compounds, it h as not yet evolved to the point where it can used to derive complete or reliable mechanisms for actual implementation in airshed models. Further work in this area, and expanding its capabilities to other types of compounds, would clearly be useful, and ultimately aid mechanism development and reactivity estimates for a wider variety of VOCs than currently possible. Adaptation to SOA Predictions . As discussed above, the initial version of SAPRC - 07 documented in this report does not fully take advantage of th e enhanced capabilities of this mechanism to represent formation of low volatility SOA precursors and how they depend on NO x 

### conditions. Work in this area is clearly the next step in developing improved models for secondary PM formation that can predict ho w PM formation varies with chemical conditions. Although the chemistry and physics of SOA formation is complex and much long -term research is needed, significant advances can be made in the short term to enhance SAPRC - 07, and its associated mechanism generation system, to take better advantage of the capability of this mechanism for SOA predictions. This could include the following.  Adding new lumped organic product model species to represent compounds of low volatility. This would include new model species for low volatility hydroperoxides (besides those formed from aromatics) and organic nitrates, as well as those formed in the oxidations in the presence of NO x 

### such as those represented in current PM models  Implementing methods to estimate product volati lity based on structure in the mechanism generation system, and using these to lump the products formed in the fully explicit generated mechanisms into the appropriate low volatility model species. In principle, this would result in generations of mechanis ms for predicting SOA as well as O 3 

### reactivity.  Evaluating the enhanced mechanisms' predictions of SOA using available environmental chamber data where PM measurement data are available. There is an increasing body of environmental chamber data suitable for this purpose, being generated at our laboratories and elsewhere that can be used for this purpose.  Conducting environmental chamber experiments with PM measurements suitable for testing predictions of the enhanced mechanism that cannot be evaluated with available data. A priority would be to evaluate the predictive capability of the mechanism generation system in this regard, and to determine which parameterization and volatility lumping approaches are most consistent with the data for the widest variety of compounds. The current mechanism does include a separate model species to represent the low volatility hydroperoxides formed from aromatics, primarily as a means to illustrate this capability, but its ability to predict SOA chamber experiments has not yet been evaluated. However, this version serves as a useful starting point in this regard, and will therefore allow a much more straightforward approach to develop models that more accurately predict how SOA formation varies with conditions of NO x 

### availabi lity. Once adapted and evaluated as indicated above, the enhanced PM mechanism would need to be implemented in actual airshed models and evaluated against ambient data. Itc ould also serve as a basis for deriving SOA reactivity scales for VOCs, should that be of interest in regulatory applications (Seinfeld et al, 1999).

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Mechanism Performance Issues . Although the updated mechanism simulates the available environmental chamber database reasonably well, the results of the mechanism evaluation carried out for this project indicated several potential problems that need to be investigated. The fact that the mechanism update caused slightly increased biases in simulations of experiments with various mixtures is an area of concern. The statistical significance of these small biases needs to be assessed, and an analysis of their potential sources needs to be carried out. The tendency of the mechanism to underpredict O 3 

### at low ROG/NO x 

### ratios is clearly statistically significant, and has not been resolved with this update. The experiments with the individual compounds do not clearly point to any specific compound or group of compound whose mechanism is causing the problems, and suggest that this is due to some change in the base mechanism. A related issue is the fact th at changes to the base mechanism have caused changes in model performance in simulations of experiments with compounds or mixtures whose mechanisms have not changed, with reduced biases for some glycols and isoparaffinic alkane mixtures, and slightly incre ased biases for some other compounds. Assessing the mechanism performance issues with mixtures, and the effects of base mechanism changes on evaluation results for individual compounds, will probably require more in - depth analysis of mechanism behavior than previously has been carried out. Application of existing uncertainty and sensitivity analysis and process analysis methods may be useful in this regard, but probably new analysis methods will need to be developed. The objective would be to determine what uncertain portions of the base mechanisms may be introducing biases in the model evaluations, the extent to which these biases may be significant when the mechanism is used in ambient simulations or control strategy assessments, whether adjustments of these uncertain areas to reduce these biases may be justifiable, and if so what adjustments should be made. This is an area where original research is needed. Mechanism Evaluation Database . Although the updated mechanism includes what we believe are improved estimates for a number of types of VOCs for which no data is available, in many cases the reliability of these estimates needs to be experimentally tested. This is particularly true for amines and those halogenated compounds for which no environmental chamber reactivity data are available. Environmental chamber reactivity studies of representatives of these and other previously unstudied chemical classes are needed to reduce uncertainties in their mechanisms and associated reactivity estimates. The reactivity tabulations include uncertainty codes indicating those compounds for which experimental data are most needed. Although in general both SAPRC - 99 and SAPRC - 07 perform reasonably well in simulating results of experiments in the various UCR chambers and al so the TVA chamber, the performance is not as satisfactory in simulating the results of some of the older UNC outdoor chamber experiments used in the SAPRC - 90 and RADM2 evaluations (Carter and Lurmann, 1990, 1991). This is true in experiments with propene, toluene, o -xylene, and a number of mixture runs. On the other hand, the SAPRC mechanisms perform reasonably well in simulating results of more recent UNC chamber experiments that were used in the evaluation of Carter and Atkinson (1996), suggesting that s ome of the differences may be reduced if more recent datasets were employed. T he difference performance in the case of aromatics may be one source of difference between the SAPRC and Carbon Bond mechanisms, since the latter relied more heavily on the UNC chamber datasets during its development (Gery et al, 1988). This needs to be investigated. An improved evaluation of mechanism performance issues, discussed above, may be useful in this regard. In the meantime, we believe that characterization uncertaintie s and background problems for the indoor SAPRC and TVA chambers are significantly less than for the earlier UNC chamber experiments, and consequently the indoor chamber data are used as the primary means of mechanism evaluation. For many types of compounds , the primary dataset for mechanism evaluation consists of incremental reactivity experiments, in which the effect of adding the compound to simplified representative ambient mixtures is assessed. This provides the only useful mechanism evaluation dataset

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for com pounds that are not radical initiators 1 

### , and more closely approximates the environments where the VOC reacts than other types of experiments. However, model sensitivity calculations indicate that results of the currently available types of increment al reactivity experiments are much less sensitive to effects of secondary reactions of reactive organic products than is calculated for the atmosphere. This means that this aspect of the mechanism is not being adequately evaluated with the available datase t. Calculations indicate that experiments with higher overall radical levels, such as experiments with longer reaction times, higher light intensities, or various radical sources, are needed to improve mechanism evaluations in this respect. The current dataset of environmental chamber experiments is also not adequate for systematically evaluating model predictions of temperature effects on secondary pollutant formation. The UCR- EPA chamber is suitable for carrying out such experiments, and in fact the plan for this project included conducting a limited number of experiments with temperature varied. However, because of problems with the light source, only a limited number of such experiments could be successfully carried out, and the conditions are not yet adequately characterized for me chanism evaluation. Additional work in this area is still needed. Mechanism Adaptation . Because the mechanism development and evaluation was not completed until well after the project was scheduled for completion, there was insufficient time and resources remaining to implement this mechanism in any com prehensive airshed model. This work remains to be done, and as indicated above we will assist the model implementers in this regard as needed. This report, and the files and additional documentation that are being made available at the SAPRC mechanism web site at http://www.cert.ucr.edu/~carter/SAPRC should provide the information needed. In addition, there was also insufficient time and resources in this project to prepare a condensed version of the updated mechanism as discussed in the proposal for this project (Carter, 2003b). Although computer capabilities are continuing to increase, for some modeling applications a more condensed, and computationally efficient, mechanism may gi ve adequate predictions, and it may be more important to apply more of the available computer resources to other modules in the model, or to enhance spatial resolution. Therefore, a more condensed version of t his updated and evaluated mechanism is still needed. Preliminary versions of SAPRC - 07 condensed mechanisms have been developed (Carter, 2008c), but these mechanisms have not yet been finalized. In order to derive a condensed mechanism for representing comp lex mixtures in airshed model applications, it is necessary to use a standard "base reactive organic gas (ROG)" mixture to represent the mixture of anthropogenic VOCs emitted into ambient atmospheres to derive the parameters for the mechanism's lum

ped mode l species. Ideally this mixture should be derived for each scenario being modeled, and procedures and data files exist for doing this for the SAPRC - 99 me chanism (Carter, 2000b, Adleman et al, 2005; Carter, 2008b), which will be adapted to the updated mechanism in the future (Carter, 2008b). However, in practice modelers have preferred to continue to use the "fixed parameter" version of the mechanism, where the parameters for the lumped model species are derived using a standard mixture used for this purpose , and incorporated in the mechanism without change. Such a fixed parameter mechanism was developed as part of this work. The updated fixed parameter mechanism developed in this work employed the same standard base ROG mixture as used for the fixed -parameter version of SAPRC - 99 (Carter, 2000b), which is the base ROG mixture used in the original reactivity calculations of Carter (1994a). This mixture was derived by Jeffries (1989) from analysis of air quality data of Lonneman (1986), with minor modifications as discussed by Carter (1994a,b). Since advances have been made in analytical methods and emissions compositions have probably changed since the mid - 80's, this mixture is out of date and needs to be

1 

### Chamber experiment s with compounds without significant internal radical sources are dominated by uncertain and variable chamber effects unless other reactants are present to provide the radical initiation.

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updated. However, attempts to obtain a documented updated base ROG mixture from the CARB or EPA have been unsuccessful. Once such a mixture becomes available, the fixed parameter version of the mechanism should be updated accordingly. Reactivity Scales Update . The updated reactivity scales developed in this work can be considered to represent the state of the science in atmospheric chemistry, though as indicated above there are uncertainties and areas where further research is needed. However, updating the scenarios and reactivity calculation methodology was beyo nd the scope of this project, so the same scenarios and methodologies were used as employed by Carter (1994a). Evaluations carried out by the Reactivity Research Working Group (RRWG) indicate that this methodology could be improved in a number of respects (NARSTO, 2007), particularly the scenarios and modeling methods. At a minimum the scenarios should be updated to represent the range of conditions currently occurring in urban areas, and the derivation of the scenarios should be better documented. The mech anism developed in this work can then be used for calculating reactivity scales with scenarios and methodology updated as well as the mechanism. Research Priorities. The priorities for the recommended research discussed above depend on the time frame and the priorities of the funding agencies. In terms of use of the mechanism for modeling, the highest near -term priorities are adaptation of the mechanism for airshed models, implementing the emissions assignments, and developing and adapting the condensed ver sion of the mechanism. This work is presently unfunded, but is needed before this mechanism can be widely used. In terms of the reactivity scales, the highest near -term priority is probably reducing uncertainties concerning availabilities of amines to react in the gas phase, assuming that suitable experimental procedures to assess this can be developed. Improved reactivity estimates for other classes of compounds may become priorities in the near future, but as far as we are aware the amines is the greatest near -term concern for the CARB. In the medium term the highest priority is probably reducing the uncertainty in the gas -phase predictions of the mechanism in general. Even for applications where PM modeling is a priority, one needs a mechanism that can appropriately simulate gas -phase processes before it can be expected to appropriately simulate formation of secondary PM. In this regard, we recommend that priority be given for research aimed as assessing the existing discrepancies between model predictions and chamber data, discussed above under the heading "Mechanism Performance Issues," and uncertainty and process analyses aimed at relating these performance issues and associated uncertainties to ambient predictions of interest. This would aid in the deve lopment of effective research agendas for improving mechanism performance in priority areas, and obtaining the data (either environmental chamber or basic laboratory measurements) most needed to serve this objective. Regardless of the results of the proces s or performance analysis, it is clear that the mechanisms for aromatics remain an important uncertainty. However, breakthroughs in fundamental studies, perhaps using improved analytical methods that actually give reliable quantitative product yields, or development of improved theoretical methods that actually have predictive capabilities, are probably needed before additional mechanism update work and chamber studies may be useful. Medium and longer term research priorities should include support for expl oratory methods that might achieve the needed breakthroughs, even if there is some risk of failure. The priority for adaptation of the mechanism for PM modeling depends on the priority to the funding agency for predictive modeling of secondary PM and SOA. The CARB should use an integrated approach for developing improved mechanisms for gas -phase and PM formation processes, and building on the mechanism development effort they supported for ozone modeling, as discussed above under the heading "Adaptation to SOA Predictions" would be consistent with this approach. If the CARB decides instead to use another mechanism as the basis for PM and SOA predictions, then the priority becomes assuring that that mechanism performs sufficiently well in simulating gas -phase processes to reliably predict rates of formation of low - volatility PM precursors from gas -phase processes. At a minimum, that mechanism should also be suitable for ozone modeling.

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The work needed to improve the scenarios and methodology for reactivity ass essment should be given sufficient priority so that it is complete by the time the next reactivity scale update is due. Otherwise, we will continue to use the poorly documented EKMA scenarios that are already way out - ofdate, and this may eventually impact the credibility of the reactivity scales as a whole. Ideally this should be funded on a national level.

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### REFERENCES Adelman, Z. J. Vukovich, and W. P. L. Carter (2005): "Integration of the SAPRC Chemical Mechanism in the SMOKE Emissions Processor for the C MAQ/Models - 3 Airshed Model," Final report to American Chemistry Council Agreement No. 1846. Available at http://www.cert.ucr.edu/~carter /absts.htm#smokespr Alvarez, R. A. and B. Moore (1994): "Quantum Yield for Production of CH 3 

### NC in the Photolysis of CH 3 

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### Concentrations," Report on Interagency Agreement DW64936024 to EPA/NREL, Research Triangle Park, NC. Bandow, H. N. and N. Washida (1985a): "Ring - cleavage reactions of aro matic hydrocarbons studied by FT - IR spectroscopy. II. Photooxidation of o - , m - and p -xylenes in the NO x 

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### , and Cl Radicals," in "Biogenic Sulfur in the Environment," E. S. Saltzman and W. J. C ooper, Editors, ACS Symposium Series 393, Ame rican Chemical Society, Washington, DC. Baugues, K. (1990): "Preliminary Planning Information for Updating the Ozone Regulatory Impact Analysis Version of EKMA," Draft Document, Source Receptor Analysis Branch, Technical Support Division, U. S. Environmental Protection Agency, Research Triangle Park, NC, January. Becker, K. H., V. Bastian, and Th. Klein (1988): "The Reactions of OH Radicals with Toluene Diisocyanate, Toluenediamine and Methylenedianiline Under Simulated Atmospheric Conditions," J. Photochem. Photobiol A., 45 195 - 205.

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Becker, K. H., et. al., (1997): "OH initiated oxidation of VO C under variable NO x 

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–2035. Berndt, T. and O. Böge (2003): "Gas -phase reaction of OH radicals with phenol," Phys. Chem. Chem. Phys. 5, 342 - 350. Berndt, T. and O. Böge (2006): "Formation of phenol and carbonyls from the atmospheric reaction of OH radicals with benzene," Phys. Chem. Chem. Phys 8, 1205 - 1214. Bennett, P. J. and J. A . Kerr (1989): "Kinetics of the Reactions of Hydroxyl Radicals with Aliphatic Esters Studied Under Simulated Atmospheric Conditions," J . Atmos. Chem. 8, 87. Bethel, H. L., R. Atkinson, and J. Arey (2001): "Kinetics and Products of the Reactions of Selected Diols with the OH Radical," Int. J. Chem. Kinet. 33, 310 - 316. Bierbach A., Barnes I., and Becker K.H. (1992): Atmos. Environ. 26A, 813 . Bierbach A., Barnes I., Becker K.H. and Wiesen E. (1994) Atmospheric chemistry of unsaturated carbonyls: Butenedial, 4 - oxo - 2 -pentenal, 3 -hexene - 2,5 - dione, maleic anhydride, 3H - furan - 2 - one, and 5 - methyl - 3H - furan - 2 - one. Environ. Sci. Technol., 28, 715 - 729. Blitz, M. A., D. E. Heard, M. J. Pilling, S. R. Arnold and M. P. Chipperfield (2004): "Pressure and temperature - dependent quantum yields for the photodissociation of acetone between 279 and 327.5 nm," Geophys. Res. Lett., 31, L06111. Bloss, C., V. Wagner , A. Bonzanini, M. E. Jenkin, K. Wirtz, M. Martin - Reviejo, and M. J. Pilling (2005): "Evaluation of detailed aromatic mechanisms (MCMv3 and MCMv3.1) against environmental chamber data, Atmos Chem Phys, 5, 623 - 639. Brauers, T., B. Bohn, F. - J. J ohnen, F. Rohrer, S. Rodriguez Bares, R. Tillmann, and A. Wahner (2003): "The Atmosphere Simulation Chamber SAPHIR: a Tool for the Investigation of Photochemistry," Presented at the EGS - AGU - EUG Joint Assembly, Nice, France, April 11, 2003. See also http://www.fz -

juelich.de/icg/icg - ii/saphir/home. Bridier, I., F. Caralp, H. Loirat, R. Leschux, B. Veyret, K. H. Becker, A. Reimer, and F. Zabel (1991): "Kinetic and Theoretical Studies of the Reactions CH 3 

### C(O)O 2 

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### + M between 248 and 393 K and betw een 30 and 760 Torr," J. Phys. Chem., 95, 3594 - 3600 Calvert, J. G., R. Atkinson, J. A. Kerr, S. Madronich, G. K. Moortgat, T. J. Wallington and G. Yarwood (2000): "The Mechanisms of Atmospheric Oxidation of Alkenes," Oxford University Press, New York. Calvert, J. G., and J. N. Pitts, Jr. (1966): "Photochemistry," John Wiley and Sons, New York. Calvert, J. G., R. Atkinson, K. H. Becker, R. M. Kamens, J. H. Seinfeld, T. J. Wallington and G. Yarwood (2002): "The Mechanisms of Atmospheric Oxidation of Aromatic Hydrocarbons," Oxford University Press, New York.

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CARB (1993): "Proposed Regulations for Low - Emission Vehicles and Clean Fuels -- Staff Report and Technical Support Document," California Air Resources Board, Sacramento, CA, August 13, 1990. See also Appendix VIII of "California Exhaust Emission Standards and Test Procedures for 1988 and Subsequent Model Passenger Cars, Light Duty Trucks and Medium Duty Vehicles," as last amended September 22, 1993. Incorporated by reference in Section 1960. CARB (2000): "Initial Statement of Reasons for the Proposed Amendments to the Regulation for Reducing Volatile Organic Compound Emissions from Aerosol Coating Products and Proposed Tables of Maximum Incremental Reactivity (MIR) Values, and Proposed Amendments to Method 31 0, ‘Determination of Volatile Organic Compounds in Consumer Products’," California Air Resources Board, Sacramento, CA, May 5. CARB (2006): "Air Resources Board Reactivity Programs." Web page at http://www.arb.ca.gov/ research/reactivity/reactivity.htm. La st updated April, 2006 CARB (2007): "Architectural Coatings Program - Reactivity." Web page at http://www.arb.ca.gov/ coatings/arch/reactivity/reactivity.htm. Last updated January, 2007. Carl, S. A. and J. N. Crowley (1998): "Sequential two (blue) photon a bsorption by NO 2 

### in the presence of H 2 

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### at 295 K," J. Phys. Chem. A, 102, 8131 - 8141. Carter, W. P. L. (1990): "A Detailed Mechanism for the Gas - Phase Atmospheric Reactions of Organic Compounds," Atmos. Environ., 24A , 481 - 518. Carter, W. P. L. (1994a): "Development of Ozone Reactivity Scales for Volatile Organic Compounds," J. Air & Waste Manage. Assoc., 44, 881 - 899. Carter, W. P. L. (1994b): "Calculation of Reactivity Scales Using an Updated Carbon Bond IV Mechanism," Report Prepared for Systems Applications International Under Funding from the Auto/Oil Air Quality Improvement Research Program, April 12. Carter, W. P. L. (199 6): "Condensed Atmospheric Photooxidation Mechanisms for Isoprene," Atmos. Environ., 30, 4275 -4290. Carter, W. P. L. (2000a): "Documentation of the SAPRC - 99 Chemical Mechanism for VOC Reactivity Assessment," Report to the California Air Resources Board, Co ntracts 92 - 329 and 95 - 308, May 8. Available at http://cert.ucr.edu/~carter/absts.htm#saprc99 and http://www.cert.ucr.edu/~carter/ reactdat.htm. Carter, W. P. L. (2000b): "Implementation of the SAPRC - 99 Chemical Mechanism into the Models - 3 Framework," Repor

t to the United States Environmental Protection Agency, January 29. Available at http://www.cert.ucr.edu/~carter/absts.htm#s99mod3. Carter, W. P. L. (2003a): "The SAPRC - 99 Chemical Mechanism and Updated VOC Reactivity Scales, Updated and Corrected Data as of February 5, 2003," Available at http://www.cert.ucr.edu /~carter/reactdat.htm. Carter, W. P. L. (2003b): "Updated Chemical Mechanism for Airshed Model Applications," Research Proposal to the California Air Resources Board, October. Carter, W. P. L. (200 4): Evaluation of a Gas - Phase Atmospheric Reaction Mechanism for Low NO x 

### Conditions," Final Report to California Air Resources Board Contract No. 01 - 305, May 5. Available at http://www.cert.ucr.edu/~carter/absts.htm#lnoxrpt. Carter, W. P. L. (2007): "Inves tigation of the Atmospheric Ozone Impacts of Methyl Iodide," Final Report to Arysta LifeScience Corporation, Contract UCR- 07041867, July 31. Available at http://www.cert.ucr.edu/~carter/absts.htm#ch3irep.

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Carter, W. P. L. (2008a). "Reactivity Estimates for Selected Consumer Product Compounds," Final Report to the California Air Resources Board Contract 06 -408, February 19. Available at http://www.cert.ucr.edu/~carter/absts.htm#aminrep. Carter, W. P. L. (2008b): "Current Project Information Page: Development of an Improved Chemical Speciation Database for Processing Emissions of Volatile Organic Compounds for Air Quality Models," Web page available at http://www.cert.ucr.edu/~carter/emitdb/, updated May 27. Carter, W. P. L. (2008c): "Development of a Condense d SAPRC - 07 Chemical Mechanism," Draft Final Report to the California Air Resources Board, May 27. Once this report is finalized, it will be made available at http://www.cert.ucr.edu/~carter/SAPRC. Carter, W. P. L. (2009a): "Investigation of the Atmospheric Ozone Imp acts of Trans 1,3,3,3 - Tetrafluoropropene," Final Report to Honeywell International Inc. Contract UCR - 09010016, February 9. Available at http://www.cert.ucr.edu/~carter/absts.htm #ZEErept. Carter, W. P. L. (2009b): "Investigation of the Atmospheri c Ozone Impacts of 2,3,3,3 - Tetra fluoropropene," Final Report to Honeywell International Inc. Contract UCR- 09010016, June 2. Available at http://www.cert.ucr.edu/~carter/absts.htm #YFrept. Carter, W. P. L. (2009c): "Updated Maximum Incremental Reactivity S cale and Hydrocarbon Bin Reactivities For Regulatory Applications," Report to the California Air Resources Board, Ju ne 22. Available at http://www.cert.ucr.edu/~carter/SAPRC. Carter, W. P. L., R. Atkinson, A. M. Winer, and J. N. Pitts, Jr. (1982): "Experimental Investigation of Chamber - Dependent Radical Sources," Int. J. Chem. Kinet., 14, 1071. Carter, W. P. L., Dodd, M. C., Long, W. D. and Atkinson, R. (1984): Outdoor Chamber Study to Test Multi - Day Effects. Volume I: Results and Discus sion. Final report, EPA - 600/3 - 84 - 115. Carter, W. P. L. and R. Atkinson (1987): "An Experimental Study of Incremental Hydrocarbon Reactivity," Environ. Sci. Technol., 21, 670 - 679 Carter, W. P. L., and F. W. Lurmann (1990): "Evaluation of the RADM Gas - Phase Chemical Mechanism, " Final Report, EPA - 600/3 - 90 - 001. Carter, W. P. L. and F. W. Lurmann (1991): "Evaluation of a Detailed Gas - Phase Atmospheric Reaction Mechanism using Environmental Chamber Data," Atm. Environ. 25A, 2771 - 2806. Carter, W. P. L., J. A. Pierce, and I. L. Malkina (1992): "Investigation of the Ozone Formation Potential of Selected Volatile Silicone Compounds," Final report to Dow - Corning Corporation, November. Carter, W. P. L., J. A . Pierce, I. L. Malkina, D. Luo and W. D. Long (1993): "Environmental Chamber Studies of Maximum Incremental Reactivities of Volatile Organic Compounds," Report to Coordinating Research Council, Project No. ME - 9, California Air Resources Board Contract No. A032 - 0692; South Coast Air Quality Management District Contract No. C91323, Unite d States Environmental Protection Agency Cooperative Agreement No. CR - 814396 - 01 - 0, University Corporation for Atmospheric Research Contract No. 59166, and Dow Corning Corporation. April 1. Available at http://www.cert.ucr.edu/~carter/absts.htm#rct1rept Carter, W. P. L., D. Luo, I. L. Malkina, and D. Fitz (1995a): "The University of California, Riverside Environmental Chamber Data Base for Evaluating Oxidant Mechanism. Indoor Chamber Experiments through 1993," Report submitted to the U. S. Environmental Protection Agency, EPA/AREAL, Research Triangle Park, NC, March 20.

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Carter, W. P. L., D. Luo, I. L. Malkina, and J. A. Pierce (1995b): "Environmental Chamber Studies of Atmospheric Reactivities of Volatile Organic Compounds. Effects of Varying Chamber and Li ght Source," Final report to National Renewable Energy Laboratory, Contract XZ - 2 - 12075, Coordinating Research Council, Inc., Project M - 9, California Air Resources Board, Contract A032 - 0692, and South Coast Air Quality Management District, Contract C91323, March 26. Carter, W. P. L., D. Luo, I. L. Malkina, and J. A. Pierce (1995c): " Environmental Chamber Studies of Atmospheric Reactivities of Volatile Organic Compounds. E ffects of Varying ROG Surrogate and NO x 

### ," Final report to Coordinating Research Council, Inc., Project ME - 9, California Air Resources Board, Contract A032 - 0692, and South Coast Air Quality Management District, Contract C91323. March 24. Carter, W. P. L. and R. Atkinson (1996): "Development and Evaluation of a Detailed Mechanism for the Atmospheric Reactions of Isoprene and NO x 

### ," Int. J. Chem. Kinet., 28, 497 - 530. Carter, W. P. L., D. Luo, and I. L. Malkina (1996a): "Investigation of the Atmospheric Ozone Formation Potential of Trichloroethylene," Report to the Halogenated Solvents Indust ry Alliance, August. Available at http://www.cert.ucr.edu/~carter/absts.htm#tcerpt. Carter, W. P. L., D. Luo, and I. L. Malkina (1996b): "Investigation of the Atmospheric Ozone Formation Potential of t - Butyl Alcohol, N - Methyl Pyrrolidinone and Propylene Carbonate," Report to ARCO Chemical Corporation, July 8. Carter, W. P. L., D. Luo, and I. L. Malkina (1997a): "Environmental Chamber Studies for Development of an Updated Photochemical Mechanism for VOC Reactivity Assessment," final report to California Air Resources Board Contract 92 - 345, Coordinating Research Council Proj ect M - 9, and National Renewable Energy Laboratory Contract ZF - 2 - 12252 - 07. November 26. Available at Carter, W. P. L., D. Luo and I. L . Malkina (1997b): "Investigation of that Atmospheric Reactions of Chloropicrin," Atmos. Environ. 31, 1425 - 1439; See also Report to the Chloropicrin Manufacturers Task Group, May 19. Report available at http://www.cert.ucr.edu/~carter/ absts.htm#clpicrin. Carter, W. P. L., D. Luo, and I. L. Malkina (1997c): "Investigation of the Atmospheric Ozone Formation Potential of Acetylene," Report to Carbide Graphite Corp., April 1. Available at http://www.cert.ucr.edu/~carter/absts.htm#acetylr Carter, W. P. L., D. Luo, I. L . Malkina, S. M. Aschmann and R. Atkinson (19 97c): "Investigation of the Atmospheric Ozone Formation Potentials of Selected Dibasic Esters," Report to the Dibasic Esters Group, SOCMA, August 29. Carter, W. P. L., D. Luo, and I. L. Malkina (1997d): "Investigation of the Atmospheric Ozone Formation Pot ential of Toluene Diisocyanate," Report to Society of the Plastics Industry, December. Carter, W. P. L., D. Luo, and I. L. Malkina (1997e): "Investigation of the Atmospheric Ozone Formation Potentials of Selected Mineral Spirits Mixtures," Report to Safety- Kleen Corporation, July 25. Available at http://www.cert.ucr.edu/~carter/absts.htm#msrept. Carter, W. P. L., D. Luo, and I. L. Malkina (1999a): "Investigation of the Atmospheric Ozone Formation Potential of Para Toluene Isocyanate and Methylene Diphenylene Diisocyanate," Report to the Chemical Manufacturers Association Diisocyanates Panel, March. 8. Available at http://www.cert.ucr.edu/~carter/absts.htm#mdirpt Carter, W. P. L., D. Luo, and I. L. Malkina (1999b): ‘Investigation of the Atmospheric Impacts and Ozone Formation Potential of Styrene," Report to the Styrene Information and Research Center. March 10. Available at http://www.cert.ucr.edu/~carter/absts.htm#styrept.

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Carter, W. P. L. and E. C. Tuazon (2000): “Atmospheric Chemistry of Bromine Containing Compounds,” Report to the Brominated Solvents Consortium, September 27. Available at http://www.cert.ucr.edu/~carter/absts.htm#brreport. Carter, W. P. L., D. Luo, and I. L. Malkina (2000a): "Investigation of the Atmospheric Ozone Formation Potentials of S elected Branched Alkanes and Mineral Spirits Samples," Report to Safety- Kleen Corporation, July 11. Available at http://www.cert.ucr.edu/~carter/absts.htm#msrpt2. Carter. W. P. L., D. Luo and I. L. Malkina (2000b): "Investigation of Atmospheric Reactivitie s of Selected Consumer Product VOCs," Report to California Air Resources Board, May 30. Available at http://www.cert.ucr.edu/~carter/absts.htm#cpreport. Carter, W. P. L., D. Luo, and I. L. Malkina (2000c): "Investigation of the Atmospheric Ozone Formation Potentials of Selected Carbonates," Report to ExxonMobil Chemical Company, November 17. Available at http://www.cert.ucr.edu/~carter/absts.htm#carbonat. Carter, W. P. L., D. Luo, and I. L. Malkina (2000d): "Investigation of the Atmospheric Ozone Formation Potential of Dimethyl Sulfoxide," Report to Gaylord Chemical Corporation, August 21. Available at http://www.cert.ucr.edu/~carter/absts.htm#dmsorpt. Carter, W. P. L., D. Luo, and I. L. Malkina (2000e): "Investigation of the Ozone Formation Potentials of Exxsol® D95, Isopar - M®, and the Exxate® Fluids," Report to ExxonMobil Chemical Company, October 31. Available at http://www.cert.ucr.edu/~carter/absts.htm#exxprods. Carter, W. P. L. and I. L. Malkina (2002): "Development and Application of Improved Methods f or Measurement of Ozone Formation Potentials of Volatile Organic Compounds," Final report to California Air Resources Board Contract 97 - 314, May 22. Available at http://www.cert.ucr.edu/~carter/absts.htm#rmethrpt. Carter, W. P. L. and I. L. Malkina (2005): "Evaluation of Atmospheric Impacts of Selected Coatings VOC Emissions," Final report to the California Air Resources Board Contract No. 00 - 333, March 21. Available at http://www.cert.ucr.edu/~carter/absts.htm#coatrpt. Carter, W. P. L., I. L. Malkina, D. R . Cocker III, and C. Song (2005a): "Environmental Chamber Studies of VOC Species in Architectural Coatings and Mobile Source Emissions," Final Report to the South Coast Air Quality Management District Contract No. 03468, July 5. Available at http://www.cert.ucr.edu/~carter/absts.htm#scaqcham. Carter, W. P. L., D. R. Cocker III, D. R. Fitz, I. L. Malkina, K. Bumiller, C. G. Sauer, J. T. Pisano, C. Bufalino, and C. Song (2005b): "A New Environmental Chamber for Evaluation of Gas - Phase Chemical Mechanisms and Secondary Aerosol Formation", Atmos. Environ. 39 7768 - 7788. Carter, W. P. L. and I. L. Malkina (2007): "Investigation of the Atmospheric Impacts of Selected Pesticides," Final Report to the California Air Resources Board Contract 04 - 334, January 10. Available at http://www.cert.ucr.edu/~carter/absts.htm#pestrep. Chen, Y. and L. Zhu (2001). "The Wavelength Dependence of the Photodissociation of Propionaldehyde in the 280 - 330 nm Region," J.Phys.Chem.A 105, 9689 - 9696. Carter, W. P. L., W. S. Goliff, R. Atkinso n, J. Arey, and S. M. Aschmann (2010): "Investigation of Atmospheric Ozone Impacts of 3 - Methoxy- 3 - Methyl - 1 - Butanol," Final report to Kuraray, Ltd. Will be made available at http://www.cert.ucr.edu/~carter/absts.htm #MMBrept when completed. (Estimated compl etion February, 2010.) Christensen, L. K., J. Sehested, O. J. Nielsen, M. Bilde, T. J. Wallington, A. Guschin, L. T. Molina, and M. J. M olina (1998): "Atmospheric Chemistry of HFE - 7200 (C 4

### F 9 

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### Radicals,"J. Phys. Chem. A, 1998, 102, 4839 -4845

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Coquet, S. and P. A. Ariya (2000): "Kinetics of the Gas - Phase Reactions of Cl Atom with Selected C2

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### 135 

### APPENDIX **A . GENERAL MECHANI**  **SM LISTING TABLES**  This appendix contains the tables giving a complete listing of the base SAPRC - 07 mechanism, including the version with added chlorine chemistry, and also a listing of the fixed parameter version of the lumped mechanism for airshed mode ls. These tables are also available in electronic form in an Excel as discussed in Appendix D. Note that Table A - 3 is only available in electronic form. This is becau se of its size and the fact that the absorption cross - section and quantum yield are generally more useful in electronic form. Table A - 1 . List of model species used in the standard base SAPRC - 07 mechanism. The lumped

model species added for the fixed parameter lumped mechanism for airshed mo dels are also listed . Name Description Constant Species. O2 Oxygen M Air H2O Water H2 Hydrogen Molecules HV Light Active Inorganic Species. O3 Ozone NO Nitric Oxide NO2 Nitrogen Dioxide NO3 Nitrate Radical N2O5 Nitrogen Pentoxide HONO Nitrous Acid HNO3 Nitric Acid HNO4 Peroxynitric Acid HO2H Hydrogen Peroxide CO Carbon Monoxide SO2 Sulfur Dioxide Active Radical Species and Operators. OH Hydroxyl Radicals HO2 Hydroperoxide Radicals MEO2 Methyl Peroxy Radicals RO2C Peroxy Radical Operator representing NO to NO 2 

### and NO 3 

### to NO 2 

### conversions, and the

effects of peroxy radical reactions on acyl peroxy and other peroxy radicals. RO2XC Peroxy Radical Operator representing NO consumption (used in conjunction with organic

nitrate formation), and the effects of peroxy radical reactions on NO 3 

### , acyl peroxy radicals, and other peroxy radicals. MECO3 Acetyl Peroxy Radicals RCO3 Peroxy Propionyl and higher peroxy acyl Radicals BZCO3 Peroxyacyl radical formed from Aromatic Aldehydes MACO3 Peroxyacyl radicals formed from methacrolein and other acroleins.

### Table 1 (continued)

136

Name Description Steady State Radical Species O3P Ground State Oxygen Atoms O1D Excited Oxygen Atoms TBUO t - Butoxy Radicals BZO Phenoxy Radicals PAN and PAN Analogues PAN Peroxy Acetyl Nitrate PAN2 PPN and other higher alkyl PAN analogues PBZN PAN analogues formed from Aromatic Aldehydes MAPAN PAN analogue formed from Methacrolein Explicit and Lumped Molecule Reactive Organic Product Species HCHO Formaldehyde CCHO Acetaldehyde RCHO Lumped C3+ Aldehydes. Mechanism based on propionaldehyde ACET Acetone MEK Ketones and other non - aldehyde oxygenated products that react with OH radicals faster than

5 x 10 - 13 

### but slower than 5 x 10 - 12 

### cm3 

### molec - 2 

### sec - 1 

### . Mechanism based on methyl ethyl ketone. MEOH Methanol HCOOH Formic Acid CCOOH Acetic Acid. Also used for peroxyacetic acid. RCOOH Higher organic acids and peroxy acids. Mechanism based on propionic acid. COOH Methyl Hydroperoxide ROOH Lumped organic hydroperoxides with 2 -4 carbons. Mechanism based n -propyl

hydroperoxide. R6OOH Lumped organic hydroperoxides with 5 or more carbons (other than those formed following

OH addition to aromatic rings, which are represented separately). Mechanism based on 3 - hexyl hydroperoxide. RAOOH Organic hydroperoxides formed following OH addition to aromatic rings, which is

represented separately because of their probable role in SOA f ormation. Mechanism based on two isomers expected to be formed in the m-xylene system. GLY Glyoxal MGLY Methyl Glyoxal BACL Biacetyl CRES Phenols and Cresols. Mechanism based on o - cresol. NPHE Nitrophenols BALD Aromatic aldehydes. Mechanism based on benzaldehyde MACR Methacrolein MVK Methyl Vinyl Ketone IPRD Lumped isoprene product species. Mechanism based on that of Carter and Atkinson (1996). Aromatic unsaturated ring fragmentation products (see discussion of aromatic mechanisms) AFG1 Lumped photoreactive monounsaturated dicarbonyl aromatic fragmentation products that

photolyze to form radicals. AFG2 Lumped photoreactive monounsaturated dicarbonyl aromatic fragmentation products that

photolyze to form non -radical products

### Table 1 (continued)

137

Name Description AFG3 Lumped diunsaturatred dicarbonyl aromatic fragmentation product. Lumped Parameter Products PROD2 Ketones and other non - aldehyde oxygenated products that react with OH radicals faster than

5 x 10 - 12 

### cm3 

### molec - 2 

### sec - 1 

### . Mechanism based on CH 3 

### C(O)CH 2 

### CH 2 

### CH 2 

### OH, CH 3 

### C(O) - CH 2 

### CH(CH 3 

### )CH 2 

### OH, CH 3 

### CH 2 

### C(O)CH 2 

### CH 2 

### CH(CH 3 

### )OH, CH 3 

### CH 2 

### C(O)CH 2 

### CH 2 

### CH(OH) - CH 2 

### CH 3 

### , and CH 3 

### CH 2 

### CH 2 

### CH(OH)CH 2 

### - CH 2 

### C(O)CH 2 

### CH 3 

### (PROD2 - 1 through 5), each weighed equally. RNO3 Lumped Organic Nitrates. Mechanism based on CH 3 

### CH 2 

### CH(CH 3 

### )ONO 2 

### , CH 3 

### CH(OH)CH 2 

### -

CH 2 

### CH 2 

### ONO 2 

### , CH 3 

### CH 2 

### CH(CH 3 

### )CH(CH 3 

### )ONO 2 

### , CH 3 

### CH 2 

### CH 2 

### CH 2 

### CH 2 

### CH(ONO 2 

### )CH 2 

### OH, CH 3 

### CH 2 

### C(CH 3 

### )(ONO 2 

### )CH 2 

### CH(CH 3 

### )CH 3 

### , and CH 3 

### CH 2 

### CH 2 

### CH 2 

### CH 2 

### CH 2 

### CH 2 

### CH(ONO 2 

### ) - CH 2 

### CH 3 

### (RNO3 - 1 through 6), each weighed equally. Steady state operators used to represent radical or product formation in pero xy radical reactions. xHO2 Formation of HO 2 

### from alkoxy radicals formed in peroxy radical reactions with NO and

NO 3 

### (100% yields) and RO 2 

### (50% yields) xOH As above, but for OH xNO2 As above, but for NO 2 

### xMEO2 As above, but for MEO2 xMECO3 As above, but for MECO3 xRCO3 As above, but for RCO3 xMACO3 As above, but for MACO3 xTBUO As above, but for TBUO xCO As above, but for CO xHCHO As above, but for HCHO xCCHO As above, but for CCHO xRCHO As above, but for RCHO xACET As above, but for ACET xMEK As above, but for MEK xPROD2 As above, but for PROD2 xGLY As above, but for GLY xMGLY As above, but for MGLY xBACL As above, but for BACL xBALD As above, but for BALD xAFG1 As above, but for AFG1 xAFG2 As above, but for AFG2 xAFG3 As above, but for AFG3 xMACR As above, but for MACR xMVK As above, but for MVK xIPRD As above, but for IPRD xRNO3 As above, but for RNO3 zRNO3 Formation of RNO3 in the RO 2 

### + NO, reaction, or formation of corresponding non -nitrate

products (represented by PROD2) formed from alkoxy radicals formed in RO 2 

### + NO 3 

### and (in 50% yields) RO 2 

### + RO 2 

### reactions. yROOH Formation of ROOH following RO 2 

### + HO 2 

### reactions, or formation of H - shift

disproportionation products (represented by MEK) in the RO 2 

### + RCO 3 

### and (in 50% yields) RO 2 

### + RO 2 

### reactions. yR6OOH As above, but with the RO 2 

### + HO 2 

### product represented by R6OOH and the H - shift products

are represented by PROD2.

### Table 1 (continued)

138

Name Description yRAOOH As above, but with the RO 2 

### + HO 2 

### product represented by R6OOH Non - Reacting Species CO2 Carbon Dioxide SULF Sulfates (SO 3 

### or H 2 

### SO 4 

### ) XC Lost Carbon or carbon in unreactive products XN Lost Nitrogen or nitrogen in unreactive products Primary Organics Represented explicitly CH4 Methane ETHENE Ethene ISOPRENE Isoprene ACETYLEN Acetylene BENZENE Benzene Lumped model species added to the base mechanism to represent various type s of emitted species in the lumped mechanism for airshed models (not part of the base mechanism) ALK1 Alkanes and other non - aromatic compounds that react only with OH, and have kOH (OH

radical rate constant) between 2 and 5 x 10 2 

### ppm- 1 

### min - 1 

### . (Primarily ethane) ALK2 Alkanes and other non - aromatic compounds that react only with OH, and have kOH

between 5 x 10 2 

### and 2.5 x 10 3 

### ppm- 1 

### min - 1 

### . (Primarily propane) ALK3 Alkanes and other non - aromatic compounds that react only with OH, and have kOH

between 2.5 x 10 3 

### and 5 x 10 3 

### ppm- 1 

### min - 1



### . ALK4 Alkanes and other non - aromatic compounds that react only with OH, and have kOH

between 5 x 10 3 

### and 1 x 10 4 

### ppm- 1 

### min - 1



### . ALK5 Alkanes and other non - aromatic compounds that react only with OH, and have kOH greater

than 1 x 10 4 

### ppm - 1 min - 1. ARO1 Aromatics with kOH < 2x10 4 

### ppm- 1 

### min - 1



### . ARO2 Aromatics with kOH > 2x10 4 

### ppm- 1 

### min - 1



### . OLE1 Alkenes (other than ethene) with kOH < 7x10 4 

### ppm- 1 

### min - 1



### . OLE2 Alkenes with kOH > 7x10 4 

### ppm- 1 

### min - 1



### . TERP Terpenes

### 139

Table A - 2 . Listing of reactions and rate parameters in the base SAPRC - 07 mechanism . Label Reaction and Products [a] Rate Parameters [b] Refs & k(300) A Ea B Notes [c] Inorganic Reactions 1 NO2 + HV = NO + O3P Phot Set= NO2 - 06 2,4 2 O3P + O2 + M = O3 + M 5.68E - 34 5.68E - 34 0.00 - 2.60 3,5 3 O3P + O3 = #2 O2 8.34E - 15 8.00E - 12 4.09 1,2,3 4 O3P + NO = NO2 1.64E - 12 Falloff, F=0.60, N=1.00 2 0: 9.00E - 32 0.00 - 1.50 inf: 3.00E - 11 0.00 0.00 5 O3P + NO2 = NO + O2 1.03E - 11 5.50E - 12 - 0.37 3 6 O3P + NO2 = NO3 3.24E - 12 Falloff, F=0.60, N=1.00 2 0: 2.50E - 31 0.00 - 1.80 inf: 2.20E - 11 0.00 - 0.70 7 O3 + NO = NO2 + O2 2.02E - 14 3.00E - 12 2.98 2 8 O3 + NO2 = O2 + NO3 3.72E - 17 1.40E - 13 4.91 1,3 9 NO + NO3 = #2 NO2 2.60E - 11 1.80E - 11 - 0.22 1,3 10 NO + NO + O2 = #2 NO2 1.93E - 38 3.30E - 39 - 1.05 1,3 11 NO2 + NO3 = N2O5 1.24E - 12 Falloff, F=0.35, N=1.33 3 0: 3.60E - 30 0.00 -4.10 inf: 1.90E - 12 0.00 0.20 12 N2O5 = NO2 + NO3 5.69E - 02 Falloff, F=0.35, N=1.33 3 0: 1.30E - 03 21.86 - 3.50 inf: 9.70E+14 22.02 0.10 13 N2O5 + H2O = #2 HNO3 2.50E - 22 3,6 14 N2O5 + H2O + H2O = #2 HNO3 + H2O 1.80E - 39 3,6 N2O5 + HV = NO3 + NO + O3P (Slow) 1 N2O5 + HV = NO3 + NO2 (Slow) 1 15 NO2 + NO3 = NO + NO2 + O2 6.75E - 16 4.50E - 14 2.50 1,3 16 NO3 + HV = NO + O2 Phot Set= NO3NO - 06 2 17 NO3 + HV = NO2 + O3P Phot Set= NO3NO2 - 6 2 18 O3 + HV = O1D + O2 Phot Set= O3O1D - 06 2,3,7 19 O3 + HV = O3P + O2 Phot Set= O3O3P - 06 2,7 20 O1D + H2O = #2 OH 1.99E - 10 1.63E - 10 - 0.12 2 21 O1D + M = O3P + M 3.28E - 11 2.38E - 11 - 0.19 2,5 22 OH + NO = HONO 7.31E - 12 Falloff, F=0.60, N=1.00 2 0: 7.00E - 31 0.00 - 2.60 inf: 3.60E - 11 0.00 - 0.10 23 HONO + HV = OH + NO Phot Set= HONO - 06 8 24 OH + HONO = H2O + NO2 5.95E - 12 2.50E - 12 - 0.52 3 25 OH + NO2 = HNO3 1.05E - 11 Falloff, F=0.60, N=1.00 2,9 0: 1.80E - 30 0.00 - 3.00 inf: 2.80E - 11 0.00 0.00 26 OH + NO3 = HO2 + NO2 2.00E - 11 1,3 27 OH + HNO3 = H2O + NO3 1.51E - 13 k =k0+k3M/(1+k3M/k2) 2 k0: 2.40E - 14 - 0.91 0.00

### Table A - 2 (continued)

140

Label Reaction and Products [a] Rate Parameters [b] Refs & k(300) A Ea B Notes [c] k2: 2.70E - 17 -4.37 0.00 k3: 6.50E - 34 - 2.65 0.00 28 HNO3 + HV = OH + NO2 Phot Set= HNO3 1,2,3,10 29 OH + CO = HO2 + CO2 2.28E - 13 k = k1 + k2 [M] 3 k1: 1.44E - 13 0.00 0.00 k2: 3.43E - 33 0.00 0.00 30 OH + O3 = HO2 + O2 7.41E - 14 1.70E - 12 1.87 2,3 31 HO2 + NO = OH + NO2 8.85E - 12 3.60E - 12 - 0.54 3 32 HO2 + NO2 = HNO4 1.12E - 12 Falloff, F=0.60, N=1.00 2 0: 2.00E - 31 0.00 - 3.40 inf: 2.90E - 12 0.00 - 1.10 33 HNO4 = HO2 + NO2 1.07E - 01 Falloff, F=0.60, N=1.00 11 0: 3.72E - 05 21.16 - 2.40 inf: 5.42E+15 22.20 - 2.30 34 HNO4 + HV = #.61 {HO2 + NO2} + #.39 {OH + NO3} Phot Set= HNO4 - 06 12 35 HNO4 + OH = H2O + NO2 + O2 4.61E - 12 1.30E - 12 - 0.76 2 36 HO2 + O3 = OH + #2 O2 2.05E - 15 2.03E - 16 - 1.38 4.57 3 37 HO2 + HO2 = HO2H + O2 2.84E - 12 k = k1 + k2 [M] 3 k1: 2.20E - 13 - 1.19 0.00 k2: 1.90E - 33 - 1.95 0.00 38 HO2 + HO2 + H2O = HO2H + O2 + H2O 6.09E - 30 k = k1 + k2 [M] 3 k1: 3.08E - 34 - 5.56 0.00 k2: 2.66E - 54 - 6.32 0.00 39 NO3 + HO2 = #.8 {OH + NO2 + O2} + #.2 {HNO3 + O2} 4.00E - 12 1,3,13 40 NO3 + NO3 = #2 NO2 + O2 2.41E - 16 8.50E - 13 4.87 1,2 41 HO2H + HV = #2 OH Phot Set= H2O2 1,10 42 HO2H + OH = HO2 + H2O 1.80E - 12 1.80E - 12 0.00 2 43 OH + HO2 = H2O + O2 1.10E - 10 4.80E - 11 - 0.50 1 44 OH + SO2 = HO2 + SULF 9.49E - 13 Falloff, F=0.60, N=1.00 2 0: 3.30E - 31 0.00 -4.30 inf: 1.60E - 12 0.00 0.00 45 OH + H2 = HO2 + H2O 7.02E - 15 7.70E - 12 4.17 1,3 Methyl peroxy and methoxy reactions BR01 MEO2 + NO = NO2 + HCHO + HO2 7.64E - 12 2.30E - 12 - 0.72 3,14 BR02 MEO2 + HO2 = COOH + O2 4.65E - 12 3.46E - 13 - 1.55 0.36 3,15 BR03 MEO2 + HO2 = HCHO + O2 + H2O 4.50E - 13 3.34E - 14 - 1.55 - 3.53 3,15 BR04 MEO2 + NO3 = HCHO + HO2 + NO2 1.30E - 12 1,3,14 BR05 MEO2 + MEO2 = MEOH + HCHO + O2 2.16E - 13 6.39E - 14 - 0.73 - 1.80 3,16 BR06 MEO2 + MEO2 = #2 {HCHO + HO2} 1.31E - 13 7.40E - 13 1.03 3 Active Peroxy Radical Operators BR07 RO2C + NO = NO2 9.23E - 12 2.60E - 12 - 0.76 3,18,17 BR08 RO2C + HO2 = 7.63E - 12 3.80E - 13 - 1.79 3,18,17

### Table A - 2 (continued)

141

Label Reaction and Products [a] Rate Parameters [b] Refs & k(300) A Ea B Notes [c] BR09 RO2C + NO3 = NO2 2.30E - 12 3,18,17 BR10 RO2C + MEO2 = #.5 HO2 + #.75 HCHO + #.25 MEOH 2.00E - 13 1,17,19 BR11 RO2C + RO2C = 3.50E - 14 1,17 BR12 RO2XC + NO = XN Same k as rxn BR07 3,17,18 BR13 RO2XC + HO2 = Same k as rxn BR08 3,17,18 BR14 RO2XC + NO3 = NO2 Same k as rxn BR09 1,17 BR15 RO2XC + MEO2 = #.5 HO2 + #.75 HCHO + #.25 MEOH Same k as rxn BR10 3,17,18 BR16 RO2XC + RO2C = Same k as rxn BR11 1,17 BR17 RO2XC + RO2XC = Same k as rxn BR11 1,17 Reactions of Acyl Peroxy Radicals, PAN, and PAN analogues BR18 MECO3 + NO2 = PAN 9.37E - 12 Falloff, F=0.30, N=1.41 20 0: 2.70E - 28 0.00 - 7.10 inf: 1.21E - 11 0.00 - 0.90 BR19 PAN = MECO3 + NO2 6.27E - 04 Falloff, F=0.30, N=1.41 20 0: 4.90E - 03 24.05 0.00 inf: 4.00E+16 27.03 0.00 BR20 PAN + HV = #.6 {MECO3 + NO2} + #.4 {MEO2 + CO2 + NO3} Phot Set= PAN 3 BR21 MECO3 + NO = MEO2 + CO2 + NO2 1.97E - 11 7.50E - 12 - 0.58 3 BR22 MECO3 + HO2 = CCOOH + #.7 O2 + #.3 O3 1.36E - 11 5.20E - 13 - 1.95 3,21 BR23 MECO3 + NO3 = MEO2 + CO2 + NO2 + O2 Same k as rxn BR09 22 BR24 MECO3 + MEO2 = #.1 {CCOOH + HCHO + O2} + #.9 {HCHO + HO2 + MEO2 + CO2} 1.06E - 11 2.00E - 12 - 0.99 3 BR25 MECO3 + RO2C = MEO2 + CO2 1.56E - 11 4.40E - 13 - 2.13 3,18,23 BR26 MECO3 + RO2XC = MEO2 + CO2 Same k as rxn BR25 3,18,23 BR27 MECO3 + MECO3 = #2 {MEO2 + CO2} + O2 1.54E - 11 2.90E - 12 - 0.99 1,3 BR28 RCO3 + NO2 = PAN2 1.21E - 11 1.21E - 11 0.00 - 1.07 24 BR29 PAN2 = RCO3 + NO2 5.48E - 04 8.30E+16 27.70 3,25 BR30 PAN2 + HV = #.6 {RCO3 + NO2} + #.4 {RO2C + xHO2 + yROOH + xCCHO + CO2 + NO3} Phot Set= PAN 26 BR31 RCO3 + NO = NO2 + RO2C + xHO2 + yROOH + xCCHO + CO2 2.08E - 11 6.70E - 12 - 0.68 3,27 BR32 RCO3 + HO2 = RCOOH + #.75 O2 + #.25 O3 Same k as rxn BR22 1,28 BR33 RCO3 + NO3 = NO2 + RO2C + xHO2 + yROOH + xCCHO + CO2 + O2 Same k as rxn BR09 1,28 BR34 RCO3 + MEO2 = HCHO + HO2 + RO2C + xHO2 + xCCHO + yROOH + CO2 Same k as rxn BR24 1,28 BR35 RCO3 + RO2C = RO2C + xHO2 + xCCHO + yROOH + CO2 Same k as rxn BR25 1,28

### Table A - 2 (continued)

142

Label Reaction and Products [a] Rate Parameters [b] Refs & k(300) A Ea B Notes [c] BR36 RCO3 + RO2XC = RO2C + xHO2 + xCCHO + yROOH + CO2 Same k as rxn BR25 1,28 BR37 RCO3 + MECO3 = #2 CO2 + MEO2 + RO2C + xHO2 + yROOH + xCCHO + O2 Same k as rxn BR27 1,28 BR38 RCO3 + RCO3 = #2 {RO2C + xHO2 + xCCHO + yROOH + CO2} Same k as rxn BR27 1,28 BR39 BZCO3 + NO2 = PBZN 1.37E - 11 1,29 BR40 PBZN = BZCO3 + NO2 4.27E - 04 7.90E+16 27.82 1,29 BR41 PBZN + HV = #.6 {BZCO3 + NO2} + #.4 {CO2 + BZO + RO2C + NO3} Phot Set= PAN 26 BR42 BZCO3 + NO = NO2 + CO2 + BZO + RO2C Same k as rxn BR31 1,28 BR43 BZCO3 + HO2 = RCOOH + #.75 O2 + #.25 O3 + #4 XC Same k as rxn BR22 1,28 BR44 BZCO3 + NO3 = NO2 + CO2 + BZO + RO2C + O2 Same k as rxn BR09 1,28 BR45 BZCO3 + MEO2 = HCHO + HO2 + RO2C + BZO + CO2 Same k as rxn BR24 1,28 BR46 BZCO3 + RO2C = RO2C + BZO + CO2 Same k as rxn BR25 1,28 BR47 BZCO3 + RO2XC = RO2C + BZO + CO2 Same k as rxn BR25 1,28 BR48 BZCO3 + MECO3 = #2 CO2 + MEO2 + BZO + RO2C Same k as rxn BR27 1,28 BR49 BZCO3 + RCO3 = #2 CO2 + RO2C + xHO2 + yROOH + xCCHO + BZO + RO2C Same k as rxn BR27 1,28 BR50 BZCO3 + BZCO3 = #2 {BZO + RO2C + CO2} Same k as rxn BR27 1,28 BR51 MACO3 + NO2 = MAPAN Same k as rxn BR28 1,28 BR52 MAPAN = MACO3 + NO2 4.79E - 04 1.60E+16 26.80 1,30 BR53 MAPAN + HV = #.6 {MACO3 + NO2} + #.4 {CO2 + HCHO + MECO3 + NO3} Phot Set= PAN 26 BR54 MACO3 + NO = NO2 + CO2 + HCHO + MECO3 Same k as rxn BR31 1,28 BR55 MACO3 + HO2 = RCOOH + #.75 O2 + #.25 O3 + XC Same k as rxn BR22 1,28 BR56 MACO3 + NO3 = NO2 + CO2 + HCHO + MECO3 + O2 Same k as rxn BR09 1,28 BR57 MACO3 + MEO2 = #2 HCHO + HO2 + CO2 + MECO3 Same k as rxn BR24 1,28 BR58 MACO3 + RO2C = CO2 + HCHO + MECO3 Same k as rxn BR25 1,28 BR59 MACO3 + RO2XC = CO2 + HCHO + MECO3 Same k as rxn BR25 1,28 BR60 MACO3 + MECO3 = #2 CO2 + MEO2 + HCHO + MECO3 + O2 Same k as rxn BR27 1,28 BR61 MACO3 + RCO3 = HCHO + MECO3 + RO2C + xHO2 + yROOH + xCCHO + #2 CO2 Same k as rxn BR27 1,28

### Table A - 2 (continued)

143

Label Reaction and Products [a] Rate Parameters [b] Refs & k(300) A Ea B Notes [c] BR62 MACO3 + BZCO3 = HCHO + MECO3 + BZO + RO2C + #2 CO2 Same k as rxn BR27 1,28 BR63 MACO3 + MACO3 = #2 {HCHO + MECO3 + CO2} Same k as rxn BR27 1,28 Other Organic Radical Species BR64 TBUO + NO2 = RNO3 + # - 2 XC 2.40E - 11 1 BR65 TBUO = ACET + MEO2 1.18E+03 7.50E+14 16.20 1 BR66 BZO + NO2 = NPHE 3.79E - 11 2.30E - 11 - 0.30 1 BR67 BZO + HO2 = CRES + # - 1 XC Same k as rxn BR08 1 BR68 BZO = CRES + RO2C + xHO2 + # - 1 XC 1.00E - 03 1,31 Steady- State Peroxy Radical operators (for formation of inorganic and radical products) RO01 xHO2 = HO2 k is variable parameter: RO2RO 32 RO02 xHO2 = k is variable parameter: RO2XRO 32 RO03 xOH = OH k is variable parameter: RO2RO 32 RO04 xOH = k is variable parameter: RO2XRO 32 RO05 xNO2 = NO2 k is variable parameter: RO2RO 32 RO06 xNO2 = XN k is variable parameter: RO2XRO 32 RO07 xMEO2 = MEO2 k is variable parameter: RO2RO 32 RO08 xMEO2 = XC k is variable parameter: RO2XRO 32 RO09 xMECO3 = MECO3 k is variable parameter: RO2RO 32 RO10 xMECO3 = #2 XC k is variable parameter: RO2XRO 32 RO11 xRCO3 = RCO3 k is variable parameter: RO2RO 32 RO12 xRCO3 = #3 XC k is variable parameter: RO2XRO 32 RO13 xMACO3 = MACO3 k is variable parameter: RO2RO 32 RO14 xMACO3 = #4 XC k is variable parameter: RO2XRO 32 RO15 xTBUO = TBUO k is variable parameter: RO2RO 32 RO16 xTBUO = #4 XC k is variable parameter: RO2XRO 32 RO17 xCO = CO k is variable parameter: RO2RO 32 RO18 xCO = XC k is variable parameter: RO2XRO 32 Explicit and Lumped Molecule Organic Products BP01 HCHO + HV = #2 HO2 + CO Phot Set= HCHOR- 06 3 BP02 HCHO + HV = H2 + CO Phot Set= HCHOM - 06 3 BP03 HCHO + OH = HO2 + CO + H2O 8.47E - 12 5.40E - 12 - 0.27 3 BP04 HCHO + HO2 = HOCOO Assumed to be negligible 34 BP07 HCHO + NO3 = HNO3 + HO2 + CO 6.06E - 16 2.00E - 12 4.83 1,33 BP08 CCHO + OH = MECO3 + H2O 1.49E - 11 4.40E - 12 - 0.73 3 BP09 CCHO + HV = CO + HO2 + MEO2 Phot Set= CCHO_R 1,3 BP10 CCHO + NO3 = HNO3 + MECO3 2.84E - 15 1.40E - 12 3.70 1,3 BP11 RCHO + OH = #.965 RCO3 + #.035 {RO2C + xHO2 + xCO + xCCHO + yROOH} 1.97E - 11 5.10E - 12 - 0.80 36,35 BP12 RCHO + HV = RO2C + xHO2 + yROOH + xCCHO + CO + HO2 Phot Set= C2CHO 1,37 BP13 RCHO + NO3 = HNO3 + RCO3 6.74E - 15 1.40E - 12 3.18 38

### Table A - 2 (continued)

144

Label Reaction and Products [a] Rate Parameters [b] Refs & k(300) A Ea B Notes [c] BP14 ACET + OH = RO2C + xMECO3 + xHCHO + yROOH 1.91E - 13 4.56E - 14 - 0.85 3.65 39 BP15 ACET + HV = #.62 MECO3 + #1.38 MEO2 + #.38 CO Phot Set= ACET - 06, qy= 0.5 40 BP16 MEK + OH = #.967 RO2C + #.039 {RO2XC + zRNO3} + #.376 xHO2 + #.51 xMECO3 + #.074 xRCO3 + #.088 xHCHO + #.504 xCCHO + #.376 xRCHO + yROOH + #.3 XC 1.20E - 12 1.30E - 12 0.05 2.00 1,3,36 BP17 MEK + HV = MECO3 + RO2C + xHO2 + xCCHO + yROOH Phot Set= MEK- 06, qy= 0.175 41 BP18 MEOH + OH = HCHO + HO2 9.02E - 13 2.85E - 12 0.69 3 BP19 HCOOH + OH = HO2 + CO2 4.50E - 13 3,42 BP20 CCOOH + OH = #.509 MEO2 + #.491 RO2C + #.509 CO2 + #.491 xHO2 + #.491 xMGLY + #.491 yROOH + # - 0.491 XC 7.26E - 13 4.20E - 14 - 1.70 3,36 BP21 RCOOH + OH = RO2C + xHO2 + #.143 CO2 + #.142 xCCHO + #.4 xRCHO + #.457 xBACL + yROOH + # - 0.455 XC 1.20E - 12 3,36 BP22 COOH + OH = H2O + #.3 {HCHO + OH} + #.7 MEO2 7.40E - 12 3.80E - 12 - 0.40 2,43 BP23 COOH + HV = HCHO + HO2 + OH Phot Set= COOH 1,3 BP24 ROOH + OH = #.744 OH + #.251 RO2C + #.004 RO2XC + #.004 zRNO3 + #.744 RCHO + #.239 xHO2 + #.012 xOH + #.012 xHCHO + #.012 xCCHO + #.205 xRCHO + #.034 xPROD2 + #.256 yROOH + # - 0.115 XC 2.50E - 11 36,45,44

BP25 ROOH + HV = RCHO + HO2 + OH Phot Set= COOH 1,45 BP26 R6OOH + OH = #.84 OH + #.222 RO2C + #.029 RO2XC + #.029 zRNO3 + #.84 PROD2 + #.09 xHO2 + #.041 xOH + #.02 xCCHO + #.075 xRCHO + #.084 xPROD2 + #.16 yROOH + #.02 XC 5.60E - 11 36,44,46

BP27 R6OOH + HV = OH + #.142 HO2 + #.782 RO2C + #.077 RO2XC + #.077 zRNO3 + #.085 RCHO + #.142 PROD2 + #.782 xHO2 + #.026 xCCHO + #.058 xRCHO + #.698 xPROD2 + #.858 yR6OOH + #.017 XC Phot Set= COOH 46

BP28 RAOOH + OH = #.139 OH + #.148 HO2 + #.589 RO2C + #.124 RO2XC + #.124 zRNO3 + #.074 PROD2 + #.147 MGLY + #.139 IPRD + #.565 xHO2 + #.024 xOH + #.448 xRCHO + #.026 xGLY + #.030 xMEK + #.252 xMGLY + #.073 xAFG1 + #.073 xAFG2 + #.713 yR6OOH + #2.674 XC 1.41E - 10 47

### Table A - 2 (continued)

145

Label Reaction and Products [a] Rate Parameters [b] Refs & k(300) A Ea B Notes [c] BP29 RAOOH + HV = OH + HO2 + #.5 {GLY + MGLY + AFG1 + AFG2} + #.5 XC Phot Set= COOH 47 BP30 GLY + HV = #2 {CO + HO2} Phot Set= GLY - 07R 48 BP31 GLY + HV = HCHO + CO Phot Set= GLY - 07M 48 BP32 GLY + OH = #.63 HO2 + #1.26 CO + #.37 RCO3 + # - .37 XC 1.10E - 11 1,3,49 BP33 GLY + NO3 = HNO3 + #.63 HO2 + #1.26 CO + #.37 RCO3 + # - .37 XC 1.02E - 15 2.80E - 12 4.72 1,50 BP34 MGLY + HV = HO2 + CO + MECO3 Phot Set= MGLY - 06 3,51 BP35 MGLY + OH = CO + MECO3 1.50E - 11 1,3 BP36 MGLY + NO3 = HNO3 + CO + MECO3 2.53E - 15 1.40E - 12 3.77 1,50 BP37 BACL + HV = #2 MECO3 Phot Set= BACL - 07 52 BP38 CRES + OH = #.2 BZO + #.8 {RO2C + xHO2 + yR6OOH} + #.25 xMGLY + #5.05 XC 4.03E - 11 1.70E - 12 - 1.89 53,54 BP39 CRES + NO3 = HNO3 + BZO + XC 1.40E - 11 1,53 BP40 NPHE + OH = BZO + XN 3.50E - 12 55 BP41 NPHE + HV = HONO + #6 XC Phot Set= NO2 - 06, qy= 1.5e - 3 56 BP42 NPHE + HV = #6 XC + XN Phot Set= NO2 - 06, qy= 1.5e - 2 57 BP43 BALD + OH = BZCO3 1.20E - 11 59,58 BP44 BALD + HV = #7 XC Phot Set= BALD - 06, qy= 0.06 60 BP45 BALD + NO3 = HNO3 + BZCO3 2.73E - 15 1.34E - 12 3.70 1,61 Lumped Unsaturated Aromatic Ring - Opening Products BP46 AFG1 + OH = #.217 MACO3 + #.723 RO2C + #.060 {RO2XC + zRNO3} + #.521 xHO2 + #.201 xMECO3 + #.334 xCO + #.407 xRCHO + #.129 xMEK + #.107 xGLY + #.267 xMGLY + #.783 yR6OOH + #.284 XC 7.40E - 11 62

BP47 AFG1 + O3 = #.826 OH + #.522 HO2 + #.652 RO2C + #.522 CO + #.174 CO2 + #.432 GLY + #.568 MGLY + #.652 xRCO3 + #.652 xHCHO + #.652 yR6OOH + # - .872 XC 9.66E - 18 62 BP48 AFG1 + HV = #1.023 HO2 + #.173 MEO2 + #.305 MECO3 + #.500 MACO3 + #.695 CO + #.195 GLY + #.305 MGLY + #.217 XC Phot Set= AFG1 62,63 BP49 AFG2 + OH = #.217 MACO3 + #.723 RO2C + #.060 {RO2XC + zRNO3} + #.521 xHO2 + #.201 xMEC O3 + #.334 xCO + #.407 xRCHO + #.129 xMEK + #.107 xGLY + #.267 xMGLY + #.783 yR6OOH + #.284 XC 7.40E - 11 62

BP50 AFG2 + O3 = #.826 OH + #.522 HO2 + #.652 RO2C + #.522 CO + #.174 CO2 + #.432 GLY + #.568 MGLY + #.652 xRCO3 + #.652 xHCHO + #.652 yR6OOH + # - .872 XC 9.66E - 18 62

### Table A - 2 (continued)

146

Label Reaction and Products [a] Rate Parameters [b] Refs & k(300) A Ea B Notes [c] BP51 AFG2 + HV = PROD2 + # - 1 XC Phot Set= AFG1 62,63 BP52 AFG3 + OH = #.206 MACO3 + #.733 RO2C + #.117 {RO2XC + zRNO3} + #.561 xHO2 + #.117 xMECO3 + #.114 xCO + #.274 xGLY + #.153 xMGLY + #.019 xBACL + #.195 xAFG1 + #. 195 xAFG2 + #.231 xIPRD + #.794 yR6OOH + #.938 XC 9.35E - 11 64

BP53 AFG3 + O3 = #.471 OH + #.554 HO2 + #.013 MECO3 + #.258 RO2C + #.007 {RO2XC + zRNO3} + #.580 CO + #.190 CO2 + #.366 GLY + #.184 MGLY + #.350 AFG1 + #.350 AFG2 + #.139 AFG3 + #.003 MACR + #.004 MVK + #.003 IPRD + #.095 xHO2 + #.163 xRCO3 + #.163 xHCHO + #.095 xMGLY + #.264 yR6OOH + # - .575 XC 1.43E - 17 64

Isoprene Products BP54 MACR + OH = #.5 MACO3 + #.5 {RO2C + xHO2} + #.416 xCO + #.084 xHCHO + #.416 xMEK + #.084 xMGLY + #.5 yROOH + # - 0.416 XC 2.84E - 11 8.00E - 12 - 0.76 3,65 BP55 MACR + O3 = #.208 OH + #.108 HO2 + #.1 RO2C + #.45 CO + #.117 CO2 + #.1 HCHO + #.9 MGLY + #.333 HCOOH + #.1 xRCO3 + #.1 xHCHO + #.1 yROOH + # - 0.1 XC 1.28E - 18 1.40E - 15 4.17 3,65 BP56 MACR + N O3 = #.5 {MACO3 + RO2C + HNO3 + xHO2 + xCO} + #.5 yROOH + #1.5 XC + #.5 XN 3.54E - 15 1.50E - 12 3.61 65,66 BP57 MACR + O3P = RCHO + XC 6.34E - 12 1,65 BP58 MACR + HV = #.33 OH + #.67 HO2 + #.34 MECO3 + #.33 MACO3 + #.33 RO2C + #.67 CO + #.34 HCHO + #.33 xMECO3 + #.33 xHCHO + #.33 yROOH Phot Set= MACR- 06 3,65,67

BP59 MVK + OH = #.975 RO2C + #.025 {RO2XC + zRNO3} + #.3 xHO2 + #.675 xMECO3 + #.3 xHCHO + #.675 xRCHO + #.3 xMGLY + yROOH + # - 0.725 XC 1.99E - 11 2.60E - 12 - 1.21 3,65 BP60 MVK + O3 = # .164 OH + #.064 HO2 + #.05 {RO2C + xHO2} + #.475 CO + #.124 CO2 + #.05 HCHO + #.95 MGLY + #.351 HCOOH + #.05 xRCO3 + #.05 xHCHO + #.05 yROOH + # - 0.05 XC 5.36E - 18 8.50E - 16 3.02 3,65

BP61 MVK + NO3 = #4 XC + XN (Slow) 1,65 BP62 MVK + O3P = #.45 RCHO + # .55 MEK + #.45 XC 4.32E - 12 1,65

### Table A - 2 (continued)

147

Label Reaction and Products [a] Rate Parameters [b] Refs & k(300) A Ea B Notes [c] BP63 MVK + HV = #.4 MEO2 + #.6 CO + #.6 PROD2 + #.4 MACO3 + # - 2.2 XC Phot Set= MVK - 06 3,68 BP64 IPRD + OH = #.289 MACO3 + #.67 {RO2C + xHO2} + #.041 {RO2XC + zRNO3} + #.336 xCO + #.055 xHCHO + #.129 xCCHO + # .013 xRCHO + #.15 xMEK + #.332 xPROD2 + #.15 xGLY + #.174 xMGLY + # - 0.504 XC + #.711 yR6OOH 6.19E - 11 1,65

BP65 IPRD + O3 = #.285 OH + #.4 HO2 + #.048 {RO2C + xRCO3} + #.498 CO + #.14 CO2 + #.124 HCHO + #.21 MEK + #.023 GLY + #.742 MGLY + #.1 HCOOH + # .372 RCOOH + #.047 xCCHO + #.001 xHCHO + #.048 yR6OOH + # - .329 XC 4.18E - 18 1,65

BP66 IPRD + NO3 = #.15 {MACO3 + HNO3} + #.799 {RO2C + xHO2} + #.051 {RO2XC + zRNO3} + #.572 xCO + #.227 xHCHO + #.218 xRCHO + #.008 xMGLY + #.572 xRNO3 + #.85 yR6OOH + #.2 78 XN + # - .815 XC 1.00E - 13 1,65

BP67 IPRD + HV = #1.233 HO2 + #.467 MECO3 + #.3 RCO3 + #1.233 CO + #.3 HCHO + #.467 CCHO + #.233 MEK + # - .233 XC Phot Set= MACR- 06 65,69 Lumped Parameter Organic Products BP68 PROD2 + OH = #.472 HO2 + #.379 xHO2 + #.029 xMECO3 + #.049 xRCO3 + #.473 RO2C + #.071 RO2XC + #.071 zRNO3 + #.002 HCHO + #.211 xHCHO + #.001 CCHO + #.083 xCCHO + #.143 RCHO + #.402 xRCHO + #.115 xMEK + #.329 PROD2 + #.007 xPROD2 + #.528 yR6OOH + #.877 XC 1.55E - 11 70

BP69 PROD2 + HV = # .913 xHO2 + #.4 MECO3 + #.6 RCO3 + #1.59 RO2C + #.087 RO2XC + #.087 zRNO3 + #.303 xHCHO + #.163 xCCHO + #.78 xRCHO + yR6OOH + # - .091 XC Phot Set= MEK- 06, qy= 4.86e - 3 70,71

BP70 RNO3 + OH = #.189 HO2 + #.305 xHO2 + #.019 NO2 + #.313 xNO2 + #.976 RO2C + #.175 RO2XC + #.175 zRNO3 + #.011 xHCHO + #.429 xCCHO + #.001 RCHO + #.036 xRCHO + #.004 xACET + #.01 MEK + #.17 xMEK + #.008 PROD2 + #.031 xPROD2 + #.189 RNO3 + #.305 xRNO3 + #.157 yROOH + #.636 yR6OOH + #.174 XN + #.04 XC 7.20E - 12 72

### Table A - 2 (continued)

148

Label Reaction and Products [a] Rate Parameters [b] Refs & k(300) A Ea B Notes [c] BP71 RNO 3 + HV = #.344 HO2 + #.554 xHO2 + NO2 + #.721 RO2C + #.102 RO2XC + #.102 zRNO3 + #.074 HCHO + #.061 xHCHO + #.214 CCHO + #.23 xCCHO + #.074 RCHO + #.063 xRCHO + #.008 xACET + #.124 MEK + #.083 xMEK + #.19 PROD2 + #.261 xPROD2 + #.066 yROOH + #.591 yR6OOH + #.396 XC Phot Set= IC3ONO2 72,73

Steady- State Peroxy Radical operators (for formation of organic product species) PO01 xHCHO = HCHO k is variable parameter: RO2RO 32 PO02 xHCHO = XC k is variable parameter: RO2XRO 32 PO03 xCCHO = CCHO k is variab le parameter: RO2RO 32 PO04 xCCHO = #2 XC k is variable parameter: RO2XRO 32 PO05 xRCHO = RCHO k is variable parameter: RO2RO 32 PO06 xRCHO = #3 XC k is variable parameter: RO2XRO 32 PO07 xACET = ACET k is variable parameter: RO2RO 32 PO08 xACET = #3 XC k is variable parameter: RO2XRO 32 PO09 xMEK = MEK k is variable parameter: RO2RO 32 PO10 xMEK = #4 XC k is variable parameter: RO2XRO 32 PO11 xPROD2 = PROD2 k is variable parameter: RO2RO 32 PO12 xPROD2 = #6 XC k is variable parameter: RO2 XRO 32 PO13 xGLY = GLY k is variable parameter: RO2RO 32 PO14 xGLY = #2 XC k is variable parameter: RO2XRO 32 PO15 xMGLY = MGLY k is variable parameter: RO2RO 32 PO16 xMGLY = #3 XC k is variable parameter: RO2XRO 32 PO17 xBACL = BACL k is variabl e parameter: RO2RO 32 PO18 xBACL = #4 XC k is variable parameter: RO2XRO 32 PO19 xBALD = BALD k is variable parameter: RO2RO 32 PO20 xBALD = #7 XC k is variable parameter: RO2XRO 32 PO21 xAFG1 = AFG1 k is variable parameter: RO2RO 32 PO22 xAFG1 = #5 XC k is variable parameter: RO2XRO 32 PO23 xAFG2 = AFG2 k is variable parameter: RO2RO 32 PO24 xAFG2 = #5 XC k is variable parameter: RO2XRO 32 PO25 xAFG3 = AFG3 k is variable parameter: RO2RO 32 PO26 xAFG3 = #7 XC k is variable parameter: RO2XRO 32 PO27 xMACR = MACR k is variable parameter: RO2RO 32 PO28 xMACR = #4 XC k is variable parameter: RO2XRO 32 PO29 xMVK = MVK k is variable parameter: RO2RO 32 PO30 xMVK = #4 XC k is variable parameter: RO2XRO 32 PO31 xIPRD = IPRD k is variable parameter: RO2RO 32 PO32 xIPRD = #5 XC k is variable parameter: RO2XRO 32 PO33 xRNO3 = RNO3 k is variable parameter: RO2RO 32 PO34 xRNO3 = #6 XC + XN k is variable parameter: RO2XRO 32 PO35 zRNO3 = RNO3 + # - 1 XN k is variable parameter: RO2NO 74 PO36 zRNO3 = PROD2 + HO2 k is variable parameter: RO22NN 74

### Table A - 2 (continued)

149

Label Reaction and Products [a] Rate Parameters [b] Refs & k(300) A Ea B Notes [c] PO37 zRNO3 = #6 XC k is variable parameter: RO2XRO 74 PO38 yROOH = ROOH + # - 3 XC k is variable parameter: RO2HO2 75 PO39 yROOH = MEK + # -4 XC k is variable parameter: RO2RO2M 75 PO40 yROO H = k is variable parameter: RO2RO 75 PO41 yR6OOH = R6OOH + # - 6 XC k is variable parameter: RO2HO2 75 PO42 yR6OOH = PROD2 + # - 6 XC k is variable parameter: RO2RO2M 75 PO43 yR6OOH = k is variable parameter: RO2RO 75 PO44 yRAOOH = RAOOH + # - 8 XC k is variable parameter: RO2HO2 75 PO45 yRAOOH = PROD2 + # - 6 XC k is variable parameter: RO2RO2M 75 PO46 yRAOOH = k is variable parameter: RO2RO 75 Explicitly Represented Primary Organics BE01 CH4 + OH = H2O + MEO2 6.62E - 15 1.85E - 12 3.36 1,59 BE02 ETHENE + OH = RO2C + xHO2 + #1.61 xHCHO + #.195 xCCHO + yROOH 8.15E - 12 Falloff, F=0.60, N=1.00 2,76 0: 1.00E - 28 0.00 -4.50 inf: 8.80E - 12 0.00 - 0.85 BE03 ETHENE + O3 = #.16 OH + #.16 HO2 + #.51 CO + #.12 CO2 + HCHO + #.37 HCOOH 1.6 8E - 18 9.14E - 15 5.13 59,77 BE04 ETHENE + NO3 = RO2C + xHO2 + xRCHO + yROOH + # - 1 XC + XN 2.24E - 16 3.30E - 12 5.72 2.00 3,76 BE05 ETHENE + O3P = #.8 HO2 + #.51 MEO2 + #.29 RO2C + #.51 CO + #.1 CCHO + #.29 xHO2 + #.278 xCO + #.278 xHCHO + #.012 xGLY + #.29 yROOH + #.2 XC 7.43E - 13 1.07E - 11 1.59 59,78

BE06 ISOPRENE + OH = #.986 RO2C + #.093 {RO2XC + zRNO3} + #.907 xHO2 + #.624 xHCHO + #.23 xMACR + #.32 xMVK + #.357 xIPRD + yR6OOH + # - 0.167 XC 9.96E - 11 2.54E - 11 - 0.81 1,65,79 BE07 ISOPRENE + O3 = #.266 OH + #.066 HO2 + #.192 RO2C + #.008 {RO2XC + zRNO3} + #.275 CO + #.122 CO2 + #.4 HCHO + #.1 PROD2 + #.39 MACR + #.16 MVK + #.15 IPRD + #.204 HCOOH + #.192 {xMACO3 + xHCHO} + #.2 yR6OOH + # - 0.559 XC 1.34E - 17 7.86E - 15 3.80 1,65

BE08 ISOPRENE + NO3 = #.936 RO2C + #.064 {RO2XC + zRNO3} + #.749 xHO2 + #.187 xNO2 + #.936 xIPRD + yR6OOH + # - 0.064 XC + #.813 XN 6.81E - 13 3.03E - 12 0.89 1,65 BE09 ISOPRENE + O3P = #.25 MEO2 + #.24 RO2C + #.01 {RO2XC + zRNO3} + #.75 PROD2 + #.24 xMACO3 + #.24 xHCHO + #.25 yR6OOH + # - 1.01 XC 3.50E - 11 65,79

BE10 ACETYLEN + OH = #.7 OH + #.3 HO2 + #.3 CO + #.7 GLY + #.3 HCOOH 7.56E - 13 Falloff, F=0.60, N=1.00 2,80,81

### Table A - 2 (continued)

150

Label Reaction and Products [a] Rate Parameters [b] Refs & k(300) A Ea B Notes [c] BE11 ACETYLEN + O3 = #.5 OH + #1.5 HO2 + #1.5 CO + #.5 CO2 1.16E - 20 1.00E - 14 8.15 2,81,82 BE12 BENZENE + OH = #.116 OH + #.29 {RO2C + xHO2} + #.024 {RO2XC + zRNO3} + #.57 {HO2 + CRES} + #.116 AFG3 + #.290 xGLY + #.029 xAFG1 + #.261 xAFG2 + #.314 yRAOOH + # - .976 XC 1.22E - 12 2.33E - 12 0.38 83

[a] Format of reaction listing: "=" s eparates reactants from products; "#number " indicates stoichiometric coefficient, "# coefficient { product list }" means that the stoichiometric coefficient is applied to all the products listed. [b] Except as indicated, the rate constants are given by k(T) = A · (T/300) B 

### · e - Ea/RT 

### , where the units of k and A are cm3 

### molec - 1 

### s - 1 

### , Ea are kcal mol - 1 

### , T is o

### K, and R=0.0019872 kcal mol - 1 

### deg - 1 

### . The following special rate constant expressions are used: Phot Set = name : The absorption cross sections and (if applicab le) quantum yields for the photolysis reaction are given in Table A - 3 , where " name " indicates the photolysis set used. If a "qy=number " notation is given, the number given is the overall quantum yield, which is assumed to be wavelength independent. Falloff : The rate constant as a function of temperature and pressure is calculated using k(T,M) = {k0(T)·[M]/[1 + k0(T)·[M]/kinf(T)]}· F Z 

### , where Z = {1 + [log10{k0(T)·[M])/kinf(T)}/N] 2 

### } - 1 

### , [M] is the total pressure in molecules cm- 3 

### , F and N are as indicated on the table, and the temperature dependences of k0 and kinf are as indicated on the table. k = k0+k3M(1+k3M/k2): The rate constant as a function of temperature and pres sure is calculated using k(T,M) = k0(T) + k3(T)·[M] ·(1 + k3(T)·[M]/k2(T)), where [M] is the total bath gas (air) concentration in molecules cm- 3, and the temperature dependences for k0, k2 and k3 are as indicated on the table. k = k1 + k2 [M]: The rate constant as a function of temperature and pressure is calculated using k(T,M) = k1(T) + k2(T)·[M], where [M] is the total bath gas (air) concentration in molecules cm- 3, and the temperature dependences for k1, and k2 are as indicated on the table . Same K as Rxn xx : Uses the same rate constant as the reaction in the base mechanism with the same label. [c] Footnotes documenting sources of rate constants and mechanisms are as follows. 1 Same as used or assumed in the SAPRC - 99 mechanism (Carter, 2000 a). 2 Rate constant or absorption coefficients and quantum yields based on NASA (2006) recommendation. Mechanism is also as recommended unless indicated by other footnotes. 3 Rate constant or absorption coefficients and quantum yields based on IUPAC (2 006) recommendation. Mechanism is also as recommended unless indicated by other footnotes. 4 Absorption cross - sections and quantum yields as recommended for 294 - 298K. This gives an 8% higher NO 2 

### photolysis rate for direct overhead sunlight than the action spectrum used in SAPRC - 99. Note that the net effect is to decrease rate constants for all other photolysis reactions by the same amount in environmental chamber simulations. 5 Separate recommendations are made for reactions with O 2 

### and N2 

### . Rate parameters used are derived to fit those calculated for a mixture of 20.95% O2 and 69.05% N2 

### over the temperature range of 250 - 350 o 

### K.

### Table A - 2 (continued)

151

6 See also Wahner et al (1998). 7 Absorption cross - sections recommended by NASA (2006) used, which are generally consistent with the IUPAC (2006) recommendations. The quantum yields for O 1 

### D formation are from the IUPAC (2006) recommendation; the NASA (2006) recommendations are consistent with these at the <306 and 329 - 340 nm range, but the parameterization for deriving quantum yields between these ranges did not give reasonable values. The quantum yield for O1D production is assumed to be zero in the high wavelength ration (wavelength > 390 nm. The O 3 

### P quantum yiel ds in the low wavelength regions are derived from the O 1 

### D quantum yields assuming unit total quantum yield for both processes. The O 3 

### P quantum yields are assumed to be unity in the high wavelength region. 8 NASA (2006) absorption cross - sections used, which give much greater resolution than those recommended by IUPAC (2006). IUPAC data sheet recommends assuming unit quantum yield for NO + OH formation throughout the relevant wavelength range. The absorption cross sections are essentially the same as use d in SAPRC - 99, but SAPRC - 99 has some formation of NO2 + H as well. 9 Rate expression from Golden et al (2003) and NASA (2006) for the reaction forming HNO 3 

### , using the NASA parameterization. The reaction forming HOONO is ignored, based on the assumption that it either decomposes or photolyzes back to the reactants. This expression is only slightly different than that given in the NASA (2003) recommendation, but gives a rate constant that is ~18% larger than that used in SAPRC - 99 for ambient conditions. 1 0 Absorption cross sections used in SAPRC - 99 are essentially the same as the NASA (2006) and IUPAC (2006) recommendations, so are not changed. Unit quantum yields are assumed. 11 Parameters derived to predict rate constants calculated from the temperature dependence expressions for the rate constants from the reverse reaction and the equilibrium constant as recommended by NASA (2006). 12 Absorption cross - sections from NASA (2006), and are essentially the same as used in SAPRC - 99. Unit quantum yield assumed, as is also the case for SAPRC - 99. 13 Measurements of the branching ratios vary, so the mechanism is uncertain. The SAPRC - 99 assignment is based on assuming the branching ratio is approximately in the middle of the range given in various evaluations, which is 0.6 - 1.0 for the OH - forming channel. 14 Methoxy radicals formed in the reaction assumed to react primarily with O2, forming HO2 + formaldehyde. 15 Recommendations are given for the total rate constant and the temperature dependence of the two competing processes. The kinetic parameters are derived so the calculated rate constants for the reactions agree with those derived from th e recommended total rate constant and rate constant ratio over the temperature range of 270 - 330 K. 16 Recommendations are given for total rate constant and the competing process only. The kinetic parameters for this process were adjusted to minimize th e sum of squares difference in rate constants between the rate constants calculated using the difference between the recommended rate constants and the calculated value, over the temperature range 270 - 330 K. 17 The species RO2C and RO2XC are used to represent the effects of peroxy radical reactions on NO, NO 2 

### , NO 3 

### , HO 2 

### , acyl peroxy radicals, and other peroxy radicals. RO2C is used to represent effects peroxy radicals that react with NO to form NO 2 

### (and the corresponding alkoxy radical, whose ultimate products re represented by separate xPROD species discussed below), while RO2XC represents effects of peroxy radicals that react with NO but do not form NO (i.e., to form organic nitrates that are represented by a separate zRNO3 species discussed below). Sep arate xPROD, yROOH, and zRNO3 species are used to represent the other radical

### Table A - 2 (continued)

152 and product species formed in peroxy radical reactions, which vary depending on the reactant and radicals formed. See separate footnotes given in conjunction with the reactions o f these species, and the discussion in the text concerning the general method used to represent peroxy radical reactions. 18 Rate constants used for generic peroxy radicals are based on recommendations for ethyl peroxy. See SAPRC - 99 mechanism documentati on (Carter, 2000) for a discussion of these peroxy radical operators. 19 Peroxy + peroxy reactions are assumed to proceed 1/2 the time forming two alkoxy radicals + O2, and the other half of the time by H - shift disproportionation reactions. 20 Rate exp ression from Bridier et al (1991), based on both NASA (2006) and IUPAC (2006) recommendations. Note that although this was intended to be the source of the rate constant used in the SAPRC - 99 mechanism (Carter, 2000a), it was incorrectly implemented using N=1 rather than N=1.61, as used by Bridier et al (1991). This amounts to about an 11% difference in the rate constants calculated for 298K and 1 atm. total pressure, but does not affect the equilibrium constant. 21 The branching ratio is based on an average of the values cited by IUPAC (2006). A third channel forming OH + O2 + CH3CO2 is assumed not to be important, though the data do not completely rule this out (IUPAC, 2005). Peroxyacetic acid (the co -product with O2) is represented by acetic acid to avoi d the necessity of adding a new species in the mechanism for this reaction. 22 No recommendations available for this rate constant. Use the same rate constant as used for generic peroxy + NO 3 

### reactions. 23 No recommendations available concerning the branching ratio. We assume that the maj or route is alkoxy radical formation, analogous to the route recommended to occur 90% of the time in the case of the reaction of acetyl peroxy with methyl peroxy. 24 Estimated assuming that the ratio of the rate const ant ratio for the reaction with NO 2 

### relative to reaction with NO is the same as for acetyl peroxy radicals at the high pressure limit. Tem perature dependence parameters derived to fit rate constants calculated using k(RCO3+NO) x kinf(CCO3+NO 2 

### )/k(CCO3+NO) o ver the temperature range 270 - 330 K. 25 The high pressure limit for the recommended PPN decomposition rate expression is used. This is to be consistent with the assumption that the formation reaction is at the high pressure limit, and also because this model species is used to represent higher PAN analogues in addition to PPN. The recommended rate expression for PPN gives a 1 atm rate constant that is about 90% the high pressure limit. 26 Photolyses of higher PAN analogues are assumed to occur with same action spectrum and analogous mechanism as the photolysis of PAN. 27 Rate constants used for generic acyl peroxy radicals and generic higher PAN analogues based on those for R=C 2 

### H 5 

### . See SAPRC - 99 documentation (Carter, 2000). 28 Reaction is assumed to be analogous to that for MECO3. Where applicable, the peroxy acid is represented by the corresponding acid to avoid adding a separate species to the mechanism to represent these products. Reaction with peroxy radicals is assumed to proceed primarily via alkoxy radical formation, the major (90%) pathway for the MECO3 + MEO2 reaction. 29 Rate constant expression based on the data of Kirchner et al (1992). 30 Rate parameters from Roberts and Bertman (1992), as used by Carter and Atkinson (1996). 31 This is added to avoid problems in the (generally unlikely) conditions where phenoxy radicals are formed when concentrations of both NO 2 

### and HO 2 

### are low. The rate constant used is that used in the SAPRC - 99 mechanism, which is arbitrary and is such that this pro cess becomes

### Table A - 2 (continued)

153 significant only if [NO 2 

### ] < ~3x10 - 6 ppm and [HO 2 

### ] < 1x10 - 5 

### ppm. The likely process is reaction with some VOC forming phenol and radicals, with the latter represented by RO2R. 32 The xPROD chemical operator species are used to represent the f ormation of radicals and products from alkoxy radicals formed in the reactions of peroxy radicals with NO, NO 3 

### , acyl peroxy radicals, and, in ~50% yields, with other peroxy radicals. These products are not formed when peroxy radicals react with HO 2 

### , and, in ~50% yields, with other peroxy radicals, since those reactions are assumed not to form alkoxy radicals, but instead form hydroperoxides or H - shift disproportion products that are represented by separate yROOH chemical operator species, discussed in a sep arate footnote. The reactions of peroxy radicals with other peroxy radicals are assumed to form alkoxy radicals 50% of the time, so the products from alkoxy radical reactions are represented as being formed in 50% yields in these reactions. The consumption and products formed from these species can be represented in several ways. The most straightforward method is to include a reaction for each of the types of peroxy radical reactions, as follows: xPROD + NO  NO + PROD xPROD + HO2  HO2 xPROD + NO3  NO3 + PROD xPROD + MECO3  MECO3 + PROD (& similar reactions for RCO3, BZCO3, and MACO3) xPROD + MEO2  MEO2 + 1/2 PROD xPROD + RO2C  RO2C + 1/2 PROD (& a similar reaction for RO2XC) where "PROD" represents the product species for the operator (e.g., HO2 for xHO2). The rate constants for these reactions should be the same as the rate constant for the corresponding reactions of RO2C or RO2XC. This is a somewhat cumbersome method because it requires 9 reactions for each of the many xPROD species. An alternative method, implemented in this table, uses the coefficient "RO2RO" to determine the rate of formation of the product species and "RO2XRO" to represent processes where the product is not formed. These are calculated as follows, where the k(RO2+..)'s refer to the rate constants for the reactions of RO2C or RO2XC with the indicated reactant. RO2RO = k(RO2+NO)[NO] + k(RO2+NO3)[NO3] + k(RO2+MECO3){[MECO3]+[RCO3]+

[BZCO3]+[MACO3]) + 0.5 k(RO2+MEO2)[MEO2] + 0.5 k(RO2+RO2) {[RO2C]+[RO2XC]) RO2XRO = k(RO2+HO2)[HO2] + 0. 5 k(RO2+MEO2)[MEO2] + 0.5 k(RO2+RO2){[RO2C]+

[RO2XC]) The steady state approximation must be used for these operators when this representation is used, and the operators must not be allowed to be diluted or transported. 33 The 298K rate constant is as estimated by IUPAC (2006). The temperature dependence used in the SAPRC - 99 mechanism is consistent with this, so is retained here. 34 This reaction is not believed to be important under atmospheric conditions or in the conditions of the chamber experiments used for mechanism evaluation. The adduct is believed to rapidly rearrange to HOCH 2 

### OO·, which can react with NO to ultimately form NO 2 

### and formic acid, or decompose back to formaldehyde + HO 2 

### , resulting in no net reaction. Based on the rate constants for the HOCH 2 

### OO· decomposition recommended by IUPAC (2006) and the expected peroxy + NO rate constant, the reaction with NO is expected to be negligible unless NO is so high that HO 2 

### levels are suppressed, so the decomposition, resulting in no net reaction, is expected to dominate. Sensitivity calculations with versions of the mechanism incorporating this reaction confirmed the negligible impact of this process. 35 Mechanism of propionaldehde used for RCHO. IUPAC (2006) recommendation used for total

### Table A - 2 (continued)

154 rate con stant. No useful recommendation given for mechanism. 36 Mechanism based on estimated relative rates of reactions at various positions and estimated rate constants or rate constant ratios for reactions of the various radicals formed, derived using current SAPRC mechanism generation system. For this reaction the generated mechanism should be essentially the same as the version developed with the SAPRC - 99 mechanism (Carter, 2000a). 37 The absorption cross sections recommended by IUPAC (2006) are the same a s used in the SAPRC - 99 mechanism. There is a discrepancy in the quantum yields at higher wavelengths from recent measurements from Chen and Ziu (2001), which indicate no falloff at the higher wavelengths, and earlier measurements from Heicklen et al (1986) that indicated a falloff in quantum yields and was the basis of previous recommendation and the propionaldehyde photolysis rates used in the SAPRC - 99 mechanism (Carter, 2000a). IUPAC (2006) and NASA (2006) make no recommendations in this regard. We assume that the earlier values are more representative of atmospheric conditions because they were based on measurements made in air while the more recent measurements were in N2 

### , and the possibility that the falloff could be due to quenching by O 2 

### , and because the photolysis rates obtained are more consistent with those measured in the Euphore chamber (Wirtz et al, 1999). Therefore, the earlier quantum yields, as used in the SAPRC - 99 mechanism, are retained. 38 298K rate constant is that recommended by IUPAC ( 2006) for propionaldehyde. Tem perature dependence estimated by assuming this reaction has same A factor as reaction of NO 3 

### with acetaldehyde. 39 Tem perature - dependent parameters derived to give best fits to the IUPAC (2006) - recommended temperature dependence expression for the temperature range 270 - 330 K. These parameters give a good estimate of the recommended rate constant at ~300 o 

### K, but underestimate the recommended rate constants by about 2% at both ends of this temperature range. 40 Absorption cro ss sections are for T=298 o

### K. Quantum yields are calculated for 1 atm and T=298 o 

### K using the complex expression recommended by IUPAC (2006) and NASA (2006). Separate recommendations are given for temperature, pressure, and wavelength - dependent quantum yields for formation of CO and formation of CH 3 

### CO, and the calculated fraction of the CO formation process relative to total fragmentation to radicals ranges from 35% to 52% for zenith angle of 0 to 80, respectively. The ratios for the indoor light sources used in the chamber experiments used for evaluating the mechanism are in this range. Rather than have two separate photolysis processes in the mechanism, a wavelength - independent ratio of 48% is assumed, which represents the weighed average of these values. How ever, using the quantum yields derived in this way gives photolysis rates that are about 1.6 times higher than used in SAPRC - 99 and significantly overpredicts reactivity in acetone incremental reactivity experiments. In order to remove this bias, it is nec essary to reduce the photolysis rates by about a factor of 2, i.e., assume the quantum yields are 1/2 the values derived using the recommended method. This inconsistency between the laboratory data and the chamber experiments need to be evaluated. However, the quantum yields that give the better fits to the chamber data are used because they are a better approximation of atmospheric conditions. 41 Absorption cross - sections from IUPAC (2006) recommendation, but are essentially the same as used in SAPRC - 99. The IUPAC (2006) -recommended overall quantum yield is 0.24 (with no recommendation given for wavelength dependence of quantum yields), but this results in a bias towards overpredicting reactivity in MEK incremental reactivity experiments. The data are better fit using an overall quantum yield of 0.175, which is slightly higher than the 0.15 value used in the SAPRC - 99 mechanism, based on simulations of the same experiments.

### Table A - 2 (continued)

155

42 The reaction would involve the eventual formation of HO 2 

### + CO 2 

### regardless of which hydrogen were abstracted in the initial reaction. 43 Branching ratio used for formation of ·CH 2 

### OOH vs. CH 3 

### OO· is as recommended by NASA (2006). ·CH 2 

### OOH is assumed to rapidly decompose to formaldehyde + OH. 44 Mechanism generation system updated to predict the NASA (2006) recommended rate constant and branching ratio for the reaction of OH with methyl hydroperoxide. The generated mechanism for n -propyl hydroperoxide incorporates the substituent effects for the - OOH group derived from this rate constant and branching ratio. 45 Mechanism for ROOH based on estimated reactions for n -propyl hydroperoxide. Photolysis and rate of reaction of OH at OOH assumed to occur at same rate as for methyl hydroperoxide. 46 Mechanism for R6OOH based on estimated re actions for 3 -hexyl hydroperoxide. Photolysis and rate of reaction of OH at OOH assumed to occur at same rate as for methyl hydroperoxide. 47 Mechanism for RAOOH is based on estimated reactions of two isomers expected to be formed in the m -xylene system. Mechanism derived using the mechanism generation system based on estimated reactions at various positions, and assumptions for the maj or process for some alkoxy radical reactions that could not be estimated using the current system. Photolysis and rates o f reaction of OH at OOH assumed to occur at the same rate as for methyl hydroperoxide. 48 Absorption cross sections used are those given by Volkamer et al (2005), which supercede the values of Plum et al (1983) used in previous recommendations. For wavel engths up to 350 nm, the quantum yields for radical production are based on those of Zhu et al (1996), which are consistent with the data of Langford and Moore (1984). The quantum yields for formaldehyde + H 2 

### production are derived based on assuming a total quantum yield of 1 in this wavelength region. For the higher wavelength region, the decline in quantum yields as a function of wavelength are derived to give photolysis rates, relative to those for NO 2 

### , that are consistent with the data of Klotz et al (2 000) based on assuming solar spectral distributions with zenith angles between 0 and 40 degrees, and that are also consistent with the formaldehyde yields, relative to total photolysis, of 13%, as given by Plum et al (1983). In both cases, the quantum yiel d is assumed to decline exponentially as a function of wavelength below 350 nm, with the decay rate adjusted to give the photolysis rate consistent with the data referenced above. 49 Mechanism based on branching ratios for subsequent reactions of the radicals formed as given by IUPAC (2006) for 1 atm air at 298 o

### K. 50 No data available for the kinetics of this reaction. Rate parameters used in SAPRC - 99 used. See Carter (2000) for method used to estimate rate constant. HCO(CO)OO. and RCO(CO)OO are represented by the lumped higher acyl peroxy species RCO3. 51 Recommended cross sections are essentially the same as used in SAPRC - 99. Quantum yields calculated using the temperature - and wavelength - dependence expression recommended by IUPAC (2006) for 760 torr N2 

### give an overall photolysis rate, relative to NO 2 

### , for ambient photolysis which are lower than those reported by Klotz et al (2003) for the Euphore outdoor chamber. However, if the quantum yields are calculated for a pressure of 472 torr, the calculated photolysis rate relative to NO 2 

### for ambient conditions agree with the data of Klotz et al (2003). Therefore, this adjustment is adopted for the quantum yields used for this mechanism. 52 The evaluations give no recommendations for the photolysis of biac etyl. The absorption cross sections used are those from Plum et al (1983), as used in the SAPRC - 99 mechanism. Quantum yields calculated using the IUPAC (2006) -recommended expression for the pressure

### Table A - 2 (continued)

156 and wavelength - dependence quantum yields for methyl glyox al, but with the effective pressure adjusted so the photolysis rate, relative to that for NO 2 

### , under ambient conditions is consistent with that measured by Klotz et al (2000) in the Euphore outdoor chamber. 53 Rate constant expression as recommended by C alvert et al (2002) for o - cresol. 54 "CRES" is used to represent phenol and cresols. (Phenol was represented separately in SAPRC - 99 but is lumped with cresols in this mechanism because the lumping had no significant effect on model simulations and the me chanisms of both are highly uncertain and approximate.) Available data (Berndt and Boge, 2003 and Olariu et al 2002) indicate that dihydroxy phenol or cresol formation occurs ~60 - 80% of the time, and kinetic data cited by Berndt and Boge (2003) suggest that in the case of phenol under atmospheric conditions OH addition occurs ~75 - 80% of the time, with phenoxy formation occurring the remainder of the time. This suggests that dihydroxybenzene formation (with HO 2 

### as the co -product) is the maj or fate of the OH addition reaction. However, this mechanism cannot simulate results of the cresol - NO x 

### air chamber experiments. In order to simulate the reactivity in those experiments, it is necessary to assume additional NO to NO 2 

### conversions occur, and it is also neces sary to some photoreactive product, such as methyl glyoxal, is also formed. In view of the inconsistency between chamber and laboratory data concerning this reaction, we retain the parameterization used in the SAPRC - 99 mechanism (Carter, 2000), which was f ound to perform the best in simulating the chamber data, after some minor adjustments to optimize fits to the data with the current mechanism. This is consistent with the laboratory data in assuming ~20% phenoxy radical formation, but does not appear to be consistent with other laboratory data in assuming an additional NO to NO 2 

### conversion is occurring. The photoreactive product(s) are represented by methyl glyoxal, which gives reasonable simulations of the observed PAN yields in the cresol experiments (Car ter, 2000). 55 Rate constant is in the range cited by Barnes (2006) for various nitrocresols. Reaction is assumed to occur via abstraction of H from OH, analogous to pathway in the phenol and cresol + OH reactions that occur with similar rates. 56 Photolysis rate forming HONO, relative to the photolysis rate of NO 2 

### , based on the data of Bej an et al (2006) for 2 -nitrophenol and various methyl substituted 2 -nitrophenols. The co products are unknown, and are assumed to go mainly into the particle phase and its gas -phase reactivity is assumed not to be significant. Loss by other photolysis processes mi ght be significant, but are ignored. 57 Nitrophenols were found to have lifetimes relative to photolysis in the Euphore chamber of 1 - 2 hours (Barnes, private communication, 2007). A photolysis rate relative to NO 2 

### of 0.015 corresponds approximately to this range. The products formed are unknown, but based on the data of Bejan et al (2006) it is apparent that NO 2 

### formation is not important and that HONO formati on represents only about 10% of this process. We assume that the products are unreactive. 58 As with SAPRC - 99, is assumed that all the reaction is at the - CHO group, and that addition to the ring is negligible. 59 Rate constant is as recommended or tabulated by Atkinson and Arey (2003). 60 Absorption cross - sections recommended by Calvert et al (2002). Overall quantum yield based on that of SAPRC - 99 mechanism, which was adjusted to approximately fit the rate of consumption of benzaldehyde measured in chamber experiments. However, the new absorption cross sections result in a ~17% decrease in the solar photolysis rate for benzaldehyde, so the overall quantum yield is adjusted upward by the same factor to yield the same overall photodecomposition rate. Th e mechanism is the same as in SAPRC - 99, which is based on the fact that the products are unknown but are apparently unreactive, and not

### Table A - 2 (continued)

157 benzene. 61 The 298 o

### K rate constant recommended by Atkinson (1994). Tem perature dependence estimated by assuming the reaction has the same A factor as the reaction of NO 3 

### with acetaldehyde. This gives the same 298 o 

### K rate constant but a slightly different temperature dependence than used in SAPRC - 99. 62 AFG1 and AFG2 are used to represent the photoreactive monounsaturate d dialdehyde or aldehyde -ketone aromatic ring fragmentation products. Their mechanistic parameters are based on those for 2 -butene 1,4 - dial (10%), 2 - methyl - 2 -butene - 1,4 - dial (21%), 4 - oxo - 2 - petenal (37%), and 2 -methyl -4 - oxo - 2 -pentenal (32%). The action spec trum for the photolysis reactions of both species is also based on weighted averages of action spectra assigned to those species. The weighting factors used for each are based on the relative yields monounsaturated dialdehydes or aldehyde - ketones estimated for toluene and the di - and tri methylbenzene isomers, each weighed equally, with 2,3 - dimethyl - 2 -butene - 1,4 - dial represented by 2 - methyl - 2 -butene - 1,4 - dial, and 3 - methyl -4 - oxo - 2 -penetnal and 2,3 - dimethyl 4 - oxo - 2 -pentenal represented by 2 - methyl -4 - oxo - 2 -pentenal. AFG1 is used to represent those compounds (or portions of the mechanisms) that photolyze to form radicals, while AFG2 is used to represent those which photolyze to form non -radical products, and each have the same OH and O 3 

### mechanism and overall action spectrum. 63 The mechanisms for the radical formation photolysis for AFG1 is based on that derived for the radical formation photolysis of the species used to derive the mechanistic parameters for the OH and O 3 

### reactions. The stable species formed in the photolysis of AFG2 are represented by PROD2. 64 AFG3 is used to represent the diunsaturated dicarbonyl products and also the monounsaturated diketone aromatic ring fragmentation products, which are assumed to have relatively low photoreactivity. There mechanisms are based on those derived for the diunsaturated dicarbonyl products 3 - methyl 2,4 -hexene - 1,6 - dial (54%), 6 - oxo - 2,4 -heptadienal (66%), and 3,5 - octadien - 2,7 - dione (6%). The weighting factors used are based on estimated diunsaturated dicarbonyls for toluene and the di - and tri - methylbenzene isomers, each weighed equally, with 2,4 -hexene - 1,6 - dial representing all dialdehydes, 3,5 - octadien - 2,7 - dione representing aldehyde -ketones, and 3,5 - octadien - 2,7 - dione representing the diketones. Although this model species is also used to represent the monounsaturated diketone products, which are also assumed to be relatively unphotoreactive, they are formed by only a few isomers and their parameters are not used to derive those used for AFG3. (Representing them explicitly does not yield significantly improved simulations of p -xylene, and 1,2,4 -trimethylbenzene, the only compounds with chamber data where such products are predicted to be formed.) 65 Except as indicated in other footnotes, the mechanism is as given by Carter (1996), based on the detailed mechanism of Carter and Atkinson (1996). (The rate constant and mechanism is unchanged from SAPRC - 99 if footnote "1" is also given). 66 IUPAC (2006) recommendation of rate constant at 298 o 

### K used. Tem perature dependence is estimated using the estimated A factor given used in the SAPRC - 99 mechanism, based on the estimate of Carter and Atkinson (1996). 67 Absorption cross sections recommended by IUPAC (2006) used. No recommendations given for quantum yield. The quantum yields were derived using the pressure and wavelength dependent expression given by IUPAC (2006) for MVK, with the total pressure adjusted so that the radical forming photolysis rates for the chamber experiments are the same as those derived by Car

ter and Atkinson (1996) to fit the chamber experiments with methacrolein. 68 Absorption cross sections recommended by IUPAC (2006) used. IUPAC (2006) also gives recommendations for quantum yields for total photodecomposition as a function of

### Table A - 2 (continued)

158 wavelength and pressure, and recommend assuming 60% forms propene + CO and the remainder involves radical formation. However, this recommendation gives photolysis rates for radical formation that are significantly higher than those found to fit chamber data for MVK (C arter and Atkinson, 1996). Using an effective pressure of 5 atmospheres gives radical formation photolysis that is consistent with modeling the chamber data, and is used in this mechanism. This is not inconsistent with the IUPAC (2006) recommendations because they stated that their recommended quantum yields should be considered to be upper limits. Iti s assumed that the radical formation process involves formation of CH 3 

### + CH 2 

### =CHCO·, as was assumed in the SAPRC - 99 mechanism. 69 Consistent with the assump tion in the SAPRC - 99 mechanism, all species represented by ISOPROD are assumed to have the same action spectrum for photolysis as used for acrolein. As indicated in the footnotes for the methacrolein photolysis reaction, some modifications were made to the methacrolein action spectrum but the photolysis rates for conditions of chamber experiments are essentially the same as used in SAPRC - 99. The other aspects of this reaction are not changed. 70 PROD2 is used to represent the more reactive non - aldehyde organic products formed in the photooxidations of various VOCs. As with SAPRC - 99, its mechanism is based on those derived for representative product compounds that are represented by PROD2, which were chosen to be CH 3 

### C(O)CH 2 

### CH 2 

### CH 2 

### OH, CH 3 

### C(O)CH 2 

### CH(CH 3 

### )CH 2 

### OH, CH 3 

### CH 2 

### C(O)CH 2 

### - CH 2 

### CH(CH 3 

### )OH, CH 3 

### CH 2 

### C(O)CH 2 

### CH 2 

### CH(OH)CH 2 

### CH 3 

### , and CH 3 

### CH 2 

### CH 2 

### CH(OH)CH 2 

### - CH 2 

### C(O)CH 2 

### CH 3 

### (Carter, 2000a). The rate constants and mechanisms for these compounds (designated PROD2 - 1 through 5, respectively) were derived using the mechanism generation s ystem, and are given in Table B -4 in Appendix B. The mechanisms for PROD2 were derived by weighing those for each of these representative compounds equally. 71 Absor

ption cross - sections for methyl ethyl ketone used for general ketone photolysis, with quantum yields declining monotonically with carbon number (see discussion of general ketone photolysis elsewhere in this report). Overall quantum yields and mechanisms averages for the compounds used to derive the mechanism for PROD2. 72 As with SAPRC - 99, the mechanism for the lumped organic nitrate product species is based on those derived for 6 compounds chosen to be representative of thee compounds, specifically CH 3 

### CH 2 

### CH(CH 3 

### )ONO 2 

### , CH 3 

### CH(OH)CH 2 

### CH 2 

### CH 2 

### ONO 2 

### , CH 3 

### CH 2 

### CH(CH 3 

### )CH(CH 3 

### )ONO 2 

### , CH 3 

### CH 2 

### CH 2 

### CH 2 

### CH 2 

### CH(ONO 2 

### )CH 2 

### OH, CH 3 

### CH 2 

### C(CH 3 

### )(ONO 2 

### )CH 2 

### CH(CH 3 

### )CH 3 

### , and CH 3 

### - CH 2 

### CH 2 

### CH 2 

### CH 2 

### CH 2 

### CH 2 

### CH(ONO 2 

### )CH 2 

### CH 3 

### (RNO3 - 1 through 6) (Carter, 2000a). The rate constants and mechanisms for these compounds were derived using the current mechanism generation system, which should be similar to those predicted using the SAPRC - 99 mechanism generation system documented by C arter (2000a). The mechanisms for RNO3 were derived by weighing those for each of these representative compounds equally. 73 Absorption cross section for isopropyl nitrate as given by IUPAC (2006) used, assuming unit quantum yields. This is the same as u sed for RNO3 in SAPRC - 99. 74 The zRNO3 chemical operator species is used to represent the formation organic nitrates formed when peroxy radicals react with NO, or formation of radicals and products from alkoxy radicals formed in the reactions of peroxy radicals with NO 3 

### , acyl peroxy radicals, and (in ~50% yields) with other peroxy radicals. These products are not formed when peroxy radicals react with HO 2 

### and (in the other ~50% of the time) with other peroxy radicals, since those reactions are assumed not form organic nitrates or alkoxy radicals, but instead form hydroperoxides or H - shift disproportion products that are represented by separate yROOH chemical operator species, discussed in a separate footnote. At present the mechanism has only one zRNO3 operator to correspond to the single lumped organic nitrate model species, but other such operators can be added if it is desired to have separate organic nitrate model

### Table A - 2 (continued)

159 species, such as, for example, those to represent semi - volatile organic nitrates that may contribute to SOA. In the case of zRNO3, the products resulting if alkoxy radicals are formed in the RCO3 or RO2 reactions would depend on reactant and individual radicals, and are approximated by PROD2 and HO2 (as might occur following the reaction of a peroxy radical with O 2 

### to form HO 2 

### and a ketone species). As with the xPROD species, the consumption and products formed from these species can be represented in several ways, with the most straightforward method being to include a reaction for each of the types of peroxy radical reactions, as follows: zRNO3 + NO  NO + RNO3 zRNO3 + HO2  HO2 zRNO3 + NO3  NO3 + PROD2 + HO2 zRNO3 + MECO3  MECO3 + PROD2 + HO2 (& similar reactions for RCO3, BZCO3, and MACO3) zRNO3 + MEO2  MEO2 + 1/2 {PROD2 + HO2} zRNO3 + RO2C  RO2C + 1/2 {PROD2 + HO2} (& a similar reaction for RO2XC) The rate constants for these reactions should be the same as the rate constant for the corresponding reactions of RO2C or RO2XC. As with xPROD, an alternative method, requiring fewer reactions, is implemented in this table. In this case, the coefficient "RO2NO" is used to determine the rate of formation of organic nitrates, "RO22NN" is used to determine the rate of formation of the alkoxy radical products, and "RO2XRO" is used to repre sent processes where these products are is not formed, and is the same as used for xPROD. These are calculated as follows, where the k(RO2+..)'s refer to the rate constants for the reactions of RO2C or RO2XC with the indicated reactant. RO2NO = k(RO2+NO)[N O] RO22NN = k(RO2+NO3)[NO3] + k(RO2+MECO3){[MECO3]+[RCO3]+[BZCO3]+

[MACO3]) + 0.5 k(RO2+MEO2)[MEO2] + 0.5 k(RO2+RO2){[RO2C]+ [RO2XC]) RO2XRO = k(RO2+HO2)[HO2] + 0.5 k(RO2+MEO2)[MEO2] + 0.5 k(RO2+RO2){[RO2C]+

[RO2XC]) (same as used for xPROD) The steady state approximation must be used for these operators when this representation is used, and the operators must not be allowed to be diluted or transported. 75 The yROOH chemical operator species is used to represent the formation of organic hydroperoxides fo rmed with peroxy radicals react with HO 2 

### , or of H - shift disproportionation products formed when peroxy radicals react (in 50% yields) with other peroxy radicals. Note that the products formed when peroxy radicals react to form alkoxy radicals or organic nitrates (in the NO reaction) are represented using separate xPROD or zRNO3 species, and together these three types of operators represent all the products and radicals formed. Separate such yROOH species are used to represent formation of hydroperoxides or H - shift disproportion products in different molecular weight ranges or volatilities, and more can be added as needed for appropriate predictions of SOA formation. The hydroperoxide formed in the HO2 reaction is represented by either ROOH, R6OOH, or RAOOH, and the H - shift disproportion products are represented by either MEK (for yROOH) or PROD2 (for the others). As with the xPROD and zRNO3 species, the consumption and products formed from these species can be represented in several ways, with the most straightforward method being to include a reaction for each of the types of peroxy radical reactions, as follows for yROOH (the reactions for the other two are analogous). yROOH + NO  NO yROOH + HO2  HO2 + ROOH

### Table A - 2 (continued)

160 yROOH + NO3  NO3 yROOH + MECO3  MECO3 (& similar reactions for RCO3, BZCO3, and MACO3) yROOH + MEO2  MEO2 + 1/2 MEK yROOH + RO2C  RO2C + 1/2 MEK (& a similar reaction for RO2XC) The rate constants for these reactions should be the same as the rate constant for the corresponding reactions of RO 2C or RO2XC. As with the other operators, an alternative method, requiring fewer reactions, is implemented in this table. In this case, the coefficient "RO2HO2" is used to determine the rate of formation of organic hydroperoxides, "RO2RO2M" to determine th e rate of formation of H - shift disproportion products, and "RO2RO" is used to represent processes where these products are is not formed. Note that the latter is the same as the coefficient that is used to represent the formation products from the xPROD sp ecies. These are calculated as follows, where the k(RO2+..)'s refer to the rate constants for the reactions of RO2C or RO2XC with the indicated reactant. RO2HO2 = k(RO2+HO2)[HO2] RO2RO2M = 0.5 k(RO2+RO2){[RO2C]+ [RO2XC]) RO2RO = k(RO2+NO)[NO] + k(RO2+NO3)[NO3] + k(RO2+MECO3){[MECO3]+[RCO3]+

[BZCO3]+[MACO3]) + 0.5 k(RO2+MEO2) [MEO2] + 0.5 k(RO2+RO2) {[RO2C]+[RO2XC]) The steady state approximation must be used for these operators when this representation is used, and the operators must not be allowed to be di luted or transported. 76 The mechanism is the same as used in SAPRC - 99, but the rate constant was updated based on a more recent evaluation. 77 Criegee biradical stabilization yield as recommended by Atkinson (1997) and IUPAC (2006). OH yield of 16% used based on recommendation of IUPAC (2006), which is higher than the 12% yield recommended by Atkinson (1997). The yields of the other decomposition pathways based on Atkinson (1997) recommendations except they were reduced by 8% to account for the higher OH yield of the IUPAC (2006) recommendation. 78 Radical fragmentation distribution as recommended by Calvert et al, (2000), ignoring H 2 

### + ketene route. Although Calvert et al. (2000) recommends assuming 95% fragmentation, it is necessary to assume ~20 % stabilization to remove biases in model simulations of ethene. This is consistent with the need to assume more -than -recommended stabilization in the analogous reaction of propene to remove biases in model simulations of propene experiments. However, this is somewhat lower than the ~50% stabilization used in the SAPRC - 99 mechanism to remove biases in simulations of the ethene experiments. 79 Rate constant expression as recommended by Calvert et al (2000) 80 Acetylene is added as an explicitly represent ed compound in the current base mechanism because of its relatively large emissions and the fact that it is not well represented by other lumped species in the mechanism. 81 The mechanism is derived as discussed by Carter et al (1997c), based in part on the data of Hatakeyama et al (1986) and in part of adjustments to fit chamber data, except that in order to fit chamber data with the current mechanism it is necessary to assume that all of the initial reaction with OH results in the formation of HOCH=CH. radicals. 82 The mechanism is based on assuming the initially formed adduct rearranges to form excited HCOCHOO Crigiee biradicals. The subsequent reaction of this excited biradical is unknown, but it is assumed that decomposition is dominant, forming CO + HCO + OH half the time and HCO 2 

### · + HCO the other half.

### Table A - 2 (continued)

161

83 Benzene is added as an explicitly represented compound in the current base mechanism because of its non -negligible emissions and the fact that it is not well represented by the other lumped aromatic species in the mechanism. The rate constant expression is as recommended by Atkinson and Arey (2003). The mechanism employs the general mechanism formulation used for aromatics in this version of the mechanism. The yield of phenol (represented by CRES) is the average of values of Berndt and Boge (2006) and Volkamer et al (2002). This is significantly higher than the values used in the SAPRC - 99 mechanism (Carter, 2000a). The glyoxal yield is as determined by Berndt and Boge (2006), which is reasonably consistent with previous studies. AFG1 and AFG2 represent the co -product(s) formed with the alpha dicarbonyls, which react with the same mechanism except that AFG1 is highly pho toreactive and AFG2 is not, and with their relative yields adjusted to fit ozone reactivity results in the benzene - NO x 

### cham

ber experiments. AFG3 is used to represent ring fragmentation products not involving alpha - dicarbonyl formation, which is assumed to involve formation of OH without NO to NO 2 

### conversions. The yields of OH, HO 2 

### , and RO2R are derived as used for general aromatics mechanisms, and are equal to the yields of AFG3, phenol, and total alpha dicarbonyls, respectively.

### 162

Table A - 3 . Absorption cross - sections and quantum yields for the all photolysis reactions in the base

mechanism. (Available in electronic form only) **Because of the size of this table, it is only available in as supplementary material in electronic form. See Appendix D.**  Table A -4 . List of model species used in the base chlorine SAPRC - 07 mechanism . Name Description Active Inorganic Species. CL2 Chlorine molecules CLNO ClNO CLONO ClONO CLNO2 ClNO2 CLONO2 ClONO2 HOCL HOCl HCL Hydrochloric acid Active Radical Species and Operators. CL Chlorine atoms CLO ClO. Radicals Steady state operators used to represent radical or product formation in peroxy radical reactions. xCL Formation of Cl radicals from alkoxy radicals formed in peroxy radical reactions with NO

and NO 3 

### (100% yields) and RO 2 

### (50% yields) xCLCCHO As above, but for CLCCHO xCLACET As above, but for CLACET Active Organic Product Species CLCCHO Chloroacetaldehyde (and other alpha - chloro aldehydes that are assumed to be similarly

photoreactive) CLACET Chloroacetone (and other alpha - chloro ketones that are assumed to be similarly

photoreactive) Low Reactivity Com

pounds Represented as Unreactive CLCHO Formyl Chloride

### 163

Table A - 5 . Listing of reactions and rate parameters added to represent the reactions of chlorine

species in the SAPRC - 07 mechanism. Label Reaction and Products [a] Rate Parameters [b] Refs & Notes [c] k(298) A Ea B Base Chlorine Mechanism CI 01 CL2 + HV = #2 CL Phot Set= CL2 1 CL + O2 + M = CLO2. + M (Ignored) 3 CLO2. + M = CL + O2 + M (Ignored) 3 CI 02 CL + NO + M = CLNO + M 7.60e - 32 7.60e - 32 0.00 - 1.80 2 CI 03 CLNO + HV = CL + NO Phot Set= CLNO - 06 1 CI 04 CL + NO2 = CLONO 1.60e - 11 Falloff, F=0.60, N=1.00 2 0: 1.30e - 30 0.00 - 2.00 inf: 1.00e - 10 0.00 - 1.00 CI 05 CL + NO2 = CLNO2 3.52e - 12 Falloff, F=0.60, N=1.00 2 0: 1.80e - 31 0.00 - 2.00 inf: 1.00e - 10 0.00 - 1.00 CI 06 CLONO + HV = CL + NO2 Phot Set= CLONO 1 CI 07 CLNO2 + HV = CL + NO2 Phot Set= CLNO2 1 CI 08 CL + HO2 = HCL + O2 3.44e - 11 3.44e - 11 0.00 - 0.56 1,4 CI 09 CL + HO2 = CLO + OH 9.41e - 12 9.41e - 12 0.00 2.10 4 CI 10 CL + O3 = CLO + O2 1.22e - 11 2.80e - 11 0.50 1 CI 11 CL + NO3 = CLO + NO2 2.40e - 11 1 CI 12 CLO + NO = CL + NO2 1.66e - 11 6.20e - 12 - 0.59 1 CI 13 CLO + NO2 = CLONO2 2.29e - 12 Falloff, F=0.60, N=1.00 2 0: 1.80e - 31 0.00 - 3.40 inf: 1.50e - 11 0.00 - 1.90 CI 14 CLONO2 + HV = CLO + NO2 Phot Set= CLONO2 - 1 1 CI 15 CLONO2 + HV = CL + NO3 Phot Set= CLONO2 - 2 1 CI 16 CLONO2 = CLO + NO2 4.12e -4 Falloff, F=0.60, N=1.00 5 0: 4.48e - 5 24.90 - 1.00 inf: 3.71e+15 24.90 3.50 CI 17 CL + CLONO2 = CL2 + NO3 1.01e - 11 6.20e - 12 - 0.29 1 CI 18 CLO + HO2 = HOCL + O2 6.83e - 12 2.20e - 12 - 0.68 1 CI 19 HOCL + HV = OH + CL Phot Set= HOCL - 06 1 CI20 CLO + CLO = #.29 CL2 + #1.42 CL + O2 1.82e - 14 1.25e - 11 3.89 6 CI21 OH + HCL = H2O + CL 7.90e - 13 1.70e - 12 0.46 1 CI22 CL + H2 = HCL + HO2 1.77e - 14 3.90e - 11 4.59 1 Chlorine reactions with common organic products CP01 HCHO + CL = HCL + HO2 + CO 7.33e - 11 8.10e - 11 0.06 1 CP02 CCHO + CL = HCL + MECO3 8.00e - 11 8.00e - 11 1 CP03 MEOH + CL = HCL + HCHO + HO2 5.50e - 11 5.50e - 11 0.00 1

### Table A - 5 (continued)

164

Label Reaction and Products [a] Rate Parameters [b] Refs & Notes [c] k(298) A Ea B CP04 RCHO + CL = HCL + #.9 RCO3 + #.1 {RO2C + xCCHO + xCO + xHO2 + yROOH} 1.23e - 10 7 CP05 ACET + CL = HCL + RO2C + xHCHO + xMECO3 + yROOH 2.75e - 12 7.70e - 11 1.99 2 CP06 MEK + CL = HCL + #.975 RO2C + #.039 RO2XC + #.039 zRNO3 + #.84 xHO2 + #.085 xMECO3 + #.036 xRCO3 + #.065 xHCHO + #.07 xCCHO + #.84 xRCHO + yROOH + #.763 XC 3.60e - 11 1,8

CP07 RNO3 + CL = HCL + #.038 NO2 + #.055 HO2 + #1.282 RO2C + #.202 RO2XC + #.202 zRNO3 + #.009 RCHO + #.018 MEK + #.012 PROD2 + #.055 RNO3 + #.159 xNO2 + #.547 xHO2 + #.045 xHCHO + #.300 xCCHO + #.020 xRCHO + #.003 xACET + #.041 xMEK + #.046 xPROD2 + #.547 xRNO 3 + #.908 yR6OOH + #.201 XN + # - .149 XC 1.92e - 10 8,9

CP08 PROD2 + CL = HCL + #.314 HO2 + #.680 RO2C + #.116 RO2XC + #.116 zRNO3 + #.198 RCHO + #.116 PROD2 + #.541 xHO2 + #.007 xMECO3 + #.022 xRCO3 + #.237 xHCHO + #.109 xCCHO + #.591 xRCHO + #.051 xMEK + #.040 xPROD2 + #.686 yR6OOH + #1.262 XC 2.00e - 10 8,9

CP09 GLY + CL = HCL + #.63 HO2 + #1.26 CO + #.37 RCO3 + # - .37 XC 7.33e - 11 8.10e - 11 0.06 10 CP10 MGLY + CL = HCL + CO + MECO3 8.00e - 11 10 CP11 CRES + CL = HCL + xHO2 + xBALD + yR6OOH 6.20e - 11 11 CP12 BALD + CL = HCL + BZCO3 8.00e - 11 12 CP13 ROOH + CL = HCL + #.414 OH + #.588 RO2C + #.414 RCHO + #.104 xOH + #.482 xHO2 + #.106 xHCHO + #.104 xCCHO + #.197 xRCHO + #.285 xMEK + #.586 yROOH + # - 0.287 XC 1.66e - 10 8

CP14 R6OOH + CL = HCL + #.145 OH + #1.078 RO2C + #.117 {RO2XC + zRNO3} + #.145 PROD2 + #.502 xOH + #.237 xHO2 + #.186 xCCHO + #.676 xRCHO + #.28 xPROD2 + #.855 yR6OOH + #.348 XC 3.00e - 10 8

### Table A - 5 (continued)

165

Label Reaction and Products [a] Rate Parameters [b] Refs & Notes [c] k(298) A Ea B CP15 RAOOH + CL = #.404 HCL + #.139 OH + #.148 HO2 + #.589 RO2C + #.124 RO2XC + #.124 zRNO3 + #.074 PROD2 + #.147 MGLY + #.139 IPRD + #.565 xHO2 + #.024 xOH + #.448 xRCHO + #.026 xGLY + #.030 xMEK + #.252 xMGLY + #.073 xAFG1 + #.073 xAFG2 + #.713 yR6OOH + #2.67 4 XC 4.29e - 10 13

CP16 MACR + CL = #.25 HCL + #.165 MACO3 + #.802 RO2C + #.033 RO2XC + #.033 zRNO3 + #.802 xHO2 + #.541 xCO + #.082 xIPRD + #.18 xCLCCHO + #.541 xCLACET + #.835 yROOH + #.208 XC 3.85e - 10 8

CP17 MVK + CL = #1.283 RO2C + #.053 {RO2XC + zRNO3} + #.322 xHO2 + #.625 xMECO3 + #.947 xCLCCHO + yROOH + #.538 XC 2.32e - 10 8 CP18 IPRD + CL = #.401 HCL + #.084 HO2 + #.154 MACO3 + #.73 RO2C + #.051 RO2XC + #.051 zRNO3 + #.042 AFG1 + #.042 AFG2 + #.712 xHO2 + #.498 xCO + # .195 xHCHO + #.017 xMGLY + #.009 xAFG1 + #.009 xAFG2 + #.115 xIPRD + #.14 xCLCCHO + #.42 xCLACET + #.762 yR6OOH + #.709 XC 4.12e - 10 8,14

Reactions of Chlorinated Organic Product Species CP19 CLCCHO + HV = HO2 + CO + RO2C + xCL + xHCHO + yROOH Ph ot Set= CLCCHO 15 CP20 CLCCHO + OH = RCO3 + # - 1 XC 3.10e - 12 16 CP21 CLCCHO + CL = HCL + RCO3 + # - 1 XC 1.29e - 11 16 CP22 CLACET + HV = MECO3 + RO2C + xCL + xHCHO + yROOH Phot Set= CLACET, qy= 0.50 17 Steady- State Peroxy Radical operators (for fo rmation of chlorine radical and product species) CP23 xCL = CL k is variable parameter: RO2RO 18 CP24 xCL = k is variable parameter: RO2XRO 18 CP25 xCLCCHO = CLCCHO k is variable parameter: RO2RO 18 CP26 xCLCCHO = #2 XC k is variable parameter: RO 2XRO 18 CP27 xCLACET = CLACET k is variable parameter: RO2RO 18 CP28 xCLACET = #3 XC k is variable parameter: RO2XRO 18 Chlorine Reactions with Explicitly Represented Primary Organics CE01 CH4 + CL = HCL + MEO2 1.02e - 13 7.30e - 12 2.54 1 CE02 E THENE + CL = #2 RO2C + xHO2 + xHCHO + CLCHO 1.04e - 10 Falloff, F=0.60, N=1.00 2

### Table A - 5 (continued)

166

Label Reaction and Products [a] Rate Parameters [b] Refs & Notes [c] k(298) A Ea B CE03 ISOPRENE + CL = #.15 HCL + #1.168 RO2C + #.085 RO2XC + #.085 zRNO3 + #.738 xHO2 + #.177 xCL + #.275 xHCHO + #.177 xMVK + #.671 xIPRD + #.067 xCLCCHO + yR6OOH + #.018 XC 4 .80e - 10 19

CE04 ACETYLEN + CL = HO2 + CO + XC 4.97e - 11 Falloff, F=0.60, N=1.00 2,20 0: 5.20e - 30 0.00 - 2.40 inf: 2.20e - 10 0.00 0.00 [a] Format of reaction listing: "=" separates reactants from products; "#number " indicates stoichiometric coefficient, "# coefficient { product lis }" means that the stoichiometric coefficient is applied to all the products listed. [b] Except as indicated, the rate constants are given by k(T) = A · (T/300) B 

### · e - Ea/RT 

### , where the units of k and A are cm3 

### molec - 1 

### s - 1 

### , Ea are kcal mol - 1 

### , T is o

### K, and R=0.0019872 kcal mol - 1 

### deg - 1 

### . The following special rate constant expressions are used: Phot Set = name : The absorption cross sections and (if applicable) quantum yields for the photolysis reaction are given in Table A - 6 , where " name " indicates the photolysis set used. If a "qy=number " notation is given, the number given is the overall quantum yield, which is assumed to be wavelength independent. Falloff : The rate constant as a function of temperature and pressure is calculated using k(T,M) = {k0(T)·[M]/[1 + k0(T)·[M]/kinf(T)]}· F Z 

### , where Z = {1 + [log10{k0(T)·[M])/kinf(T)}/N] 2 

### } - 1 

### , [M] is the total pressure in molecules cm- 3 

### , F and N are as indicated on the table, and the temperature dependences of k0 and kinf are as indicated on the table. Same K as Rxn xx : Uses the same rate constant as the reaction in the base mechanism with the same label (see Table A - 2 ) [c] Footnotes documenting sources of rate constants and mechanisms are as follows. 1 Rate constant or absorption coefficients and quantum yields based on IUPAC (2006) recommendation. Mechanism is also as recommended unless indicated by other footnotes. 2 Rate constant or absorption coefficients and quantum yields based on NASA (2006) recommendation. Mechanism is also as recommended unless indicated by other footnotes. 3 Reaction is rapidly reversed and can be ignored. 4 IUPAC (2006) gives a recommendation for the total CL + HO 2 

### rate constant and for the temperature dependence of the rate constant ratio. Temperature - dependent parameters derived to give best fits to the recommended temperature dependence expression for the temperature range 270 - 330 o 

### K. 5 No information could be found concerning the kinetics of this reaction. The temperature - and pressure - dependence expression for the rate constant was estimated from that for the reverse reaction and the equilibrium constant obtained from the thermochemical data given by NASA (2006) for 298 o

### K. The falloff parameters were derived by fitting the falloff expression to the rate constant derived from the rate constant calculated for the reverse reaction and the equilibrium constant as a function of temperature and pressure.

### Table A - 5 (continued)

167

6 This reaction is not important under most atmospheric conditions, but may be non -negligible under certain situations near Cl 2 

### emissions sources. The reaction can form either Cl 2 

### + O 2 

### , Cl + ClOO, or Cl + OClO. To avoid introducing new species into the mechanism for this relatively unimportant reaction , OClO is represented by Cl. ClOO is also represented by Cl because it is expected to rapidly decompose to Cl. The rate expression for the total reaction is derived by fitting an Arrhenius expression to the sum of the temperature - dependent rate constants recommended by IUPAC (2006). The relative product yields are the IUPAC (2006) recommended values for 298K; the temperature dependence of the relative product yields is ignored. 7 The rate constant used for the reaction of Cl with propionaldehyde is the average of values listed by Le Crane et al (2005), who also obtained data indicating that abstraction from - CHO occurs ~88% of the time. The rest of the reaction is assumed to occur at the CH2 

### group, resulting in ultimate formation of the corresponding alkoxy radical, which is estimated to decompose primarily to acetaldehyde and HCO (Carter, 2000a). 8 Mechanism estimated using the current mechanism generation system, with rates of initial reactions determined by estimated rates of Cl reactions at various po sitions. In most cases the reactions of the radicals formed are the same as derived for the SAPRC - 99 mechanism generation system documented by Carter (2000a). The total rate constant also estimated, unless another footnote indicates otherwise. 9 Mechanis m derived using the mechanism generation system based on the mixture of organic nitrate or higher ketone product compounds used to derive the other mechanistic parameters for the RNO3 or PROD2 model species. 10 Same rate constant as used for formaldehyde (for glyoxal) or acetaldehyde (for methyl glyoxal). Same mechanism as for OH reaction, except HCl formed. 11 Assumed to have same rate constant as used for toluene, which is average of values tabulated by Wang et al (2005). Mechanism based on assuming reaction only involves abstraction from CH 3 

### . 12 Same rate constant as used for acetaldehyde. Reaction is assumed to proceed only by abstraction from - CHO. 13 Mechanism could not be generated completely. The mechanism estimation system was used to estimate the total rate constant and the HCL yield. The set of products formed in the OH reaction are used to approximate the reminder of the products radicals formed. 14 Mechanism derived for HCOC(CH 3 

### )=CHCH 2 

### OH, which is taken as representative of the compound s represented by this model species. 0.5 AFG1 + 0.5 AFG2 are used to represent the CH3 - C(CHO)=CH - CHO product predicted to be formed. 15 This is used to represent alpha - chloro aldehydes, which need to be represented separately because of their significantly higher photolysis rates (see Carter and Malkina, 2007). Absorption cross - sections from NASA (2006), and are given in Table 5. Unit quantum yields assumed. See Carter and Malkina (2007) for a discussion of the mechanism. 16 Rate constants from Scollard et al (1993). Represented as forming same products as corresponding reaction of propionaldehyde. 17 Absorption cross - sections from NASA (2006) evaluation. Overall quantum yield of 0.5 assumed, based on quantum yields measured at 308 and 351 nm (NASA, 20 06). 18 See footnotes in Table A - 2 for a discussion of these xPROD operators.

### Table A - 5 (continued)

168

19 Rate constant is Atkinson (1997) recommendation. Mechanism derived using the mechanism generation system, with assignments for the formation and reactions of the initially formed radicals based on the mechanism of Fan and Zhang (2004). Note that if it is desired to represent CMBO and CMBA explicitly, the "IPRD" yield should be reduced to 0.272 and the CMBO and CMBA should be added with yields of 0.221 and 0.178, respectively. Their subsequent reactions can be approximated by the mechanism of IPRD. 20 Mechanism based on assuming that reaction involves formation of ClCH=CH· radicals, which react with O 2 

### to form HCO and ClCHO. The latter is assumed to be relatively unreactive and is not represented.

### 169

Table A - 6 . Absorption cross - sections and quantum yields for the all photolysis reactions added for

the chlorine chemistry mechanism .

a) Phot set CL2 : Chlorine absorption cross - sections. wl abs wl abs wl abs wl abs wl abs wl abs 280 2.60e - 20 320 2.37e - 19 360 1.32e - 19 400 1.80e - 20 440 5.40e - 21 480 - 290 6.20e - 20 330 2.55e - 19 370 8.40e - 20 410 1.30e - 20 450 3.80e - 21 300 1.19e - 19 340 2.35e - 19 380 5.00e - 20 420 9.60e - 21 460 2.60e - 21 310 1.85e - 19 350 1.88e - 19 390 2.90e - 20 430 7.30e - 21 470 1.60e - 21 

### Wavelengths in nm and absorption cross - sections in cm- 2 

### . IUPAC (2006) recommendation for absorption cross sections. Unit quantum yield assumed. b) Phot Set CLNO - 06 : ClNO absorption cross - sections. wl abs wl abs wl abs wl abs wl abs wl abs 280 1.06e - 19 304 1.05e - 19 328 1.46e - 19 355 1.36e - 19 415 3.38e - 20 475 2.61e - 20 282 1.02e - 19 306 1.08e - 19 330 1.47e - 19 360 1.29e - 19 420 2.89e - 20 480 2.53e - 20 284 9.99e - 20 308 1.11e - 19 332 1.49e - 19 365 1.20e - 19 425 2.45e - 20 485 2.33e - 20 286 9.84e - 20 310 1.15e - 19 334 1.51e - 19 370 1.10e - 19 430 2.21e - 20 490 2.07e - 20 288 9.71e - 20 312 1.19e - 19 336 1.53e - 19 375 9.95e - 20 435 2.20e - 20 495 1.78e - 20 290 9.64e - 20 314 1.22e - 19 338 1.53e - 19 380 8.86e - 20 440 2.20e - 20 500 1.50e - 20 292 9.63e - 20 316 1.25e - 19 340 1.52e - 19 385 7.82e - 20 445 2.07e - 20 527 - 294 9.69e - 20 318 1.30e - 19 342 1.53e - 19 390 6.86e - 20 450 1.87e - 20 296 9.71e - 20 320 1.34e - 19 344 1.51e - 19 395 5.97e - 20 455 1.79e - 20 298 9.89e - 20 322 1.36e - 19 346 1.51e - 19 400 5.13e - 20 460 1.95e - 20 300 1.00e - 19 324 1.40e - 19 348 1.49e - 19 405 4.40e - 20 465 2.25e - 20 302 1.03e - 19 326 1.43e - 19 350 1.45e - 19 410 3.83e - 20 470 2.50e - 20 

### Wavelengths in nm and absorption cross - sections in cm- 2 

### . IUPAC (2006) recommendation. Unit quantum yields assumed. Wavelength where absorption goes to zero estimated by extrapolation. c) Phot set CLONO : ClONO absorption cross - sections. wl abs wl abs wl abs wl abs wl abs wl abs 280 1.32e - 18 305 1.14e - 18 330 5.87e - 19 355 2.29e - 19 380 4.10e - 20 405 - 285 1.44e - 18 310 1.05e - 18 335 5.77e - 19 360 1.61e - 19 385 3.30e - 20 290 1.44e - 18 315 9.81e - 19 340 4.37e - 19 365 1.13e - 19 390 2.20e - 20 295 1.42e - 18 320 8.03e - 19 345 3.57e - 19 370 9.00e - 20 395 1.50e - 20 300 1.29e - 18 325 7.54e - 19 350 2.69e - 19 375 6.90e - 20 400 6.00e - 21 

### Wavelengths in nm and absorption cross - sections in cm- 2 

### . IUPAC (2006) recommendation for absorption cross - sections. Unit quantum yield assumed.

### Table A - 6 (continued)

170 d) Phot set CLNO2 : ClNO2 absorption cross - sections wl abs wl abs wl abs wl abs 280 2.20e - 19 310 1.21e - 19 340 3.54e - 20 370 6.90e - 21 290 1.73e - 19 320 8.87e - 20 350 2.04e - 20 380 - 300 1.49e - 19 330 5.84e - 20 360 1.15e - 20 

### Wavelengths in nm and absorption cross - sections in cm- 2 

### . IUPAC (2006) recommendation. Unit quantum yields assumed. e) Phot Set CLONO2 - 1 : ClONO2 + hv = CLO + NO2 wl abs qy wl abs qy wl abs qy wl abs qy 280 1.19e - 19 0.400 305 2.24e - 20 0.400 330 4.66e - 21 0.243 355 2.08e - 21 0.064 285 8.80e - 20 0.400 310 1.60e - 20 0.386 335 3.67e - 21 0.207 360 2.00e - 21 0.029 290 6.41e - 20 0.400 315 1.14e - 20 0.350 340 3.02e - 21 0.171 365 1.80e - 21 0.000 295 4.38e - 20 0.400 320 8.31e - 21 0.314 345 2.58e - 21 0.136 300 3.13e - 20 0.400 325 6.13e - 21 0.279 350 2.29e - 21 0.100 

### Wavelengths in nm and absorption cross - sections in cm- 2 

### . Absorption cross - sections and quantum yields recommended by IUPAC (2006). f) Phot Set CLONO2 - 2 : ClONO2 + hv = Cl + NO3 wl abs qy wl abs qy wl abs qy wl abs qy 280 1.19e - 19 0.600 320 8.31e - 21 0.686 360 2.00e - 21 0.971 400 6.40e - 22 1.000 285 8.80e - 20 0.600 325 6.13e - 21 0.721 365 1.80e - 21 1.000 405 5.40e - 22 1.000 290 6.41e - 20 0.600 330 4.66e - 21 0.757 370 1.59e - 21 1.000 410 4.40e - 22 1.000 295 4.38e - 20 0.600 335 3.67e - 21 0.793 375 1.41e - 21 1.000 415 3.60e - 22 1.000 300 3.13e - 20 0.600 340 3.02e - 21 0.829 380 1.21e - 21 1.000 420 3.20e - 22 1.000 305 2.24e - 20 0.600 345 2.58e - 21 0.864 385 1.37e - 21 1.000 425 2.30e - 22 1.000 310 1.60e - 20 0.614 350 2.29e - 21 0.900 390 9.10e - 22 1.000 430 1.90e - 22 1.000 315 1.14e - 20 0.650 355 2.08e - 21 0.936 395 7.60e - 22 1.000 435 - 1.000 

### Wavelengths in nm and absorption cross - sections in cm- 2 

### . Absorption cross - sections and quantum yields recommended by IUPAC (2006). g) Phot set HOCL - 06 : HOCl absorption cross - sections. wl abs wl abs wl abs wl abs wl abs wl abs 280 4.64e - 20 304 6.12e - 20 328 3.79e - 20 352 1.33e - 20 376 7.86e - 21 400 2.88e - 21 282 4.62e - 20 306 6.12e - 20 330 3.50e - 20 354 1.24e - 20 378 7.48e - 21 402 2.54e - 21 284 4.68e - 20 308 6.07e - 20 332 3.21e - 20 356 1.17e - 20 380 7.08e - 21 404 2.22e - 21 286 4.79e - 20 310 5.97e - 20 334 2.94e - 20 358 1.11e - 20 382 6.67e - 21 406 1.94e - 21 288 4.95e - 20 312 5.84e - 20 336 2.68e - 20 360 1.06e - 20 384 6.24e - 21 408 1.68e - 21 290 5.13e - 20 314 5.66e - 20 338 2.44e - 20 362 1.02e - 20 386 5.80e - 21 410 1.44e - 21 292 5.33e - 20 316 5.45e - 20 340 2.22e - 20 364 9.85e - 21 388 5.35e - 21 412 1.24e - 21 294 5.52e - 20 318 5.21e - 20 342 2.03e - 20 366 9.51e - 21 390 4.91e - 21 414 1.05e - 21 296 5.71e - 20 320 4.95e - 20 344 1.84e - 20 368 9.19e - 21 392 4.47e - 21 416 8.90e - 22 298 5.86e - 20 322 4.67e - 20 346 1.69e - 20 370 8.88e - 21 394 4.05e - 21 418 7.50e - 22 300 5.99e - 20 324 4.38e - 20 348 1.55e - 20 372 8.55e - 21 396 3.64e - 21 420 6.30e - 22

### Table A - 6 (continued)

171

302 6.08e - 20 326 4.09e - 20 350 1.43e - 20 374 8.22e - 21 398 3.25e - 21 422 - 

### Wavelengths in nm and absorption cross - sections in cm- 2 

### . IUPAC (2006) recommendation for absorption cross - sections. Unit quantum yields assumed.

h) Phot set CLCCHO : Chloroacetaldehyde absorption cross - sections. wl abs wl abs wl abs wl abs wl abs wl abs 280 3.99e - 20 293 5.14e - 20 306 5.48e - 20 319 3.78e - 20 332 1.68e - 20 345 1.59e - 21 281 4.23e - 20 294 5.48e - 20 307 5.34e - 20 320 3.84e - 20 333 1.42e - 20 346 1.36e - 21 282 4.09e - 20 295 5.47e - 20 308 5.44e - 20 321 3.43e - 20 334 1.36e - 20 347 9.77e - 22 283 4.15e - 20 296 5.64e - 20 309 5.37e - 20 322 3.26e - 20 335 1.06e - 20 348 7.91e - 22 284 4.31e - 20 297 5.56e - 20 310 5.03e - 20 323 2.49e - 20 336 7.47e - 21 349 6.23e - 22 285 4.55e - 20 298 5.75e - 20 311 4.61e - 20 324 2.11e - 20 337 6.22e - 21 350 5.45e - 22 286 4.64e - 20 299 5.63e - 20 312 3.92e - 20 325 1.92e - 20 338 5.02e - 21 351 5.58e - 22 287 4.80e - 20 300 5.57e - 20 313 3.71e - 20 326 1.87e - 20 339 4.11e - 21 352 6.03e - 22 288 4.99e - 20 301 5.10e - 20 314 3.73e - 20 327 1.87e - 20 340 3.40e - 21 353 6.33e - 22 289 5.03e - 20 302 4.92e - 20 315 3.96e - 20 328 1.70e - 20 341 2.81e - 21 354 5.65e - 22 290 5.20e - 20 303 5.01e - 20 316 3.85e - 20 329 1.92e - 20 342 2.47e - 21 355 3.77e - 22 291 4.95e - 20 304 5.30e - 20 317 4.16e - 20 330 1.64e - 20 343 2.13e - 21 356 2.39e - 22 292 4.94e - 20 305 5.27e - 20 318 3.84e - 20 331 1.52e - 20 344 1.90e - 21 357 1.23e - 22 358 - 

### Wavelengths in nm and absorption cross - sections in cm- 2 

### . Absorption cross - sections from NASA (2006) evaluation. Unit quantum yields assumed.

g) Phot set CLACET : Chloroacetone absorption cross - sections. wl abs wl abs wl abs wl abs wl abs wl abs 280 9.03e - 20 294 1.01e - 19 308 7.34e - 20 322 3.04e - 20 336 5.06e - 21 350 4.58e - 22 281 9.23e - 20 295 1.00e - 19 309 7.06e - 20 323 2.80e - 20 337 4.27e - 21 351 4.11e - 22 282 9.41e - 20 296 9.89e - 20 310 6.77e - 20 324 2.58e - 20 338 3.61e - 21 352 3.28e - 22 283 9.56e - 20 297 9.77e - 20 311 6.50e - 20 325 2.37e - 20 339 3.02e - 21 353 3.19e - 22 284 9.69e - 20 298 9.66e - 20 312 6.22e - 20 326 2.16e - 20 340 2.52e - 21 354 2.20e - 22 285 9.80e - 20 299 9.54e - 20 313 5.93e - 20 327 1.95e - 20 341 2.12e - 21 355 1.93e - 22 286 9.89e - 20 300 9.41e - 20 314 5.61e - 20 328 1.73e - 20 342 1.76e - 21 356 1.38e - 22 287 9.98e - 20 301 9.25e - 20 315 5.28e - 20 329 1.52e - 20 343 1.45e - 21 357 1.34e - 22 288 1.00e - 19 302 9.04e - 20 316 4.92e - 20 330 1.33e - 20 344 1.20e - 21 358 9.17e - 23 289 1.01e - 19 303 8.80e - 20 317 4.57e - 20 331 1.14e - 20 345 1.03e - 21 359 1.55e - 22 290 1.02e - 19 304 8.53e - 20 318 4.22e - 20 332 9.79e - 21 346 8.87e - 22 360 1.28e - 22 291 1.02e - 19 305 8.24e - 20 319 3.89e - 20 333 8.32e - 21 347 7.57e - 22 365 - 292 1.02e - 19 306 7.94e - 20 320 3.58e - 20 334 7.07e - 21 348 6.42e - 22 293 1.02e - 19 307 7.63e - 20 321 3.30e - 20 335 5.98e - 21 349 5.47e - 22 

### Wavelengths in nm and absorption cross - sections in cm- 2 

### . NASA (2006) recommendation for absorption cross - sections. Unit quantum yields assumed.

### 172

Table A - 7 . Listing of reactions and rate parameters used for the lumped model species in the fixed

parameter version of the lumped SAPRC - 07 mechanism . Label Reaction and Products [a] Rate Parameters [b] k(300) A Ea B Reactions Added to the Standard Base Mechanism BL01 ALK1 + OH = xHO2 + RO2C + xCCHO + yROOH 2.54E - 13 1.34E - 12 0.992 2.0 BL02 ALK2 + OH = #.965 xHO2 + #.965 RO2C + #.035 RO2XC + #.035 zRNO3 + #.261 xRCHO + #.704 xACET + yROOH + # - .105 XC 1.11E - 12 1.49E - 12 0.173 2.0 BL03 ALK3 + OH = #.695 xHO2 + #.236 xTBUO + #1.253 RO2C + #.07 RO2XC + #.07 zRNO3 + #.026 xHCHO + #.445 xCCHO + #.122 xRCHO + #.024 xACET + #.332 xMEK + #.983 yROOH + #.017 yR6OOH + # - .046 XC 2.31E - 12 1.51E - 12 - 0.251

BL04 ALK4 + OH = #.83 xHO2 + #.01 xMEO2 + #.011 xMECO3 + #1.763 RO2C + #.149 RO2XC + #.149 zRNO3 + #.002 xCO + #.029 xHCHO + #.438 xCCHO + #.236 xRCHO + #.426 xACET + #.106 xMEK + #.146 xPROD2 + yR6OOH + # - .119 XC 4.34E - 12 3.75E - 12 - 0.088

BL05 ALK5 + OH = #.647 xHO2 + #1.605 RO2C + #.353 RO2XC + #.353 zRNO3 + #.04 xHCHO + #.106 xCCHO + #.209 xRCHO + #.071 xACET + #.086 xMEK + #.407 xPROD2 + yR6OOH + #2.004 XC 9.40E - 12 2.70E - 12 - 0.744

BL06 OLE1 + OH = #.904 xHO2 + #.001 xMEO2 + #1.138 RO2C + #.095 RO2XC + #.095 zRNO3 + #.7 xHCHO + #.301 xCCHO + #.47 xRCHO + #.005 xACET + #.026 xMACR + #.008 xMVK + #.006 xIPRD + #.119 xPROD2 + #.413 yROOH + #.587 yR6OOH + #.822 XC 3.29E - 11 6.18E - 12 - 0.996

BL07 OLE1 + O3 = #.116 HO2 + #.04 xHO2 + #.193 OH + #.104 MEO2 + #.063 RO2C + #.004 RO2XC + #.004 zRNO3 + #.368 CO + #.125 CO2 + #.5 HCHO + #.147 CCHO + #.007 xCCHO + #.353 RCHO + #.031 xRCHO + #.002 xACET + #.006 MEK + #.185 HCOOH + #.022 CCOOH + #.112 RCOOH + #.189 PROD2 + #.007 yROOH + #.037 yR6OOH + #.69 XC 1.09E - 17 3.15E - 15 3.379

BL08 OLE1 + NO3 = #.824 xHO2 + #1.312 RO2C + #.176 RO2XC + #.176 zRNO3 + #.009 xCCHO + #.002 xRCHO + #.024 xACET + #.546 xRNO3 + #.413 yROOH + #.587 yR6OOH + #.454 XN + #.572 XC 1.44E - 14 4.73E - 13 2.081

BL09 OLE1 + O3P = #.45 RCHO + #.437 MEK + #.113 PROD2 + #1.224 XC 5.02E - 12 1.49E - 11 0.648

### Table A - 7 (continued)

173

Label Reaction and Products [a] Rate Parameters [b] k(300) A Ea B BL10 OLE2 + OH = #.914 xHO2 + #.966 RO2C + #.086 RO2XC + #.086 zRNO3 + #.209 xHCHO + #.788 xCCHO + #.481 xRCHO + #.136 xACET + #.076 xMEK + #.027 xMACR + #.002 xMVK + #.037 xIPRD + #.022 xPROD2 + #.357 yROOH + #.643 yR6OO H + #.111 XC 6.42E - 11 1.26E - 11 - 0.969

BL11 OLE2 + O3 = #.093 HO2 + #.039 xHO2 + #.423 OH + #.29 MEO2 + #.147 xMECO3 + #.008 xRCO3 + #.2 RO2C + #.003 RO2XC + #.003 zRNO3 + #.297 CO + #.162 CO2 + #.152 HCHO + #.108 xHCHO + #.428 CCHO + #.067 xCCHO + #.315 RCHO + #.018 xRCHO + #.048 ACET + #.031 MEK + #.001 xMEK + #.033 HCOOH + #.061 CCOOH + #.222 RCOOH + #.028 MACR + #.021 MVK + #.042 PROD2 + #.069 yROOH + #.128 yR6OOH + #.125 XC 1.24E - 16 8.14E - 15 2.494

BL12 OLE2 + NO3 = #.423 xHO2 + #.409 xNO2 + #.033 xMEO2 + #1.185 RO2C + #.136 RO2XC + #.136 zRNO3 + #.074 xHCHO + #.546 xCCHO + #.154 xRCHO + #.11 xACET + #.002 xMEK + #.026 xMVK + #.007 xIPRD + #.322 xRNO3 + #.357 yROOH + #.643 yR6OOH + #.269 XN + #.114 XC 7.85E - 13 2.20E - 13 - 0.759

BL13 OLE2 + O3P = #. 014 HO2 + #.007 xHO2 + #.007 xMACO3 + #.013 RO2C + #.001 RO2XC + #.001 zRNO3 + #.006 xCO + #.074 RCHO + #.709 MEK + #.006 xMACR + #.202 PROD2 + #.014 yROOH + #.666 XC 2.07E - 11 1.43E - 11 - 0.220

BL14 ARO1 + OH = #.166 HO2 + #.482 xHO2 + #.284 OH + #.482 RO2C + #.068 RO2XC + #.068 zRNO3 + #.218 xGLY + #.138 xMGLY + #.166 CRES + #.049 xBALD + #.164 xAFG1 + #.193 xAFG2 + #.284 AFG3 + #.077 xPROD2 + #.403 yRAOOH + #.147 yR6OOH + #.002 XC 6.15E - 12

BL15 ARO2 + OH = #.108 HO2 + #.58 xHO2 + #.202 OH + #.58 RO2C + #.11 RO2XC + #.11 zRNO3 + #.116 xGLY + #.286 xMGLY + #.104 xBACL + #.108 CRES + #.039 xBALD + #.217 xAFG1 + #.21 xAFG2 + #.202 AFG3 + #.08 xAFG3 + #.035 xPROD2 + #.089 yR6OOH + #.601 yRAOOH + #1.486 XC 2.57E - 11

### Table A - 7 (continued)

174

Label Reaction and Products [a] Rate Parameters [b] k(300) A Ea B BL16 TERP + OH = #.7 59 xHO2 + #.042 xRCO3 + #1.147 RO2C + #.2 RO2XC + #.2 zRNO3 + #.001 xCO + #.264 xHCHO + #.533 xRCHO + #.036 xACET + #.005 xMEK + #.009 xMGLY + #.014 xBACL + #.002 xMVK + #.001 xIPRD + #.255 xPROD2 + yR6OOH + #5.056 XC 7.98E - 11 1.87E - 11 - 0.864

BL17 TERP + O3 = #.052 HO2 + #.067 xHO2 + #.585 OH + #.126 xMECO3 + #.149 xRCO3 + #.875 RO2C + #.203 RO2XC + #.203 zRNO3 + #.166 CO + #.019 xCO + #.045 CO2 + #.079 HCHO + #.15 xHCHO + #.22 xRCHO + #.165 xACET + #.004 MEK + #.107 HCOOH + #.043 RCOOH + #.001 xGLY + #. 002 xMGLY + #.055 xBACL + #.001 xMACR + #.001 xIPRD + #.409 PROD2 + #.545 yR6OOH + #3.526 XC 6.99E - 17 9.57E - 16 1.560

BL18 TERP + NO3 = #.162 xHO2 + #.421 xNO2 + #.019 xRCO3 + #1.509 RO2C + #.397 RO2XC + #.397 zRNO3 + #.01 xCO + #.017 xHCHO + #.001 xCCHO + #.509 xRCHO + #.175 xACET + #.001 xMGLY + #.003 xMACR + #.001 xMVK + #.002 xIPRD + #.163 xRNO3 + yR6OOH + #.416 XN + #4.473 XC 6.53E - 12 1.28E - 12 - 0.974

BL19 TERP + O3P = #.147 RCHO + #.853 PROD2 + #4.441 XC 3.71E - 11 Reactions Added to the Base Mechanism with Chlorine Chemistry BC01 ALK1 + CL = xHO2 + RO2C + HCL + xCCHO + yROOH 5.95E - 11 8.30E - 11 0.199 BC02 ALK2 + CL = #.97 xHO2 + #.97 RO2C + #.03 RO2XC + #.03 zRNO3 + HCL + #.482 xRCHO + #.488 xACET + yROOH + # - .09 XC 1.37E - 10 1.20E - 10 - 0.079 BC03 ALK3 + CL = #.835 xHO2 + #.094 xTBUO + #1.361 RO2C + #.07 RO2XC + #.07 zRNO3 + HCL + #.078 xHCHO + #.34 xCCHO + #.343 xRCHO + #.075 xACET + #.253 xMEK + #.983 yROOH + #.017 yR6OOH + #.18 XC 1.86E - 10

BC04 ALK4 + CL = #.827 xHO2 + #.00 3 xMEO2 + #.004 xMECO3 + #1.737 RO2C + #.165 RO2XC + #.165 zRNO3 + HCL + #.003 xCO + #.034 xHCHO + #.287 xCCHO + #.412 xRCHO + #.247 xACET + #.076 xMEK + #.13 xPROD2 + yR6OOH + #.327 XC 2.63E - 10

### Table A - 7 (continued)

175

Label Reaction and Products [a] Rate Parameters [b] k(300) A Ea B BC05 ALK5 + CL = #.647 xHO2 + #1.541 RO2C + #.352 RO2XC + #.352 zRNO3 + HCL + #.022 xHCHO + #.08 xCCHO + #.258 xRCHO + #.044 xACET + #.041 xMEK + #.378 xPROD2 + yR6OOH + #2.368 XC 4.21E - 10

BC06 OLE1 + CL = #.902 xHO2 + #1.42 RO2C + #.098 RO2XC + #.098 zRNO3 + #.308 HCL + #.025 xHCHO + #.146 xCCHO + #.051 xRCHO + #.188 xMACR + #.014 xMVK + #.027 xIPRD + #.225 xCLCCHO + #.396 xCLACET + #.413 yROOH + #.587 yR6OOH + #1.361 XC 3.55E - 10

BC07 OLE2 + CL = #.447 xHO2 + #.448 xCL + #.001 xMEO2 + #1.514 RO2C + #.104 RO2XC + #.104 zRNO3 + #.263 HCL + #.228 xHCHO + #.361 xCCHO + #.3 xRCHO + #.081 xACET + #.04 xMEK + #.049 xMACR + #.055 xMVK + #.179 xIPRD + #.012 xCLCCHO + #.18 xCLACET + #.357 yROOH + #.643 yR6OOH + #.247 XC 3.83E - 10

BC08 ARO1 + CL = #.88 xHO2 + #.88 RO2C + #.12 RO2XC + #.12 zRNO3 + #.671 xBALD + #.21 xPROD2 + #.323 XC 1.00E - 10 BC09 ARO2 + CL = #.842 xHO2 + #.842 RO2C + #.158 RO2XC + #.158 zRNO3 + #.618 xBALD + #.224 xPROD2 + #2.382 XC 2.18E - 10 BC10 TERP + CL = #.252 xHO2 + #.068 xCL + #.034 xMECO3 + #.05 xRCO3 + #.016 xMACO3 + #2.258 RO2C + #.582 RO2XC + #.582 zRNO3 + #.548 HCL + #.035 xCO + #.158 xHCHO + #.185 xRCHO + #.274 xACET + #.007 xGLY + #.003 xBACL + #.003 xMVK + #.158 xIPRD + #.006 xAFG1 + #.006 xAFG2 + #.001 xAFG3 + #.109 xCLCCHO + yR6OOH + #3.543 XC 5.46E - 10

[a] Format of reaction listing: "=" separates reactants from products; "#number " indicates stoichiometric coefficient, "# coefficient { product list }" means that the stoichiometric coefficient is applied to all the products listed. [b] The rate constants are given by k(T) = A · e - Ea/RT 

### , where the units of k and A are cm3 

### molec - 1 

### s - 1 

### , Ea are kcal mol - 1 

### , T is o 

### K, and R=0.0019872 kcal mol - 1 

### deg - 1



### .

### 176



### APPENDIX B. MECHANIS **M AND REACTIVITY LIS TINGS FOR INDIVIDUAL**  **VOCS** This Appendix contains the tables documenting the mechanisms and giving the calculated atmospheric reactivity values and associated codes for the individual VOCs for which mechanistic assignments have been made. These tables are also available in electronic form in an Excel file, as discussed in Appendix D. Because of their size, Table B - 2 , Table B - 3 , Table B - 10 , and Table B - 1 1 are only available in this electronic format.

### 177

Table B - 1 . Listing of detailed model species, their representation in the model, and calculated

atmospheric reactivity values in various reactivity scales Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base Alkanes methane 74 - 82 - 8 16.04 Exp 1 0 6 .0144 .0085 .0060 .0073±.0016 ethane 74 - 84 - 0 30.07 Exp 1 3 0 1 0.28 0.196 0.142 0.167±0.045 propane 74 - 98 - 6 44.10 Exp 1 3 0 1 0.49 0.34 0.25 0.29±0.07 cyclopropane 75 - 19 - 4 42.08 Exp 1 0 6 0.087 0.061 0.043 0.051±0.015 n -butane 106 - 97 - 8 58.12 Exp 1 2 0 1 1.15 0.76 0.52 0.64±0.17 isobutane 75 - 28 - 5 58.12 Exp 1 3 0 2 1.23 0.73 0.50 0.62±0.14 cyclobutane 287 - 23 - 0 56.11 Exp 1 0 6 1.20 0.80 0.54 0.66±0.22 n -pentane 109 - 66 - 0 72.15 Exp 1 0 6 1.31 0.88 0.56 0.70±0.21 branched C5 alkanes 72.15 LM 0 8 1.45 0.93 0.65 0.79±0.20 neopentane 463 - 82 - 1 72.15 Exp 1 0 6 0.67 0.39 0.26 0.33±0.08 isopentane 78 - 78 - 4 72.15 Exp 1 0 6 1.45 0.93 0.65 0.79±0.20 cyclopentane 287 - 92 - 3 70.13 AdjP 1 0 6 2.39 1.41 0.89 1.15±0.35 n - hexane 110 - 54 - 3 86.18 Exp 1 3 0 2 1.24 0.84 0.50 0.65±0.22 branched C6 alkanes 86.18 LM 0 8 1.31 0.83 0.55 0.68±0.18 2,2 - dimethyl butane 75 - 83 - 2 86.18 Exp 1 0 6 1.17 0.71 0.46 0.58±0.16 2,3 - dimethyl butane 79 - 29 - 8 86.18 Exp 1 0 6 0.97 0.65 0.44 0.54±0.13 2 - methyl pentane 107 - 83 - 5 86.18 Exp 1 0 6 1.50 0.92 0.57 0.74±0.23 3 - methyl pentane 96 - 14 - 0 86.18 Exp 1 0 6 1.80 1.11 0.73 0.92±0.26 C6 cycloalkanes 84.16 LM 0 8 1.25 0.82 0.47 0.63±0.22 cyclohexane 110 - 82 - 7 84.16 AdjP 1 2 0 2 1.25 0.82 0.47 0.63±0.22 isopropyl cyclopropane 3638 - 35 - 5 84.16 Exp 1 0 6 1.22 0.80 0.54 0.66±0.18 methyl cyclopentane 96 - 37 - 7 84.16 AdjP 0 7 2.19 1.23 0.73 0.98±0.33 Unspeciated C6 Alkanes 85.51 Mix 0 8 1.27 0.83 0.50 0.65±0.21 n - heptane 142 - 82 - 5 100.20 Exp 1 0 6 1.07 0.73 0.39 0.54±0.21 2,2,3 - trimethyl butane 464 - 06 - 2 100.20 Exp 1 0 6 1.11 0.66 0.42 0.54±0.14 2,2 - dimethyl pentane 590 - 35 - 2 100.20 Exp 1 0 6 1.12 0.68 0.41 0.54±0.17 2,3 - dimethyl pentane 565 - 59 - 3 100.20 Exp 0 7 1.34 0.83 0.52 0.67±0.19 2,4 - dimethyl pentane 108 - 08 - 7 100.20 Exp 1 0 6 1.55 0.90 0.55 0.72±0.22 2 - methyl hexane 591 - 76 - 4 100.20 AdjP 0 7 1.19 0.76 0.42 0.58±0.21 3,3 - dimethyl pentane 562 - 49 - 2 100.20 Exp 0 7 1.20 0.76 0.49 0.62±0.18 3 - methyl hexane 589 - 34 - 4 100.20 Exp 0 7 1.61 0.96 0.57 0.76±0.26 3 - ethyl pentane 617 - 78 - 7 100.20 Exp 0 7 1.90 1.11 0.69 0.90±0.27 branched C7 alkanes 100.20 LM 0 8 1.48 0.88 0.52 0.69±0.22 1,1 - dimethyl cyclopentane 1638 - 26 - 2 98.19 AdjP 0 7 1.08 0.66 0.35 0.49±0.19 1,2 - dimethyl cyclopentane 2452 - 99 - 5 98.19 AdjP 0 7 1.99 1.10 0.61 0.85±0.31 C7 cycloalkanes 98.19 LM 0 7 1.70 1.00 0.53 0.75±0.29 1,3 - dimethyl cyclopentane 2453 - 00 - 1 98.19 AdjP 0 7 1.94 1.06 0.58 0.82±0.30 cycloheptane 291 - 64 - 5 98.19 AdjP 1 0 6 1.96 1.11 0.61 0.85±0.32 ethyl cyclopentane 1640 - 89 - 7 98.19 AdjP 0 7 2.01 1.13 0.63 0.87±0.33 methyl cyclohexane 108 - 87 - 2 98.19 AdjP 1 0 6 1.70 1.00 0.53 0.75±0.29 Unspeciated C7 Alkanes 99.53 Mix 0 8 1.41 0.87 0.48 0.66±0.24 n - octane 111 - 65 - 9 114.23 Exp 1 1 0 2 0.90 0.61 0.29 0.43±0.19 branched C8 alkanes 114.23 LM 0 8 1.45 0.86 0.46 0.64±0.24 2,2,3,3 - tetramethyl butane 594 - 82 - 1 114.23 Exp 1 0 6 0.33 0.20 0.113 0.154±0.052 2,2,4 - trimethyl pentane 540 - 84 - 1 114.23 Exp 1 3 0 2 1.26 0.71 0.44 0.57±0.17

### Table B - 1 (continued)

178

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base 2,2 - dimethyl hexane 590 - 73 - 8 114.23 Exp 1 0 6 1.02 0.61 0.33 0.46±0.17 2,3,4 - trimethyl pentane 565 - 75 - 3 114.23 Exp 1 0 6 1.03 0.65 0.39 0.51±0.16 2,3 - dimethyl hexane 584 - 94 - 1 114.23 Exp 0 7 1.19 0.75 0.42 0.57±0.20 2,4 - dimethyl hexane 589 - 43 - 5 114.23 Exp 0 7 1.73 0.98 0.54 0.75±0.27 2,5 - dimethyl hexane 592 - 13 - 2 114.23 Exp 0 7 1.46 0.86 0.47 0.65±0.24 2 - methyl heptane 592 - 27 - 8 114.23 Exp 0 7 1.07 0.69 0.35 0.50±0.21 3 - methyl heptane 589 - 81 - 1 114.23 Exp 0 7 1.24 0.78 0.41 0.58±0.23 4 - methyl heptane 589 - 53 - 7 114.23 Exp 0 7 1.25 0.76 0.40 0.57±0.23 2,3,3 - trimethyl pentane 560 - 21 - 4 114.23 Exp 0 7 1.02 0.65 0.41 0.52±0.15 3,3 - dimethyl hexane 563 - 16 - 6 114.23 Exp 0 7 1.24 0.75 0.43 0.58±0.20 2,2,3 - trimethyl pentane 564 - 02 - 3 114.23 Exp 0 7 1.22 0.71 0.42 0.56±0.17 3,4 - dimethyl hexane 583 - 48 - 2 114.23 Exp 0 7 1.51 0.91 0.54 0.71±0.23 3 - ethyl 2 - methyl pentane 609 - 26 - 7 114.23 Exp 0 7 1.33 0.79 0.46 0.62±0.21 C8 bicycloalkanes 110.20 LM 0 8 1.51 0.89 0.48 0.67±0.26 1,1,2 - trimethyl cyclopentane 4259 - 00 - 1 112.21 Exp 0 7 1.12 0.65 0.33 0.48±0.20 1,1,3 - trimethyl cyclopentane 4516 - 69 - 2 112.21 Exp 0 7 1.01 0.60 0.29 0.43±0.19 1,1 - dimethyl cyclohexane 590 - 66 - 9 112.21 Exp 0 7 1.22 0.73 0.37 0.53±0.22 1,2,3 - trimethyl cyclopentane 112.21 Exp 0 7 1.63 0.93 0.49 0.70±0.27 1,2,4 - trimethyl cyclopentane 112.21 Exp 0 7 1.53 0.85 0.43 0.63±0.26 1 - methyl - 3 - ethyl cyclopentane 112.21 AdjP 0 7 1.64 0.92 0.47 0.68±0.29 1,2 - dimethyl cyclohexane 583 - 57 - 3 112.21 AdjP 0 7 1.41 0.87 0.43 0.63±0.28 1,4 - dimethyl cyclohexane 589 - 90 - 2 112.21 AdjP 0 7 1.62 0.91 0.45 0.67±0.29 C8 cycloalkanes 112.21 LM 0 8 1.47 0.87 0.45 0.65±0.26 1,3 - dimethyl cyclohexane 591 - 21 - 9 112.21 AdjP 0 7 1.52 0.86 0.41 0.62±0.28 cyclooctane 292 - 64 - 8 112.21 AdjP 1 0 6 1.46 0.84 0.41 0.61±0.28 ethyl cyclohexane 1678 - 91 - 7 112.21 Exp 0 7 1.47 0.87 0.45 0.65±0.26 propyl cyclopentane 2040 - 96 - 2 112.21 AdjP 0 7 1.69 0.94 0.48 0.70±0.30 Unspeciated C8 Alkanes 113.56 Mix 0 8 1.27 0.78 0.40 0.57±0.23 n - nonane 111 - 84 - 2 128.26 Exp 1 0,+ 6 b 0.78 0.53 0.23 0.36±0.18 branched C9 alkanes 128.26 LM 0 8 b 1.14 0.69 0.33 0.49±0.22 2,2,5 - trimethyl hexane 3522 - 94 - 9 128.26 Exp 0 7 b 1.13 0.65 0.36 0.50±0.18 2,3,5 - trimethyl hexane 1069 - 53 - 0 128.26 AdjP 1 0 6 b 1.22 0.73 0.39 0.55±0.20 2,4 - dimethyl heptane 2213 - 23 - 2 128.26 Exp 0 7 b 1.38 0.79 0.39 0.58±0.25 2 - methyl octane 3221 - 61 - 2 128.26 Exp 1 0,+ 6 b 0.83 0.55 0.24 0.38±0.19 3,3 - diethyl pentane 1067 - 20 - 5 128.26 Exp 1 0,+ 6 b 1.21 0.74 0.44 0.58±0.20 3,5 - dimethyl heptane 926 - 82 - 9 128.26 Exp 0 7 b 1.56 0.92 0.48 0.69±0.28 4 - ethyl heptane 2216 - 32 - 2 128.26 Exp 0 7 b 1.22 0.74 0.37 0.54±0.23 4 - methyl octane 2216 - 34 - 4 128.26 Exp 1 0,+ 6 b 0.95 0.62 0.29 0.43±0.20 2,4,4 - trimethyl hexane 16747 - 30 - 1 128.26 Exp 0 7 b 1.34 0.76 0.42 0.58±0.21 3,3 - dimethyl heptane 4032 - 86 - 4 128.26 Exp 0 7 b 1.13 0.69 0.37 0.52±0.20 4,4 - dimethyl heptane 1068 - 19 - 5 128.26 Exp 0 7 b 1.27 0.73 0.39 0.55±0.22 2,2 - dimethyl heptane 1071 - 26 - 7 128.26 Exp 0 7 b 1.00 0.59 0.30 0.44±0.18 2,2,4 - trimethyl hexane 16747 - 26 - 5 128.26 Exp 0 7 b 1.26 0.71 0.36 0.53±0.21 2,6 - dimethyl heptane 1072 - 05 - 5 128.26 Exp 0 7 b 1.04 0.63 0.31 0.46±0.20 2,3 - dimethyl heptane 3074 - 71 - 3 128.26 Exp 0 7 b 1.09 0.69 0.35 0.50±0.21 2,5 - dimethyl heptane 2216 - 30 - 0 128.26 Exp 0 7 b 1.35 0.82 0.43 0.61±0.24 3 - methyl octane 2216 - 33 - 3 128.26 Exp 0 7 b 0.99 0.63 0.30 0.45±0.20 3,4 - dimethyl heptane 922 - 28 - 1 128.26 Exp 0 7 b 1.24 0.76 0.41 0.57±0.22 3 - ethyl heptane 15869 - 80 - 4 128.26 Exp 0 7 b 1.10 0.68 0.33 0.49±0.22

### Table B - 1 (continued)

179

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base cis - hydrindane; bicyclo[4.3.0]nonane 496 - 10 - 6 124.22 AdjP 0 7 b 1.31 0.76 0.32 0.52±0.28 C9 bicycloalkanes 124.22 LM 0 8 b 1.39 0.80 0.39 0.58±0.26 1,2,3 - trimethyl cyclohexane 1678 - 97 - 3 126.24 AdjP 0 7 b 1.22 0.75 0.33 0.52±0.26 1,3,5 - trimethyl cyclohexane 1839 - 63 - 0 126.24 Exp 0 7 b 1.15 0.66 0.28 0.46±0.24 1,1,3 - trimethyl cyclohexane 3073 - 66 - 3 126.24 Exp 1 0 6 b 1.19 0.68 0.31 0.48±0.23 1 - ethyl - 4 - methyl cyclohexane 3728 - 56 - 1 126.24 AdjP 0 7 b 1.44 0.82 0.38 0.59±0.28 propyl cyclohexane 1678 - 92 - 8 126.24 Exp 0 7 b 1.29 0.76 0.38 0.55±0.24 C9 cycloalkanes 126.24 LM 0 8 b 1.36 0.79 0.38 0.57±0.26 Unspeciated C9 Alkanes 127.59 Mix 0 8 1.09 0.67 0.31 0.47±0.22 n - decane 124 - 18 - 5 142.28 Exp 1 0,+ 6 b 0.68 0.47 0.184 0.30±0.17 branched C10 alkanes 142.28 LM 0 8 b 0.94 0.58 0.26 0.40±0.20 2,4,6 - trimethyl heptane 2613 - 61 - 8 142.28 Exp 0 7 b 1.28 0.72 0.34 0.52±0.23 2,4 - dimethyl octane 4032 - 94 - 4 142.28 Exp 0 7 b 1.03 0.62 0.28 0.44±0.21 2,6 - dimethyl octane 2051 - 30 - 1 142.28 Exp 1 2 0,+ 2 b 1.08 0.64 0.31 0.46±0.21 2 - methyl nonane 871 - 83 - 0 142.28 Exp 1 2 0,+ 2 b 0.73 0.49 0.195 0.32±0.18 3,4 - diethyl hexane 19398 - 77 - 7 142.28 Exp 1 2 0,+ 2 b 0.89 0.55 0.28 0.40±0.17 3 - methyl nonane 5911 - 04 - 6 142.28 Exp 0 7 b 0.75 0.50 0.20 0.33±0.18 4 - methyl nonane 17301 - 94 - 9 142.28 Exp 0 7 b 0.86 0.55 0.24 0.38±0.19 4 -propyl heptane 3178 - 29 - 8 142.28 Exp 0 7 b 1.02 0.62 0.29 0.44±0.21 2,4,4 - trimethyl heptane 142.28 Exp 0 7 b 1.31 0.72 0.37 0.54±0.22 2,5,5 - trimethyl heptane 142.28 Exp 0 7 b 1.25 0.72 0.38 0.54±0.21 3,3 - dimethyl octane 4110 - 44 - 5 142.28 Exp 0 7 b 1.09 0.65 0.33 0.48±0.20 4,4 - dimethyl octane 15869 - 95 - 1 142.28 Exp 0 7 b 1.14 0.67 0.33 0.49±0.21 2,2 - dimethyl octane 15869 - 87 - 1 142.28 Exp 0 7 b 0.83 0.50 0.23 0.35±0.16 2,2,4 - trimethyl heptane 14720 - 74 - 2 142.28 Exp 0 7 b 1.16 0.64 0.31 0.47±0.20 2,2,5 - trimethyl heptane 142.28 Exp 0 7 b 1.26 0.72 0.39 0.55±0.20 2,3,6 - trimethyl heptane 4032 - 93 - 3 142.28 AdjP 0 7 b 0.90 0.58 0.27 0.40±0.19 2,3 - dimethyl octane 7146 - 60 - 3 142.28 Exp 0 7 b 0.86 0.56 0.26 0.39±0.19 2,5 - dimethyl octane 142.28 Exp 0 7 b 1.03 0.63 0.29 0.44±0.22 2 - methyl - 3 - ethyl heptane 14676 - 29 - 0 142.28 Exp 0 7 b 0.99 0.62 0.30 0.44±0.20 4 - ethyl octane 15869 - 86 - 0 142.28 AdjP 0 7 b 0.79 0.53 0.20 0.34±0.21 C10 bicycloalkanes 138.25 LM 0 8 b 1.09 0.65 0.30 0.46±0.22 isobutyl cyclohexane; (2 - methylpropyl) cyclohexane 1678 - 98 - 4 140.27 LM 0 8 b 0.99 0.61 0.28 0.43±0.21 sec -butyl cyclohexane 7058 - 01 - 7 140.27 LM 0 8 b 0.99 0.61 0.28 0.43±0.21 C10 cycloalkanes 140.27 LM 0 8 b 1.07 0.65 0.30 0.46±0.22 1,3 - diethyl cyclohexane 1678 - 99 - 5 140.27 AdjP 0 7 b 1.26 0.74 0.34 0.52±0.25 1,4 - diethyl cyclohexane 1679 - 00 - 1 140.27 Exp 0 7 b 1.23 0.71 0.33 0.50±0.24 1 - methyl - 3 - isopropyl cyclohexane 16580 - 24 - 8 140.27 Exp 0 7 b 1.00 0.62 0.29 0.43±0.21 butyl cyclohexane 1678 - 93 - 9 140.27 Exp 1 0 6 b 0.99 0.61 0.28 0.43±0.21 unspeciated C10 alkanes 141.61 Mix 0 8 0.90 0.56 0.25 0.39±0.20 n - undecane 1120 - 21 - 4 156.31 Exp 1 0,+ 6 b 0.61 0.42 0.157 0.27±0.16 branched C11 alkanes 156.31 LM 0 8 b 0.73 0.47 0.188 0.31±0.18 2,3,4,6 - tetramethyl heptane 61868 - 54 - 0 156.31 Exp 0 7 b 1.11 0.67 0.33 0.48±0.21 2,6 - dimethyl nonane 17302 - 28 - 2 156.31 Exp 0 7 b 0.79 0.50 0.21 0.33±0.18 3,5 - diethyl heptane 61869 - 02 - 1 156.31 Exp 0 7 b 1.11 0.66 0.30 0.46±0.23 3 - methyl decane 13151 - 34 - 3 156.31 Exp 0 7 b 0.65 0.44 0.163 0.28±0.17

### Table B - 1 (continued)

180

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base 4 - methyl decane 2847 - 72 - 5 156.31 Exp 0 7 b 0.68 0.45 0.174 0.29±0.17 C11 bicycloalkanes 152.28 LM 0 8 b 0.91 0.56 0.24 0.38±0.21 C11 cycloalkanes 154.29 LM 0 8 b 0.90 0.56 0.23 0.38±0.21 1,3 - diethyl - 5 - me thyl cyclohexane 164259 - 42 - 1 154.29 Exp 0 7 b 1.04 0.61 0.26 0.42±0.22 1 - ethyl - 2 -propyl cyclohexane 62238 - 33 - 9 154.29 AdjP 0 7 b 0.81 0.53 0.21 0.35±0.21 pentyl cyclohexane 4292 - 92 - 6 154.29 Exp 0 7 b 0.84 0.53 0.23 0.36±0.19 unspeciated C11 alkanes 155.64 Mix 0 8 0.74 0.48 0.193 0.32±0.18 n - dodecane 112 - 40 - 3 170.33 Exp 1 2 0,+ 3 b 0.55 0.38 0.139 0.24±0.15 branched C12 alkanes 170.33 LM 0 8 b 0.63 0.43 0.141 0.26±0.18 2,3,5,7 - tetramethyl octane 62199 - 32 - 0 170.33 Exp 0 7 b 0.91 0.55 0.23 0.38±0.20 2,6 - diethyl octane 62183 - 94 - 2 170.33 Exp 0 7 b 0.97 0.59 0.27 0.42±0.20 3,6 - dimethyl decane 17312 - 53 - 7 170.33 AdjP 0 7 b 0.70 0.47 0.156 0.29±0.19 3 - methyl undecane 1002 - 43 - 3 170.33 Exp 0 7 b 0.59 0.40 0.145 0.25±0.16 5 - methyl undecane 1632 - 70 - 8 170.33 AdjP 0 7 b 0.55 0.39 0.105 0.22±0.18 C12 tricycloalkanes 164.29 LM 0 8 b 0.82 0.51 0.196 0.33±0.20 C12 bicycloalkanes 166.30 LM 0 8 b 0.81 0.50 0.194 0.33±0.20 C12 cycloalkanes 168.32 LM 0 8 b 0.80 0.49 0.192 0.32±0.19 1,3,5 - triethyl cyclohexane 164259 - 43 - 2 168.32 Exp 0 7 b 1.02 0.59 0.27 0.42±0.21 1 - methyl - 4 -pentyl cyclohexane 75736 - 67 - 3 168.32 Exp 0 7 b 0.72 0.46 0.177 0.30±0.18 hexyl cyclohexane 4292 - 75 - 5 168.32 AdjP 1 2 0 2 b 0.65 0.43 0.133 0.26±0.19 unspeciated C12 alkanes 169.66 Mix 0 8 0.66 0.44 0.157 0.28±0.18 n - tridecane 629 - 50 - 5 184.36 Exp 1 0,+ 6 b 0.53 0.37 0.133 0.23±0.15 branched C13 alkanes 184.36 LM 0 8 b 0.60 0.40 0.140 0.25±0.16 2,3,6 - trimethyl 4 - isopropyl heptane 184.36 Exp 0 7 b 0.93 0.55 0.25 0.39±0.19 2,4,6,8 - tetramethyl nonane 14638 - 54 - 1 184.36 AdjP 0 7 b 0.76 0.47 0.170 0.30±0.19 3,6 - dimethyl undecane 17301 - 28 - 9 184.36 Exp 0 7 b 0.69 0.44 0.175 0.29±0.17 3,7 - diethyl nonane 184.36 Exp 0 7 b 0.89 0.52 0.23 0.37±0.19 3 - methyl dodecane 17312 - 57 - 1 184.36 Exp 0 7 b 0.54 0.37 0.134 0.24±0.15 5 - methyl dodecane 17453 - 93 - 9 184.36 AdjP 0 7 b 0.47 0.34 0.079 0.188±0.168 C13 tricycloalkanes 178.31 LM 0 8 b 0.71 0.46 0.173 0.30±0.18 C13 bicycloalkanes 180.33 LM 0 8 b 0.70 0.45 0.171 0.29±0.18 C13 cycloalkanes 182.35 LM 0 8 b 0.70 0.45 0.170 0.29±0.18 1,3 - diethyl - 5 -propyl cyclohexane 182.35 Exp 0 7 b 0.96 0.56 0.25 0.39±0.20 1 - methyl - 2 - hexyl cyclohexane 92031 - 93 - 1 182.35 Exp 0 7 b 0.58 0.40 0.144 0.25±0.17 heptyl cyclohexane 5617 - 41 - 4 182.35 AdjP 0 7 b 0.55 0.38 0.113 0.23±0.18 unspeciated C13 alkanes 183.69 Mix 0 8 0.61 0.40 0.148 0.26±0.16 n - tetradecane 629 - 59 - 4 198.39 Exp 1 2 0,+ 3 b 0.51 0.36 0.133 0.23±0.14 branched C14 alkanes 198.39 LM 0 8 b 0.55 0.37 0.130 0.23±0.15 2,4,5,6,8 -pentamethyl nonane 198.39 Exp 0 7 b 0.95 0.59 0.26 0.41±0.21 2 - methyl 3,5 - diisopropyl heptane 198.39 AdjP 0 7 b 0.56 0.37 0.123 0.23±0.16 3,7 - dimethyl dodecane 82144 - 67 - 0 198.39 Exp 0 7 b 0.62 0.40 0.158 0.26±0.16 3,8 - diethyl decane 6224 - 52 - 8 198.39 AdjP 0 7 b 0.60 0.40 0.136 0.25±0.17 3 - methyl tridecane 6418 - 41 - 3 198.39 Exp 0 7 b 0.51 0.35 0.126 0.22±0.14 6 - methyl tridecane 13287 - 21 - 3 198.39 AdjP 0 7 b 0.46 0.33 0.079 0.183±0.162 C14 tricycloalkanes 192.34 LM 0 8 b 0.66 0.42 0.161 0.27±0.17

### Table B - 1 (continued)

181

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base C14 bicycloalkanes 194.36 LM 0 8 b 0.66 0.42 0.159 0.27±0.17 C14 cycloalkanes 196.37 LM 0 8 b 0.65 0.41 0.157 0.27±0.17 1,3 - dipropyl - 5 - ethyl cyclohexane 196.37 Exp 0 7 b 0.91 0.53 0.24 0.37±0.19 trans - 1 - methyl - 4 -heptyl cyclohexane 205324 - 73 - 8 196.37 Exp 0 7 b 0.53 0.36 0.125 0.22±0.16 octyl cyclohexane 1795 - 15 - 9 196.37 AdjP 2 0 7 b 0.51 0.36 0.106 0.21±0.17 unspeciated C14 alkanes 197.72 Mix 0 8 0.57 0.38 0.140 0.24±0.16 n -pentadecane 629 - 62 - 9 212.41 Exp 1 4 0,+ 3 b 0.50 0.34 0.133 0.22±0.14 branched C15 alkanes 212.41 LM 0 8 b 0.50 0.34 0.119 0.21±0.15 2,6,8 - trimethyl 4 - isopropyl nonane 212.41 Exp 0 7 b 0.63 0.40 0.154 0.26±0.16 3,7 - dimethyl tridecane 212.41 Exp 0 7 b 0.55 0.37 0.140 0.24±0.15 3,9 - diethyl undecane 13286 - 72 - 1 212.41 Exp 0 7 b 0.51 0.35 0.128 0.22±0.14 3 - methyl tetradecane 18435 - 22 - 8 212.41 Exp 0 7 b 0.48 0.33 0.122 0.21±0.14 6 - methyl tetradecane 26730 - 16 - 5 212.41 AdjP 0 7 b 0.42 0.31 0.072 0.169±0.153 C15 tricycloalkanes 206.37 LM 0 8 b 0.63 0.40 0.154 0.26±0.16 C15 bicycloalkanes 208.38 LM 0 8 b 0.62 0.40 0.152 0.26±0.16 C15 cycloalkanes 210.40 LM 0 8 b 0.61 0.39 0.151 0.26±0.16 1,3,5 - tripropyl cyclohexane 210.40 Exp 0 7 b 0.87 0.50 0.23 0.36±0.18 1 - methyl - 2 - octyl cyclohexane 210.40 AdjP 0 7 b 0.50 0.35 0.127 0.22±0.15 nonyl cyclohexane 2883 - 02 - 5 210.40 AdjP 0 7 b 0.47 0.33 0.093 0.193±0.157 1,3 - diethyl - 5 -pentyl cyclohexane 210.40 Exp 0 7 b 0.66 0.41 0.159 0.27±0.16 unspeciated C15 alkanes 211.74 Mix 0 8 0.54 0.36 0.134 0.23±0.15 n - C16 544 - 76 - 3 226.44 AdjP 1 3 0,+ 3 b 0.45 0.32 0.104 0.194±0.144 branched C16 alkanes 226.44 LM 0 8 b 0.47 0.33 0.120 0.21±0.13 2,7 - dimethyl 3,5 - diisopropyl heptane 226.44 AdjP 0 7 b 0.52 0.35 0.114 0.22±0.16 3 - methyl pentadecane 2882 - 96 - 4 226.44 Exp 0 7 b 0.46 0.32 0.118 0.20±0.13 4,8 - dimethyl tetradecane 175032 - 36 - 7 226.44 Exp 0 7 b 0.49 0.33 0.124 0.21±0.14 7 - methyl pentadecane 6165 - 40 - 8 226.44 Exp 0 7 b 0.45 0.32 0.117 0.20±0.13 C16 tricycloalkanes 220.39 LM 0 8 b 0.59 0.37 0.144 0.24±0.15 C16 bicycloalkanes 222.41 LM 0 8 b 0.58 0.37 0.143 0.24±0.15 C16 cycloalkanes 224.43 LM 0 8 b 0.55 0.36 0.135 0.23±0.15 1,3 -propyl - 5 -butyl cyclohexane 224.43 Exp 0 7 b 0.75 0.45 0.20 0.31±0.16 1 - methyl - 4 - nonyl cyclohexane 39762 - 40 - 8 224.43 Exp 0 7 b 0.46 0.32 0.115 0.20±0.14 decyl cyclohexane 1795 - 16 - 0 224.43 AdjP 0 7 b 0.43 0.31 0.087 0.180±0.149 unspeciated C16 alkanes 225.77 Mix 0 8 0.49 0.34 0.120 0.21±0.14 n - C17 629 - 78 - 7 240.47 LM 0,+ 7 b 0.42 0.30 0.098 0.183±0.136 branched C17 alkanes 240.47 LM 0 8 b 0.44 0.31 0.113 0.194±0.126 C17 tricycloalkanes 234.42 LM 0 8 b 0.55 0.35 0.135 0.23±0.14 C17 bicycloalkanes 236.44 LM 0 8 b 0.55 0.35 0.134 0.23±0.14 C17 cycloalkanes 238.45 LM 0 8 b 0.52 0.34 0.127 0.22±0.14 unspeciated C17 alkanes 239.80 Mix 0 8 0.46 0.32 0.113 0.198±0.134 n - C18 593 - 45 - 3 254.49 LM 0,+ 7 b 0.40 0.29 0.093 0.173±0.129 branched C18 alkanes 254.49 LM 0 8 b 0.42 0.29 0.107 0.184±0.119 C18 tricycloalkanes 248.45 LM 0 8 b 0.52 0.33 0.128 0.22±0.14 C18 bicycloalkanes 250.46 LM 0 8 b 0.52 0.33 0.127 0.21±0.13

### Table B - 1 (continued)

182

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base C18 cycloalkanes 252.48 LM 0 8 b 0.49 0.32 0.120 0.21±0.13 unspeciated C18 alkanes 253.82 Mix 0 8 0.44 0.30 0.107 0.187±0.127 n - C19 629 - 92 - 5 268.52 LM 0,+ 7 b 0.38 0.27 0.088 0.164±0.122 branched C19 alkanes 268.52 LM 0 8 b 0.40 0.27 0.102 0.174±0.113 C19 tricycloalkanes 262.47 LM 0 8 b 0.49 0.31 0.121 0.20±0.13 C19 bicycloalkanes 264.49 LM 0 8 b 0.49 0.31 0.120 0.20±0.13 C19 cycloalkanes 266.51 LM 0 8 b 0.46 0.30 0.113 0.194±0.126 n - C20 112 - 95 - 8 282.55 LM 0,+ 7 b 0.36 0.26 0.084 0.156±0.116 branched C20 alkanes 282.55 LM 0 8 b 0.38 0.26 0.097 0.165±0.108 C20 tricycloalkanes 276.50 LM 0 8 b 0.47 0.30 0.115 0.194±0.121 C20 bicycloalkanes 278.52 LM 0 8 b 0.46 0.30 0.114 0.193±0.121 C20 cycloalkanes 280.53 LM 0 8 b 0.44 0.29 0.108 0.185±0.119 n - C21 629 - 94 - 7 296.57 LM 0,+ 7 b 0.34 0.25 0.080 0.148±0.110 branched C21 alkanes 296.57 LM 0 8 b 0.36 0.25 0.092 0.158±0.103 C21 tricycloalkanes 290.53 LM 0 8 b 0.44 0.28 0.109 0.185±0.116 C21 bicycloalkanes 292.54 LM 0 8 b 0.44 0.28 0.108 0.184±0.115 C21 cycloalkanes 294.56 LM 0 8 b 0.42 0.27 0.103 0.176±0.114 n - C22 629 - 97 - 0 310.60 LM 0,+ 7 b 0.33 0.23 0.076 0.142±0.105 branched C22 alkanes 310.60 LM 0 8 b 0.34 0.24 0.088 0.151±0.098 C22 tricycloalkanes 304.55 LM 0 8 b 0.42 0.27 0.104 0.177±0.110 C22 bicycloalkanes 306.57 LM 0 8 b 0.42 0.27 0.103 0.175±0.110 C22 cycloalkanes 308.58 LM 0 8 b 0.40 0.26 0.098 0.168±0.108 Alkenes ethene 74 - 85 - 1 28.05 Exp 1 1 0 3 d 9.00 3.64 2.21 3.11±1.08 propene 115 - 07 - 1 42.08 Exp 1 1 0 3 d 11.66 4.44 2.73 3.85±1.38 1,2 -propadiene (allene) 463 - 49 - 0 40.06 Exp 1 0 11 8.45 3.99 2.53 3.36±1.01 1 -butene 106 - 98 - 9 56.11 Exp 1 3 0 3 d 9.73 3.82 2.37 3.30±1.13 C4 terminal alkenes 56.11 LM 0 7 9.73 3.82 2.37 3.30±1.13 isobutene 115 - 11 - 7 56.11 Exp 1 3 0 3 6.29 2.16 1.18 1.83±0.83 cis - 2 -butene 590 - 18 - 1 56.11 Exp 1 0 6 14.24 5.08 3.08 4.45±1.78 trans - 2 -butene 624 - 64 - 6 56.11 Exp 1 1 0 3 15.16 5.30 3.16 4.63±1.93 C4 internal alkenes 56.11 LM 0 7 14.70 5.19 3.12 4.54±1.85 1,2 -butadiene 590 - 19 - 2 54.09 Exp 1 0 11 9.35 4.02 2.53 3.43±1.08 1,3 -butadiene 106 - 99 - 0 54.09 Exp 1 0 6 12.61 4.71 2.88 4.07±1.46 C4 alkenes 56.11 LM 0 8 12.22 4.51 2.74 3.92±1.48 1 -pentene 109 - 67 - 1 70.13 Exp 1 0 6 d 7.21 2.88 1.78 2.47±0.84 3 - methyl - 1 -butene 563 - 45 - 1 70.13 Exp 1 0 6 d 6.99 2.81 1.74 2.41±0.81 C5 terminal alkenes 70.13 LM 0 7 7.21 2.88 1.78 2.47±0.84 2 - methyl - 1 -butene 563 - 46 - 2 70.13 Exp 1 0 8 6.40 2.30 1.31 1.96±0.81 2 - methyl - 2 -butene 513 - 35 - 9 70.13 Exp 1 0 6 14.08 4.57 2.57 3.99±1.96 cis - 2 -pentene 627 - 20 - 3 70.13 Exp 1 0 6 10.38 3.94 2.45 3.44±1.22 trans - 2 -pentene 646 - 04 - 8 70.13 Exp 1 0 6 10.56 3.97 2.45 3.46±1.25 2 -pentenes 70.13 LM 0 7 10.47 3.95 2.45 3.45±1.24 C5 internal alkenes 70.13 LM 0 7 10.47 3.95 2.45 3.45±1.24 cyclopentene 142 - 29 - 0 68.12 Exp 1 0 8 6.77 2.53 1.55 2.20±0.80 trans - 1,3 -pentadiene 2004 - 70 - 8 68.12 Exp 0 8 12.50 4.76 2.95 4.12±1.43 cis - 1,3 -pentadiene 1574 - 41 - 0 68.12 LM 0 8 12.50 4.76 2.95 4.12±1.43 1,4 -pentadiene 591 - 93 - 5 68.12 Exp 1 0 8 9.24 3.73 2.40 3.25±1.03

### Table B - 1 (continued)

183

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base 1,2 -pentadiene 591 - 95 - 7 68.12 Exp 1 0 11 7.86 3.23 2.00 2.76±0.90 3 - methyl - 1,2 -butadiene 598 - 25 - 4 68.12 Exp 1 0 11 10.29 3.98 2.44 3.43±1.18 isoprene (2 - methyl - 1,3 - butadiene) 78 - 79 - 5 68.12 Exp 1 2 0 1 10.61 3.92 2.35 3.37±1.25 cyclopentadiene 542 - 92 - 7 66.10 LM 0 8 6.98 2.61 1.59 2.27±0.82 C5 alkenes 70.13 LM 0 8 8.84 3.42 2.11 2.96±1.04 1 -hexene 592 - 41 - 6 84.16 Exp 1 4 0 4 d 5.49 2.33 1.45 1.98±0.65 3,3 - dimethyl - 1 -butene 558 - 37 - 2 84.16 Exp 1 0 8 d 5.82 2.42 1.51 2.07±0.67 3 - methyl - 1 -pentene 760 - 20 - 3 84.16 Exp 0 8 6.14 2.52 1.56 2.15±0.72 4 - methyl - 1 -pentene 691 - 37 - 2 84.16 Exp 0 8 5.68 2.30 1.40 1.96±0.67 C6 terminal alkenes 84.16 LM 0 8 5.49 2.33 1.45 1.98±0.65 2,3 - dimethyl - 1 -butene 563 - 78 - 0 84.16 Exp 0 8 4.75 1.75 0.99 1.48±0.60 2 - ethyl - 1 -butene 760 - 21 - 4 84.16 Exp 0 8 5.07 1.85 1.05 1.57±0.64 2 - methyl - 1 -pentene 763 - 29 - 1 84.16 Exp 1 0 8 5.26 1.90 1.07 1.61±0.67 2,3 - dimethyl - 2 -butene 563 - 79 - 1 84.16 Exp 1 0 8 12.49 3.78 1.96 3.28±1.91 2 - methyl - 2 -pentene 625 - 27 - 4 84.16 Exp 1 0 8 11.00 3.75 2.15 3.25±1.46 cis 4 - methyl - 2 -pentene 84.16 LM 0 8 8.12 3.11 1.92 2.70±0.97 cis - 2 -hexene 7688 - 21 - 3 84.16 Exp 0 8 8.31 3.20 1.98 2.78±0.98 cis - 3 -hexene 7642 - 09 - 3 84.16 Exp 0 8 7.61 3.07 1.94 2.66±0.88 cis - 3 - methyl - 2 -pentene 922 - 62 - 3 84.16 Exp 0 8 12.49 4.22 2.42 3.67±1.69 trans - 3 - methyl - 2 -pentene 616 - 12 - 6 84.16 Exp 0 8 13.17 4.42 2.52 3.84±1.78 trans - 4 - methyl - 2 -pentene 674 - 76 - 0 84.16 Exp 1 0 8 8.12 3.11 1.92 2.70±0.97 trans - 2 - hexene 4050 - 45 - 7 84.16 Exp 0 8 8.62 3.24 1.99 2.82±1.03 trans - 3 - hexene 13269 - 52 - 8 84.16 Exp 0 8 7.57 3.04 1.92 2.63±0.88 2 -hexenes 592 - 43 - 8 84.16 LM 0 8 8.47 3.22 1.99 2.80±1.00 C6 internal alkenes 84.16 LM 0 8 8.47 3.22 1.99 2.80±1.00 3 - methyl cyclopentene 1120 - 62 - 3 82.14 Exp 0 8 5.10 2.05 1.29 1.77±0.60 1 - methyl cyclopentene 693 - 89 - 0 82.14 AdjP 0 8 12.49 4.32 2.49 3.74±1.63 cyclohexene 110 - 83 - 8 82.14 Exp 1 4 0 4 5.00 2.04 1.29 1.76±0.59 trans,trans - 2,4 -hexadiene 5194 - 51 - 4 82.14 LM 0 8 8.83 3.32 2.04 2.89±1.06 trans - 1,3 -hexadiene 20237 - 34 - 7 82.14 LM 0 8 10.37 3.95 2.45 3.42±1.19 trans - 1,4 -hexadiene 7319 - 00 - 8 82.14 Exp 1 0 8 8.64 3.33 2.06 2.88±1.01 C6 cyclic olefins or di - olefins 82.14 LM 0 8 8.68 3.30 2.04 2.87±1.03 C6 alkenes 84.16 LM 0 8 6.98 2.77 1.72 2.39±0.82 1 - methyl cyclohexene 591 - 49 - 1 96.17 Exp 1 0 8 6.61 2.44 1.41 2.08±0.86 4 - methyl cyclohexene 591 - 47 - 9 96.17 Exp 0 8 4.18 1.71 1.07 1.47±0.50 C7 cyclic olefins or di - olefins 96.17 LM 0 8 7.29 2.83 1.74 2.44±0.88 1 -heptene 592 - 76 - 7 98.19 AdjP 1 0 8 d 4.43 1.91 1.14 1.59±0.54 3,4 - dimethyl - 1 -pentene 7385 - 78 - 6 98.19 Exp 0 8 4.84 2.00 1.21 1.69±0.57 3 - methyl - 1 - hexene 3404 - 61 - 3 98.19 Exp 0 8 4.41 1.92 1.15 1.60±0.54 2,4 - dimethyl - 1 -pentene 2213 - 32 - 3 98.19 AdjP 0 8 6.01 2.39 1.42 2.02±0.72 2,3 - dimethyl - 1 -pentene 3404 - 72 - 6 98.19 Exp 0 8 5.15 2.12 1.24 1.77±0.64 3,3 - dimethyl - 1 -pentene 3404 - 73 - 7 98.19 Exp 0 8 4.91 2.17 1.39 1.85±0.56 2 - methyl - 1 - hexene 6094 - 02 - 6 98.19 Exp 0 8 5.10 2.11 1.22 1.75±0.64 2,3,3 - trimethyl - 1 -butene 594 - 56 - 9 98.19 Exp 0 8 4.49 1.78 1.06 1.51±0.54 4,4 - dimethyl - cis - 2 -pentene 762 - 63 - 0 98.19 Exp 0 8 6.64 2.54 1.53 2.19±0.81 2,4 - dimethyl - 2 -pentene 625 - 65 - 0 98.19 Exp 0 8 9.29 3.15 1.79 2.73±1.25 2 - methyl - 2 - hexene 2738 - 19 - 4 98.19 Exp 0 8 9.47 3.21 1.81 2.77±1.28 3 - ethyl - 2 -pentene 816 - 79 - 5 98.19 Exp 0 8 9.75 3.43 1.99 2.97±1.31

### Table B - 1 (continued)

184

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base 3 - methyl - trans - 3 -hexene 3899 - 36 - 3 98.19 Exp 0 8 9.72 3.45 2.01 2.98±1.26 cis - 2 -heptene 6443 - 92 - 1 98.19 Exp 0 8 7.16 2.78 1.70 2.40±0.86 2 - methyl - trans - 3 -hexene 692 - 24 - 0 98.19 Exp 0 8 6.25 2.55 1.60 2.20±0.73 3 - methyl - cis - 3 - hexene 4914 - 89 - 0 98.19 Exp 0 8 9.72 3.45 2.01 2.98±1.26 3,4 - dimethyl - cis - 2 -pentene 4914 - 91 - 4 98.19 Exp 0 8 9.15 3.10 1.72 2.66±1.28 2,3 - dimethyl - 2 -pentene 10574 - 37 - 5 98.19 Exp 1 0 8 9.74 3.11 1.65 2.67±1.43 cis - 3 -heptene 7642 - 10 - 6 98.19 Exp 0 8 6.33 2.58 1.62 2.22±0.74 trans - 4,4 - dimethyl - 2 -pentene 690 - 08 - 4 98.19 Exp 1 0 8 6.64 2.54 1.54 2.19±0.81 trans - 2 - heptene 14686 - 13 - 6 98.19 Exp 1 0 8 7.14 2.77 1.70 2.39±0.86 trans - 3 - heptene 14686 - 14 - 7 98.19 Exp 0 8 6.32 2.57 1.62 2.22±0.74 cis - 3 - methyl - 2 - hexene 10574 - 36 - 4 98.19 Exp 0 8 10.07 3.46 1.975 2.99±1.36 trans - 4 - methyl - 2 -hexene 98.19 Exp 0 8 7.18 2.78 1.71 2.40±0.86 trans - 3 - methyl - 2 -hexene 98.19 Exp 0 8 10.07 3.46 1.98 2.99±1.36 2 -heptenes 98.19 LM 0 8 6.32 2.58 1.62 2.22±0.74 C7 terminal alkenes 98.19 LM 0 8 4.43 1.91 1.14 1.59±0.54 C7 internal alkenes 98.19 LM 0 8 6.32 2.57 1.62 2.22±0.74 C7 alkenes 98.19 LM 0 8 5.37 2.24 1.38 1.91±0.64 1,2 - dimethyl cyclohexene 1674 - 10 - 8 110.20 Exp 0 8 5.63 2 .09 1.11 1.73±0.78 C8 cyclic olefins or di - olefins 110.20 LM 0 8 4.89 2.02 1.21 1.70±0.61 1 - octene 111 - 66 - 0 112.21 Exp 0 8 3.25 1.42 0.82 1.16±0.42 2,4,4 - trimethyl - 1 -pentene 107 - 39 - 1 112.21 Exp 0 8 3.34 1.23 0.66 1.02±0.43 3 - methyl - 2 - isopropyl - 1 -butene 111823 - 35 - 9 112.21 AdjP 0 8 3.31 1.40 0.78 1.14±0.43 trans - 2 - octene 13389 - 42 - 9 112.21 Exp 0 8 6.00 2.33 1.42 2.00±0.73 2 - methyl - 2 - heptene 627 - 97 - 4 112.21 Exp 0 8 8.33 2.86 1.60 2.45±1.13 cis - 4 - octene 7642 - 15 - 1 112.21 AdjP 0 8 4.73 1.97 1.18 1.65±0.59 trans - 2,2 - dimethyl 3 - hexene 690 - 93 - 7 112.21 Exp 0 8 5.00 2.11 1.32 1.80±0.60 trans - 2,5 - dimethyl 3 - hexene 692 - 70 - 6 112.21 AdjP 0 8 4.82 2.04 1.29 1.75±0.57 trans - 3 - octene 14919 - 01 - 8 112.21 AdjP 0 8 5.34 2.22 1.37 1.89±0.65 trans - 4 - octene 14850 - 23 - 8 112.21 AdjP 1 0 8 4.81 1.98 1.18 1.67±0.59 2,4,4 - trimethyl - 2 -pentene 107 - 40 - 4 112.21 Exp 0 8 6.29 2.23 1.24 1.89±0.84 2,3 - dimethyl - 2 - hexene 112.21 Exp 0 8 8.53 2.74 1.44 2.35±1.25 3 - octenes 112.21 LM 0 8 5.34 2.22 1.37 1.89±0.65 C8 terminal alkenes 112.21 LM 0 8 3.25 1.42 0.82 1.16±0.42 C8 internal alkenes 112.21 LM 0 8 4.81 1.98 1.18 1.67±0.59 C8 alkenes 112.21 LM 0 8 4.03 1.70 1.00 1.41±0.51 1 -nonene 124 - 11 - 8 126.24 Exp 0 8 2.60 1.16 0.65 0.94±0 .35 C9 terminal alkenes 126.24 LM 0 8 2.60 1.16 0.65 0.94±0.35 4,4 - dimethyl - 1 -pentene 762 - 62 - 9 126.24 Exp 0 8 3.13 1.34 0.77 1.10±0.40 4 -nonene 2198 - 23 - 4 126.24 LM 0 8 4.54 1.90 1.15 1.60±0.56 3 -nonenes 126.24 LM 0 8 4.54 1.90 1.15 1.60±0 .56 C9 internal alkenes 126.24 LM 0 8 4.54 1.90 1.15 1.60±0.56 trans - 4 - nonene 10405 - 85 - 3 126.24 AdjP 0 8 4.54 1.90 1.15 1.60±0.56 C9 cyclic olefins or di - olefins 124.22 LM 0 8 4.62 1.93 1.17 1.63±0.57 C9 alkenes 126.24 LM 0 8 3.57 1.53 0 .90 1.27±0.45 1 - decene 872 - 05 - 9 140.27 Exp 0 8 2.17 0.98 0.54 0.78±0.30 C10 terminal alkenes 140.27 LM 0 8 2.17 0.98 0.54 0.78±0.30 3,4 - diethyl - 2 -hexene 59643 - 70 - 8 140.27 Exp 0 8 3.38 1.50 0.85 1.22±0.46 cis - 5 - decene 7433 - 78 - 5 140.27 AdjP 0 8 3.66 1.57 0.91 1.29±0.48 trans - 4 - decene 19398 - 89 - 1 140.27 AdjP 0 8 3.87 1.64 0.98 1.37±0.49

### Table B - 1 (continued)

185

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base C10 3 - alkenes 140.27 LM 0 8 3.87 1.64 0.98 1.37±0.49 C10 internal alkenes 140.27 LM 0 8 3.87 1.64 0.98 1.37±0.49 C10 cyclic olefins or di - olefins 138.25 LM 0 8 3.93 1.67 0.99 1.39±0.50 3 - carene 13466 - 78 - 9 136.23 Exp 1 3 0 4 3.24 1.28 0.75 1.08±0.40 alpha -pinene 80 - 56 - 8 136.23 Exp 1 2 0 4 4.51 1.65 0.89 1.38±0.60 beta -pinene 127 - 91 - 3 136.23 Exp 1 2 0 4 3.52 1.44 0.79 1.17±0.46 d - limonene 5989 - 27 - 5 136.23 Exp 1 2 0 4 4.55 1.70 0.96 1.44±0.60 sabinene 3387 - 41 - 5 136.23 Exp 1 3 0 4 4.19 1.70 0.97 1.41±0.53 Terpinolene 586 - 62 - 9 136.23 Exp 0 8 6.36 2.22 1.18 1.88±0.93 Camphene 79 - 92 - 5 136.23 LM 0 8 4.51 1.65 0.89 1.38±0.60 terpene (monoterpenes) 136.23 LM 0 8 4.04 1.55 0.86 1.29±0.52 C10 alkenes 140.27 LM 0 8 3.31 1.42 0.83 1.17±0.43 1 -undecene 821 - 95 - 4 154.29 Exp 0 8 1.87 0.86 0.46 0.67±0.27 C11 terminal alkenes 154.29 LM 0 8 1.87 0.86 0.46 0.67±0.27 trans - 5 - undecene 764 - 97 - 6 154.29 AdjP 0 8 3.60 1.54 0.92 1.28±0.46 C11 3 - alkenes 154.29 LM 0 8 3.60 1.54 0.92 1.28±0.46 C11 internal alkenes 154.29 LM 0 8 3.60 1.54 0.92 1.28±0.46 C11 cyclic olefins or di - olefins 152.28 LM 0 8 3.65 1.56 0.93 1.30±0.47 C11 alkenes 154.29 LM 0 8 2.73 1.20 0.69 0.98±0.36 C12 terminal alkenes 168.32 LM 0 8 1.64 0.76 0.41 0.60±0.24 1 - dodecene 112 - 41 - 4 168.32 Exp 0 8 1.64 0.76 0.41 0.60±0.24 C12 2 - alkenes 168.32 LM 0 8 3.14 1.36 0.79 1.12±0.41 C12 3 - alkene s 168.32 LM 0 8 3.14 1.36 0.79 1.12±0.41 C12 internal alkenes 168.32 LM 0 8 3.14 1.36 0.79 1.12±0.41 trans - 5 - dodecene 7206 - 16 - 8 168.32 AdjP 0 8 3.14 1.36 0.79 1.12±0.41 C12 cyclic olefins or di - olefins 166.30 LM 0 8 3.18 1.37 0.80 1.13±0. 42 C12 alkenes 168.32 LM 0 8 2.39 1.06 0.60 0.86±0.32 1 - tridecene 2437 - 56 - 1 182.35 Exp 0 8 1.48 0.69 0.37 0.54±0.22 C13 terminal alkenes 182.35 LM 0 8 1.48 0.69 0.37 0.54±0.22 trans - 5 - tridecene 23051 - 84 - 5 182.35 Exp 0 8 2.59 1.13 0.67 0.9 3±0.35 C13 3 - alkenes 182.35 LM 0 8 2.59 1.13 0.67 0.93±0.35 C13 internal alkenes 182.35 LM 0 8 2.59 1.13 0.67 0.93±0.35 C13 cyclic olefins or di - olefins 180.33 LM 0 8 2.62 1.14 0.67 0.94±0.35 C13 alkenes 182.35 LM 0 8 2.03 0.91 0.52 0.7 4±0.28 1 - tetradecene 1120 - 36 - 1 196.37 Exp 0 8 1.34 0.63 0.33 0.49±0.20 C14 terminal alkenes 196.37 LM 0 8 1.34 0.63 0.33 0.49±0.20 trans - 5 - tetradecene 41446 - 66 - 6 196.37 Exp 0 8 2.35 1.03 0.61 0.85±0.32 C14 3 - alkenes 196.37 LM 0 8 2.35 1.0 3 0.61 0.85±0.32 C14 internal alkenes 196.37 LM 0 8 2.35 1.03 0.61 0.85±0.32 C14 cyclic olefins or di - olefins 194.36 LM 0 8 2.38 1.04 0.61 0.86±0.33 C14 alkenes 196.37 LM 0 8 1.85 0.83 0.47 0.67±0.26 1 -pentadecene 13360 - 61 - 7 210.40 LM 0 8 1.25 0.59 0.31 0.46±0.19 C15 terminal alkenes 210.40 LM 0 8 1.25 0.59 0.31 0.46±0.19 trans - 5 -pentadecene 74392 - 33 - 9 210.40 Exp 0 8 2.16 0.95 0.56 0.78±0.30 C15 3 - alkenes 210.40 LM 0 8 2.16 0.95 0.56 0.78±0.30 C15 internal alkenes 210.40 LM 0 8 2.16 0.95 0.56 0.78±0.30 C15 cyclic olefins or di - olefins 208.38 LM 0 8 2.19 0.96 0.56 0.79±0.30 C15 alkenes 210.40 LM 0 8 1.71 0.77 0.43 0.62±0.24

### Table B - 1 (continued)

186

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base Aromatic Hydrocarbons benzene 71 - 43 - 2 78.11 Exp 1 2 0? 4 0.72 0.101 - 0.1 59 - .008±0.185 toluene 108 - 88 - 3 92.14 Exp 1 2 0 4 4.00 1.36 0.52 1.02±0.60 ethyl benzene 100 - 41 - 4 106.17 Exp 1 3 0 4 3.04 1.15 0.50 0.88±0.44 m - xylene 108 - 38 - 3 106.17 Exp 1 1 0 4 9.75 3.09 1.48 2.53±1.30 o - xylene 95 - 47 - 6 106.17 Exp 1 2 0 4 7.64 2.5 1 1.16 2.02±1.04 p - xylene 106 - 42 - 3 106.17 Exp 1 3 0 4 5.84 1.93 0.82 1.51±0.82 C8 disubstituted benzenes 1330 - 20 - 7 106.17 LM 0 8 7.76 2.51 1.15 2.02±1.05 isomers of ethylbenzene 106.17 LM 0 8 6.57 2.17 0.99 1.73±0.90 styrene 100 - 42 - 5 104.15 Exp 1 2 0 2 1.73 0.21 - 0.48 - .107±0.500 Unspeciated C8 Aromatics 106.17 Mix 0 8 7.64 2.49 1.15 2.01±1.03 C9 monosubstituted benzenes 120.19 LM 0 8 2.03 0.82 0.36 0.62±0.30 n -propyl benzene 103 - 65 - 1 120.19 Exp 1 0 8 2.03 0.82 0.36 0.62±0.30 isop ropyl benzene (cumene) 98 - 82 - 8 120.19 Exp 1 0 8 2.52 0.94 0.39 0.71±0.37 C9 disubstituted benzenes 120.19 LM 0 8 5.81 1.95 0.89 1.55±0.79 m - ethyl toluene 620 - 14 - 4 120.19 Exp 1 0 8 7.39 2.40 1.13 1.95±0.99 o - ethyl toluene 611 - 14 - 3 120.19 Exp 1 0 8 5.59 1.90 0.87 1.51±0.76 p - ethyl toluene 622 - 96 - 8 120.19 Exp 1 0 8 4.44 1.54 0.67 1.20±0.62 C9 trisubstituted benzenes 25551 - 13 - 7 120.19 LM 0 8 10.87 3.59 1.94 3.04±1.38 1,2,3 - trimethyl benzene 526 - 73 - 8 120.19 Exp 1 2 0 4 11.97 3.93 2.12 3.33± 1.52 1,2,4 - trimethyl benzene 95 - 63 - 6 120.19 Exp 1 2 0 4 8.87 3.05 1.65 2.56±1.12 1,3,5 - trimethyl benzene 108 - 67 - 8 120.19 Exp 1 2 0 4 11.76 3.80 2.05 3.24±1.51 isomers of propyl benzene 120.19 LM 0 8 6.23 2.12 1.06 1.74±0.82 indene 95 - 13 - 6 116.16 LM 0 10 1.55 0.191 - 0.43 - .095±0.448 indane 496 - 11 - 7 118.18 LM 0 10 3.32 1.18 0.47 0.89±0.48 allylbenzene 300 - 57 - 2 118.18 LM 0 8 1.53 0.188 - 0.43 - .094±0.441 α - methyl styrene 98 - 83 - 9 118.18 LM 0 8 1.53 0.188 - 0.43 - .094±0.441 C9 styrenes 1 18.18 LM 0 8 1.53 0.188 - 0.43 - .094±0.441 β - methyl styrene 637 - 50 - 3 118.18 Exp 1 0 8 1.01 0.155 - 0.32 - .074±0.300 Unspeciated C9 Aromatics 120.09 Mix 0 8 7.99 2.68 1.38 2.23±1.03 C10 monosubstituted benzenes 134.22 Exp 0 8 2.36 0.94 0.42 0. 72±0.34 n -butyl benzene 104 - 51 - 8 134.22 LM 0 8 2.36 0.94 0.42 0.72±0.34 sec -butyl benzene 135 - 98 - 8 134.22 LM 0 8 2.36 0.94 0.42 0.72±0.34 tert -butyl benzene 98 - 06 - 6 134.22 Exp 1 0 8 1.95 0.70 0.27 0.52±0.30 o - cymene; 1 - methyl - 2 - (1 - methylethyl) benzene 527 - 84 - 4 134.22 LM 0 8 5.49 1.87 0.89 1.51±0.74 1 - methyl - 2 - n -propyl benzene 1074 - 17 - 5 134.22 LM 0 8 5.49 1.87 0.89 1.51±0.74 m - cymene; 1 - methyl - 3 - (1 - methylethyl) benzene 535 - 77 - 3 134.22 LM 0 8 7.10 2.30 1.12 1.89±0.94 1 - methyl - 3 - n -propyl benzene 1074 - 43 - 7 134.22 LM 0 8 7.10 2.30 1.12 1.89±0.94 1 - methyl - 4 - n -propyl benzene 1074 - 55 - 1 134.22 LM 0 8 4.43 1.54 0.71 1.22±0.61 C10 disubstituted benzenes 134.22 LM 0 8 5.68 1.91 0.91 1.54±0.76 m - C10 disubstituted benzenes 134.22 Exp 0 8 7.10 2.30 1.12 1.89±0.94 o - C10 disubstituted benzenes 134.22 Exp 0 8 5.49 1.87 0.89 1.51±0.74 p - C10 disubstituted benzenes 134.22 Exp 0 8 4.43 1.54 0.71 1.22±0.61 m - diethyl benzene 141 - 93 - 5 134.22 LM 0 8 7.10 2.30 1.12 1.89±0.94 o - die thyl benzene 135 - 01 - 3 134.22 LM 0 8 5.49 1.87 0.89 1.51±0.74 1 - methyl - 4 - isopropyl benzene (p - cymene) 99 - 87 - 6 134.22 Exp 1 0 8 4.44 1.52 0.67 1.19±0.61

### Table B - 1 (continued)

187

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base p - diethyl benzene 105 - 05 - 5 134.22 LM 0 8 4.43 1.54 0.71 1.22±0.61 1,2,3 - C10 trisubstituted benzenes 134.22 Exp 0 8 10.15 3.37 1.81 2.85±1.29 1,2,4 - C10 trisubstituted benzenes 134.22 Exp 0 8 7.55 2.62 1.41 2.19±0.96 1,3,5 - C10 trisubstituted benzenes 134.22 Exp 0 8 10.08 3.28 1.77 2.79±1.29 1,2,3,4 - tetramethyl benzene 488 - 23 - 3 134.22 LM 0 8 9.26 3.09 1.67 2.61±1.18 1,2,4,5 - tetramethyl benzene 95 - 93 - 2 134.22 LM 0 8 9.26 3.09 1.67 2.61±1.18 1,2 - dimethyl - 3 - ethyl benzene 933 - 98 - 2 134.22 LM 0 8 10.15 3.37 1.81 2.85±1.29 1,2 - dimethyl - 4 - ethyl benzene 934 - 80 - 5 134.22 LM 0 8 7.55 2.62 1.41 2.19±0.96 1,3 - dimethyl - 2 - ethyl benzene 2870 - 04 - 4 134.22 LM 0 8 10.15 3.37 1.81 2.85±1.29 1,3 - dimethyl - 4 - ethyl benzene 874 - 41 - 9 134.22 LM 0 8 7.55 2.62 1.41 2.19±0.96 1,3 - dimethyl - 5 - ethyl benzene 934 - 74 - 7 134.22 LM 0 8 10.08 3.28 1.7 7 2.79±1.29 1,4 - dimethyl - 2 - ethyl benzene 1758 - 88 - 9 134.22 LM 0 8 7.55 2.62 1.41 2.19±0.96 1,2,3,5 - tetramethyl benzene 527 - 53 - 7 134.22 LM 0 8 9.26 3.09 1.67 2.61±1.18 C10 trisubstituted benzenes 134.22 LM 0 8 9.26 3.09 1.67 2.61±1.18 C10 tetra substituted benzenes 134.22 LM 0 8 9.26 3.09 1.67 2.61±1.18 butylbenzenes 134.22 LM 0 8 5.76 1.98 1.00 1.62±0.75 methyl indanes 132.20 LM 0 10 2.97 1.05 0.42 0.80±0.43 tetralin (1,2,3,4 - tetrahydronaphthalene) 119 - 64 - 2 132.20 Exp 1 4 + 5 2.9 7 1.05 0.42 0.80±0.43 naphthalene 91 - 20 - 3 128.17 Exp 1 4 + 5 3.34 1.14 0.49 0.90±0.46 C10 styrenes 132.20 LM 0 8 1.37 0.168 - 0.38 - .084±0.394 Unspeciated C10 Aromatics 133.91 Mix 0 8 7.07 2.37 1.22 1.97±0.92 n -pentyl benzene 538 - 68 - 1 148.24 LM 0 8 2.12 0.86 0.40 0.66±0.30 C11 monosubstituted benzenes 148.24 Exp 0 8 2.12 0.86 0.40 0.66±0.30 m - C11 disubstituted benzenes 148.24 Exp 0 8 6.15 2.02 0.99 1.66±0.82 o - C11 disubstituted benzenes 148.24 Exp 0 8 4.73 1.64 0.79 1.32±0.63 p - C11 disubstituted benzenes 148.24 Exp 0 8 3.88 1.38 0.64 1.09±0.53 1 -butyl - 2 - methyl benzene 148.24 LM 0 8 4.73 1.64 0.79 1.32±0.63 1 - ethyl - 2 - n -propyl benzene 148.24 LM 0 8 4.73 1.64 0.79 1.32±0.63 o - tert -butyl toluene; 1 - (1,1 - dimethylethyl ) - 2 - methyl benzene 1074 - 92 - 6 148.24 LM 0 8 4.73 1.64 0.79 1.32±0.63 1 - methyl - 3 - n -butyl benzene 1595 - 04 - 6 148.24 LM 0 8 6.15 2.02 0.99 1.66±0.82 p - isobutyl toluene; 1 - me thyl - 4 - (2 - methylpropyl) benzene 5161 - 04 - 6 148.24 LM 0 8 3.88 1.38 0.64 1.09±0 .53 C11 disubstituted benzenes 148.24 LM 0 8 4.92 1.68 0.81 1.36±0.66 1,2,3 - C11 trisubstituted benzenes 148.24 Exp 0 8 8.88 2.96 1.60 2.50±1.13 1,2,4 - C11 trisubstituted benzenes 148.24 Exp 0 8 6.62 2.31 1.25 1.94±0.84 1,3,5 - C11 trisubstituted benzenes 148.24 Exp 0 8 8.90 2.91 1.57 2.47±1.14 pentamethyl benzene 700 - 12 - 9 148.24 LM 0 8 8.13 2.73 1.47 2.30±1.03 1 - methyl - 3,5 - diethyl benzene 2050 - 24 - 0 148.24 LM 0 8 8.90 2.91 1.57 2.47±1.14 C11 trisubstituted benzenes 148.24 LM 0 8 8.13 2.73 1.47 2.30±1.03 C11 tetrasubstituted benzenes 148.24 LM 0 8 8.13 2.73 1.47 2.30±1.03

### Table B - 1 (continued)

188

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base C11 pentasubstituted benzenes 148.24 LM 0 8 8.13 2.73 1.47 2.30±1.03 pentyl benzenes 148.24 LM 0 8 4.90 1.71 0.87 1.40±0.64 C11 tetralins or indanes 146.23 LM + 10 2.69 0.95 0.38 0.72±0.39 methyl naphthalenes 1321 - 94 - 4 142.20 Exp + 10 3.06 1.02 0.42 0.79±0.43 1 - methyl naphthalene 90 - 12 - 0 142.20 LM + 10 3.06 1.02 0.42 0.79±0.43 2 - methyl naphthalene 91 - 57 - 6 142.20 LM + 10 3.06 1.02 0. 42 0.79±0.43 Unspeciated C11 Aromatics 147.72 Mix 0 8 6.95 2.34 1.23 1.96±0.89 C12 monosubstituted benzenes 162.27 Exp 0 8 1.90 0.79 0.37 0.61±0.27 m - C12 disubstituted benzenes 162.27 Exp 0 8 5.49 1.81 0.89 1.49±0.73 o - C12 disubstituted benzenes 162.27 Exp 0 8 4.23 1.48 0.71 1.19±0.57 p - C12 disubstituted benzenes 162.27 Exp 0 8 3.49 1.25 0.59 0.99±0.47 1,3 - di -n -propyl benzene 162.27 LM 0 8 4.23 1.48 0.71 1.19±0.57 1,4 di - isopropyl benzene 162.27 LM 0 8 3.49 1.25 0.59 0.99± 0.47 3 - isopropyl cumene; 1,3 - di isopropyl benzene 99 - 62 - 7 162.27 LM 0 8 5.49 1.81 0.89 1.49±0.73 C12 disubstituted benzenes 162.27 LM 0 8 4.40 1.51 0.73 1.22±0.59 1,2,3 - C12 trisubstituted benzenes 162.27 Exp 0 8 7.95 2.66 1.44 2.25±1.01 1,2, 4 - C12 trisubstituted benzenes 162.27 Exp 0 8 5.94 2.08 1.13 1.74±0.75 1,3,5 - C12 trisubstituted benzenes 162.27 Exp 0 8 8.02 2.62 1.42 2.23±1.03 1 - (1,1 - dimethylethyl) - 3,5 - dimethylbenzene 98 - 19 - 1 162.27 LM 0 8 8.02 2.62 1.42 2.23±1.03 C12 trisu bstituted benzenes 162.27 LM 0 8 7.30 2.46 1.33 2.07±0.93 C12 tetrasubstituted benzenes 162.27 LM 0 8 7.30 2.46 1.33 2.07±0.93 C12 pentasubstituted benzenes 162.27 LM 0 8 7.30 2.46 1.33 2.07±0.93 C12 hexasubstituted benzenes 162.27 LM 0 8 7.30 2.46 1.33 2.07±0.93 hexyl benzenes 162.27 LM 0 8 4.39 1.55 0.79 1.27±0.57 C12 tetralins or indanes 160.26 LM 0 10 2.45 0.87 0.34 0.66±0.35 1 - ethyl naphthalene 1127 - 76 - 0 156.22 LM + 10 2.78 0.93 0.38 0.72±0.39 C12 naphthalenes 156.22 LM + 10 3.89 1.28 0.59 1.03±0.52 C12 monosubstituted naphthalene 156.22 LM + 10 2.78 0.93 0.38 0.72±0.39 C12 disubstituted naphthalenes 156.22 LM + 10 4.99 1.62 0.80 1.34±0.66 2,3 - dimethyl naphthalene 581 - 40 - 8 156.22 Exp 1 4 + 5 4.99 1.62 0. 80 1.34±0.66 dimethyl naphthalenes 156.22 LM + 10 4.99 1.62 0.80 1.34±0.66 Unspeciated C12 Aromatics 159.90 Mix 0 8 6.02 2.02 1.06 1.69±0.77 C13 monosubstituted benzenes 176.30 Exp 0 8 1.74 0.74 0.35 0.57±0.25 m - C13 disubstituted benzenes 176.30 Exp 0 8 4.93 1.64 0.81 1.35±0.65 o - C13 disubstituted benzenes 176.30 Exp 0 8 3.78 1.34 0.65 1.08±0.50 p - C13 disubstituted benzenes 176.30 Exp 0 8 3.13 1.14 0.54 0.90±0.42 C13 disubstituted benzenes 176.30 LM 0 8 3.95 1.37 0.67 1.11 ±0.52 1,2,3 - C13 trisubstituted benzenes 176.30 Exp 0 8 7.13 2.40 1.30 2.02±0.91 1,2,4 - C13 trisubstituted benzenes 176.30 Exp 0 8 5.35 1.88 1.02 1.58±0.67 1,3,5 - C13 trisubstituted benzenes 176.30 Exp 0 8 7.24 2.38 1.29 2.02±0.93

### Table B - 1 (continued)

189

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base C13 trisubstituted benzenes 176.30 LM 0 8 6.57 2.22 1.20 1.87±0.84 C13 tetralins or indanes 174.28 LM 0 10 2.25 0.80 0.32 0.61±0.33 C13 naphthalenes 170.25 LM 0 10 3.57 1.17 0.54 0.95±0.48 C13 monosubstituted naphthalene 170.25 LM 0 10 2.55 0.85 0.3 5 0.66±0.36 C13 disubstituted naphthalenes 170.25 LM 0 10 4.58 1.49 0.74 1.23±0.60 C13 trisubstituted naphthalenes 170.25 LM 0 10 4.58 1.49 0.74 1.23±0.60 Unspeciated C13 Aromatics 175.85 Mix 0 8 4.81 1.61 0.82 1.34±0.62 C14 monosubstituted benzenes 190.32 Exp 0 8 1.60 0.69 0.33 0.53±0.23 m - C14 disubstituted benzenes 190.32 Exp 0 8 4.45 1.49 0.74 1.23±0.59 o - C14 disubstituted benzenes 190.32 Exp 0 8 3.40 1.22 0.60 0.98±0.45 p - C14 disubstituted benzenes 190.32 Exp 0 8 2.84 1.04 0.50 0.83±0.38 C14 disubstituted benzenes 190.32 LM 0 8 3.56 1.25 0.61 1.01±0.47 1,2,3 - C14 trisubstituted benzenes 190.32 Exp 0 8 6.49 2.19 1.19 1.85±0.82 1,2,4 - C14 trisubstituted benzenes 190.32 Exp 0 8 4.89 1.73 0.94 1.45±0.62 1,3,5 - C14 trisubstituted benzenes 190.32 Exp 0 8 6.63 2.18 1.18 1.86±0.85 C14 trisubstituted benzenes 190.32 LM 0 8 6.00 2.03 1.10 1.72±0.76 C14 tetralins or indanes 188.31 LM 0 10 2.09 0.74 0.29 0.56±0.30 C14 naphthalenes 184.28 LM 0 10 3.30 1.08 0.50 0.88±0.44 Unspeciated C14 Aromatics 189.87 Mix 0 8 3.80 1.27 0.62 1.04±0.50 C15 monosubstituted benzenes 204.35 Exp 0 8 1.48 0.64 0.32 0.50±0.21 C15 disubstituted benzenes 204.35 LM 0 8 3.25 1.15 0.57 0.93±0.43 m - C15 disubstituted benzenes 204.35 Exp 0 8 4.04 1.37 0.68 1.12±0.53 o - C15 disubstituted benzenes 204.35 Exp 0 8 3.09 1.12 0.56 0.90±0.41 p - C15 disubstituted benzenes 204.35 Exp 0 8 2.59 0.96 0.47 0.77±0.35 C15 trisubstituted benzenes 204.35 LM 0 8 5.50 1. 87 1.02 1.58±0.70 1,2,3 - C15 trisubstituted benzenes 204.35 Exp 0 8 5.94 2.01 1.09 1.70±0.75 1,2,4 - C15 trisubstituted benzenes 204.35 Exp 0 8 4.47 1.59 0.87 1.33±0.56 1,3,5 - C15 trisubstituted benzenes 204.35 Exp 0 8 6.10 2.01 1.09 1.71±0.78 C15 tetralins or indanes 202.34 LM 0 10 1.94 0.69 0.27 0.52±0.28 C15 naphthalenes 198.30 LM 0 10 3.06 1.01 0.47 0.81±0.41 Unspeciated C15 Aromatics 203.90 Mix 0 8 3.20 1.06 0.50 0.86±0.42 C16 monosubstituted benzenes 218.38 Exp 0 8 1.38 0.61 0.30 0.47±0.20 m - C16 disubstituted benzenes 218.38 Exp 0 8 3.71 1.26 0.63 1.04±0.49 o - C16 disubstituted benzenes 218.38 Exp 0 8 2.83 1.03 0.52 0.83±0.37 p - C16 disubstituted benzenes 218.38 Exp 0 8 2.38 0.89 0.44 0.71±0.32 C16 disubstituted benzenes 218.38 LM 0 8 2.97 1.06 0.53 0.86±0.39 1,2,3 - C16 trisubstituted benzenes 218.38 Exp 0 8 5.46 1.86 1.01 1.57±0.69 1,2,4 - C16 trisubstituted benzenes 218.38 Exp 0 8 4.13 1.47 0.80 1.23±0.52 1,3,5 - C16 trisubstituted benzenes 218.3 8 Exp 0 8 5.63 1.86 1.01 1.58±0.72

### Table B - 1 (continued)

190

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base C16 trisubstituted benzenes 218.38 LM 0 8 5.07 1.73 0.94 1.46±0.64 C16 tetralins or indanes 216.36 LM 0 10 1.82 0.64 0.26 0.49±0.26 C16 naphthalenes 212.33 LM 0 10 2.86 0.94 0.43 0.76±0.38 Unspeciated C 16 Aromatics 217.93 Mix 0 8 2.79 0.92 0.42 0.74±0.37 C17 monosubstituted benzenes 232.40 LM 0 8 1.30 0.57 0.29 0.44±0.18 C17 disubstituted benzenes 232.40 LM 0 8 2.79 1.00 0.50 0.81±0.37 C17 trisubstituted benzenes 232.40 LM 0 8 4.77 1.6 3 0.89 1.37±0.60 C17 tetralins or indanes 230.39 LM 0 10 1.70 0.60 0.24 0.46±0.25 C17 naphthalenes 226.36 LM 0 10 2.68 0.88 0.41 0.71±0.36 C18 monosubstituted benzenes 246.43 LM 0 8 1.23 0.54 0.27 0.42±0.17 C18 disubstituted benzenes 246.4 3 LM 0 8 2.63 0.94 0.47 0.76±0.35 C18 trisubstituted benzenes 246.43 LM 0 8 4.49 1.53 0.83 1.29±0.57 C18 tetralins or indanes 244.41 LM 0 10 1.61 0.57 0.23 0.43±0.23 C18 naphthalenes 240.38 LM 0 10 2.53 0.83 0.38 0.67±0.34 C19 monosubstituted benzenes 260.46 LM 0 8 1.16 0.51 0.25 0.40±0.16 C19 disubstituted benzenes 260.46 LM 0 8 2.49 0.89 0.44 0.72±0.33 C19 trisubstituted benzenes 260.46 LM 0 8 4.25 1.45 0.79 1.22±0.54 C19 tetralins or indanes 258.44 LM 0 10 1.52 0.54 0.21 0.41±0.22 C19 naphthalenes 254.41 LM 0 10 2.39 0.78 0.36 0.63±0.32 C20 monosubstituted benzenes 274.48 LM 0 8 1.10 0.48 0.24 0.37±0.16 C20 disubstituted benzenes 274.48 LM 0 8 2.36 0.84 0.42 0.68±0.31 C20 trisubstituted benzenes 274.4 8 LM 0 8 4.04 1.38 0.75 1.16±0.51 C20 tetralins or indanes 272.47 LM 0 10 1.44 0.51 0.20 0.39±0.21 C20 naphthalenes 268.44 LM 0 10 2.26 0.74 0.34 0.60±0.30 C21 monosubstituted benzenes 288.51 LM 0 8 1.05 0.46 0.23 0.36±0.15 C21 disubstituted benzenes 288.51 LM 0 8 2.25 0.80 0.40 0.65±0.30 C21 trisubstituted benzenes 288.51 LM 0 8 3.84 1.31 0.71 1.11±0.49 C21 tetralins or indanes 286.49 LM 0 10 1.37 0.49 0.193 0.37±0.20 C21 naphthalenes 282.46 LM 0 10 2.15 0.71 0.33 0.57 ±0.29 C22 monosubstituted benzenes 302.54 LM 0 8 1.00 0.44 0.22 0.34±0.14 C22 disubstituted benzenes 302.54 LM 0 8 2.14 0.77 0.38 0.62±0.28 C22 trisubstituted benzenes 302.54 LM 0 8 3.66 1.25 0.68 1.05±0.46 C22 tetralins or indanes 300.52 LM 0 10 1.31 0.46 0.184 0.35±0.19 C22 naphthalenes 296.49 LM 0 10 2.05 0.67 0.31 0.54±0.27 Oxygenated Organics carbon monoxide 630 - 08 - 0 28.01 Exp 1 2 0 1 0.056 0.039 0.029 0.034±0.007 formaldehyde 50 - 00 - 0 30.03 Exp 1 1 0 1 b 9.46 2.68 1.27 2.27±1.40 methanol 67 - 56 - 1 32.04 Exp 1 3 0 2 0.67 0.31 0.190 0.26±0.08 formic acid 64 - 18 - 6 46.03 Exp 1 0 6 0.066 0.046 0.034 0.040±0.008 ethylene oxide 75 - 21 - 8 44.05 Exp 1 0 6 0.039 0.034 0.028 0.030±0.006 acetaldehyde 75 - 07 - 0 44.05 Exp 1 2 0 1 6.54 2.49 1.61 2.20±0.72 ethanol 64 - 17 - 5 46.07 Exp 1 3 0 2 1.53 0.87 0.59 0.74±0.22 dimethyl ether 115 - 10 - 6 46.07 Exp 1 3 0 2 0.81 0.56 0.44 0.50±0.08 glyoxal 107 - 22 - 2 58.04 Exp 1 0 6 12.50 3.68 1.84 3.15±1.82 methyl formate 107 - 31 - 3 60.05 Exp 1 0 6 0.057 0.046 0.037 0.041±0.007 acetic acid 64 - 19 - 7 60.05 Exp 1 0 6 0.68 0.33 0.21 0.27±0.09 glycolaldehyde 141 - 46 - 8 60.05 Exp 0 7 5.10 1.88 1.20 1.66±0.57 ethylene glycol 107 - 21 - 1 62.07 Exp 1 2 0 2 3.13 1.51 1.02 1.30±0.37

### Table B - 1 (continued)

191

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base glycolic ac id 79 - 14 - 1 76.05 AdjP 0 8 2.38 0.89 0.47 0.72±0.33 peroxyacetic acid 79 - 21 - 0 76.05 LM 0 8 0.54 0.26 0.162 0.22±0.07 acrolein 107 - 02 - 8 56.06 Exp 1 3 0 2 7.45 2.66 1.62 2.31±0.85 trimethylene oxide 503 - 30 - 0 58.08 Exp 1 0 6 4.56 2.51 1.82 2.20±0.5 9 propylene oxide 75 - 56 - 9 58.08 Exp 1 0 6 0.29 0.22 0.169 0.192±0.037 propionaldehyde 123 - 38 - 6 58.08 Exp 1 0 6 7.08 2.73 1.75 2.39±0.80 acetone 67 - 64 - 1 58.08 Exp 1 1 0 2 0.36 0.147 0.089 0.124±0.041 isopropyl alcohol 67 - 63 - 0 60.10 Exp 1 2 0 2 0.6 1 0.36 0.25 0.31±0.07 n -propyl alcohol 71 - 23 - 8 60.10 Exp 1 0 6 2.50 1.28 0.83 1.07±0.36 acrylic acid 79 - 10 - 7 72.06 AdjP 0 8 11.38 3.84 2.18 3.31±1.45 methyl glyoxal 78 - 98 - 8 72.06 Exp 1 0 6 16.56 4.93 2.64 4.28±2.25 1,3 - dioxolane 646 - 06 - 0 74.08 E xp 0 7 4.96 2.23 1.61 2.00±0.51 ethyl formate 109 - 94 - 4 74.08 Exp 1 0 6 0.48 0.29 0.21 0.25±0.07 methyl acetate 79 - 20 - 9 74.08 Exp 1 2 0 2 0.072 0.059 0.046 0.052±0.010 propionic acid 79 - 09 - 4 74.08 Exp 0 7 1.22 0.58 0.35 0.48±0.17 hydroxy acetone 116 - 09 - 6 74.08 Exp 1 0 8 3.23 1.16 0.64 0.97±0.41 propylene glycol 57 - 55 - 6 76.09 AdjP 1 2 0 2 2.58 1.17 0.76 1.01±0.30 dimethoxy methane 109 - 87 - 5 76.09 AdjP 1 0 6 0.94 0.66 0.51 0.59±0.10 2 - methoxy ethanol 109 - 86 - 4 76.09 Exp 1 0 6 2.93 1.29 0.8 4 1.11±0.33 dimethyl carbonate 616 - 38 - 6 90.08 Exp 1 2 0 2 0.059 0.048 0.038 0.042±0.008 dihydroxy acetone 96 - 26 - 4 90.08 Exp 0 8 3.99 1.44 0.80 1.21±0.50 glycerol 56 - 81 - 5 92.09 AdjP 0 7 3.15 1.37 0.84 1.15±0.39 furan 110 - 00 - 9 68.07 Exp 1 3 - 4 9 .15 3.51 2.06 2.98±1.12 crotonaldehyde 4170 - 30 - 3 70.09 Exp 1 0 8 9.39 3.26 1.94 2.84±1.11 methacrolein 78 - 85 - 3 70.09 Exp 1 2 0 2 6.01 2.15 1.33 1.88±0.68 cyclobutanone 1191 - 95 - 3 70.09 Exp 1 0 8 0.62 0.37 0.25 0.31±0.09 methylvinyl ketone 78 - 94 - 4 7 0.09 Exp 1 3 0 2 9.65 3.63 2.23 3.15±1.13 tetrahydrofuran 109 - 99 - 9 72.11 Exp 1 0 6 4.31 2.19 1.47 1.87±0.53 1,2 - epoxy butane 106 - 88 - 7 72.11 Exp 1 0 6 0.91 0.66 0.49 0.57±0.13 2 - methyl propanal 78 - 84 - 2 72.11 Exp 1 0 7 5.25 2.08 1.38 1.84±0.58 butanal 123 - 72 - 8 72.11 Exp 1 0 7 5.97 2.31 1.48 2.02±0.67 C4 aldehydes 72.11 LM 0 7 5.97 2.31 1.48 2.02±0.67 methyl ethyl ketone 78 - 93 - 3 72.11 Exp 1 2 0 2 1.48 0.63 0.39 0.53±0.18 isobutyl alcohol 78 - 83 - 1 74.12 Exp 1 0 6 2.51 1.19 0.75 1.00±0.32 n -butyl alcohol 71 - 36 - 3 74.12 Exp 1 0 6 2.88 1.43 0.92 1.20±0.39 sec -butyl alcohol 78 - 92 - 2 74.12 Exp 1 0 6 1.36 0.76 0.51 0.64±0.17 tert -butyl alcohol 75 - 65 - 0 74.12 Exp 1 2 + 2 0.41 0.23 0.144 0.187±0.050 diethyl ether 60 - 29 - 7 74.12 Exp 1 2 0 2 3. 76 1.75 1.13 1.49±0.42 gamma -buty

rolactone 96 - 48 - 0 86.09 Exp 0 7 0.96 0.61 0.41 0.51±0.14 methacrylic acid 79 - 41 - 4 86.09 Exp 0 8 18.50 5.87 3.34 5.12±2.37 methyl acrylate 96 - 33 - 3 86.09 Exp 0 8 11.48 3.74 2.09 3.22±1.47 vinyl acetate 108 - 05 - 4 8 6.09 Exp 0 8 3.20 1.18 0.70 1.02±0.39 hydroxyl - me thacrolein 40364 - 84 - 9 86.09 Exp 0 8 6.24 2.33 1.41 2.01±0.71 biacetyl 431 - 03 - 8 86.09 Exp 1 0 6 20.09 6.09 3.43 5.35±2.63 1,4 - dioxane 123 - 91 - 1 88.11 Exp 0 7 2.62 1.32 0.92 1.14±0.29 ethyl acetate 141 - 78 - 6 88.11 Exp 1 2 0 3 0.63 0.37 0.25 0.31±0.08 methyl propionate 554 - 12 - 1 88.11 Exp 1 0 6 0.66 0.33 0.21 0.27±0.09 n -propyl formate 110 - 74 - 7 88.11 Exp 1 0 6 0.78 0.48 0.33 0.40±0.14 isopropyl formate 625 - 55 - 8 88.11 Exp 0 7 0.37 0.26 0.18 9 0.22±0.05

### Table B - 1 (continued)

192

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base isobutyric acid 79 - 31 - 2 88.11 Exp 0 7 1.20 0.61 0.39 0.51±0.15 butanoic acid 107 - 92 - 6 88.11 AdjP 0 7 1.82 0.90 0.56 0.75±0.23 methoxy - acetone 5878 - 19 - 3 88.11 Exp 1 0 8 2.03 0.97 0.66 0.84±0.22 1,3 -butanediol 107 - 88 - 0 90.12 Exp 1 0 6 3.36 1.63 1.06 1.38±0.42 1,2 -butandiol 584 - 03 - 2 90.12 AdjP 1 0 6 2.52 1.13 0.73 0.97±0.29 1,4 -butanediol 110 - 63 - 4 90.12 Exp 0 7 2.72 1.29 0.82 1.08±0.36 2,3 -butanediol 90.12 AdjP 1 0 6 4.38 1.85 1.07 1.53±0.60 1 - methoxy - 2 -propanol 107 - 98 - 2 9 0.12 AdjP 1 2 0 2 2.44 1.24 0.86 1.08±0.28 2 - ethoxy - ethanol 110 - 80 - 5 90.12 Exp 1 3 0 2 3.71 1.64 1.03 1.39±0.43 2 - methoxy - 1 -propanol 1589 - 47 - 5 90.12 Exp 0 7 3.01 1.19 0.73 1.02±0.35 3 - methoxy - 1 -propanol 1320 - 67 - 8 90.12 Exp 0 7 3.84 1.63 1.03 1.4 0±0.44 propylene carbonate 108 - 32 - 7 102.09 Exp 1 2 + 2 0.28 0.196 0.146 0.170±0.037 methyl lactate 547 - 64 - 8 104.10 Exp 1 0 6 2.67 1.05 0.58 0.86±0.36 diethylene glycol 111 - 46 - 6 106.12 AdjP 0 7 3.35 1.44 0.90 1.23±0.39 malic acid 6915 - 15 - 7 134.09 AdjP 0 8 6.94 2.36 1.29 2.00±0.89 2 - methyl furan 534 - 22 - 5 82.10 Exp 1 3 0 4 8.30 3.12 1.84 2.66±1.01 3 - methyl furan 930 - 27 - 8 82.10 Exp 1 3 0 4 6.90 2.75 1.66 2.34±0.82 cyclopentanone 120 - 92 - 3 84.12 Exp 1 0 8 1.15 0.70 0.46 0.58±0.18 C5 cyclic ke tones 84.12 LM 0 8 1.15 0.70 0.46 0.58±0.18 cyclopentanol 96 - 41 - 3 86.13 Exp 1 0 6 1.72 0.90 0.59 0.76±0.22 alpha - methyl tetrahydrofuran 96 - 47 - 9 86.13 Exp 1 0 6 3.97 1.94 1.28 1.65±0.48 tetrahydropyran 142 - 68 - 7 86.13 Exp 1 0 6 3.22 1.73 1.14 1. 45±0.41 2 - methyl - 3 -butene - 2 - ol 115 - 18 - 4 86.13 Exp 1 0 8 4.91 2.01 1.29 1.74±0.55 2,2 - dimethylpropanal (pivaldehyde) 630 - 19 - 3 86.13 Exp 1 0 8 4.89 1.88 1.23 1.66±0.54 3 - methylbutanal (isovaleraldehyde) 590 - 86 - 3 86.13 Exp 1 0 8 4.97 1.91 1.23 1.68±0 .55 pentanal (valeraldehyde) 110 - 62 - 3 86.13 Exp 1 0 8 5.08 1.99 1.29 1.75±0.56 C5 aldehydes 86.13 LM 0 8 5.08 1.99 1.29 1.75±0.56 2 -pentanone 107 - 87 - 9 86.13 Exp 1 2 0 2 2.81 1.38 0.89 1.16±0.34 3 -pentanone 96 - 22 - 0 86.13 Exp 1 0 6 1.24 0.63 0.4 0 0.52±0.18 C5 ketones 86.13 LM 0 7 2.81 1.38 0.89 1.16±0.34 methyl isopropyl ketone 563 - 80 - 4 86.13 Exp 1 0 6 1.65 0.82 0.53 0.69±0.20 2 -pentanol 6032 - 29 - 7 88.15 Exp 1 0 6 1.61 0.86 0.57 0.73±0.20 3 -pentanol 584 - 02 - 1 88.15 Exp 1 0 6 1.63 0.85 0.57 0.72±0.21 pentyl alcohol 71 - 41 - 0 88.15 Exp 1 0 6 2.83 1.38 0.88 1.16±0.37 isoamyl alcohol (3 - methyl - 1 - butanol) 123 - 51 - 3 88.15 Exp 1 0 6 3.16 1.44 0.92 1.23±0.38 2 - methyl - 1 -butanol 137 - 32 - 6 88.15 Exp 0 7 2.40 1.17 0.75 0.98±0.30 ethyl isopropyl ether 625 - 54 - 7 88.15 Exp 0 7 3.74 1.62 1.04 1.39±0.42 methyl n -butyl ether 628 - 28 - 4 88.15 Exp 1 0 6 3.15 1.64 1.09 1.39±0.40 methyl t -butyl ether 1634 - 04 - 4 88.15 Exp 1 3 0 2 0.73 0.46 0.31 0.38±0.09 ethyl acrylate 140 - 88 - 5 100.12 Exp 0 8 7 .77 2.81 1.64 2.41±0.94 methyl methacrylate 80 - 62 - 6 100.12 Exp 0 8 15.61 4.95 2.80 4.31±2.00 glutaraldehyde 111 - 30 - 8 100.12 Exp 0 8 4.31 1.70 1.14 1.51±0.46 lumped C5+ unsaturated carbonyl species 100.12 Exp 0 8 6.38 2.30 1.36 1.98±0.75 2,4 -p entanedione 123 - 54 - 6 100.12 Exp 0 8 1.01 0.39 0.22 0.32±0.12

### Table B - 1 (continued)

193

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base tetrahydro - 2 - furanmethanol (tetrahydrofurfuryl alcohol) 97 - 99 - 4 102.13 Exp 0 7 3.31 1.42 0.89 1.21±0.38 ethyl propionate 105 - 37 - 3 102.13 Exp 1 0 6 0.77 0.45 0.30 0.37±0.11 isopropyl ac etate 108 - 21 - 4 102.13 Exp 1 2 0 2 1.07 0.59 0.40 0.50±0.12 methyl butyrate 623 - 42 - 7 102.13 Exp 1 0 6 1.09 0.57 0.36 0.47±0.14 methyl isobutyrate 547 - 63 - 7 102.13 Exp 1 2 0 2 0.61 0.36 0.23 0.30±0.09 n -butyl formate 592 - 84 - 7 102.13 Exp 1 0 6 0.83 0. 52 0.35 0.44±0.14 propyl acetate 109 - 60 - 4 102.13 Exp 1 0 6 0.78 0.49 0.34 0.41±0.12 3 - methyl butanoic acid 503 - 74 - 2 102.13 AdjP 0 7 4.23 1.66 0.96 1.39±0.53 2,2 - dimethoxy -propane 77 - 76 - 9 104.15 Exp 0 7 0.48 0.31 0.21 0.26±0.06 1 - ethoxy - 2 -propanol 1569 - 02 - 4 104.15 Exp 0 7 3.09 1.52 0.97 1.27±0.37 2 -propoxy - ethanol 2807 - 30 - 9 104.15 AdjP 0 7 3.30 1.53 0.99 1.30±0.38 3 - ethoxy - 1 -propanol 111 - 35 - 3 104.15 Exp 1 0 6 4.09 1.76 1.10 1.50±0.47 3 - methoxy - 1 -butanol 2517 - 43 - 3 104.15 Exp 1 0 6 3.8 7 1.54 0.95 1.32±0.45 2 - methoxyethyl acetate 110 - 49 - 6 118.13 Exp 0 7 1.15 0.68 0.48 0.58±0.13 ethyl lactate 97 - 64 - 3 118.13 Exp 1 0 6 2.48 1.05 0.61 0.87±0.33 methyl isopropyl carbonate 51729 - 83 - 0 118.13 Exp 1 2 0 2 0.62 0.35 0.24 0.30±0.07 2 - (2 - methoxyethoxy) ethanol 111 - 77 - 3 120.15 AdjP 0 7 2.66 1.29 0.87 1.11±0.30 pentaerythritol 115 - 77 - 5 136.15 AdjP 0 7 2.17 1.01 0.65 0.86±0.28 phenol 108 - 95 - 2 94.11 LM 0 8 2.76 0.173 - 0.85 - 0.22±0.76 2 - ethyl furan 3208 - 16 - 0 96.13 LM 0 8 7.09 2.67 1.57 2.27±0.86 2,5 - dimethyl furan 625 - 86 - 5 96.13 Exp 1 3 0 4 7.88 2.89 1.69 2.47±0.96 cyclohexanone 108 - 94 - 1 98.14 Exp 1 2 0 2 1.35 0.79 0.48 0.63±0.22 C6 cyclic ketones 98.14 LM 0 7 1.35 0.79 0.48 0.63±0.22 mesityl oxide (2 - methyl - 2 - penten - 4 - one) 141 - 79 - 7 98.14 LM 0 8 6.51 2.34 1.39 2.02±0.77 cyclohexanol 108 - 93 - 0 100.16 AdjP 1 0 6 1.95 1.07 0.68 0.88±0.27 hexanal 66 - 25 - 1 100.16 Exp 1 0 8 4.35 1.71 1.10 1.49±0.48 C6 aldehydes 100.16 LM 0 8 4.35 1.71 1.10 1.49±0.48 4 - methyl - 2 -pentanone 108 - 10 - 1 100.16 Exp 1 2 0 3 3.88 1.68 1.08 1.44±0.43 methyl n -butyl ketone 591 - 78 - 6 100.16 Exp 1 0 8 3.14 1.54 0.99 1.30±0.39 methyl tert -butyl ketone 75 - 97 - 8 100.16 Exp 1 0 8 0.65 0.34 0.21 0.28±0.08 C6 ketones 100.16 LM 0 8 3.14 1.54 0.9 9 1.30±0.39 1 -hexanol 111 - 27 - 3 102.17 AdjP 1 0 6 2.69 1.35 0.86 1.13±0.36 2 -hexanol 626 - 93 - 7 102.17 AdjP 1 0 6 2.08 1.21 0.78 1.00±0.30 4 - methyl - 2 -pentanol (methyl isobutyl carbinol) 108 - 11 - 2 102.17 AdjP 0 7 2.64 1.39 0.90 1.16±0.33 di -n -propyl ether 111 - 43 - 3 102.17 Exp 1 0 6 3.08 1.60 1.08 1.36±0.36 ethyl n -butyl ether 628 - 81 - 9 102.17 Exp 1 0 6 3.48 1.66 1.07 1.40±0.41 ethyl tert -butyl ether 637 - 92 - 3 102.17 Exp 1 0 6 2.01 0.99 0.63 0.83±0.23 methyl tert - amyl ether (TAME) 994 - 05 - 8 102.17 Exp 1 0 6 1.69 0.94 0.61 0.78±0.21 diisopropyl ether 108 - 20 - 3 102.17 Exp 0 7 3.52 1.45 0.89 1.23±0.41 ethyl methacrylate 97 - 63 - 2 114.14 Exp 0 8 12.47 4.02 2.27 3.49±1.59 ethyl butyrate 105 - 54 - 4 116.16 Exp 1 0 6 1.17 0.64 0.41 0.53±0.15 isobutyl acetate 110 - 19 - 0 116.16 Exp 0 7 0.62 0.43 0.30 0.36±0.08 methyl pivalate 598 - 98 - 1 116.16 Exp 1 2 0 2 0.35 0.22 0.133 0.172±0.054 n -butyl acetate 123 - 86 - 4 116.16 Exp 1 2 0,+ 2 0.83 0.54 0.35 0.43±0.13 n -propyl propionate 106 - 36 - 5 116.16 Exp 1 0 6 0.84 0.52 0.33 0.42±0.14 sec -butyl acetate 105 - 46 - 4 116.16 Exp 1 0 6 1.32 0.79 0.54 0.67±0.17

### Table B - 1 (continued)

194

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base tert -butyl acetate 540 - 88 - 5 116.16 Exp 1 3 0 2 0.180 0.102 0.062 0.082±0.024 diacetone alcohol 123 - 42 - 2 116.16 Exp 0 8 0.60 0.32 0.20 0.26±0.09 methyl pentanoate; methyl valerate 624 - 24 - 8 116.16 Exp 0 7 1.05 0.59 0.37 0.48±0.15 1,2 - dihydroxyhexane 6920 - 22 - 5 118.17 AdjP 0 7 2.55 1.21 0.76 1.01±0.33 2 - methyl - 2,4 -pentanediol 107 - 41 - 5 118.17 Exp 1 0 6 1.45 0.69 0.45 0.59±0.17 ethylene glycol di ethyl ether; 1,2 - diethoxyethane 629 - 14 - 1 118.17 Exp 0 7 2.95 1.44 0.93 1.21±0.35 acetal (1,1 - diethoxyethane) 105 - 57 - 7 118.17 Exp 0 7 3.58 1.53 0.99 1.32±0.40 1 -propoxy - 2 -propanol (propylene glycol n -propyl ether) 1569 - 01 - 3 118.17 AdjP 0 7 2.68 1 .36 0.92 1.16±0.31 2 -butoxy - ethanol 111 - 76 - 2 118.17 Exp 1 2 0 2 2.90 1.30 0.79 1.08±0.35 3 methoxy - 3 methyl -butanol 56539 - 66 - 3 118.17 Exp 1 2 0 2 2.88 1.32 0.84 1.12±0.34 n -propoxy -propanol 30136 - 13 - 1 118.17 Exp 0 7 3.77 1.69 1.07 1.43±0.44 hydroxypropyl acrylate 2918 - 23 - 2 130.14 Exp 0 8 4.90 1.94 1.18 1.65±0.57 1 - methoxy - 2 -propyl acetate 108 - 65 - 6 132.16 Exp 1 2 0,+ 2 1.70 0.86 0.58 0.73±0.19 2 - ethoxyethyl acetate 111 - 15 - 9 132.16 Exp 0 7 1.84 0.92 0.60 0.77±0.21 2 - methyoxy - 1 -propyl acetate 70657 - 70 - 4 132.16 Exp 0 7 1.12 0.60 0.42 0.52±0.12 methoxypropanol acetate 84540 - 57 - 8 132.16 Exp 0 7 1.86 0.98 0.64 0.82±0.24 2 - (2 - ethoxyethoxy) ethanol 111 - 90 - 0 134.17 Exp 1 3 0 2 3.26 1.50 0.94 1.26±0.39 dipropylene glycol isomer (1 - [2 -hydroxypropyl] - 2 -propanol) 110 - 98 - 5 134.17 AdjP 0 7 2.31 1.18 0.79 1.00±0.28 dimethyl succinate 106 - 65 - 0 146.14 Exp 1 2 0 2 0.23 0.142 0.089 0.114±0.033 ethylene glycol diacetate 111 - 55 - 7 146.14 Exp 0 7 0.66 0.40 0.27 0.33±0.12 adipic acid (hexanedioic acid) 124 - 04 - 9 146.14 AdjP 0 8 3.08 1.46 0.93 1.23±0.40 triethylene glycol 112 - 27 - 6 150.17 Exp 0 7 3.25 1.51 0.94 1.26±0.40 benzaldehyde 100 - 52 - 7 106.12 Exp 1 3 0 2 - 0.67 - 0.69 - 1.05 - 0.90±0.29 C7 alkyl phenols 1319 - 77 - 3 108.14 LM 0 5 2.40 0. 150 - 0.74 - .187±0.661 m - cresol 108 - 39 - 4 108.14 LM 4 - ,0 5 2.40 0.150 - 0.74 - .187±0.661 p - cresol 106 - 44 - 5 108.14 LM 4 0? 5 2.40 0.150 - 0.74 - .187±0.661 o - cresol 95 - 48 - 7 108.14 Exp 1 4 ? 5 2.40 0.150 - 0.74 - .187±0.661 benzyl alcohol 100 - 51 - 6 108.14 Exp 1 2 0 4 5.11 1.73 0.82 1.40±0.69 methoxybenzene; anisole 100 - 66 - 3 108.14 Exp 1 0 8 6.66 2.19 1.00 1.76±0.91 C7 cyclic ketones 112.17 LM 0 8 1.18 0.69 0.42 0.55±0.19 heptanal 111 - 71 - 7 114.19 Exp 1 0 8 3.69 1.45 0.92 1.26±0.41 C7 aldehydes 114.19 LM 0 8 3.69 1.45 0.92 1.26±0.41 2 - methyl -hexanal 925 - 54 - 2 114.19 Exp 0 8 3.54 1.43 0.91 1.24±0.40 2 -heptanone 110 - 43 - 0 114.19 Exp 1 3 ? 4 2.36 1.23 0.75 1.00±0.33 2 - methyl - 3 - hexanone 7379 - 12 - 6 114.19 Exp 0 8 1.53 0.83 0.52 0.68±0.23 di - isopropyl ketone 565 - 80 - 0 114.19 Exp 1 0 8 1.31 0.72 0.45 0.58±0.21 C7 ketones 114.19 LM 0 8 2.36 1.23 0.75 1.00±0.33 5 - methyl - 2 - hexanone 110 - 12 - 3 114.19 AdjP 1 0 8 2.41 1.26 0.82 1.05±0.32 3 - methyl - 2 - hexanone 2550 - 21 - 2 114.19 Exp 0 8 2.55 1 .32 0.83 1.09±0.34 1 -heptanol 111 - 70 - 6 116.20 Exp 1 0 6 1.84 0.97 0.59 0.79±0.26 dimethylpentanol (2,3 - dimethyl - 1 -pentanol) 10143 - 23 - 4 116.20 Exp 0 7 2.23 1.09 0.67 0.90±0.29 4,4 - diethyl - 3 - oxahexane 919 - 94 - 8 116.20 Exp 0 7 1.95 0.97 0.60 0.80±0. 24 n -butyl acrylate 141 - 32 - 2 128.17 Exp 0 8 5.02 1.90 1.09 1.60±0.61

### Table B - 1 (continued)

195

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base isobutyl acrylate 106 - 63 - 8 128.17 AdjP 0 8 4.72 1.80 1.02 1.51±0.59 butyl propionate 590 - 01 - 2 130.18 Exp 0 7 0.84 0.52 0.32 0.42±0.14 amyl acetate (n -pentyl acetate) 628 - 63 - 7 130.18 AdjP 0 7 0.84 0.55 0.32 0.42±0.14 n -propyl butyrate 105 - 66 - 8 130.18 Exp 1 0 6 1.05 0.61 0.38 0.49±0.16 isoamyl acetate (3 - methyl -butyl acetate) 123 - 92 - 2 130.18 Exp 0 7 1.09 0.65 0.40 0.52±0.17 2 - methyl - 1 -butyl acetate 624 - 41 - 9 130.18 Exp 0 7 1.08 0.67 0.43 0.55±0.15 methyl hexanoate 106 - 70 - 7 130.18 Exp 0 7 1.02 0.60 0.35 0.47±0.16 1 - tert -butoxy - 2 -propanol 57018 - 52 - 7 132.20 AdjP 0 7 1.61 0.85 0.54 0.70±0.21 2 - tert -butoxy - 1 -propanol 94023 - 15 - 1 132.20 Exp 0 7 1.81 0.72 0.41 0. 60±0.22 n -butoxy - 2 -propanol (propylene glycol n -butyl ether) 5131 - 66 - 8 132.20 Exp 0 7 2.72 1.33 0.85 1.12±0.34 ethyl 3 - ethoxy propionate 763 - 69 - 9 146.18 AdjP 0 7 3.58 1.45 0.85 1.21±0.43 diisopropyl carbonate 6482 - 34 - 4 146.18 Exp 0 7 0.98 0.51 0.32 0.42±0.12 2 - (2 -propoxyethoxy) ethanol 6881 - 94 - 3 148.20 Exp 0 7 2.85 1.37 0.86 1.14±0.35 dipropylene glycol methyl ether: 1 - methoxy - 2 - (2 - hydroxypropoxy) -propane 148.20 AdjP 0 7 1.98 0.99 0.66 0.84±0.23 dipropylene glycol methyl ether: 2 - (2 - me thoxypropoxy) - 1 - propanol 13588 - 28 - 8 148.20 AdjP 0 7 2.58 1.16 0.73 0.98±0.30 1,2 -propylene glycol diacetate 623 - 84 - 7 160.17 Exp 0 7 0.61 0.38 0.26 0.32±0.08 dimethyl glutarate 1119 - 40 - 0 160.17 AdjP 1 2 0 2 0.42 0.25 0.124 0.182±0.073 2 - [2 - (2 - methoxyethoxy) ethoxy] ethanol 112 - 35 - 6 164.20 Exp 0 7 2.58 1.27 0.80 1.06±0.32 tolualdehyde 120.15 LM 0 7 - 0.59 - 0.61 - 0.93 - 0.79±0.26 4 - vinyl phenol 2628 - 17 - 3 120.15 LM 0 11 1.50 0.185 - 0.42 - .092±0.434 2,4 - dimethyl phenol 105 - 67 - 9 122.16 LM 0 8 2.12 0.133 - 0.66 - .166±0.585 2,5 - dimethyl phenol 122.16 LM 0 8 2.12 0.133 - 0.66 - .166±0.585 3,4 - dimethyl phenol 95 - 65 - 8 122.16 LM 0 8 2.12 0.133 - 0.66 - .166±0.585 2,3 - dimethyl phenol 526 - 75 - 0 122.16 LM 0 8 2.12 0.133 - 0.66 - .166±0.585 2,6 - dimethyl phenol 576 - 26 - 1 122.16 LM 0 8 2.12 0.133 - 0.66 - .166±0.585 C8 alkyl phenols 122.16 LM 0 8 2.12 0.133 - 0.66 - .166±0.585 β -phenethyl alcohol (2 -phenyl ethyl alcohol) 98 - 85 - 1 122.16 LM - 11 4.53 1.53 0.73 1.24±0.61 C8 cyclic ketones 126.20 LM 0 8 1.05 0.61 0.37 0.49±0.17 2 -butyl tetrahydrofuran 1004 - 29 - 1 128.21 Exp 0 7 2.13 1.06 0.62 0.85±0.31 octanal 124 - 13 - 0 128.21 Exp 0 8 3.16 1.24 0.77 1.07±0.36 C8 aldehydes 128.21 LM 0 8 3.16 1.24 0.77 1.07±0.36 2 - octanone 111 - 13 - 7 128.21 Exp 1 0 8 1.40 0.80 0.44 0.61±0.23 C8 ketones 128.21 LM 0 8 1.40 0.80 0.44 0.61±0.23 1 - octanol 111 - 87 - 5 130.23 Exp 1 2 + 2 1.43 0.79 0.45 0.62±0.22 2 - ethyl - 1 - hexanol 104 - 76 - 7 130.23 Exp 0 7 2.00 0.99 0.58 0.80±0.27 2 - octanol 4128 - 31 - 8 130.23 Exp 1 2 + 2 1.97 1.04 0.63 0.84±0.28 3 - octanol 20296 - 29 - 1 130.23 Exp 1 2 + 2 2.28 1.16 0.72 0.95±0.31 4 - octanol 589 - 62 - 8 130.23 AdjP 1 0 6 2.23 1.18 0.71 0.95±0.32 5 - methyl - 1 - heptanol 7212 - 53 - 5 130.23 AdjP 0 7 1.79 0.91 0.52 0.72±0.26 di - isobutyl ether 628 - 55 - 7 130.23 Exp 1 0 6 1.20 0.67 0.41 0.54±0.17 di -n -butyl ether 142 - 96 - 1 130.23 Exp 1 0 6 2.84 1.40 0.88 1.16±0.37

### Table B - 1 (continued)

196

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base 2 -phenoxyethanol; ethylene glycol phenyl ether 122 - 99 - 6 138.16 Exp 0 8 4.49 1.62 0.84 1.33±0.58 butyl methacrylate 97 - 88 - 1 142.20 Exp 0 8 8.70 2.85 1.58 2.45±1.12 isobutyl methacrylate 97 - 86 - 9 142.20 Exp 0 8 8.62 2.81 1.55 2.41±1.11 hexyl acetates 144.21 LM 0 7 0.80 0.51 0.28 0.38±0.14 2,3 - dimethylbutyl acetate 144.21 Exp 0 7 0.75 0.48 0.28 0.37±0.12 2 - methylpentyl acetate 144.21 Exp 0 7 0.98 0.59 0.33 0.45±0.17 3 - methylpentyl acetate 144.21 AdjP 0 7 1.07 0.64 0.38 0.50±0.17 4 - methylpentyl acetate 144.21 Exp 0 7 0.82 0.50 0.28 0.38±0.14 isobutyl isobutyrate 97 - 85 - 8 144.21 Exp 0 7 0.60 0.39 0.23 0.30±0.10 n -butyl butyrate 109 - 21 - 7 144.21 Exp 1 0 6 1.08 0.62 0.36 0.49±0.17 n - hexyl acetate 142 - 92 - 7 144.21 AdjP 0 7 0.69 0.47 0.24 0.34±0.14 methyl amyl acetate (4 - methyl 2 -pentanol acetate) 108 - 84 - 9 144.21 Exp 0 7 1.35 0.72 0.40 0.56±0.19 n -pentyl propionate 624 - 54 - 4 144.21 AdjP 0 7 0.71 0.46 0.24 0.34±0.13 2 - ethyl hexanoic acid 149 - 57 - 5 144.21 Exp 0 7 3.32 1.42 0.79 1.15±0.43 methyl heptanoate 106 - 73 - 0 144.21 Exp 0 7 0.82 0.51 0.27 0.38±0.15 2 - ethyl - 1,3 -hexanediol 94 - 96 - 2 146.23 AdjP 0 7 2.05 1.03 0.64 0.85±0.28 2 -n - hexyloxyethanol 112 - 25 - 4 146.23 AdjP 0 7 2.09 1.05 0.63 0.85±0.28 2,2,4 - trimethyl - 1,3 -pentanediol 144 - 19 - 4 146.23 Exp 0 7 1.54 0.81 0.51 0.67±0.21 phthalic anhydride 85 - 44 - 9 148.12 Exp 0 8 2.58 0.92 0.40 0.71±0.37 methylparaben (4 - Hydroxybenzoic acid, methyl ester) 99 - 76 - 3 152.15 LM 0 11 1.71 0.107 - 0.53 - .133±0.470 2 -butoxyethyl acetate 112 - 07 - 2 160.21 Exp 0 7 1.62 0.85 0.53 0.70±0.21 2 - methoxy - 1 - (2 - methoxy - 1 - methylethoxy) -propane; dipropylene glycol dimethyl ether 89399 - 28 - 0 162.23 AdjP 0 7 2.02 0.98 0.64 0.83±0.23 2 - (2 -butoxyethoxy) - ethanol 112 - 34 - 5 162.23 Exp 2 0 7 2.39 1.15 0.69 0.94±0.32 dipropylene glycol ethyl ether 15764 - 24 - 6 162.23 Exp 0 7 2.72 1.24 0.75 1.03±0.34 dimethyl adipate 627 - 93 - 0 174.19 AdjP 1 0 6 1.80 0.84 0.48 0.68±0.25 2 - (2 - ethoxyethoxy) ethyl acetate 112 - 15 - 2 176.21 AdjP 0 7 1.48 0.78 0.50 0.64±0.18 2 - [2 - (2 - ethoxyethoxy) ethoxy] ethanol 112 - 50 - 5 178.23 Exp 0 7 2.46 1.21 0.75 1.00±0.32 tetraethylene glycol 112 - 60 - 7 194.23 Exp 0 7 2.51 1.20 0.75 1.00±0.32 cinnamic aldehyde 104 - 55 - 2 132.16 LM 0 10 4.84 1.74 1.03 1.50±0.57 Cinnamic alcohol 104 - 54 - 1 134.18 LM - 1 10 0.89 0.136 - 0.28 - .065±0.265 2,3,5 - trimethyl phenol 697 - 82 - 5 136.19 LM 0 8 1.90 0.119 - 0.59 - .149±0.525 2,3,6 - trimethyl phenol 2416 - 94 - 6 136.19 LM 0 8 1.90 0.119 - 0.59 - .149±0.525 C9 alkyl phenols 136.19 LM 0 8 1.90 0.119 - 0.59 - .149±0.525 isophorone (3,5,5 - trimethyl - 2 - cyclohexenone) 78 - 59 - 1 138.21 LM 0 8 4.63 1.66 0.99 1.44±0.54 C9 cyclic ketones 140.22 LM 0 8 0.94 0.55 0.33 0.44±0.15 2 -propyl cyclohexanone 94 - 65 - 5 140.22 AdjP 0 8 1.54 0.85 0.46 0.65±0.27 4 -propyl cyclohexanone 40649 - 36 - 3 140.22 Exp 0 8 1.85 0.97 0.56 0.77±0.29 1 -nonene - 4 - one 61168 - 10 - 3 140.22 Exp 0 8 3.14 1.28 0.74 1.06±0.39 trimethyl cyclohexanol 1321 - 60 - 4 142.24 AdjP 0 7 1.86 1.01 0.56 0.78±0.29

### Table B - 1 (continued)

197

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base 2 -nonanone 821 - 55 - 6 142.24 Exp 1 0 8 1.08 0.64 0.32 0.47±0.20 di - isobutyl ketone (2,6 - dimethyl - 4 - heptanone) 108 - 83 - 8 142.24 Exp 1 0 8 2.68 1.20 0.72 0.99±0.33 C9 ketones 142.24 LM 0 8 1.08 0.64 0.32 0.47±0.20 dimethyl heptanol (2,6 - dimethyl - 2 - heptanol) 13254 - 34 - 7 144.25 Exp 0 7 0.94 0.53 0.28 0.40±0.16 2,6 - dimethyl - 4 - heptanol 108 - 82 - 7 144.25 AdjP 0 7 2.09 1.06 0.62 0.85±0.30 1 -phenoxy - 2 -propanol 770 - 35 - 4 152.19 LM 0 8 1.60 0.65 0.28 0.49±0.24 2,4 - dimethylpentyl acetate 158.24 Exp 0 7 0.92 0.53 0.26 0.39±0.16 2 - methylhexyl acetate 158.24 AdjP 0 7 0.69 0.45 0.21 0.31±0.15 3 - ethylpentyl acetate 158.24 Exp 0 7 1.10 0.65 0.36 0.50±0.19 3 - methylhexyl acetate 158.24 Exp 0 7 0.89 0.55 0.28 0.40±0.17 4 - methylhexyl acetate 158.24 Exp 0 7 0.82 0.50 0.26 0.37±0.15 5 - methylhexyl acetate 158.24 AdjP 0 7 0.59 0.39 0.167 0.27±0.14 isoamyl isobutyrate 2050 - 01 - 3 158.24 Exp 0 7 0.82 0.48 0.26 0.36±0.14 n - heptyl acetate 112 - 06 - 1 158.24 Exp 0 7 0.65 0.44 0.20 0.30±0.14 methyl octanoate 111 - 11 - 5 158.24 Exp 0 7 0.69 0.44 0.20 0.31±0.14 1 - (butoxyethoxy) - 2 -propanol 124 - 16 - 3 176.25 AdjP 0 7 1.93 1.00 0.63 0.83±0.25 dipropylene glycol n -propyl ether isomer #1 176.25 AdjP 0 7 2.00 1.01 0.64 0.84±0.25 dipropylene glycol methyl ether acetate isomer #1 190.24 AdjP 0 7 1.38 0.72 0.45 0.59±0.17 dipropylene glycol methyl ether acetate isomer #2 190.24 AdjP 0 7 1.52 0.77 0.48 0.63±0.19 dipropylene glycol methyl ether acetate isomers 88917 - 22 - 0 190.24 LM 0 7 1.45 0.74 0.46 0.61±0.18 2 - [2 - (2 -propoxyethoxy) ethoxy] ethanol 23305 - 64 - 8 192.25 Exp 0 7 2.17 1.08 0.66 0.88±0.29 tripropylene glycol 24800 - 44 - 0 192.25 Exp 0 7 2.18 1.10 0.68 0.90±0.29 2,5,8,11 - tetraoxatridecan- 13 - ol 23783 - 42 - 8 208.25 Exp 0 7 1.97 1.00 0.62 0.82±0.27 glyceryl triacetate 102 - 76 - 1 218.20 Exp 0 7 0.55 0.34 0.20 0.27±0.09 anethol (p -propenyl - anisole) 104 - 46 - 1 148.20 LM 0 11 0.80 0.123 - 0.25 - .059±0.239 C10 alkyl phenols 150.22 LM 0 8 1.73 0.108 - 0.53 - .135±0.476 cam phor 76 - 22 - 2 152.23 Exp 0 8 0.49 0.31 0.129 0.21±0.12 α - terpineol 98 - 55 - 5 154.25 Exp 0 8 4.63 1.63 0.89 1.38±0.64 citronellol (3,7 - dimethy - 6 - octen - 1 - ol) 106 - 22 - 9 154.25 Exp 0 8 5.79 1.99 1.09 1.70±0.79 hydroxycitronella 107 - 75 - 5 154.25 Exp 0 8 2.61 1.03 0.64 0.89±0.30 C10 cyclic ketones 154.25 LM 0 8 0.86 0.50 0.30 0.40±0.14 menthol 89 - 78 - 1 156.27 Exp 0 7 1.43 0.76 0.44 0.60±0.22 linalool 78 - 70 - 6 156.27 Exp 0 8 5.43 1.91 1.07 1.63±0.75 2 - decanone 693 - 54 - 9 156.27 AdjP 1 0 8 0.90 0.55 0.25 0.38±0.19 C10 ketones 156.27 LM 0 8 0.90 0.55 0.25 0.38±0.19 8 - methyl - 1 - nonanol (isodecyl alcohol) 25339 - 17 - 7 158.28 Exp 0 7 1.06 0.58 0.30 0.44±0.18 1 - decanol 112 - 30 - 1 158.28 Exp 0 7 1.06 0.59 0.31 0.45±0.18 3,7 - dimethyl - 1 - octanol 106 - 21 - 8 158.28 Exp 0 7 1.20 0.63 0.34 0.49±0.19 di -n -pentyl ether 693 - 65 - 2 158.28 AdjP 1 0 6 2.15 1.16 0.71 0.94±0.31 1,2 - diacetyl benzene 704 - 00 - 7 162.19 Exp 1 0 8 2.25 0.79 0.33 0.60±0.33

### Table B - 1 (continued)

198

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base 2,4 - dimethylhexyl acetate 172.26 AdjP 0 7 0.76 0.47 0.21 0.33±0.16 2 - ethyl -hexyl acetate 103 - 09 - 3 172.26 AdjP 0 7 0.66 0.43 0.175 0.28±0.15 3,4 - dimethyl - hexyl acetate 172.26 AdjP 0 7 0.87 0.55 0.28 0.40±0.17 3,5 - dimethyl - hexyl acetate 172.26 Exp 0 7 0.99 0.58 0.28 0.41±0.18 3 - ethyl -hexyl acetate 172.26 Exp 0 7 0.91 0.55 0.28 0.40±0.17 3 - methyl -heptyl acetate 172.26 Exp 0 7 0.67 0.44 0.194 0.30±0.15 4,5 - dimethyl - hexyl acetate 172.26 AdjP 0 7 0.68 0.43 0.20 0.30±0.14 4 - methyl -heptyl acetate 172.26 Exp 0 7 0.66 0.42 0.187 0.29±0.14 5 - methyl -heptyl acetate 172.26 AdjP 0 7 0.61 0.41 0.163 0.27±0.15 n - octyl acetate 112 - 14 - 1 172.26 Exp 0 7 0.57 0.39 0.163 0.26±0.14 geraniol 106 - 24 - 1 172.26 Exp 0 8 5.12 1.84 1.04 1.58±0.71 methyl nonanoate 1731 - 84 - 6 172.26 Exp 0 7 0.59 0.39 0.161 0.26±0.14 2 - (2 - ethylhexyloxy) ethanol 1559 - 35 - 9 174.28 AdjP 0 7 1.55 0.83 0.44 0.63±0.25 propylparaben 94 - 13 - 3 180.20 LM 0 11 1.44 0.090 - 0.45 - .112±0.397 2 - (2 -hexyloxyethoxy) ethanol 112 - 59 - 4 190.28 AdjP 0 7 1.84 0.97 0.57 0.77±0.26 glycol ether DPnB (dipropylene glycol n -butyl ether) (1 - [2 - butoxy - 1 - me thylethoxy] - 2 - propanol) 29911 - 28 - 2 190.28 AdjP 0 7 1.83 0.93 0.57 0.76±0.24 2 - (2 -butoxyethoxy) ethyl acetate 124 - 17 - 4 204.26 Exp 0 7 1.38 0.73 0.44 0.59±0.20 2 - [2 - (2 -butoxyethoxy) ethoxy] ethanol 143 - 22 - 6 206.28 Exp 0 7 1.96 0.98 0.60 0.80±0.27 tripropylene glycol mo nomethyl ether 25498 - 49 - 1 206.28 Exp 0 7 1.92 0.96 0.59 0.78±0.26 C11 alkyl phenols 164.24 LM 0 8 1.58 0.099 - 0.49 - .123±0.435 2 - ethyl -hexyl acrylate 103 - 11 - 7 184.28 Exp 0 8 2.52 0.99 0.50 0.79±0.33 2,3,5 - trimethyl -hexyl acetate 186.29 AdjP 0 7 0.85 0.51 0.24 0.37±0.16 2,3 - dimethyl - heptyl acetate 186.29 Exp 0 7 0.71 0.46 0.21 0.32±0.15 2,4 - dimethyl - heptyl acetate 186.29 AdjP 0 7 0.68 0.42 0.164 0.28±0.16 2,5 - dimethyl - heptyl acetate 186.29 Exp 0 7 0.78 0.49 0.23 0.35±0.16 2 - methyloctyl acetate 186.29 AdjP 0 7 0.52 0.35 0.118 0.22±0.15 3,5 - dimethyl - heptyl acetate 186.29 AdjP 0 7 0.81 0.50 0.21 0.34±0.18 3,6 - dimethyl - heptyl acetate 186.29 Exp 0 7 0.78 0.48 0.21 0.33±0.17 3 - ethyl -heptyl acetate 186.29 Exp 0 7 0.63 0.41 0.172 0.28±0.15 4,5 - dimethyl - heptyl acetate 186.29 AdjP 0 7 0.69 0.44 0.196 0.30±0.15 4,6 - dimethyl - heptyl acetate 186.29 Exp 0 7 0.78 0.47 0.21 0.33±0.16 4 - methyloctyl acetate 186.29 Exp 0 7 0.61 0.40 0.167 0.27±0.14 5 - methyloctyl acetate 186.29 AdjP 0 7 0.56 0.38 0.134 0.24±0.15 n - nonyl acetate 143 - 13 - 5 186.29 Exp 0 7 0.52 0.36 0.139 0.23±0.13 methyl decanoate 110 - 42 - 9 186.29 Exp 0 7 0.53 0.35 0.136 0.23±0.13 C12 alkyl phenols 178.27 LM 0 8 1.46 0.091 - 0.45 - .114±0.401 2,6,8 - trimethyl - 4 - nonanone (isobutyl heptyl ketone) 123 - 18 - 2 184.32 Exp 0 8 1.66 0.81 0.44 0.63±0.24 trimethylnonanolthreoerythro (2,6,8 - trimethyl - 4 - nonanol) 123 - 17 - 1 186.33 AdjP 0 7 1.33 0.70 0.36 0.53±0.22 3,6 - dimethyl - octyl acetate 200.32 Exp 0 7 0.79 0.48 0.22 0.34±0.17 3 - isopropyl - heptyl acetate 200.32 AdjP 0 7 0.54 0.37 0.134 0.23±0.15 4,6 - dimethyl - octyl acetate 200.32 Exp 0 7 0.76 0.46 0.20 0.32±0.16

### Table B - 1 (continued)

199

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base methyl undecanoate 1731 - 86 - 8 200.32 Exp 0 7 0.50 0.33 0.123 0.21±0.13 1 -hydroxy - 2,2,4 - trimethylpentyl - 3 - isobutyrate 18491 - 15 - 1 216.32 Exp 0 7 0.89 0.43 0.23 0.34±0.13 3 -hydroxy - 2,2,4 - trimethylpentyl - 1 - isobutyrate 77 - 68 - 9 216.32 AdjP 0 7 0.77 0.43 0.22 0.32±0.13 2,2,4 - trimethyl - 1,3 -pentanediol mo noisobutyrate and isomers (texanol®) 25265 - 77 - 4 216.32 LM 1 2 0 2 0.81 0.43 0.23 0.33±0.13 substituted C7 ester (C12) 216.32 LM 0 7 0.81 0.43 0.23 0.33±0.13 substituted C9 ester (C12) 216.32 LM 0 7 0.81 0.43 0.23 0.33±0.13 diethylene glycol mono(2 - ethylhexyl) ether 1559 - 36 - 0 218.33 Exp 0 7 1.56 0.82 0.47 0.64±0.24 diethyl phthalate 84 - 66 - 2 222.24 Exp 0 8 1.62 0.60 0.26 0.46±0.23 dimethyl sebacate 106 - 79 - 6 230.30 Exp 0 7 0.43 0.28 0.102 0.178±0.106 diisopropyl adipate 6938 - 94 - 9 230.30 Exp 0 7 1.28 0.55 0.25 0.41±0.19 3,6,9,12 - tetraoxa -hexadecan - 1 - ol 1559 - 34 - 8 250.33 AdjP 0 7 1.72 0.88 0.53 0.71±0.24 triethyl citrate 77 - 93 - 0 276.28 Exp 0 8 0.70 0.33 0.171 0.25±0.10 3,5,7 - trimethyl - octyl acetate 214.34 AdjP 0 7 0.66 0.41 0.157 0.27±0.16 3 - ethyl - 6 - methyl - octyl acetate 214.34 AdjP 0 7 0.63 0.41 0.158 0.27±0.16 4,7 - dimethyl - nonyl acetate 214.34 AdjP 0 7 0.50 0.34 0.109 0.21±0.14 methyl dodecanoate (methyl laurate) 111 - 82 - 0 214.34 Exp 0 7 0.47 0.31 0.114 0.199±0.124 tripropylene glycol n -butyl ether 55934 - 93 - 5 248.36 Exp 0 7 1.64 0.80 0.47 0.64±0.23 amyl cinnamal 122 - 40 - 7 202.29 LM 0 10 3.16 1.14 0.68 0.98±0.37 isobornyl methacrylate 7534 - 94 - 3 222.32 LM + 10 5.51 1.80 0.99 1.54±0.71 2,3,5,7 - tetramethyl - octyl acetate 228.37 Exp 0 7 0.62 0.39 0.161 0.26±0.15 3,5,7 - trimethyl -nonyl acetate 228.37 AdjP 0 7 0.62 0.38 0.149 0.25±0.15 3,6,8 - trimethyl -nonyl acetate 228.37 AdjP 0 7 0.59 0.37 0.130 0.24±0.15 methyl tridecanoate 1731 - 88 - 0 228.37 Exp 0 7 0.45 0.30 0.109 0.190±0.119 hexyl cinnamal 101 - 86 - 0 216.32 LM 0 10 2.96 1.06 0.63 0.92±0.35 2,6 - di - tert -butyl -p - cresol 128 - 37 - 0 220.35 LM 0 10 1.18 0.074 - 0.36 - .092±0.324 2 - ethyl -hexyl benzoate 5444 - 75 - 7 234.33 Exp 0 10 0.98 0.46 0.20 0.33±0.16 2,4,6,8 - tetramethyl - nonyl acetate 242.40 AdjP 0 7 0.51 0.32 0.107 0.20±0.14 3 - ethyl - 6,7 - dimethyl -nonyl acetate 242.40 AdjP 0 7 0.61 0.40 0.156 0.26±0.15 4,7,9 - trimethyl - decyl acetate 242.40 AdjP 0 7 0.42 0.28 0.072 0.160±0.134 methyl myristate (methyl tetradecanoate) 124 - 10 - 7 242.40 Exp 0 7 0.43 0.29 0.106 0.184±0.115 methyl cis - 9 -pentadecenoate 254.41 Exp 0 8 1.80 0.79 0.46 0.65±0.25 methyl pentadecanoate 7132 - 64 - 1 256.42 Exp 0 7 0.47 0.30 0.125 0.20±0.12 2,3,5,6,8 -pentamethyl - nonyl acetate 256.42 Exp 0 7 0.65 0.42 0.183 0.29±0.15 3,5,7,9 - tetramethyl - decyl acetate 256.42 AdjP 0 7 0.48 0.31 0.098 0.190±0.143 5 - ethyl - 3,6,8 - trimethyl -nonyl acetate 256.42 AdjP 0 7 0.77 0.46 0.20 0.32±0.16

### Table B - 1 (continued)

200

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base dibutyl phthalate 84 - 74 - 2 278.34 Exp 0 8 1.25 0.49 0.23 0.38±0.18 2,2,4 - trimethyl - 1,3 -pentanediol diisobutyrate 6846 - 50 - 0 286.41 Exp 0 7 0.38 0.24 0.092 0.157±0.091 methyl cis - 9 - hexadecenoate (methyl palmitoleate) 1120 - 25 - 8 268.43 LM 0 8 1.70 0.75 0.44 0.62±0.23 methyl hexadecanoate (methyl palmitate) 112 - 39 - 0 270.45 LM 0 7 0.44 0.29 0.118 0.192±0.111 Methyl cis - 9 - heptadecenoate 282.46 LM 0 8 1.62 0.71 0.42 0.58±0.22 methyl heptadecanoate (methyl margarate) 1731 - 92 - 6 284.48 LM 0 7 0.42 0.27 0.113 0.182±0.105 methyl linolenate (methyl cis,cis,cis - 9,12,15 - octadecatrienoate) 301 - 00 - 8 292.46 Exp 0 8 2.32 0.95 0.57 0.80±0.29 methyl linoelate (methyl cis,cis 9,12 - octadecadienoate) 112 - 63 - 0 294.47 Exp 0 8 1.84 0.78 0.47 0.65±0.24 methyl cis - 9 - octadecenoate (methyl oleate) 112 - 62 - 9 296.49 LM 0 8 1.54 0.68 0.40 0.56±0.21 methyl octadecanoate (methyl stearate) 112 - 61 - 8 298.50 LM 0 7 0.40 0.26 0.107 0.174±0.100 Other Organic Compounds methylamine 74 - 89 - 5 31.06 Exp 1 + 13 a,n 7.70 4.24 2.72 3.51±1.06 methyl chloride 74 - 87 - 3 50.49 Exp 1 0 10 0.038 0.022 .0140 .0179±.0050 methyl nitrite 624 - 91 - 9 61.04 Exp 1 0 6 10.84 4.41 3.89 4.49±1.13 nitromethane 75 - 52 - 5 61.04 Exp 1 0 8 0.068 0.042 0.031 0.037±0.007 carbon disulfide 75 - 15 - 0 76.14 Exp 1 2 0 2 0.25 0.161 0.121 0.141±0.025 dichloromethane 75 - 09 - 2 84.93 Exp 1 0 10 0.041 0.029 0.021 0.024±0.006 methyl bromide 74 - 83 - 9 94.94 Exp 1 0 10 .0187 .0106 .0068 .0088±.0024 chloroform 67 - 66 - 3 119.38 Exp 1 0 10 0.022 .0152 .0107 .0127±.0033 methyl iodide 74 - 88 - 4 141.94 Exp 0 3 - 0.56 - 2.10 - 2.76 - 2.30±0.67 carbon tetrachloride 56 - 23 - 5 153.82 LM 0 1 0 0 0 0 chloropicrin (trichloro -nitro methane) 76 - 06 - 2 164.38 Exp 1 2 0 1 1.85 1.04 1.13 1.13±0.20 methylene bromide 74 - 95 - 3 173.83 LM 0 1 0 0 0 0 acetylene 74 - 86 - 2 26.04 Exp 1 2 - 3 0.95 0.37 0.189 0.30±0.14 dimethyl amine 124 - 40 - 3 45.08 Exp 1 + 13 a,n 3.17 2.07 1.47 1.74±0.59 ethyl amine 75 - 04 - 7 45.08 Exp 1 + 13 a,n 5.78 3.10 1.99 2.58±0.78 ethanolamine 141 - 43 - 5 61.08 Exp 3a + 12 a,n 6.81 3.05 1.88 2.56±0.82 vinyl chloride 75 - 01 - 4 62.50 Exp 1 0 10 2.83 1.48 0.99 1.26±0.34 ethyl chloride 75 - 00 - 3 64.51 Exp 1 0 10 0.29 0.182 0.122 0.151±0.044 1,1 - difluoroethane; HFC - 152a 75 - 37 - 6 66.05 Exp 1 + 6 .0175 .0123 .0089 .0105±.0028 methyl isothiocyanate 556 - 61 - 6 73.12 Exp 1 2 0 2 0.32 0.21 0.180 0.195±0.027 nitroethane 79 - 24 - 3 75.07 Exp 1 0 7 0.063 0.044 0.032 0.038±0.010 dimethyl sulfoxide (DMSO) 67 - 68 - 5 78.13 Exp 1 2 - 2,0 4 6.68 2.37 1.46 2.08±0.81 chloroacetaldehyde 107 - 20 - 0 78.50 Exp 1 0 7 12.30 3.52 1.74 3.00±1.71 1,1 - dichloroethene 75 - 35 - 4 96.94 Exp 0 10 1.79 0.96 0.65 0.82±0.22 trans - 1,2 - dichloroethene 156 - 60 - 5 96.94 Exp 1 0 10 1.70 0.76 0.45 0.62±0.22 cis - 1,2 - dichloroethene 96.94 LM 0 10 1.70 0.76 0.45 0.62±0.22 1,1 - dichloroethane 75 - 34 - 3 98.96 Exp 1 0 10 0.069 0.047 0.033 0.040±0.010 1,2 - dichloroethane 107 - 06 - 2 98.96 Exp 1 0 10 0.21 0.103 0.061 0.083±0.028

### Table B - 1 (continued)

201

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base 1,1,1,2 - tetrafluoroethane; HFC 134a 811 - 97 - 2 102.03 Exp 1 0 6 .0007 .0007 .0006 .0007±.0001 ethyl bromide 74 - 96 - 4 108.97 Exp 1 0 20 0.129 0.082 0.055 0.068±0.020 trichloroethylene 79 - 01 - 6 131.39 Exp 1 2x +2 20 0.64 0.35 0.23 0.29±0.08 1,1,1 - trichloroethane 71 - 55 - 6 133.40 Exp 1 0 10 .0049 .0031 .0021 .0026±.0006 1,1,2 - trichloroethane 79 - 00 - 5 133.40 Exp 1 0 10 0.086 0.045 0.028 0.037±0.011 perchloroethylene 127 - 18 - 4 165.83 Exp 1 0 10 0.031 0.022 .0149 .0179±.0051 1,2 - dibromoethane 106 - 93 - 4 187.86 Exp 1 0 20 0.102 0.049 0.029 0.040±0.013 methyl acetylene 74 - 99 - 7 40.06 Exp 1 - 7 6.72 2.45 1.37 2.06±0.86 acrylonitrile 107 - 13 - 1 53.06 Exp 1 0 10 2.24 1.08 0.72 0.93±0.25 trimethyl amine 75 - 50 - 3 59.11 Exp 1 + 13 a,n 6.32 3.05 1.95 2.57±0.79 isopropyl amine 75 - 31 - 0 59.11 Exp 4a + 12 a,n 7.23 3.32 2.09 2.80±0.86 1 - amino - 2 -propanol 78 - 96 - 6 75.11 Exp + 13 a,n 5.42 2.64 1.71 2.23±0.66 3 - chloropropene 76.52 Exp 0 10 12.22 3.84 2.05 3.28±1.60 1 -nitropropane 108 - 03 - 2 89.09 Exp 0 8 0.22 0.158 0.116 0.135±0.029 2 -nitropropane 79 - 46 - 9 89.09 Exp 1 0 6 0.110 0.071 0.049 0.059±0.019 chloroacetone 78 - 95 - 5 92.52 Exp 1 0 7 9.41 2.64 1.30 2.24±1.29 trans - 1,3 - dichloropropene 10061 - 02 - 6 110.97 Exp 1 2m 0 3 5.03 1.78 1.00 1.50±0.63 cis - 1,3 - dichloropropene 10061 - 01 - 5 110.97 Exp 1 2m 0 3 3.70 1.41 0.81 1.18±0.46 1,3 - dichloropropene mixture 110.97 LM 1 2 0 2 4.29 1.57 0.90 1.32±0.53 1,2 - dichloropropane 78 - 87 - 5 112.99 Exp 0 10 0.29 0.143 0.087 0.117±0.038 trans - 1,3,3,3 - tetrafluoropropene 1645 - 83 - 6 114.04 Exp 1 2 0 1 0.098 0.076 0.055 0.065±0.013 2,3,3,3 - tetrafluoropropene 754 - 12 - 1 114.04 Exp 1 2 0 1 0.28 0.155 0.107 0.133±0.031 n -propyl bromide 106 - 94 - 5 122.99 Exp 1 2x - ,+2 20 n 0.42 0.23 0.147 0.190±0.061 1,1,1,3,3 -pentafluoropropane 460 - 73 - 1 134.05 Exp 1 0 6 .0008 .0006 .0004 .0005±.0001 3,3 - dichloro - 1,1,1,2,2 - pentafluoropropane;HCFC 225ca 422 - 56 - 0 202.94 Exp 1 0 6 .0029 .0020 .0014 .0017±.0005 1,3 - dichloro - 1,1,2,2,3 - pentafluoropropane;HCFC 225cb 507 - 55 - 1 202.94 Exp 1 0 6 .0011 .0007 .0005 .0006±.0002 1,3 -butadiyne 460 - 12 - 8 50.06 Exp 0 11 5.76 2.64 1.73 2.26±0.73 1 -buten - 3 - yne (vinyl acetylene) 689 - 97 - 4 52.07 LM 0 11 10.48 4.12 2.55 3.55±1.22 2 -butyne 503 - 17 - 3 54.09 Exp 1 0 10 16.32 5.40 3.07 4.67±2.05 ethyl acetylene 107 - 00 - 6 54.09 Exp 1 - 7 6.11 2.23 1.25 1.87±0.78 tert -butyl amine 75 - 64 - 9 73.14 Exp 1 4a - 12 a - 0.39 - 0.83 - 1.86 - 1.41±0.68 mo rpholine 110 - 91 - 8 87.12 Exp + 13 a,n 1.98 1.21 0.84 1.01±0.35 ethyl methyl ketone oxime (methyl ethyl ketoxime) 96 - 29 - 7 87.12 Exp 0 10 1.58 1.32 1.47 1.42±0.33 dimethylaminoethanol 108 - 01 - 0 89.14 Exp 1 + 13 a,n 5.62 2.32 1.46 1.99±0.65 2 - amino - 1 -butanol 96 - 20 - 8 89.14 Exp + 13 a,n 4.98 2.18 1.34 1.83±0.60 2 - amino - 2 - methyl - 1 -propanol 124 - 68 - 5 89.14 Exp 3a - 12 a 0.25 - 0.19 - 1.03 - 0.66±0.54 1 - chlorobutane 109 - 69 - 3 92.57 Exp 0 10 1.10 0.63 0.40 0.52±0.15 diethanol - amine 111 - 42 - 2 105.14 Exp + 13 a,n 2.47 1.17 0.76 0.99±0.32 2 - (chloro - methyl) - 3 - chloro propene 1871 - 57 - 4 125.00 Exp 1 4 - 20 7.00 2.31 1.28 1.96±0.87 n -butyl bromide 109 - 65 - 9 137.02 Exp 1 2x - ,+2 20 n 0.82 0.47 0.30 0.38±0.11 1,1,1,3,3 -pentafluorobutane; HFC - 365mfc 406 - 58 - 6 148.07 Exp 1 0 6 .0006 .0005 .0003 .0004±.0001

### Table B - 1 (continued)

202

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base 2 - amino - 2 - ethyl - 1,3 - propanediol 115 - 70 - 8 119.16 Exp - 13 a 0.78 0.163 - 0.44 - .161±0.380 n - methyl - 2 -py

rrolidone 872 - 50 - 4 99.13 Exp 1 2 0 2 2.41 1.24 0.74 1.00±0.34 methyl - nonafluoro -butyl ether 163702 - 07 - 6 234.06 Exp 0 8 0.055 0.044 0.032 0.037±0.008 methyl - nonafluoro - isobutyl ether 163702 - 08 - 7 234.06 LM 0 8 0.055 0.044 0.032 0.037±0.008 methoxy -perfluoro - n -butane 163702 - 07 - 6 250.06 Exp 1 0 6 .0006 .0005 .0003 .0004±.0001 methoxy -perfluoro - isobutene 163702 - 08 - 7 250.06 LM 1 0 6 .0006 .0005 .0003 .0004±.0001 1,1,1,2,2,3,4,5,5,5 - decafluoropentane; HFC - 43 - 10mee 138495 - 42 - 8 252.05 Exp 1 0 6 .0002 .0001 .0001 .0001±.0000 triethyl amine 121 - 44 - 8 101.19 Exp + 13 a,n 3.84 1.72 1.05 1.43±0.48 triethylene diamine 280 - 57 - 9 112.17 LM + 13 a,n 3.46 1.55 0.95 1.29±0.44 mo nochlorobenzene 108 - 90 - 7 112.56 Exp 1 0 8 0.32 0.043 - 0.074 - .006±0.084 nitrobenzene 98 - 95 - 3 123.11 Exp 1 0 8 0.056 .0070 - 0.014 - .002±0.015 p - dichlorobenzene 106 - 46 - 7 147.00 Exp 0 10 0.178 0.024 - 0.042 - .004±0.047 o - dichlorobenzene 95 - 50 - 1 147.00 LM 0 8 0.178 0.024 - 0.042 - .004±0.047 triethanolamine 102 - 71 - 6 149.19 Exp + 13 a,n 4.21 1.62 0.93 1.36±0.54 hexamethyl - disiloxane 107 - 46 - 0 162.38 Exp 1 3 0 5 - 0.025 0.026 0.036 0.028±0.018 hydroxymethyl - disiloxane 164.35 Exp 1 3 0 5 - 0.133 - 0.011 0.021 - .001±0.036 hexafluoro -benzene 392 - 56 - 3 186.05 Exp 1 0 8 0.047 .0057 - 0.012 - .002±0.013 ethoxy -perfluoro -n -butane 163702 - 05 - 4 264.09 Exp 1 0 6 .0082 .0049 .0032 .0040±.0011 ethoxy -perfluoro - isobutane 163702 - 06 - 5 264.09 Exp 1 0 6 .0098 .0059 .0038 .0049±.0013 ethyl nonafluorobutyl ether 163702 - 05 - 4 264.09 Exp + 8 0.21 0.132 0.088 0.109±0.026 ethyl nonafluoroisobutyl ether 163702 - 06 - 5 264.09 LM + 8 0.21 0.132 0.088 0.109±0.026 perfluoro - n - hexane 355 - 42 - 0 338.04 LM 0 1 0 0 0 0 2 - chlorotoluene 95 - 49 - 8 126.58 LM 1 8 2.92 0.99 0.38 0.75±0.44 m - nitrotoluene 99 - 08 - 1 137.14 Exp 1 0 8 0.50 0.164 0.028 0.103±0.092 benzotrifluoride 98 - 08 - 8 146.11 Exp 1 0 8 0.29 0.108 0.040 0.079±0.047 p - trifluoromethyl - chloro benzene 98 - 56 - 6 180.55 Exp 1 0 8 0.126 0.046 .0173 0.034±0.020 p - toluene isocyanate 622 - 58 - 2 133.15 Exp 1 2 0 5 1.06 - 0.085 - 0.53 - 0.25±0.34 3 - (chloromethyl) - heptane 123 - 04 - 6 148.67 LM 0 10 0.95 0.60 0.32 0.44±0.17 cyclosiloxane D4 (octamethylcyclotetrasiloxane) 556 - 67 - 2 296.62 Exp 1 3 0 5 - 0.058 - 0.011 .0029 - .006±0.014 2,4 - toluene diisocyanate 584 - 84 - 9 174.16 Exp 1 2 0 5 - 0.065 - 0.52 - 0.81 - 0.64±0.23 2,6 - toluene diisocyanate 91 - 08 - 7 174.16 LM 4 0 5 - 0.065 - 0.52 - 0.81 - 0.64±0.23 toluene diisocyanate (mixed isomers) 26471 - 62 - 5 174.16 LM 0 5 - 0.065 - 0.52 - 0.81 - 0.64±0.23 mo linate (S - ethyl hexahydro 1H - azepine - 1 - carbothioate) 2212 - 67 - 1 187.30 Exp 0 7 1.51 0.74 0.46 0.62±0.20 EPTC (S - ethyl dipropyl thiocarbamate) 759 - 94 - 4 189.32 Exp 1 2 0 2 1.67 0.87 0.54 0.71±0.23 triisopropanolamine 122 - 20 - 3 191.27 Exp + 13 a,n 2.70 1.18 0.70 0.98±0.35 pebulate (S -propyl butylethylthiocarbamate) 1114 - 71 - 2 203.34 Exp 0 7 1.67 0.84 0.50 0.68±0.23 cyclosiloxane D5 (decamethylcyclopentasiloxane) 541 - 02 - 6 370.77 Exp 1 4 0 5 - 0.069 - 0.013 .0030 - .008±0.017 thiobencarb (S - [4 - chlorobenzyl] N,N - diethylthiolcarbamate) 28249 - 77 - 6 257.78 Exp 0 8 0.68 0.29 0.110 0.20±0.11

### Table B - 1 (continued)

203

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base methylene diphenylene diisocyanate 101 - 68 - 8 250.25 Exp 0 8 0.89 0.021 - 0.30 - .100±0.240 lauryl pyrrolidone 2687 - 96 - 9 253.42 LM 0 11 0.94 0.48 0.29 0.39±0.13 CARB Hydrocarbon Bins CARB Hydrocarbon Bin 1 14.25 Mix 0 7 c 1.42 0.90 0.55 0.72±0.22 CARB Hydrocarbon Bin 2 14.37 Mix 0 7 c 1.31 0.85 0.53 0.68±0.20 CARB Hydrocarbon Bin 3 14.03 Mix 0 7 c 1.63 1.01 0.60 0.80±0.26 CARB Hydrocarbon Bin 4 14.19 Mix 0 7 c 1.47 0.90 0.53 0.71±0.23 CARB Hydrocarbon Bin 5 14.06 Mix 0 7 c 1.56 0.88 0.50 0.69±0.23 CARB Hydrocarbon Bin 6 14.18 Mix 0 7 c 1.17 0.72 0.35 0.52±0.23 CARB Hydrocarbon Bin 7 14.26 Mix 0 7 c 1.03 0.66 0.32 0.47±0.21 CARB Hydrocarbon Bin 8 14.03 Mix 0 7 c 1.44 0.84 0.43 0.62±0.26 CARB Hydrocarbon Bin 9 14.13 Mix 0 7 c 1.44 0.79 0.39 0.58±0.25 CARB Hydrocarbon Bin 10 14.04 Mix 0 7 c 1.98 0.94 0.45 0.70±0.30 CARB Hydrocarbon Bin 11 14.14 Mix 0 8 c 0.70 0.46 0.174 0.30±0.18 CARB Hydrocarbon Bin 12 14.20 Mix 0 8 c 0.62 0.42 0.150 0.26±0.17 CARB Hydrocarbon Bin 13 14.03 Mix 0 8 c 0.86 0.53 0.22 0.36±0.20 CARB Hydrocarbon Bin 14 14.10 Mix 0 8 c 0.99 0.54 0.22 0.37±0.19 CARB Hydrocarbon Bin 15 14.02 Mix 0 8 c 1.57 0.72 0.32 0.52±0.24 CARB Hydrocarbon Bin 16 14.11 Mix 0 8 c 0.52 0.35 0.131 0.22±0.15 CARB Hydrocarbon Bin 17 14.16 Mix 0 8 c 0.48 0.33 0.122 0.21±0.14 CARB Hydrocarbon Bin 18 14.03 Mix 0 8 c 0.60 0.39 0.148 0.25±0.16 CARB Hydrocarbon Bin 19 14.09 Mix 0 8 c 0.66 0.39 0.150 0.26±0.15 CARB Hydrocarbon Bin 20 14.03 Mix 0 10 c 0.95 0.46 0.190 0.33±0.17 CARB Hydrocarbon Bin 21 13.27 Mix 0 8 c 7.64 2.49 1.16 2.01±1.03 CARB Hydrocarbon Bin 22 13.36 Mix 0 8 c 7.60 2.55 1.31 2.12±0.98 CARB Hydrocarbon Bin 23 13.41 Mix 0 10 c 6.85 2.31 1.21 1.93±0.88 CARB Hydrocarbon Bin 24 13.47 Mix 0 11 c 3.82 1.27 0.63 1.04±0.50 Other Complex Mixtures Base ROG Mixture 14.44 Mix 0 7 3.60 1.44 0.81 1.19±0.45 final LEV

– RFA 14.03 Mix 0 7 3.54 1.41 0.76 1.15±0.45 TLEV Exhaust -- RFA 14.04 Mix 0 7 3.98 1.55 0.84 1.27±0.51 TLEV exhaust

– phase 2 14.12 Mix 0 7 3.89 1.53 0.84 1.26±0.49 Final LEV -- Phase 2 14.22 Mix 0 7 3.45 1.39 0.76 1.13±0.44 TLEV Exhaust -- LPG 14.86 Mix 0 7 2.04 0.89 0.55 0.75±0.24 TLEV Exhaust -- CNG 15.22 Mix 0 7 0.73 0.35 0.22 0.29±0.08 TLEV Exhaust -- E - 85 20.74 Mix 0 7 2.55 1.19 0.76 1.01±0.30 TLEV Exhaust -- M - 85 27.45 Mix 0 7 1.56 0.59 0.33 0.49±0.20 composite mineral spirit (naphthas or lactol spirits) (CARB Profile ID 802) 14.06 Mix 0 7 1.92 0.87 0.41 0.66±0.29 Safety - Kleen Mineral Spirits "A " (Ty pe I - B, 91% Alkanes) 14.08 Mix 2 0,+ 7 1.25 0.65 0.29 0.46±0.22 Safety - Kleen Mineral Spirits "B" (Type II - C) 14.10 Mix 2 0,+ 7 0.70 0.45 0.171 0.29±0.18 Safety - Kleen Mineral Spirits "C" (Type II - C) 14.11 Mix 2 0,+ 7 0.71 0.46 0.173 0.30±0.18 Exxon Exxol® D95 Fluid 14.11 Mix 2 0 7 0.60 0.40 0.146 0.25±0.16

### Table B - 1 (continued)

204

Description CAS MWt Codes [a] Reactivity (gm O3 / gm VOC) Rep k a Expt Bias Unc MIR MOIR EBIR Base Safety - Kleen Mineral Spirits "D " (Ty pe II - C) 14.12 Mix 2 0,+ 7 0.71 0.46 0.173 0.30±0.18 Exxon Isopar® M Fluid 14.15 Mix 2 0 8 0.57 0.38 0.136 0.24±0.16 thinning solvent/mineral spirits (Cal Poly SLO 1996) 14.40 Mix 0 7 1.93 0.91 0.46 0.69±0.28 Aromatic 100® 13.36 Mix 2 0 7 7.38 2.47 1.25 2.04±0.96 Kerosene 13.94 Mix 2 0 7 1.62 0.73 0.33 0.54±0.24 Regular mineral spirits 13.97 Mix 2 0 7 1.89 0.84 0.39 0.63±0.28 Reduced Aromatics Mineral Spirits 14.05 Mix 2 0 7 1.19 0.64 0.28 0.45±0.22 Dearomatized Alkanes, mixed, predominately C10 - C12 14.09 Mix 2 0 7 0.87 0.54 0.23 0.37±0.20 VMP Naphtha 14.16 Mix 2 0 7 1.23 0.74 0.36 0.53±0.23 Synthetic isoparaffinic alkane mixture, predominately C10 - C12 14.20 Mix 2 0 8 0.75 0.49 0.195 0.32±0.18 Oxo - Tridecyl Acetate 16.19 Mix 0 7 0.55 0.35 0.123 0.22±0.14 Oxo - Dodecyl Acetate 16.30 Mix 0 7 0.59 0.37 0.139 0.24±0.15 Oxo - Decyl Acetate 16.71 Mix 2 0 7 0.70 0.44 0.187 0.30±0.16 Oxo -Nonyl Acetate 16.89 Mix 0 7 0.72 0.45 0.193 0.31±0.16 Oxo - Octyl Acetate 17.23 Mix 0 7 0.81 0.50 0.24 0.36±0.16 Oxo - Heptyl Acetate 17.58 Mix 0 7 0.83 0.51 0.26 0.37±0.16 Oxo - Hexyl Acetate 18.02 Mix 0 7 0.86 0.54 0.30 0.41±0.15 turpentine 8006 - 64 - 2 13.62 Mix 0 7 4.28 1.60 0.87 1.33±0.56 soy methyl esters; alkyl C16 - C18 methyl esters 15.57 Mix 0 8 1.58 0.69 0.40 0.57±0.22 [a] Codes used in this tabulation are as follows: "Rep" ... Codes for method used to represent the VOC in the mechanism Exp An explicit mechanism assignment has been made for this compound or model species. See Table B - 2 for the mechanism. AdjP An explicit mechanism assignment has been made for this compound and the adjusted product version of the mechanism has been used when calculating its atmospheri c reactivity values. The adjusted product mechanism is given in Table B - 3 . LM This compound is represented using the "Lumped Molecule" method. See Table B - 9 . Mix This is represented by a complex mixture of detailed model species. The compositions of these mixtures are given in Table B - 10 . "k a" ... Codes indicating of measurement data for the reaction rate constants 1 The OH radical rate constant has been measured. See Table B - 2 or Table B - 4 for the rate constant and reference citation. If the compound is consumed primarily by photolysis, this code means that absorption cross - section and quantum yield are available. In this case, see Table B - 6 for the photolysis set, overall quantum yields (if applicable) and documentation, and Table A - 3 or Table B - 8 for the absorption cross sections and (if applicable) wavelength - depend ent quantum yields. blank The OH radical rate constant or (if primarily photoreactive) the photolysis rate parameters had to be estimated. See Table B - 2 or Table B - 4 for the estimated OH rate constant and documentation on how the estimate wa s made, and Table B - 6 for the method used to estimate the photolysis rate.

### Table B - 1 (continued)

205

"Expt" ... Environmental Chamber Data Availability Codes (if blank, no suitable evaluation data are available). 1 Extensive evaluation data for a variety of conditions. 2 Sufficient data available. At least 2 and often 3 types of evaluation experiments to test data under different conditions. 3 Limited evaluation data; usually representing one set of conditions, or some inconsistencies in evaluation results. 3a Evaluation data exist for 2 or more sets of conditions, but uncertainties exist concerning amount of compound available to react in the gas phase. See Carter (2008). 4 Data from only a single experiment is available, results from different experiments gave inconsistent results, or problems exist with the data. 4a Data from only a single experiment is available, and uncertainties exist concerning the amount of compound available for reaction in the gas phase. See Carter (2008). m This compound was studied in a mixture with the other isomer. Since the reactivities of the two isomers are different, the uncertainty classification has been increased over that of the mixture that was studied. x No attempt was made to improve the mechanism performance to fit the available data. "Bias" ... Probable reactivity prediction bias codes (if blank, this compound has not been rated)

Chamber data available No chamber data available 0 No apparent bias Direction of bias is unknown + Some indication of positive bias Positive bias considered to be more likely than not

- Some indication of negative bias Negative bias is considered to be more likely than not  2 Bias found to be relatively large Bias may be relatively large x,x If two codes given, first indicates observed or probable bias for predictions of rates of NO oxidation and O 3 formation, which is important in affecting MIR reactivity, and the second indicates observed or probable bias for low NO x conditions. E.g. "0,+" if chamber data available indicates that the model simulated rates of NO oxidation and O 3 formation but overpredicted final O 3 yields in NO x - limited experiments. ? There is some inconsistency in the data concerning this bias indication (or lack thereof), or the bias is unknown but may be large. a The reactivity predictions and representation in the mechanism is based on the assumption that this compound is completely available for reaction in the gas pha se. This is likely not to be the case for this compound. Thus the reactivity estimate may be high for compounds that have positive O3 impacts and low for compounds that are calculated to be inhibitors. "Unc" ... Uncertainty codes (if blank, this compound has not been rated) The following codes are used when experimental data are available to evaluate the reactivity predictions of the mechanism and the mechanism was (or would have been) adjusted to fit the data as appropriate to improve the fits. 1 The mec hanism appears to be reasonably well established or at least its predictions appear to be are reasonably well evaluated. This does not rule out possible changes in reactivity values if the base mechanism, scenario conditions, or reactivity metrics are chan ged. Also used for compounds known or expected to be inert or to have upper limit reactivities much less than methane. 2 The mechanism has been evaluated at least to some extent, rate constant data are available for its major reactions, and is not considered to have large uncertainties. If a likely bias is indicated it is probably not large.

### Table B - 1 (continued)

206 3 The mechanism has been evaluated at least to some extent and rate constant data are available for its major reactions, but the mechanism has some uncertainties or apparent inconsistencies with available laboratory data, or there are some uncertainties in the evaluation data. If a likely bias is indicated it is probably not large. 4 The mechanism has been evaluated at least to some extent and rate constant data are available for its major reactions, but the mechanism has some uncertainties, apparent inconsistencies with available laboratory data exist that may be significant, or the available evaluation database is limited or has problems. If a likely bias of  1 is indicated it is probably not large. 5 A highly parameterized mechanism has been adjusted to simulate chamber data. The appropriateness of the parameterization, and its ability to extrapolate to ambient conditions, is uncertain. The following codes are used for compounds for which no experimental data exist to evaluate reactivity predictions of the mechanism, or where such data, if any, were not taken into account when developing the mechanism. 6 The mechanism has not been evaluated but at least the important reaction rate(s) have been measured and the methods used to estimate the mechanism have been found to generally perform reasonably well for compounds where evaluation data are available, or the mechanisms are not expected to be highly complex. If a like ly bias is indicated it is based on evaluation results for similar compounds. 7 The mechanism has not been evaluated and the reaction rates had to be estimated, but the methods used to estimate the rate constant(s) and mechanism have been found to general ly perform reasonably well for compounds where evaluation data are available. If a likely bias is indicated it is based on evaluation results for similar compounds. This code is also used for mixture or lumped molecule or mixture representations that are c onsidered to be reasonably appropriate. 8 The estimated mechanism and/or relevant rate constant(s) or photolysis rates have some uncertainties, but mechanisms based on similar assumptions have been found to perform satisfactorily for related compounds, or the mechanisms are not expected to be highly complex. The applicability of these assumptions to this compound, or the extrapolation of mechanisms for smaller compounds to one of this size, has some uncertainty. This code is also used for mixture or lumped mo lecule representations whose appropriateness has some uncertainty. The uncertainty codes below mean that use of the reactivity values in regulatory applications is problematical. 10 The estimated mechanism is sufficiently uncertain that it needs to be evaluated. This code is also used for mixture or lumped molecule representations whose appropriateness is considered to be highly uncertain. However, the representation employed is the current best estimate, and the direction of the bias is unknown. 11 T he estimated mechanism is extremely uncertain that it needs to be evaluated. This code is also used for mixture or lumped molecule representations whose appropriateness is questionable, but no better alternative exists, and the bias of using the representation is unknown. However, the representation employed is the current best estimate, and the direction of the bias is unknown.

### Table B - 1 (continued)

207 12 An estimated mechanism for the gas -phase reactions for this compound has been developed and has been evaluated at least qualitatively against available chamber data, but its estimated atmospheric ozone impact is highly uncertain because the amount of emitted compound available for reaction in the gas -phase is unknown. One important issue is that this compound may be removed by gas -phase reaction with HNO 3 , whose presence depends on ambient conditions and may not be appropriately represented in the scenarios used for reactivity assessment. For such compounds two reactivity values are given, and "upper limit magnitude" reactivity value based on assuming that all the emitted VOC is available for gas -phase reaction and that reaction with HNO 3 is negligible (as may be applicable if the HNO 3 formed in gas - phase reactions is removed from the gas phase by other means) and one also as suming that all the emitted VOC is available for gas -phase reaction except that the reaction with gas -phase HNO 3 is fast and there is no other sink for HNO 3 formed in the gas -phase reactions. 13 Same as code 12 except that no chamber data are available to test the estimated gas -phase mechanism. 20 The representation or estimated mechanism used is considered to be biased, and the direction of the likely bias is indicted by the bias code. Best estimate mechanisms have not been developed. Additional codes u sed where applicable s Portions of the mechanism are unknown or highly uncertain and simplified or parameterized representation has been adjusted at lest in part to fit available data for this or relate compounds. This is used primarily for alkylbenzenes. d Portions of this mechanism appear to be inconsistent with available laboratory data. This is used primarily for the 1 - alkenes, where radical yields in O 3 reactions have to be reduced to simulate chamber data. u The mechanism is unknown and a parameterized mechanism adjusted to fit the data for this or related compounds employed. m This uncertainty code is only applicable for mixtures whose composition has been analyzed using state - of

- the - science methods. Rating of effects of compositional uncertaintie s is beyond the scope of the project (but see discussion in Carter and Malkina (2005) for hydrocarbon mixtures). b The reactivity predictions may be more sensitive than usual to changes in the base mechanism or scenario conditions. n Chamber data for this or related compounds suggest that the mechanism may overpredict ozone under conditions where NO x is limited. This should affect MIR values but will lead to too high reactivities in lower NO x scenarios. a This compound may react with HNO 3 to form a no n - volatile salt, which may reduce the availability for this compound to react in the gas phase. The importance of this process under atmospheric conditions is uncertain because (a) the salt may revolatilize to the gas phase species and the equilibrium cons tant is unknown, (b) the sources and other sinks for HNO 3 may vary significantly from scenario to scenario and have not been established for the reactivity assessment scenarios, and (c) if ammonia or other amines are present they may compete for the HNO 3 and reduce the importance of this process for this amine, and the importance of these processes have not been established for the reactivity scenarios. In order to derive an upper limit ozone impact estimate, the reactivities of these compounds have been calculated assuming that removal by reaction with HNO 3 is uncertain. If this process is important, the magnitude of the actual ozone impact may be an order of magnitude or more low . Therefore, the tabulated reactivity values are upper limits for positively reactive compounds, and lower limits for ozone inhibitors. c CARB hydrocarbon bins are defined as described by Kwok et al (2000), but their reactivities are calculated based on their estimated compositions, which are derived as discussed by Carter (2009c). The uncertainties involved with this derivation are also discussed by Carter (2009c).

### Table B - 1 (continued)

208 + This may appropriately be considered to be an upper limit estimate in the ozone impact of this compound.

-- This may appropriately be considered to be an upper limit estimate in the amount of ozone inhibition caused by this compound. The upper limit reactivity is zero.

### 209

Table B - 2 . Listing of mechanisms for all VOCs for which mechanism assignments have been

derived. (Available in electronic form only) **Because of the size of this table, it is only available in as**  **supplementary material in electronic form. See Appendix D.** (The room temperature rate constant and photolysis parameter assignments and their reference citations that are incorporated in this table are also given in Table B -4 through Table B - 6 ) Table B - 3 . Listing of adjusted product mechanisms for all VOCs for which such mechanisms have

been derived . (Available in electronic form only) **Because of the size of this table, it is only available in as sup**  **plementary material in electronic form. See Appendix D.**

### 210

Table B -4 . Listing of compounds for which mechanisms have been derived. 1. OH radical rate

constants at 300 o

### K, mechanism types, and structures used for compounds with generated mechanisms . Com pound kOH [a] Mec Structure [c] k(300) Ref [b] Methane 6.62E - 15 1 1 Ethane 2.54E - 13 1 2 CH 3 CH 3 Propane 1.11E - 12 1 2 CH 3 CH 2 CH 3 Cyclopropane 8.34E - 14 1 2 CH 2 *CH 2 CH 2 * n - Butane 2.38E - 12 1 2 CH 3 CH 2 CH 2 CH 3 Isobutane 2.14E - 12 1 2 CH 3 CH(CH 3 )CH 3 Cyclobutane 2.05E - 12 1 2 CH 2 *CH 2 CH 2 CH 2 * n - Pentane 3.84E - 12 1 2 CH 3 CH 2 CH 2 CH 2 CH 3 Neopentane 8.38E - 13 1 2 CH 3 C(CH 3 )(CH 3 )CH 3 Iso - Pentane 3.60E - 12 1 2 CH 3 CH 2 CH(CH 3 )CH 3 Cyclopentane 5.02E - 12 1 2,A CH 2 *CH 2 CH 2 CH 2 CH 2 * n - Hexane 5.25E - 12 1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 3 2,2 - Dimethyl Butane 2.27E - 12 1 2 CH 3 CH 2 C(CH 3 )(CH 3 )CH 3 2,3 - Dimethyl Butane 5.79E - 12 1 2 CH 3 CH(CH 3 )CH(CH 3 )CH 3 2 - Methyl Pentane 5.20E - 12 1 2 CH 3 CH 2 CH 2 CH(CH 3 )CH 3 3 - Methylpentane 5.20E - 12 1 2 CH 3 CH 2 CH(CH 3 )CH 2 CH 3 Cyclohexane 7.02E - 12 1 2,A CH 2 *CH 2 CH 2 CH 2 CH 2 CH 2 * Isopropyl Cyclopropane 2.61E - 12 1 2 CH 3 CH(CH 3 )CH*CH 2 CH 2 * Methylcyclopentane 5.68E - 12 e1 2,A CH 3 CH*CH 2 CH 2 CH 2 CH 2 * n - Heptane 6.81E - 12 1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 2,2,3 - Trimethyl Butane 3.82E - 12 1 2 CH 3 CH(CH 3 )C(CH 3 )(CH 3 )CH 3 2,2 - Dimethyl Pentane 3.40E - 12 2 2 CH 3 CH 2 CH 2 C(CH 3 )(CH 3 )CH 3 2,3 - Dimethyl Pentane 7.15E - 12 e1 2 CH 3 CH 2 CH(CH 3 )CH(CH 3 )CH 3 2,4 - Dimethyl Pentane 4.77E - 12 1 2 CH 3 CH(CH 3 )CH 2 CH(CH 3 )CH 3 2 - Methyl Hexane 6.89E - 12 e1 2,A CH 3 CH 2 CH 2 CH 2 CH(CH 3 )CH 3 3,3 - Dimethyl Pentane 3.00E - 12 e1 2 CH 3 CH 2 C(CH 3 )(CH 3 )CH 2 CH 3 3 - Methyl Hexane 7.17E - 12 e1 2 CH 3 CH 2 CH 2 CH(CH 3 )CH 2 CH 3 3 - ethylpentane 7.58E - 12 e1 2 CH 3 CH 2 CH(CH 2 CH 3 )CH 2 CH 3 1,1 - dimethylcyclopentane 3.98E - 12 e1 2,A CH 3 C*(CH 3 )CH 2 CH 2 CH 2 CH 2 * 1,2 - dimethylcyclopentane 6.82E - 12 e1 2,A CH 3 CH*CH 2 CH 2 CH 2 CH*CH 3 1,3 - Dimethyl Cyclopentane 6.82E - 12 e1 2,A CH 3 CH*CH 2 CH 2 CH(CH 3 )CH 2 * Cycloheptane 1.24E - 11 1 2,A CH 2 *CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 * Ethyl Cyclopentane 7.27E - 12 e1 2,A CH 3 CH 2 CH*CH 2 CH 2 CH 2 CH 2 * Methylcyclohexane 9.64E - 12 1 2,A CH 3 CH*CH 2 CH 2 CH 2 CH 2 CH 2 * n - Octane 8.16E - 12 1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 2,2,3,3 - Tetramethyl Butane 9.89E - 13 1 2 CH 3 C(CH 3 )(CH 3 )C(CH 3 )(CH 3 )CH 3 2,2,4 - Trimethyl Pentane 3.38E - 12 1 2 CH 3 CH(CH 3 )CH 2 C(CH 3 )(CH 3 )CH 3 2,2 - Dimethyl Hexane 4.80E - 12 2 2 CH 3 CH 2 CH 2 CH 2 C(CH 3 )(CH 3 )CH 3 2,3,4 - Trimethyl Pentane 6.60E - 12 1 2 CH 3 CH(CH 3 )CH(CH 3 )CH(CH 3 )CH 3 2,3 - Dimethyl Hexane 8.57E - 12 e1 2 CH 3 CH 2 CH 2 CH(CH 3 )CH(CH 3 )CH 3 2,4 - Dimethyl Hexane 8.57E - 12 e1 2 CH 3 CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 3 2,5 - Dimethyl Hexane 8.29E - 12 e1 2 CH 3 CH(CH 3 )CH 2 CH 2 CH(CH 3 )CH 3 2 - Methyl Heptane 8.31E - 12 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 3 3 - Methyl Heptane 8.59E - 12 e1 2 CH 3 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 3 4 - Methyl Heptane 8.59E - 12 e1 2 CH 3 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH 3

### Table B -4 (continued)

211

Com pound kOH [a] Mec Structure [c] k(300) Ref [b] 2,3,3 - trimethylpentane 4.40E - 12 e1 2 CH 3 CH 2 C(CH 3 )(CH 3 )CH(CH 3 )CH 3 3,3 - dimethyl hexane 4.42E - 12 e1 2 CH 3 CH 2 CH 2 C(CH 3 )(CH 3 )CH 2 CH 3 2,2,3 - trimethyl -pentane 4.94E - 12 e1 2 CH 3 CH 2 CH(CH 3 )C(CH 3 )(CH 3 )CH 3 3,4 - dimethylhexane 8.85E - 12 e1 2 CH 3 CH 2 CH(CH 3 )CH(CH 3 )CH 2 CH 3 3 - Ethyl 2 - Methyl Pentane 8.98E - 12 e1 2 CH 3 CH 2 CH(CH 2 CH 3 )CH(CH 3 )CH 3 1,1,2 - trimethylc yclopentane 5.11E - 12 e1 2 CH 3 CH*CH 2 CH 2 CH 2 C*(CH 3 )CH 3 1,1,3 - trimethylcyclopentane 5.11E - 12 e1 2 CH 3 CH*CH 2 CH 2 C(CH 3 )(CH 3 )CH 2 * 1,1 - Dimethyl Cyclohexane 7.44E - 12 e1 2 CH 3 C*(CH 3 )CH 2 CH 2 CH 2 CH 2 CH 2 * 1,2,3 - trimethylcyclopentane 7.95E - 12 e1 2 CH 3 CH*CH 2 CH 2 CH(CH 3 )CH*C H 3 1,2,4 - trimethylcyclopentane 7.95E - 12 e1 2 CH 3 CH*CH 2 CH(CH 3 )CH(CH 3 )CH 2 * 1 - methyl - 3 - ethylcyclopentane 8.40E - 12 e1 2,A CH 3 CH 2 CH*CH 2 CH 2 CH(CH 3 )CH 2 * 1,2 - dimethylcyclohexane 1.19E - 11 e1 2,A CH 3 CH*CH 2 CH 2 CH 2 CH 2 CH*CH 3 1,4 - dimethylcyclohexane 1.19E - 11 e1 2,A CH 3 CH*CH 2 CH 2 CH(CH 3 )CH 2 CH 2 * 1,3 - Dimethyl Cyclohexane 1.19E - 11 e1 2,A CH 3 CH*CH 2 CH 2 CH 2 CH(CH 3 )CH 2 * Cyclooctane 1.33E - 11 1 2,A CH 2 *CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 * Ethylcyclohexane 1.20E - 11 e1 2 CH 3 CH 2 CH*CH 2 CH 2 CH 2 CH 2 CH 2 * Propyl Cyclopentane 8.69E - 12 e1 2,A CH 3 CH 2 CH 2 CH* CH 2 CH 2 CH 2 CH 2 * n -Nonane 9.75E - 12 1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 2,2,5 - Trimethyl Hexane 6.08E - 12 e1 2 CH 3 CH(CH 3 )CH 2 CH 2 C(CH 3 )(CH 3 )CH 3 2,3,5 - Trimethyl Hexane 7.90E - 12 2 2,A CH 3 CH(CH 3 )CH 2 CH(CH 3 )CH(CH 3 )CH 3 2,4 - Dimethyl Heptane 9.99E - 12 e1 2 CH 3 CH 2 CH 2 CH(CH 3 ) CH 2 CH(CH 3 )CH 3 2 - Methyl Octane 1.01E - 11 2 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 3 3,3 - Diethyl Pentane 4.80E - 12 1 2 CH 3 CH 2 C(CH 2 CH 3 )(CH 2 CH 3 )CH 2 CH 3 3,5 - Dimethyl Heptane 1.03E - 11 e1 2 CH 3 CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 2 CH 3 4 - Ethyl Heptane 1.04E - 11 e1 2 CH 3 CH 2 CH 2 CH(CH 2 CH 3 )CH 2 CH 2 CH 3 4 - Methyl Octane 9.70E - 12 2 2 CH 3 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH 3 2,4,4 - trimethylhexane 5.82E - 12 e1 2 CH 3 CH 2 C(CH 3 )(CH 3 )CH 2 CH(CH 3 )CH 3 3,3 - dimethylheptane 5.84E - 12 e1 2 CH 3 CH 2 CH 2 CH 2 C(CH 3 )(CH 3 )CH 2 CH 3 4,4 - dimethyl heptane 5.84E - 12 e1 2 CH 3 CH 2 CH 2 C(CH 3 )(CH 3 )C H 2 CH 2 CH 3 2,2 - dimethyl heptane 6.10E - 12 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 C(CH 3 )(CH 3 )CH 3 2,2,4 - trimethylhexane 6.36E - 12 e1 2 CH 3 CH 2 CH(CH 3 )CH 2 C(CH 3 )(CH 3 )CH 3 2,6 - dimethylheptane 9.71E - 12 e1 2 CH 3 CH(CH 3 )CH 2 CH 2 CH 2 CH(CH 3 )CH 3 2,3 - dimethylheptane 9.99E - 12 e1 2 CH 3 CH 2 CH 2 CH 2 C H(CH 3 )CH(CH 3 )CH 3 2,5 - dimethylheptane 9.99E - 12 e1 2 CH 3 CH 2 CH(CH 3 )CH 2 CH 2 CH(CH 3 )CH 3 3 - methyloctane 1.00E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 3 3,4 - dimethylheptane 1.03E - 11 e1 2 CH 3 CH 2 CH 2 CH(CH 3 )CH(CH 3 )CH 2 CH 3 3 - ethylheptane 1.04E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH(CH 2 CH 3 )CH 2 CH 3 Cis - hydrindane; Bicyclo[4.3.0]nonane 1.71E - 11 e1 2,A CH 2 *1 CH 2 CH 2 CH*2CH 2 CH 2 CH 2 CH* 2CH 2 *1 1,2,3 - trimethylcyclohexane 1.36E - 11 e1 2,A CH 3 CH*CH 2 CH 2 CH 2 CH(CH 3 )CH*CH 3 1,3,5 - trimethylcyclohexane 1.36E - 11 e1 2 CH 3 CH*CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 2 * 1,1,3 - Trimethyl Cyclohexane 8.70E - 12 2 2 CH 3 CH*CH 2 CH 2 CH 2 C(CH 3 )(CH 3 )CH 2 * 1 - Ethyl - 4 - Methyl Cyclohexane 1.37E - 11 e1 2,A CH 3 CH 2 CH*CH 2 CH 2 CH(CH 3 )CH 2 CH 2 * Propyl Cyclohexane 1.34E - 11 e1 2 CH 3 CH 2 CH 2 CH*CH 2 CH 2 CH 2 CH 2 CH 2 * n - Decane 1.10E - 11 1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 2, 4,6 - Trimethyl Heptane 1.14E - 11 e1 2 CH 3 CH(CH 3 )CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 3 2,4 - Dimethyl Octane 1.14E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 3 2,6 - Dimethyl Octane 1.29E - 11 3 2 CH 3 CH 2 CH(CH 3 )CH 2 CH 2 CH 2 CH(CH 3 )CH 3

### Table B -4 (continued)

212

Com pound kOH [a] Mec Structure [c] k(300) Ref [b] 2 - Methyl Nonane 1.28E - 11 3 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 3 3,4 - Diethyl Hexane 6.92E - 12 1 2 CH 3 CH 2 CH(CH 2 CH 3 )CH(CH 2 CH 3 )CH 2 CH 3 3 - Methyl Nonane 1.14E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 3 4 - Methyl Nonane 1.14E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH 3 4 - Propyl Heptane 1.18E - 11 e1 2 CH 3 CH 2 CH 2 CH(CH 2 CH 2 CH 3 )CH 2 CH 2 CH 3 2,4,4 - trimethylheptane 7.24E - 12 e1 2 CH 3 CH 2 CH 2 C(CH 3 )(CH 3 )CH 2 CH(CH 3 )CH 3 2,5,5 - trimethylheptane 7.24E - 12 e1 2 CH 3 CH 2 C(CH 3 )(CH 3 )CH 2 CH 2 CH(CH 3 )CH 3 3,3 - dimethyloctane 7.26E - 12 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 C(CH 3 )(CH 3 )CH 2 CH 3 4,4 - dimethyloctane 7.26E - 12 e1 2 CH 3 CH 2 CH 2 CH 2 C(CH 3 )(CH 3 )CH 2 CH 2 CH 3 2,2 - dimethyloctane 7.52E - 12 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 C(CH 3 )(CH 3 )CH 3 2,2,4 - trimethylheptane 7.78E - 12 e1 2 CH 3 CH 2 CH 2 CH(CH 3 )CH 2 C(CH 3 )(CH 3 )CH 3 2,2,5 - trimethylheptane 7.78E - 12 e1 2 CH 3 CH 2 CH(CH 3 )CH 2 CH 2 C(CH 3 )(CH 3 )CH 3 2,3,6 - trime thylheptane 1.14E - 11 e1 2,A CH 3 CH(CH 3 )CH 2 CH 2 CH(CH 3 )CH(CH 3 )CH 3 2,3 - dimethyloctane 1.14E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH(CH 3 )CH 3 2,5 - dimethyloctane 1.14E - 11 e1 2 CH 3 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH(CH 3 )CH 3 2 - methyl - 3 - ethylheptane 1.18E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH(CH 2 CH 3 )CH(CH 3 )CH 3 4 - ethyloctane 1.18E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 CH(CH 2 CH 3 )CH 2 CH 2 CH 3 1,3 - Diethyl - Cyclohexane 1.55E - 11 e1 2,A CH 3 CH 2 CH*CH 2 CH 2 CH 2 CH(CH 2 CH 3 )CH 2 * 1,4 - Diethyl - Cyclohexane 1.55E - 11 e1 2 CH 3 CH 2 CH*CH 2 CH 2 CH(CH 2 CH 3 )CH 2 CH 2 * 1 - Methyl - 3 - Isopropyl Cyclohexane 1 .51E - 11 e1 2 CH 3 CH*CH 2 CH 2 CH 2 CH(CH 2 *) CH(CH 3 )CH 3 Butyl Cyclohexane 1.47E - 11 1 2 CH 3 CH 2 CH 2 CH 2 CH*CH 2 CH 2 CH 2 CH 2 CH 2 * n - Undecane 1.23E - 11 1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 2,3,4,6 - Tetramethyl Heptane 1.31E - 11 e1 2 CH 3 CH(CH 3 )CH 2 CH(CH 3 )CH(CH 3 )CH(CH 3 )CH 3 2,6 - Dimethyl Nonane 1.28E - 11 e1 2 CH 3 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH 2 CH(CH 3 )CH 3 3,5 - Diethyl Heptane 1.39E - 11 e1 2 CH 3 CH 2 CH(CH 2 CH 3 )CH 2 CH(CH 2 CH 3 )CH 2 CH 3 3 - Methyl Decane 1.29E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 3 4 - Methyl Decane 1.29E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH(C H 3 )CH 2 CH 2 CH 3 1,3 - Diethyl - 5 - Methyl Cyclohexane 1.72E - 11 e1 2 CH 3 CH 2 CH*CH 2 CH(CH 3 )CH 2 CH(CH 2 CH 3 )CH 2 * 1 - Ethyl - 2 - Propyl Cyclohexane 1.70E - 11 e1 2,A CH 3 CH 2 CH 2 CH*CH 2 CH 2 CH 2 CH 2 CH*CH 2 CH 3 Pentyl Cyclohexane 1.63E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH*CH 2 CH 2 CH 2 CH 2 CH 2 * n - Dodecane 1.32E - 11 1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 2,3,5,7 - Tetramethyl Octane 1.45E - 11 e1 2 CH 3 CH(CH 3 )CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH(CH 3 )CH 3 2,6 - Diethyl Octane 1.53E - 11 e1 2 CH 3 CH 2 CH(CH 2 CH 3 )CH 2 CH 2 CH(CH 2 CH 3 )CH 2 CH 3 3,6 - Dimethyl Decane 1.45E - 11 e1 2,A CH 3 CH 2 CH 2 C H 2 CH(CH 3 )CH 2 CH 2 CH(CH 3 )CH 2 CH 3 3 - Methyl Undecane 1.43E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 3 5 - Methyl Undecane 1.43E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH 2 CH 3 1,3,5 - Triethyl Cyclohexane 1.90E - 11 e1 2 CH 3 CH 2 CH*CH 2 CH(CH 2 CH 3 )CH 2 CH(CH 2 CH 3 )CH 2 * 1 - Methyl - 4 - Pentyl Cyclohexane 1.80E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH*CH 2 CH 2 CH(CH 3 )CH 2 CH 2 * Hexyl Cyclohexane 1.78E - 11 3 2,A CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH*CH 2 CH 2 CH 2 CH 2 CH 2 * n - Tridecane 1.51E - 11 1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 2,3,6 - Trimethyl 4 - Isopropyl Heptane 1.63E - 11 e1 2 CH 3 CH(CH 3 )CH 2 CH(CH(CH 3 )CH 3 )CH(CH 3 )CH(CH 3 )CH 3 2,4,6,8 - Tetramethyl Nonane 1.59E - 11 e1 2,A CH 3 CH(CH 3 )CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 3 3,6 - Dimethyl Undecane 1.60E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH(CH 3 )CH 2 CH 3 3,7 - Diethyl Nonane 1.68E - 11 e1 2 CH 3 CH 2 CH(CH 2 CH 3 )CH 2 CH 2 CH 2 CH(CH 2 CH 3 )CH 2 CH 3 3 - Methyl Dodecane 1.57E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 3

### Table B -4 (continued)

213

Com pound kOH [a] Mec Structure [c] k(300) Ref [b] 5 - Methyl Dodecane 1.57E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH 2 CH 3 1,3 - Diethyl - 5 - Propyl Cyclohexane 2.05E - 11 e1 2 CH 3 CH 2 CH 2 C H*CH 2 CH(CH 2 CH 3 )CH 2 CH(CH 2 CH 3 )CH 2 * 1 - Methyl - 2 - Hexyl Cyclohexane 1.94E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH*CH 2 CH 2 CH 2 CH 2 CH*CH 3 Heptyl Cyclohexane 1.91E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH*CH 2 CH 2 CH 2 CH 2 CH 2 * n - Tetradecane 1.79E - 11 1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 C H 2 CH 2 CH 3 2,4,5,6,8 - Pentamethyl Nonane 1.76E - 11 e1 2 CH 3 CH(CH 3 )CH 2 CH(CH 3 )CH(CH 3 )CH(CH 3 )CH 2 CH(CH 3 ) CH 3 2 - Methyl 3,5 - Diisopropyl Heptane 1.81E - 11 e1 2,A CH 3 CH 2 CH(CH 2 CH(CH(CH 3 )CH 3 )CH(CH 3 )CH 3 )CH(CH 3 ) CH 3 3,7 - Dimethyl Dodecane 1.74E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 3 3,8 - Diethyl Decane 1.82E - 11 e1 2,A CH 3 CH 2 CH(CH 2 CH 3 )CH 2 CH 2 CH 2 CH 2 CH(CH 2 CH 3 )CH 2 CH 3 3 - Methyl Tridecane 1.71E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 3 6 - Methyl Tridecane 1.71E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH 2 CH 2 CH 3 1,3 - Dipropyl - 5 - Ethyl Cyclohexane 2.19E - 11 e1 2 CH 3 CH 2 CH 2 CH*CH 2 CH(CH 2 CH 3 )CH 2 CH(CH 2 CH 2 CH 3 )C H 2 * trans 1 - Methyl - 4 - Heptyl Cyclohexane 2.08E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH*CH 2 CH 2 CH(CH 3 )CH 2 CH 2 * Octyl Cyclohexane 2.05E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH*CH 2 CH 2 CH 2 CH 2 CH 2 * n - Pentadecane 2.07E - 11 1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 2,6,8 - Trimethyl 4 - Isopropyl Nonane 1.91E - 11 e1 2 CH 3 CH(CH 3 )CH 2 CH(CH 3 )CH 2 CH(CH 2 CH(CH 3 )CH 3 )CH(C H 3 )CH 3 3,7 - Dimethyl Tridecane 1.88E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH(C H 3 )CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 3 3,9 - Diethyl Undecane 1.96E - 11 e1 2 CH 3 CH 2 CH(CH 2 CH 3 )CH 2 CH 2 CH 2 CH 2 CH 2 CH(CH 2 CH 3 )CH 2 CH 3 3 - Methyl Tetradecane 1.85E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 3 6 - Methyl Tetradecane 1.85E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 C H(CH 3 )CH 2 CH 2 CH 2 CH 2 CH 3 1,3,5 - Tripropyl Cyclohexane 2.33E - 11 e1 2 CH 3 CH 2 CH 2 CH*CH 2 CH(CH 2 CH 2 CH 3 )CH 2 CH(CH 2 CH 2 CH 3 )CH 2 * 1 - Methyl - 2 - Octyl Cyclohexane 2.22E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH*CH 2 CH 2 CH 2 CH 2 CH* CH 3 Nonyl Cyclohexane 2.20E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH*CH 2 CH 2 CH 2 CH 2 CH 2 * 1,3 - diethyl - 5 -pentyl cyclohexane 1.75E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH*CH 2 CH 2 CH 2 C(CH 2 CH 3 )(CH 2 CH 3 ) CH 2 * n - C16 2.32E - 11 1 2,A CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 2,7 - Dimethyl 3,5 - Diisopropyl Heptane 2.09E - 11 e1 2,A CH 3 CH(CH 3 )CH 2 CH(CH 2 CH(CH(CH 3 )CH 3 )CH(CH 3 )CH 3 ) CH(CH 3 )CH 3 3 - Methyl Pentadecane 2.00E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH(CH 3 ) CH 2 CH 3

### Table B -4 (continued)

214

Com pound kOH [a] Mec Structure [c] k(300) Ref [b] 4,8 - Dimethyl Tetradecane 2.02E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH 3 7 - Methyl Pentadecane 2.00 E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 1,3 - Propyl - 5 - Butyl Cyclohexane 2.47E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH*CH 2 CH(CH 2 CH 2 CH 3 )CH 2 CH(CH 2 CH 2 CH 3 )CH 2 * 1 - Methyl - 4 -Nonyl Cyclohexane 2.36E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH*CH 2 CH 2 CH(CH 3 ) CH 2 CH 2 * De cyl Cyclohexane 2.34E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH*CH 2 CH 2 CH 2 CH 2 CH 2 * Ethene 8.15E - 12 1 1 Propene 2.60E - 11 1 2 CH 2 =CHCH 3 1,2 -propadiene (allene) 9.80E - 12 1 3 CH 2 =C=CH 2 1 - Butene 3.11E - 11 1 2 CH 2 =CHCH 2 CH 3 Isobutene 5.08E - 11 1 2 CH 2 =C(CH 3 )CH 3 cis - 2 - Butene 5.58E - 11 1 2 CH 3 ^CH=CHvCH 3 trans - 2 - Butene 6.32E - 11 1 2 CH 3 ^CH=CH^CH 3 1,2 - Butadiene 2.60E - 11 1 3 CH 2 =C=CHCH 3 1,3 - Butadiene 6.59E - 11 1 3 CH 2 =CHCH=CH 2 1 - Pentene 3.14E - 11 1 2 CH 2 =CHCH 2 CH 2 CH 3 3 - Methyl - 1 - Butene 3.14E - 11 1 2 CH 2 =CHCH(CH 3 )CH 3 2 - Methyl - 1 - Butene 6.10E - 11 1 2 CH 2 =C(CH 3 )CH 2 CH 3 2 - Methyl - 2 - Butene 8.60E - 11 1 2 CH 3 CH=C(CH 3 )CH 3 cis - 2 - Pentene 6.50E - 11 1 2 CH 3 ^CH=CHvCH 2 CH 3 trans - 2 - Pentene 6.70E - 11 1 2 CH 3 ^CH=CH^CH 2 CH 3 Cyclopentene 6.70E - 11 1 2 CH*=CHCH 2 CH 2 CH 2 * Trans 1,3 - Pentadiene 1 .01E - 10 e2 3 CH 2 =CH^CH=CH^CH 3 1,4 - Pentadiene 5.30E - 11 1 3 CH 2 =CHCH 2 CH=CH 2 1,2 - Pentadiene 3.55E - 11 1 3 CH 2 =C=CHCH 2 CH 3 3 - Methyl - 1,2 - Butadiene 5.70E - 11 1 3 CH 2 =C=C(CH 3 )CH 3 Isoprene 9.96E - 11 1 1 1 - Hexene 3.70E - 11 1 2 CH 2 =CHCH 2 CH 2 CH 2 CH 3 3,3 - Dimethyl - 1 - Butene 2.80E - 11 1 2 CH 2 =CHC(CH 3 )(CH 3 )CH 3 3 - Methyl - 1 - Pentene 3.55E - 11 e1 2 CH 2 =CHCH(CH 3 )CH 2 CH 3 4 - Methyl - 1 - Pentene 3.55E - 11 e1 2 CH 2 =CHCH 2 CH(CH 3 )CH 3 2,3 - Dimethyl - 1 - Butene 6.03E - 11 e1 2 CH 2 =C(CH 3 )CH(CH 3 )CH 3 2 - Ethyl - 1 - Butene 6.01E - 11 e1 2 CH 2 =C(CH 2 CH 3 )CH 2 CH 3 2 - Methyl - 1 - Pentene 6.30E - 11 1 2 CH 2 =C(CH 3 )CH 2 CH 2 CH 3 2,3 - Dimethyl - 2 - Butene 1.10E - 10 1 2 CH 3 C(CH 3 )=C(CH 3 )CH 3 2 - Methyl - 2 - Pentene 8.90E - 11 1 2 CH 3 CH 2 CH=C(CH 3 )CH 3 Cis - 2 - Hexene 6.60E - 11 e1 2 CH 3 ^CH=CHvCH 2 CH 2 CH 3 Cis - 3 - Hexene 6.56E - 11 e1 2 CH 3 CH 2 ^CH=CHvCH 2 CH 3 Cis - 3 - Methyl - 2 - Pentene 8.85E - 11 e1 2 CH 3 ^CH=C(^CH 3 )CH 2 CH 3 Trans 3 - Methyl - 2 - Pentene 8.85E - 11 e1 2 CH 3 ^CH=C(vCH 3 )CH 2 CH 3 Trans 4 - Methyl - 2 - Pentene 5.98E - 11 4 2 CH 3 ^CH=CH^CH(CH 3 )CH 3 Trans - 2 - Hexene 6.60E - 11 e1 2 CH 3 ^CH=CH^CH 2 CH 2 CH 3 Trans - 3 - Hexene 6.56E - 11 e1 2 CH 3 CH 2 ^CH=CH^CH 2 CH 3 3 - methylcyclopentene 6.67E - 11 e1 2 CH 3 CH*CH=CHCH 2 CH 2 * 1 - Methyl cyclopentene 8.96E - 11 e1 2,A CH 3 C*=CHCH 2 CH 2 CH 2 *

### Table B -4 (continued)

215

Com pound kOH [a] Mec Structure [c] k(300) Ref [b] Cyclohexene 6.77E - 11 1 2 CH*=CHCH 2 CH 2 CH 2 CH 2 * Trans 1,4 - Hexadiene 9.10E - 11 1 3 CH 2 =CHCH 2 ^CH=CH^CH 3 1 - Methyl Cyclohe xene 9.40E - 11 1 2 CH 3 C*=CHCH 2 CH 2 CH 2 CH 2 * 4 - Methyl Cyclohexene 7.02E - 11 e1 2 CH 3 CH*CH 2 ^CH=CHvCH 2 CH 2 * 1 - Heptene 4.00E - 11 1 2,A CH 2 =CHCH 2 CH 2 CH 2 CH 2 CH 3 3,4 - dimethyl - 1 -pentene 3.69E - 11 e1 2 CH 2 =CHCH(CH 3 )CH(CH 3 )CH 3 3 - methyl - 1 - hexene 3.69E - 11 e1 2 CH 2 =CHCH(CH 3 ) CH 2 CH 2 CH 3 2,4 - dimethyl - 1 -pentene 6.19E - 11 e1 2,A CH 2 =C(CH 3 )CH 2 CH(CH 3 )CH 3 2,3 - dimethyl - 1 -pentene 6.19E - 11 e1 2 CH 2 =C(CH 3 )CH(CH 3 )CH 2 CH 3 3,3 - dimethyl - 1 -pentene 3.33E - 11 e1 2 CH 2 =CHC(CH 3 )(CH 3 )CH 2 CH 3 2 - methyl - 1 - hexene 6.19E - 11 e1 2 CH 2 =C(CH 3 )CH 2 CH 2 CH 2 CH 3 2 ,3,3 - trimethyl - 1 - Butene 5.86E - 11 e1 2 CH 2 =C(CH 3 )C(CH 3 )(CH 3 )CH 3 4,4 - dimethyl - cis - 2 -pentene 5.46E - 11 e1 2 CH 3 ^CH=CHvC(CH 3 )(CH 3 )CH 3 2,4 - dimethyl - 2 -pentene 8.97E - 11 e1 2 CH 3 C(CH 3 )=CHCH(CH 3 )CH 3 2 - methyl - 2 - hexene 8.99E - 11 e1 2 CH 3 CH 2 CH 2 CH=C(CH 3 )CH 3 3 - ethyl - 2 -pentene 8.95E - 11 e1 2 CH 3 CH=C(CH 2 CH 3 )CH 2 CH 3 3 - methyl - trans - 3 -hexene 8.95E - 11 e1 2 CH 3 CH 2 ^CH=C(CH 3 )vCH 2 CH 3 cis - 2 -heptene 6.74E - 11 e1 2 CH 3 ^CH=CHvCH 2 CH 2 CH 2 CH 3 2 - Methyl - trans - 3 - Hexene 6.68E - 11 e1 2 CH 3 CH 2 ^CH=CH^CH(CH 3 )CH 3 3 - methyl - cis - 3 - hexene 8.95E - 11 e 1 2 CH 3 CH 2 ^CH=C(CH 3 )^CH 2 CH 3 3,4 - dimethyl - cis - 2 -pentene 8.97E - 11 e1 2 CH 3 ^CH=C(CH 3 )^CH(CH 3 )CH 3 2,3 - Dimethyl - 2 - Pentene 1.03E - 10 1 2 CH 3 CH 2 C(CH 3 )=C(CH 3 )CH 3 Cis - 3 - Heptene 6.70E - 11 e1 2 CH 3 CH 2 ^CH=CHvCH 2 CH 2 CH 3 Trans 4,4 - dimethyl - 2 - Pentene 5.50E - 11 1 2 CH 3 ^CH =CH^C(CH 3 )(CH 3 )CH 3 Trans - 2 - Heptene 6.80E - 11 1 2 CH 3 ^CH=CH^CH 2 CH 2 CH 2 CH 3 Trans - 3 - Heptene 6.70E - 11 e1 2 CH 3 CH 2 ^CH=CH^CH 2 CH 2 CH 3 cis - 3 - methyl - 2 - hexene 8.99E - 11 e1 2 CH 3 ^CH=C(^CH 3 )CH 2 CH 2 CH 3 trans 4 - methyl - 2 - hexene 6.74E - 11 e1 2 CH 3 ^CH=CH^CH(CH 3 )CH 2 CH 3 trans 3 - methyl - 2 - hexene 8.99E - 11 e1 2 CH 3 ^CH=C(vCH 3 )CH 2 CH 2 CH 3 1,2 - Dimethyl Cyclohexene 1.11E - 10 e1 2 CH 3 C*=C(CH 3 )CH 2 CH 2 CH 2 CH 2 * 1 - Octene 3.83E - 11 e1 2 CH 2 =CHCH 2 CH 2 CH 2 CH 2 CH 2 CH 3 2,4,4 - trimethyl - 1 -pentene 5.97E - 11 e1 2 CH 2 =C(CH 3 )CH 2 C(CH 3 )(CH 3 )CH 3 3 - Methyl - 2 - Iso propyl - 1 - Butene 6.25E - 11 e1 2,A CH 2 =C(CH(CH 3 )CH 3 )CH(CH 3 )CH 3 trans - 2 - octene 6.89E - 11 e1 2 CH 3 ^CH=CH^CH 2 CH 2 CH 2 CH 2 CH 3 2 - Methyl - 2 - heptene 9.13E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH=C(CH 3 )CH 3 Cis - 4 - Octene 6.84E - 11 e1 2,A CH 3 CH 2 CH 2 ^CH=CHvCH 2 CH 2 CH 3 Trans 2,2 - Dimethyl 3 - Hex ene 6.50E - 11 e1 2 CH 3 CH 2 ^CH=CH^C(CH 3 )(CH 3 )CH 3 Trans 2,5 - Dimethyl 3 - Hexene 6.80E - 11 e1 2,A CH 3 CH(CH 3 )^CH=CH^CH(CH 3 )CH 3 Trans - 3 - Octene 6.84E - 11 e1 2,A CH 3 CH 2 ^CH=CH^CH 2 CH 2 CH 2 CH 3 Trans - 4 - Octene 6.90E - 11 1 2,A CH 3 CH 2 CH 2 ^CH=CH^CH 2 CH 2 CH 3 2,4,4 - trimethyl - 2 - Pentene 8.79E - 11 e1 2 CH 3 C(CH 3 )=CHC(CH 3 )(CH 3 )CH 3 2,3 - dimethyl - 2 - hexene 1.08E - 10 e1 2 CH 3 CH 2 CH 2 C(CH 3 )=C(CH 3 )CH 3 1 -Nonene 3.98E - 11 e1 2 CH 2 =CHCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 4,4 - dimethyl - 1 -pentene 3.58E - 11 e1 2 CH 2 =CHCH 2 C(CH 3 )(CH 3 )CH 2 CH 2 CH 3 Trans - 4 -Nonene 6.98E - 11 e1 2,A CH 3 CH 2 CH 2 ^CH=CH^CH 2 CH 2 CH 2 CH 3 1 - Decene 4.12E - 11 e1 2 CH 2 =CHCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 3,4 - Diethyl - 2 - Hexene 9.39E - 11 e1 2 CH 3 CH=C(CH 2 CH 3 )CH(CH 2 CH 3 )CH 2 CH 3 Cis - 5 - Decene 7.12E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 ^CH=CHvCH 2 CH 2 CH 2 CH 3

### Table B -4 (continued)

216

Com pound kOH [a] Mec Structure [c] k(300) Ref [b] Trans - 4 - Decene 7.12E - 11 e1 2,A CH 3 CH 2 CH 2 ^CH=CH^CH 2 CH 2 CH 2 CH 2 CH 3 3 - Carene 8.80E - 11 1 3 CH 3 C*1=CHCH 2 CH*2CH(CH 2 *1)C*2(CH 3 )CH 3 a - Pinene 5.18E - 11 1 3 CH 3 C*1=CHCH 2 CH*2CH 2 CH* 1C* 2(CH 3 )CH 3 b - Pinene 7.35E - 11 1 3 CH 2 =C*1CH 2 CH 2 CH*2CH 2 CH* 1C* 2(CH 3 )CH 3 d - Limonene 1.63E - 10 1 3 CH 2 =C(CH 3 )CH*CH 2 CH=C(CH 3 )CH 2 CH 2 * Sabinene 1.17E - 10 1 3 CH 2 =C*1CH 2 CH 2 C* 2(CH 2 CH* 12)CH(CH 3 )CH 3 Terpinolene 1.96E - 10 e1 3 CH 3 C(CH 3 )=C*CH 2 CH=C(CH 3 )CH 2 CH 2 * 1 -Undecene 4.26E - 11 e1 2 CH 2 =CHCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 Trans - 5 -Undecene 7.26E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 ^CH=CH^CH 2 CH 2 CH 2 CH 2 CH 3 1 - Dodecene 4.40E - 11 e1 2 CH 2 =CHCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 Trans - 5 - Dodecene 7.40E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 ^CH=CH^CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 1 - Tridecene 4.54E - 11 e1 2 CH 2 =CHCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 Trans - 5 - Tridecene 7.55E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 ^CH=CH^CH 2 C H 2 CH 2 CH 2 CH 2 CH 2 CH 3 1 - Tetradecene 4.69E - 11 e1 2 CH 2 =CHCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 Trans - 5 - Tetradecene 7.69E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 ^CH=CH^CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 Trans - 5 - Pentadecene 7.83E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 ^CH=CH^CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 Benz ene 1.22E - 12 1 1 Toluene 5.58E - 12 1 5 Ethyl Benzene 7.00E - 12 1 5 m - Xylene 2.31E - 11 1 5 o - Xylene 1.36E - 11 1 5 p - Xylene 1.43E - 11 1 5 Styrene 5.80E - 11 1 4 n - Propyl Benzene 5.80E - 12 1 5 Isopropyl Benzene (cumene) 6.30E - 12 1 5 m - Ethyl Toluene 1.86E - 11 1 5 o - Ethyl Toluene 1.19E - 11 1 5 p - Ethyl Toluene 1.18E - 11 1 5 1,2,3 - Trimethyl Benzene 3.27E - 11 1 5 1,2,4 - Trimethyl Benzene 3.25E - 11 1 5 1,3,5 - Trimethyl Benzene 5.67E - 11 1 5 b - Methyl Styrene 5.70E - 11 1 4 C10 Monosubstituted Benzenes 9 .58E - 12 e3 5 t - Butyl Benzene 4.50E - 12 1 5 m - c10 disubstituted benzenes 2.55E - 11 e4 5 o - c10 disubstituted benzenes 1.64E - 11 e4 5 p - c10 disubstituted benzenes 1.64E - 11 e4 5 1 - methyl - 4 - isopropylbenzene (p - cymene) 1.45E - 11 5 5 1,2,3 - c10 trisubstituted benzenes 3.41E - 11 e5 5 1,2,4 - c10 trisubstituted benzenes 3.41E - 11 e5 5

### Table B -4 (continued)

217

Com pound kOH [a] Mec Structure [c] k(300) Ref [b] 1,3,5 - c10 trisubstituted benzenes 5.77E - 11 e5 5 Tetralin 3.40E - 11 1 6 Naphthalene 2.30E - 11 1 5 C11 Monosubstituted Benzenes 1.10E - 11 e3 5 m - c11 disubstituted benzenes 2. 74E - 11 e4 5 o - c11 disubstituted benzenes 1.82E - 11 e4 5 p - c11 disubstituted benzenes 1.82E - 11 e4 5 1,2,3 - c11 trisubstituted benzenes 3.57E - 11 e5 5 1,2,4 - c11 trisubstituted benzenes 3.57E - 11 e5 5 1,3,5 - c11 trisubstituted benzenes 5.93E - 11 e5 5 Me thyl Naphthalenes 1.59E - 11 e6 6 C12 Monosubstituted Benzenes 1.24E - 11 e3 5 m - c12 disubstituted benzenes 2.82E - 11 e4 5 o - c12 disubstituted benzenes 1.90E - 11 e4 5 p - c12 disubstituted benzenes 1.90E - 11 e4 5 1,2,3 - c12 trisubstituted benzenes 3.66E - 11 e5 5 1,2,4 - c12 trisubstituted benzenes 3.66E - 11 e5 5 1,3,5 - c12 trisubstituted benzenes 6.01E - 11 e5 5 2,3 - Dimethyl Naphthalene 7.68E - 11 5 6 C13 Monosubstituted Benzenes 1.38E - 11 e3 5 m - c13 disubstituted benzenes 2.96E - 11 e4 5 o - c13 disubstitute d benzenes 2.05E - 11 e4 5 p - c13 disubstituted benzenes 2.05E - 11 e4 5 1,2,3 - c13 trisubstituted benzenes 3.81E - 11 e5 5 1,2,4 - c13 trisubstituted benzenes 3.81E - 11 e5 5 1,3,5 - c13 trisubstituted benzenes 6.17E - 11 e5 5 C14 Monosubstituted Benzenes 1.53E - 11 e3 5 m - c14 disubstituted benzenes 3.11E - 11 e4 5 o - c14 disubstituted benzenes 2.19E - 11 e4 5 p - c14 disubstituted benzenes 2.19E - 11 e4 5 1,2,3 - c14 trisubstituted benzenes 3.93E - 11 e5 5 1,2,4 - c14 trisubstituted benzenes 3.93E - 11 e5 5

### Table B -4 (continued)

218

Com pound kOH [a] Mec Structure [c] k(300) Ref [b] 1,3,5 - c14 trisubstituted benzenes 6.28E - 11 e5 5 C15 Monosubstituted Benzenes 1.67E - 11 e3 5 m - c15 disubstituted benzenes 3.25E - 11 e4 5 o - c15 disubstituted benzenes 2.33E - 11 e4 5 p - c15 disubstituted benzenes 2.33E - 11 e4 5 1,2,3 - c15 trisubstituted benzenes 4. 04E - 11 e5 5 1,2,4 - c15 trisubstituted benzenes 4.04E - 11 e5 5 1,3,5 - c15 trisubstituted benzenes 6.40E - 11 e5 5 C16 Monosubstituted Benzenes 1.81E - 11 e3 5 m - c16 disubstituted benzenes 3.39E - 11 e4 5 o - c16 disubstituted benzenes 2.48E - 11 e4 5 p - c16 disubstituted benzenes 2.47E - 11 e4 5 1,2,3 - c16 trisubstituted benzenes 4.17E - 11 e5 5 1,2,4 - c16 trisubstituted benzenes 4.17E - 11 e5 5 1,3,5 - c16 trisubstituted benzenes 6.52E - 11 e5 5 formaldehyde 8.47E - 12 1 1 methanol 9.02E - 13 1 1 formic acid 4.50 E - 13 29 1 Ethylene Oxide 7.60E - 14 20 2 CH 2 *CH 2 O* acetaldehyde 1.49E - 11 1 1 Ethanol 3.21E - 12 1 2 CH 3 CH 2 OH Dimethyl Ether 2.83E - 12 1 2 CH 3 OCH 3 glyoxal 1.10E - 11 1 1 Methyl Formate 2.27E - 13 19 2 CH 3 OCHO acetic acid 7.26E - 13 29 1 glycolaldehyde 1.49 E - 11 e18 24 Ethylene Glycol 1.47E - 11 8 2 HOCH 2 CH 2 OH Glycolic Acid 3.08E - 12 e1 2 HOCH 2 C(O)OH Acrolein 1.99E - 11 20 8,A CH 2 =CHCHO Trimethylene Oxide 1.03E - 11 10 2 CH 2 *CH 2 OCH 2 * Propylene Oxide 5.20E - 13 20 2 CH 3 CH*CH 2 O* propionaldehyde 1.97E - 11 1 1 ace tone 1.91E - 13 1 1 Isopropyl Alcohol 5.09E - 12 1 2 CH 3 CH(CH 3 )OH n - Propyl Alcohol 5.81E - 12 1 2 CH 3 CH 2 CH 2 OH Acrylic Acid 2.85E - 11 e1 2 CH 2 =CHC(O)OH methyl glyoxal 1.50E - 11 1 1 1,3 - dioxolane 5.36E - 11 e1 2 CH 2 *CH 2 OCH 2 O* Ethyl Formate 1.02E - 12 19 2 CH 3 CH 2 OCHO

### Table B -4 (continued)

219

Com pound kOH [a] Mec Structure [c] k(300) Ref [b] Methyl Acetate 3.49E - 13 19 2 CH 3 C(O)OCH 3 Propionic Acid 1.20E - 12 29 1 CH 3 CH 2 C(O)OH Hydroxy Acetone 3.02E - 12 10 8 CH 3 C(O)CH 2 OH Propylene Glycol 2.15E - 11 8 2,A CH 3 CH(OH)CH 2 OH Dimethoxy methane 4.90E - 12 11 2,A CH 3 OCH 2 OCH 3 2 - Methoxyethanol 1.33E - 11 10 2 CH 3 OCH 2 CH 2 OH Dimethyl Carbonate 3.30E - 13 11 2 CH 3 OC(O)OCH 3 dihydroxyacetone 6.01E - 12 e1 9 HOCH 2 C(O)CH 2 OH Glycerol 1.87E - 11 e1 2,A HOCH 2 CH(OH)CH 2 OH Furan 4.02E - 11 5 7 Crotonaldehyde 3.64E - 11 33 8 CH 3 CH=CHCHO methacrolein 2.84E - 11 1 1 Cyclobutanone 8.70E - 13 1 8 CH 2 *CH 2 C(O)CH 2 * methylvinyl ketone 1.99E - 11 1 1 Tetrahydrofuran 1.61E - 11 6 2 CH 2 *CH 2 CH 2 OCH 2 * 1,2 - Epoxybutane 1.91E - 12 28 2 CH 3 CH 2 CH*CH 2 O* 2 - Methylpropanal 2.68E - 11 1 2 CH 3 CH(CH 3 )CHO Butanal 2.35E - 11 1 2 CH 3 CH 2 CH 2 CHO methyl ethyl ke tone 1.20E - 12 1 1 Isobutyl Alcohol 9.30E - 12 1 2 CH 3 CH(CH 3 )CH 2 OH n - Butyl Alcohol 8.45E - 12 1 2 CH 3 CH 2 CH 2 CH 2 OH s - Butyl Alcohol 8.70E - 12 1 2 CH 3 CH 2 CH(CH 3 )OH t - Butyl Alcohol 1.07E - 12 1 2 CH 3 C(CH 3 )(CH 3 )OH Diethyl Ether 1.31E - 11 1 2 CH 3 CH 2 OCH 2 CH 3 gamma - butyrolactone 2.32E - 12 e1 2 CH 2 *CH 2 C(O)OCH 2 * Methacrylic Acid 5.24E - 11 e1 2 CH 2 =C(CH 3 )C(O)OH Methyl Acrylate 2.87E - 11 e1 2 CH 2 =CHC(O)OCH 3 Vinyl Acetate 3.16E - 11 e1 2 CH 2 =CHOC(O)CH 3 Hydroxy Methacrolein 4.30E - 11 e8 8 CH 2 =C(CHO)CH 2 OH Biacetyl 0 51 1 1,4 - dioxane 3.83E - 11 e1 2 CH 2 *CH 2 OCH 2 CH 2 O* Ethyl Acetate 1.60E - 12 20 2 CH 3 CH 2 OC(O)CH 3 Methyl Propionate 1.03E - 12 19 2 CH 3 CH 2 C(O)OCH 3 n - Propyl Formate 2.38E - 12 19 2 CH 3 CH 2 CH 2 OCHO Isopropyl Formate 2.09E - 12 e1 2 CH 3 CH(CH 3 )OCHO isobutyric acid 2.62E - 12 e1 2 CH 3 CH(CH 3 )C(O)OH butanoic acid 4.77E - 12 e1 2 CH 3 CH 2 CH 2 C(O)OH Methoxy Acetone 6.77E - 12 10 8 CH 3 C(O)CH 2 OCH 3 1,3 - Butanediol 3.32E - 11 9 2 CH 3 CH(OH)CH 2 CH 2 OH 1,2 - Butandiol 2.70E - 11 9 2,A CH 3 CH 2 CH(OH)CH 2 OH 1,4 - Butanediol 1.12E - 11 e1 2 HOCH 2 CH 2 CH 2 CH 2 OH 2,3 - Butanediol 2.36E - 11 9 2,A CH 3 CH(OH)CH(CH 3 )OH 1 - Methoxy - 2 - Propanol 2.00E - 11 15 2,A CH 3 OCH 2 CH(CH 3 )OH 2 - Ethoxyethanol 1.87E - 11 16 2 CH 3 CH 2 OCH 2 CH 2 OH 2 - Methoxy - 1 - Propanol 2.53E - 11 e1 2 CH 3 OCH(CH 3 )CH 2 OH 3 - methoxy - 1 -propanol 1.63E - 11 e1 2 CH 3 OCH 2 CH 2 CH 2 OH Propylene Carbonate 6.90E - 13 24 2 CH 3 CH*CH 2 OC(O)O* Methyl Lactate 2.76E - 12 25 2 CH 3 OC(O)CH(CH 3 )OH

### Table B -4 (continued)

220

Com pound kOH [a] Mec Structure [c] k(300) Ref [b] Diethylene Glycol 2.75E - 11 e1 2,A HOCH 2 CH 2 OCH 2 CH 2 OH malic acid 2.28E - 11 e1 2 HOC(O)CH 2 CH(OH)C(O)OH 2 - methyl furan 6.19E - 11 31 7 3 - methyl furan 9.35E - 11 32 7 Cyclopentanone 2.90E - 12 1 8 CH 2 *CH 2 CH 2 C(O)CH 2 * Cyclopentanol 1.10E - 11 1 2 HOCH*CH 2 CH 2 CH 2 CH 2 * Alpha - Methyltetrahydrofuran 2.20E - 11 12 2 CH 3 CH*CH 2 CH 2 CH 2 O* Tetrahydropyran 1.38E - 11 10 2 CH 2 *CH 2 CH 2 OCH 2 CH 2 * 2 - Methyl - 3 - Butene - 2 - ol 6.26E - 11 30 2 CH 2 =CHC(C H 3 )(CH 3 )OH 2,2 - Dimethylpropanal (pivaldehyde) 2.78E - 11 1 2 CH 3 C(CH 3 )(CH 3 )CHO 3 - Methylbutanal (Isovaleraldehyde) 2.70E - 11 1 2 CH 3 CH(CH 3 )CH 2 CHO Pentanal (Valeraldehyde) 2.78E - 11 1 2 CH 3 CH 2 CH 2 CH 2 CHO 2 - Pentanone 4.40E - 12 1 8 CH 3 CH 2 CH 2 C(O)CH 3 3 - Pentanone 2 .00E - 12 1 8 CH 3 CH 2 C(O)CH 2 CH 3 Methyl Isopropyl Ketone 3.01E - 12 1 8 CH 3 C(O)CH(CH 3 )CH 3 2 - Pentanol 1.20E - 11 1 2 CH 3 CH 2 CH 2 CH(CH 3 )OH 3 - Pentanol 1.30E - 11 1 2 CH 3 CH 2 CH(OH)CH 2 CH 3 Pentyl Alcohol 1.10E - 11 1 2 CH 3 CH 2 CH 2 CH 2 CH 2 OH isoamyl alcohol (3 - methyl - 1 - butanol ) 1.30E - 11 1 2 CH 3 CH(CH 3 )CH 2 CH 2 OH 2 - methyl - 1 -butanol 8.61E - 12 e1 2 CH 3 CH 2 CH(CH 3 )CH 2 OH Ethyl Isopropyl Ether 2.44E - 11 e1 2 CH 3 CH 2 OCH(CH 3 )CH 3 Methyl n - Butyl Ether 1.48E - 11 6 2 CH 3 CH 2 CH 2 CH 2 OCH 3 Methyl t - Butyl Ether 2.95E - 12 1 2 CH 3 OC(CH 3 )(CH 3 )CH 3 Ethyl Acrylate 3.01E - 11 e1 2 CH 2 =CHC(O)OCH 2 CH 3 Methyl Methacrylate 5.25E - 11 e1 2 CH 2 =C(CH 3 )C(O)OCH 3 Glutaraldehyde 4.16E - 11 e1 2 HCOCH 2 CH 2 CH 2 CHO 2,4 -pentanedione 7.41E - 13 e1 8 CH 3 C(O)CH 2 C(O)CH 3 tetrahydro - 2 - furanmethanol 2.77E - 11 e1 2 HOCH 2 CH*CH 2 CH 2 CH 2 O* Ethyl Propionate 2.14E - 12 19 2 CH 3 CH 2 C(O)OCH 2 CH 3 Isopropyl Acetate 3.40E - 12 20 2 CH 3 C(O)OCH(CH 3 )CH 3 Methyl Butyrate 3.04E - 12 19 2 CH 3 CH 2 CH 2 C(O)OCH 3 Methyl Isobutyrate 1.73E - 12 21 2 CH 3 OC(O)CH(CH 3 )CH 3 n - Butyl Formate 3.12E - 12 19 2 CH 3 CH 2 CH 2 CH 2 OCHO Propyl Acetate 3.40E - 12 20 2 CH 3 CH 2 CH 2 OC(O)CH 3 3 - Methylbutanoic acid 8.81E - 12 e1 2 CH 3 CH(CH 3 )CH 2 C(O)OH 2,2 - Dimethoxy Propane 2.65E - 12 e1 2 CH 3 OC(CH 3 )(CH 3 )OCH 3 1 - Ethoxy - 2 - Propanol 2.62E - 11 e1 2 CH 3 CH 2 OCH 2 CH(CH 3 )OH 2 - Propoxyethanol 2.47E - 11 e1 2,A CH 3 CH 2 CH 2 OCH 2 CH 2 OH 3 - Ethoxy - 1 - Propanol 2.20E - 11 10 2 CH 3 CH 2 OCH 2 CH 2 CH 2 OH 3 - Methoxy - 1 - Butanol 2.36E - 11 10 2 CH 3 OCH(CH 3 )CH 2 CH 2 OH 2 - Methoxyethyl Acetate 1.26E - 11 e1 2 CH 3 C(O)OCH 2 CH 2 OCH 3 Ethyl Lactate 3.91E - 12 25 2 CH 3 CH 2 OC(O)CH(CH 3 )OH Methyl Isopropyl Carbonate 2.55E - 12 26 2 CH 3 OC(O)OCH(CH 3 )CH 3 2 - (2 - Methoxyethoxy) Ethanol 3.41E - 11 e1 2,A CH 3 OCH 2 CH 2 OCH 2 CH 2 OH pentaerythritol 1.68E - 11 e1 2,A HOCH 2 C(CH 2 OH)(CH 2 OH)CH 2 OH 2,5 - dimethyl furan 1.32E - 10 31 7

### Table B -4 (continued)

221

Com pound kOH [a] Mec Structure [c] k(300) Ref [b] Cyclohexanone 6.40E - 12 1 9 CH 2 *CH 2 CH 2 C(O)CH 2 CH 2 * Cyclohexanol 1.90E - 11 1 2,A HOCH*CH 2 CH 2 CH 2 CH 2 CH 2 * Hexanal 3.00E - 11 1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CHO 4 - Methyl - 2 - Pentanone 1.27E - 11 1 8 CH 3 C(O)CH 2 CH(CH 3 )CH 3 Methyl n - Butyl Ketone 9.10E - 12 1 8 CH 3 CH 2 CH 2 CH 2 C(O)CH 3 Methyl t - Butyl Ketone 1.20E - 12 1 8 CH 3 C(O)C(CH 3 )(CH 3 )CH 3 1 - Hexanol 1. 50E - 11 1 2,A CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 OH 2 - Hexanol 1.20E - 11 1 2,A CH 3 CH 2 CH 2 CH 2 CH(CH 3 )OH 4 - methyl - 2 -pentanol (methyl isobutyl carbinol) 1.28E - 11 e1 2,A CH 3 CH(CH 3 )CH 2 CH(CH 3 )OH Di n - Propyl Ether 1.85E - 11 6 2 CH 3 CH 2 CH 2 OCH 2 CH 2 CH 3 Ethyl n - Butyl Ether 2.13E - 11 6 2 C H 3 CH 2 CH 2 CH 2 OCH 2 CH 3 Ethyl t - Butyl Ether 8.68E - 12 1 2 CH 3 CH 2 OC(CH 3 )(CH 3 )CH 3 Methyl t - Amyl Ether 6.06E - 12 1 2 CH 3 CH 2 C(CH 3 )(CH 3 )OCH 3 diisopropyl ether 3.28E - 11 e1 2 CH 3 CH(CH 3 )OCH(CH 3 )CH 3 Ethyl Methacrylate 5.39E - 11 e1 2 CH 2 =C(CH 3 )C(O)OCH 2 CH 3 Ethyl Butyrate 4.94E - 12 19 2 CH 3 CH 2 CH 2 C(O)OCH 2 CH 3 Isobutyl Acetate 4.61E - 12 e1 2 CH 3 C(O)OCH 2 CH(CH 3 )CH 3 Methyl Pivalate 1.20E - 12 22 2 CH 3 OC(O)C(CH 3 )(CH 3 )CH 3 n - Butyl Acetate 4.20E - 12 20 2 CH 3 CH 2 CH 2 CH 2 OC(O)CH 3 n - Propyl Propionate 4.02E - 12 19 2 CH 3 CH 2 CH 2 OC(O)CH 2 CH 3 s - Butyl Acetate 5.50E - 12 20 2 CH 3 CH 2 CH(CH 3 )OC(O)CH 3 t - Butyl Acetate 4.25E - 13 23 2 CH 3 C(O)OC(CH 3 )(CH 3 )CH 3 Diacetone Alcohol 1.49E - 12 e1 9 CH 3 C(O)CH 2 C(CH 3 )(CH 3 )OH methyl pentanoate; methyl valerate 3.33E - 12 e1 2 CH 3 CH 2 CH 2 CH 2 C(O)OCH 3 1,2 - Dihydroxy Hexane 1. 87E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 CH(OH)CH 2 OH 2 - Methyl - 2,4 - Pentanediol 2.77E - 11 9 2 CH 3 CH(OH)CH 2 C(CH 3 )(CH 3 )OH ethylene glycol diethyl ether; 1,2 - diethoxyethane 3.51E - 11 e1 2 CH 3 CH 2 OCH 2 CH 2 OCH 2 CH 3 acetal (1,1 - diethoxyethane) 1.49E - 10 e1 2 CH 3 CH 2 OCH(CH 3 )OCH 2 CH 3 1 - Propoxy - 2 - Propanol (Propylene glycol n -propyl ether) 2.91E - 11 e1 2,A CH 3 CH 2 CH 2 OCH 2 CH(CH 3 )OH 2 - Butoxyethanol 2.57E - 11 17 2 CH 3 CH 2 CH 2 CH 2 OCH 2 CH 2 OH 3 methoxy - 3 methyl - Butanol 1.64E - 11 54 23 CH 3 OC(CH 3 )(CH 3 )CH 2 CH 2 OH n -propoxypropanol 2.61E - 11 e1 2 CH 3 CH 2 CH 2 OCH 2 CH 2 CH 2 OH hydroxypropyl acrylate 3.59E - 11 e1 2 CH 2 =CHC(O)OCH 2 CH 2 CH 2 OH 1 - Methoxy - 2 - Propyl Acetate 1.44E - 11 7 2 CH 3 C(O)OCH(CH 3 )CH 2 OCH 3 2 - Ethoxyethyl Acetate 1.94E - 11 e1 2 CH 3 CH 2 OCH 2 CH 2 OC(O)CH 3 2 - Methyoxy - 1 -propyl Acetate 2.30E - 11 e1 2 CH 3 C(O)OCH 2 CH(CH 3 )OCH 3 methoxypropanol acetate 1.40E - 11 e1 2 CH 3 C(O)OCH 2 CH 2 CH 2 OCH 3 2 - (2 - Ethoxyethoxy) Ethanol 5.08E - 11 18 2 CH 3 CH 2 OCH 2 CH 2 OCH 2 CH 2 OH Dipropylene Glycol Isomer (1 - [2 -hydroxypropyl] - 2 - propanol) 3.64E - 11 e1 2,A CH 3 CH(OH)CH 2 OCH 2 CH(CH 3 )OH Dimethyl Succinate 1 .50E - 12 27 2 CH 3 OC(O)CH 2 CH 2 C(O)OCH 3 Ethylene Glycol Diacetate 3.78E - 12 e1 2 CH 3 C(O)OCH 2 CH 2 OC(O)CH 3 adipic acid 1.09E - 11 e1 2 HOC(O)CH 2 CH 2 CH 2 CH 2 C(O)OH

### Table B -4 (continued)

222

Com pound kOH [a] Mec Structure [c] k(300) Ref [b] triethylene glycol 4.67E - 11 e1 2 HOCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OH benzaldehyde 1.20E - 11 1 1 o - cresol 4.03E - 1 1 5 1 Benzyl alcohol 2.29E - 11 34 10 Methoxybenzene; Anisole 1.73E - 11 32 11 Heptanal 3.00E - 11 1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CHO 2 - methyl -hexanal 2.54E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH(CH 3 )CHO 2 - Heptanone 1.10E - 11 1 8 CH 3 CH 2 CH 2 CH 2 CH 2 C(O)CH 3 2 - Methyl - 3 - Hexanone 7.21E - 12 e1 8 CH 3 CH 2 CH 2 C(O)CH(CH 3 )CH 3 Di - Isopropyl Ketone 5.00E - 12 1 8 CH 3 CH(CH 3 )C(O)CH(CH 3 )CH 3 5 - Methyl - 2 - Hexanone 1.16E - 11 1 8,A CH 3 C(O)CH 2 CH 2 CH(CH 3 )CH 3 3 - Methyl - 2 - Hexanone 8.23E - 12 e1 8 CH 3 CH 2 CH 2 CH(CH 3 )C(O)CH 3 1 - Heptanol 1.40E - 11 1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 OH dimethylpentanol (2,3 - dimethyl - 1 -pentanol) 1.17E - 11 e1 2 CH 3 CH 2 CH(CH 3 )CH(CH 3 )CH 2 OH 4,4 - Dimethyl - 3 - oxahexane 9.63E - 12 e1 2 CH 3 CH 2 OC(CH 3 )(CH 3 )CH 2 CH 3 n -butyl acrylate 3.30E - 11 e1 2 CH 2 =CHC(O)OCH 2 CH 2 CH 2 CH 3 isobutyl acrylate 3.30E - 11 e1 2 CH 2 =CHC(O)OCH 2 C H(CH 3 )CH 3 Butyl Propionate 5.06E - 12 e1 2 CH 3 CH 2 CH 2 CH 2 OC(O)CH 2 CH 3 Amyl Acetate 6.05E - 12 e1 2,A CH 3 CH 2 CH 2 CH 2 CH 2 OC(O)CH 3 n - Propyl Butyrate 7.41E - 12 19 2 CH 3 CH 2 CH 2 C(O)OCH 2 CH 2 CH 3 isoamyl acetate (3 - methylbutyl acetate) 6.03E - 12 e1 2 CH 3 C(O)OCH 2 CH 2 CH(CH 3 )CH 3 2 - methyl - 1 -butyl acetate 6.31E - 12 e1 2 CH 3 CH 2 CH(CH 3 )CH 2 OC(O)CH 3 methyl hexanoate 4.75E - 12 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 C(O)OCH 3 1 - tert - Butoxy - 2 - Propanol 1.87E - 11 e1 2,A CH 3 CH(OH)CH 2 OC(CH 3 )(CH 3 )CH 3 2 - tert - Butoxy - 1 - Propanol 2.46E - 11 e1 2 CH 3 CH(CH 2 OH)OC(CH 3 )(CH 3 ) CH 3 n - Butoxy - 2 - Propanol (Propylene Glycol n - Butyl Ether) 3.76E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 OCH 2 CH(CH 3 )OH Ethyl 3 - Ethoxy Propionate 1.96E - 11 e1 2,A CH 3 CH 2 OCH 2 CH 2 C(O)OCH 2 CH 3 Diisopropyl Carbonate 6.88E - 12 e1 2 CH 3 CH(CH 3 )OC(O)OCH(CH 3 )CH 3 2 - (2 - Propoxyethoxy) ethanol 4.38E - 11 e1 2 CH 3 CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OH Dipropylene Glycol Methyl Ether isomer (1 - methoxy - 2 - [2 - hydroxypropoxy] -propane) 4.88E - 11 e1 2,A CH 3 OCH 2 CH(CH 3 )OCH 2 CH(CH 3 )OH Dipropylene Glycol Methyl Ether isomer (2 - [2 - methoxypropoxy] - 1 -propanol) 5.48E - 11 e1 2, A CH 3 OCH(CH 3 )CH 2 OCH(CH 3 )CH 2 OH 1,2 - Propylene glycol diacetate 5.91E - 12 e1 2 CH 3 C(O)OCH 2 CH(CH 3 )OC(O)CH 3 Dimethyl Glutarate 3.50E - 12 27 2,A CH 3 OC(O)CH 2 CH 2 CH 2 C(O)OCH 3 2 - [2 - (2 - Methoxyethoxy) ethoxy] ethanol 5.32E - 11 e1 2 CH 3 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OH 2 - Butyl Tetrahydrofuran 2.76E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH*CH 2 CH 2 CH 2 O* Octanal 2.71E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CHO 2 - Octanone 1.10E - 11 1 8 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 C(O)CH 3 1 - Octanol 1.40E - 11 1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 OH 2 - Ethyl - 1 - Hexanol 1.33E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH( CH 2 CH 3 )CH 2 OH 2 - Octanol 2.52E - 11 7 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )OH

### Table B -4 (continued)

223

Com pound kOH [a] Mec Structure [c] k(300) Ref [b] 3 - Octanol 3.14E - 11 7 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH(OH)CH 2 CH 3 4 - Octanol 2.87E - 11 7 2,A CH 3 CH 2 CH 2 CH 2 CH(OH)CH 2 CH 2 CH 3 5 - methyl - 1 - heptanol 1.29E - 11 e1 2,A CH 3 CH 2 CH(CH 3 )CH 2 CH 2 CH 2 CH 2 OH Di - Isobutyl Ether 2 .60E - 11 13 2 CH 3 CH(CH 3 )CH 2 OCH 2 CH(CH 3 )CH 3 Di - n -butyl Ether 2.88E - 11 6 2 CH 3 CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 CH 3 2 - Phenoxyethanol; Ethylene glycol phenyl ether 2.99E - 11 e9 11 Butyl Methacrylate 5.68E - 11 e1 2 CH 2 =C(CH 3 )C(O)OCH 2 CH 2 CH 2 CH 3 Isobutyl Methacrylate 5.68E - 11 e1 2 CH 2 =C(CH 3 )C(O)OCH 2 CH(CH 3 )CH 3 2,3 - Dimethylbutyl Acetate 7.71E - 12 e1 2 CH 3 C(O)OCH 2 CH(CH 3 )CH(CH 3 )CH 3 2 - Methylpentyl Acetate 7.73E - 12 e1 2 CH 3 CH 2 CH 2 CH(CH 3 )CH 2 OC(O)CH 3 3 - Methylpentyl Acetate 7.73E - 12 e1 2,A CH 3 CH 2 CH(CH 3 )CH 2 CH 2 OC(O)CH 3 4 - Methylpentyl Ac etate 7.45E - 12 e1 2 CH 3 C(O)OCH 2 CH 2 CH 2 CH(CH 3 )CH 3 Isobutyl Isobutyrate 5.52E - 12 e1 2 CH 3 CH(CH 3 )CH 2 OC(O)CH(CH 3 )CH 3 n - Butyl Butyrate 1.06E - 11 19 2 CH 3 CH 2 CH 2 CH 2 OC(O)CH 2 CH 2 CH 3 n - Hexyl Acetate 7.47E - 12 e1 2,A CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 OC(O)CH 3 methyl amyl acetate (4 - methyl - 2 -pentanol acetate) 8.16E - 12 e1 2 CH 3 C(O)OCH(CH 3 )CH 2 CH(CH 3 )CH 3 n -pentyl propionate 6.48E - 12 e1 2,A CH 3 CH 2 CH 2 CH 2 CH 2 OC(O)CH 2 CH 3 2 - Ethyl Hexanoic Acid 1.33E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH(CH 2 CH 3 )C(O)OH methyl heptanoate 6.17E - 12 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 C(O)O CH 3 2 - Ethyl - 1,3 -hexanediol 2.22E - 11 e1 2,A CH 3 CH 2 CH 2 CH(OH)CH(CH 2 CH 3 )CH 2 OH 2 - Hexyloxyethanol 2.89E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 OCH 2 CH 2 OH 2,2,4 - Trimethyl - 1,3 - Pentanediol 1.76E - 11 e1 2 CH 3 CH(CH 3 )CH(OH)C(CH 3 )(CH 3 )CH 2 OH Phthalic Anhydride 4.00E - 12 e10 11 2 - Butoxyethyl Acetate 2.38E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 OCH 2 CH 2 OC(O)CH 3 2 - methoxy - 1 - (2 - methoxy - 1 - methylethoxy) -propane 6.13E - 11 e1 2,A CH 3 OCH 2 CH(CH 3 )OCH 2 CH(CH 3 )OCH 3 2 - (2 - Butoxyethoxy) - Ethanol 7.44E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OH dipropylene glycol ethyl e ther 6.16E - 11 e1 2 CH 3 CH 2 OCH(CH 3 )CH 2 OCH(CH 3 )CH 2 OH Dimethyl Adipate 8.80E - 12 27 2,A CH 3 OC(O)CH 2 CH 2 CH 2 CH 2 C(O)OCH 3 2 - (2 - Ethoxyethoxy) ethyl acetate 3.86E - 11 e1 2,A CH 3 CH 2 OCH 2 CH 2 OCH 2 CH 2 OC(O)CH 3 2 - [2 - (2 - Ethoxyethoxy) ethoxy] Ethanol 6.00E - 11 e1 2 CH 3 CH 2 OCH 2 C H 2 OCH 2 CH 2 OCH 2 CH 2 OH tetraethylene glycol 6.58E - 11 e1 2 HOCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OH 2 -propyl cyclohexanone 1.70E - 11 e1 9,A CH 3 CH 2 CH 2 CH*CH 2 CH 2 C(O)CH 2 CH 2 * 4 -propyl cyclohexanone 1.92E - 11 e1 9 CH 3 CH 2 CH 2 CH*CH 2 CH 2 CH 2 CH 2 CO* 1 -nonene - 4 - one 4.04E - 11 e1 9 CH 2 =CHCH 2 C(O)CH 2 CH 2 CH 2 CH 2 CH 3 trimethylcyclohexanol 2.25E - 11 e1 2,A CH 3 CH*CH 2 CH 2 CH(OH)CH(CH 3 )CH*CH 3 2 -Nonanone 1.20E - 11 1 9 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 C(O)CH 3 Di - isobutyl ketone (2,6 - dimethyl - 4 - heptanone) 2.60E - 11 1 9 CH 3 CH(CH 3 )CH 2 C(O)CH 2 CH(CH 3 )CH 3 dimethylheptanol (2,6 - dimethyl - 2 - heptanol) 7.50E - 12 e1 2 CH 3 CH(CH 3 )CH 2 CH 2 CH 2 C(CH 3 )(CH 3 )OH 2,6 - dimethyl - 4 - heptanol 1.86E - 11 e1 2,A CH 3 CH(CH 3 )CH 2 CH(OH)CH 2 CH(CH 3 )CH 3 2,4 - Dimethylpentyl Acetate 9.13E - 12 e1 2 CH 3 C(O)OCH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 3 2 - Methylhexyl Acetate 9.15E - 12 e1 2,A CH 3 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 OC(O)CH 3

### Table B -4 (continued)

224

Com pound kOH [a] Mec Structure [c] k(300) Ref [b] 3 - Ethylpentyl Acetate 9.56E - 12 e1 2 CH 3 CH 2 CH(CH 2 CH 3 )CH 2 CH 2 OC(O)CH 3 3 - Methylhexyl Acetate 9.15E - 12 e1 2 CH 3 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 OC(O)CH 3 4 - Methylhexyl Acetate 9.15E - 12 e1 2 CH 3 CH 2 CH(CH 3 )CH 2 CH 2 CH 2 OC(O)CH 3 5 - Methylhexyl Acetate 8.87E - 12 e1 2,A CH 3 C(O)OCH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 3 Isoamyl Isobutyrate 6.94E - 12 e1 2 CH 3 CH(CH 3 )CH 2 CH 2 OC(O)CH(CH 3 )CH 3 n - Heptyl Acetate 8.89E - 12 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 OC(O)CH 3 methyl octanoate 7.59E - 12 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 C(O)OCH 3 1 - (buto xyethoxy) - 2 -propanol 4.97E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 OCH 2 CH 2 OCH 2 CH(CH 3 )OH Dipropylene glycol n -propyl ether isomer #1 5.86E - 11 e1 2,A CH 3 CH 2 CH 2 OCH 2 CH(CH 3 )OCH 2 CH(CH 3 )OH Dipropylene glycol methyl ether acetate isomer #1 4.42E - 11 e1 2,A CH 3 C(O)OCH(CH 3 )CH 2 OCH(CH 3 )CH 2 OCH 3 Dipropylene glycol methyl ether acetate isomer #2 4.42E - 11 e1 2,A CH 3 C(O)OCH(CH 3 )CH 2 OCH 2 CH(CH 3 )OCH 3 2 - [2 - (2 - Propoxyethoxy) ethoxy] Ethanol 6.30E - 11 e1 2 CH 3 CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OH tripropylene glycol 6.59E - 11 e1 2 CH 3 CH(OH)CH 2 OCH 2 CH(CH 3 ) OCH 2 CH(CH 3 )OH 2,5,8,11 - Tetraoxatridecan- 13 - ol 7.24E - 11 e1 2 CH 3 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OH glyceryl triacetate 8.49E - 12 e1 2 CH 3 C(O)OCH 2 CH(CH 2 OC(O)CH 3 )OC(O)CH 3 Camphor 4.60E - 12 e1 9 CH 3 C*1(CH 3 )CH* 2CH 2 CH 2 C* 1(CH 3 )C(O)CH 2 *2 a - terpineol 9.51E - 11 e1 2 CH 3 C*=CHCH 2 CH(CH 2 CH 2 *)C(CH 3 )(CH 3 )OH Citronellol (3,7 - dimethy - 6 - octen - 1 - ol) 9.87E - 11 e1 2 CH 3 C(CH 3 )=CHCH 2 CH 2 CH(CH 3 )CH 2 CH 2 OH Hydroxycitronellal 2.80E - 11 e1 2 CH 3 CH(CH 2 CHO)CH 2 CH 2 CH 2 C(CH 3 )(CH 3 )OH menthol 2.40E - 11 e1 2 CH 3 CH(CH 3 )CH*CH 2 CH 2 CH(CH 3 )CH 2 CH*OH Linal ool 1.22E - 10 e1 3 CH 2 =CHC(CH 3 )(OH)CH 2 CH 2 CH=C(CH 3 )CH 3 2 - Decanone 1.30E - 11 1 9,A CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 C(O)CH 3 8 - Methyl - 1 -Nonanol (Isodecyl Alcohol) 1.54E - 11 e1 2 CH 3 CH(CH 3 )CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 OH 1 - decanol 1.55E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 OH 3,7 - dimethyl - 1 - octanol 1.57E - 11 e1 2 CH 3 CH(CH 3 )CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 OH Di - n - Pentyl Ether 3.47E - 11 14 2,A CH 3 CH 2 CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 CH 2 CH 3 1,2 - Diacetyl benzene 4.00E - 12 35 11 2,4 - Dimethylhexyl Acetate 1.08E - 11 e1 2,A CH 3 CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 2 OC(O)CH 3 2 - Ethyl - Hexyl Acetate 1.10E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 CH(CH 2 CH 3 )CH 2 OC(O)CH 3 3,4 - Dimethylhexyl Acetate 1.08E - 11 e1 2,A CH 3 CH 2 CH(CH 3 )CH(CH 3 )CH 2 CH 2 OC(O)CH 3 3,5 - Dimethylhexyl Acetate 1.06E - 11 e1 2 CH 3 C(O)OCH 2 CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 3 3 - Ethylhexyl Acetate 1.10E - 11 e1 2 CH 3 CH 2 CH 2 CH(CH 2 CH 3 )CH 2 CH 2 OC(O)CH 3 3 - Methylheptyl Aceate 1.06E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 OC(O)CH 3 4,5 - Dimethylhexyl Acetate 1.06E - 11 e1 2,A CH 3 C(O)OCH 2 CH 2 CH 2 CH(CH 3 )CH(CH 3 )CH 3 4 - Methylheptyl Acetate 1.06E - 11 e1 2 CH 3 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH 2 OC (O)CH 3 5 - Methylheptyl Aceate 1.06E - 11 e1 2,A CH 3 CH 2 CH(CH 3 )CH 2 CH 2 CH 2 CH 2 OC(O)CH 3 n - Octyl Acetate 1.03E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 OC(O)CH 3 Geraniol 1.80E - 10 e1 3 CH 3 C(CH 3 )=CHCH 2 CH 2 C(CH 3 )=CHCH 2 OH methyl nonanoate 9.01E - 12 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 C(O)OCH 3 2 - (2 - Ethylhexyloxy) Ethanol 3.24E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 CH(CH 2 CH 3 )CH 2 OCH 2 CH 2 OH 2 - (2 - Hexyloxyethoxy) Ethanol 4.81E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OH

### Table B -4 (continued)

225

Com pound kOH [a] Mec Structure [c] k(300) Ref [b] glycol ether dpnb {1 - (2 - butoxy - 1 - me thylethoxy) - 2 - propanol} 6.00E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 OCH 2 CH(CH 3 )OCH 2 CH(CH 3 )OH 2 - (2 - Butoxyethoxy) ethyl acetate 4.29E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OC(O)CH 3 2 - [2 - (2 - Butoxyethoxy) ethoxy] Ethanol 6.44E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OH Tripropylene Glycol Monomethyl Ether 7.83E - 11 e1 2 CH 3 O CH 2 CH(CH 3 )OCH 2 CH(CH 3 )OCH 2 CH(CH 3 )OH 2 - Ethyl - Hexyl Acrylate 3.94E - 11 e1 2 CH 2 =CHC(O)OCH 2 CH(CH 2 CH 3 )CH 2 CH 2 CH 2 CH 3 2,3,5 - Teimethylhexyl Acetate 1.22E - 11 e1 2,A CH 3 C(O)OCH 2 CH(CH 3 )CH(CH 3 )CH 2 CH(CH 3 )CH 3 2,3 - Dimethylheptyl Acetate 1.23E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH(CH 3 ) CH(CH 3 )CH 2 OC(O)CH 3 2,4 - Dimethylheptyl Acetate 1.23E - 11 e1 2,A CH 3 CH 2 CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 2 OC(O)CH 3 2,5 - Dimethylheptyl Acetate 1.23E - 11 e1 2 CH 3 CH 2 CH(CH 3 )CH 2 CH 2 CH(CH 3 )CH 2 OC(O)CH 3 2 - Methyloctyl Acetate 1.20E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 OC(O)CH 3 3,5 - Dimethylheptyl Acetate 1.23E - 11 e1 2,A CH 3 CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 2 CH 2 OC(O)CH 3 3,6 - Dimethylheptyl Acetate 1.20E - 11 e1 2 CH 3 C(O)OCH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH(CH 3 )CH 3 3 - Ethylheptyl Acetate 1.24E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH(CH 2 CH 3 )CH 2 CH 2 OC(O)CH 3 4,5 - Dimethylheptyl Acetate 1.23E - 11 e1 2,A CH 3 CH 2 CH(CH 3 )CH(CH 3 )CH 2 CH 2 CH 2 OC(O)CH 3 4,6 - Dimethylheptyl Acetate 1.20E - 11 e1 2 CH 3 C(O)OCH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 3 4 - Methyloctyl Acetate 1.20E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH 2 OC(O)CH 3 5 - Methyloctyl Acetate 1.20E - 11 e1 2,A CH 3 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH 2 CH 2 OC(O)CH 3 n -Nonyl Acetate 1.17E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 OC(O)CH 3 methyl decanoate 1.04E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 C(O)OCH 3 2,6,8 - trimethyl - 4 - nonanone; Isobutyl heptyl ketone 2.31E - 11 e1 9 CH 3 CH(CH 3 )CH 2 C(O)C H 2 CH(CH 3 )CH 2 CH(CH 3 )CH 3 Trimethylnonanolthreoerythro; 2,6,8 - Trimethyl - 4 - nonanol 2.32E - 11 e1 2,A CH 3 CH(CH 3 )CH 2 CH(CH 3 )CH 2 CH(OH)CH 2 CH(CH 3 )CH 3 3,6 - Dimethyloctyl Acetate 1.37E - 11 e1 2 CH 3 CH 2 CH(CH 3 )CH 2 CH 2 CH(CH 3 )CH 2 CH 2 OC(O)CH 3 3 - Isopropylheptyl Acetate 1.38E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 CH(CH 2 CH 2 OC(O)CH 3 )CH(CH 3 )CH 3 4,6 - Dimethyloctyl Acetate 1.37E - 11 e1 2 CH 3 CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 2 CH 2 CH 2 OC(O)CH 3 methyl undecanoate 1.19E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 C(O)OCH 3 1 - Hydroxy - 2,2,4 - Trimethylpentyl - 3 - Isobutyrate 1.29E - 11 e1 2 CH 3 CH(CH 3 )C(O)OCH(CH(CH 3 )CH 3 )C(CH 3 )(CH 3 )CH 2 OH 3 - Hydroxy - 2,2,4 - Trimethylpentyl - 1 - Isobutyrate 1.62E - 11 e1 2,A CH 3 CH(CH 3 )C(O)OCH 2 C(CH 3 )(CH 3 )CH(OH)CH(CH 3 )CH 3 diethylene glycol mono(2 - ethylhexyl) ether 5.16E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH(CH 2 CH 3 )CH 2 OCH 2 CH 2 OC H 2 CH 2 OH Diethyl Phthalate 5.67E - 12 e11 11 Dimethyl Sebacate 9.69E - 12 e1 2 CH 3 OC(O)CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 C(O)OCH 3 diisopropyl adipate 1.04E - 11 e1 2 CH 3 CH(CH 3 )OC(O)CH 2 CH 2 CH 2 CH 2 C(O)OCH(CH 3 )CH 3 3,6,9,12 - Tetraoxahexadecan 1 - ol 8.35E - 11 e1 2,A CH 3 CH 2 CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 O H triethyl citrate 5.91E - 12 e1 2 CH 3 CH 2 OC(O)CH 2 C(OH)(CH 2 C(O)OCH 2 CH 3 )C(O)OCH 2 C H 3 3,5,7 - Trimethyloctyl Acetate 1.51E - 11 e1 2,A CH 3 C(O)OCH 2 CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 3 3 - Ethyl - 6 - Methyloctyl Acetate 1.55E - 11 e1 2,A CH 3 CH 2 C H(CH 3 )CH 2 CH 2 CH(CH 2 CH 3 )CH 2 CH 2 OC(O)CH 3 4,7 - Dimethylnonyl Acetate 1.51E - 11 e1 2,A CH 3 CH 2 CH(CH 3 )CH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH 2 OC(O)CH 3 methyl dodecanoate {methyl laurate} 1.33E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 C(O)OCH 3

### Table B -4 (continued)

226

Com pound kOH [a] Mec Structure [c] k(300) Ref [b] tripropylene glycol n -butyl ether 9.54 E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 OCH 2 CH(CH 3 )OCH 2 CH(CH 3 )OCH(CH 3 )C H 2 OH 2,3,5,7 - Tetramethyloctyl Acetate 1.68E - 11 e1 2 CH 3 C(O)OCH 2 CH(CH 3 )CH(CH 3 )CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 3 3,5,7 - Trimethylnonyl Acetate 1.68E - 11 e1 2,A CH 3 CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 2 CH 2 OC(O) CH 3 3,6,8 - Trimethylnonyl Acetate 1.65E - 11 e1 2,A CH 3 C(O)OCH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH(CH 3 )CH 2 CH(CH 3 ) CH 3 methyl tridecanoate 1.47E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 C(O)OC H 3 2 - ethylhexyl benzoate 1.37E - 11 e12 11 2,4,6,8 - Tetramethylnonyl Acetate 1.82E - 11 e1 2,A CH 3 C(O)OCH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 2 CH( CH 3 )CH 3 3 - Ethyl - 6,7 - Dimethylnonyl Acetate 1.86E - 11 e1 2,A CH 3 CH 2 CH(CH 2 CH 2 OC(O)CH 3 )CH 2 CH 2 CH(CH 3 )CH(CH 3 ) CH 2 CH 3 4,7,9 - Trimethyldecyl Acetate 1.79E - 11 e1 2,A CH 3 C(O)OCH 2 CH 2 CH 2 CH(CH 3 )CH 2 CH 2 CH(CH 3 )CH 2 CH( CH 3 )CH 3 methyl myristate {methyl tetradecanoate} 1.61E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 C(O) OCH 3 methyl cis - 9 -pentadecenoate 7.76E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH=CHCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 C(O)OCH 3 methyl pentadecanoate 2.10E - 11 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 C(O)CH 3 2,3,5,6,8 - Pentaamethylnonyl Acetate 1.99E - 11 e1 2 CH 3 C(O)OCH 2 CH(CH 3 )CH(CH 3 )CH 2 CH(CH 3 )CH(CH 3 )CH 2 CH(CH 3 )CH 3 3,5,7,9 - Tetramethyldecyl Acetate 1.96E - 11 e1 2,A CH 3 C(O)OCH 2 CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 3 5 - Ethyl - 3,6,8 - Trime thylnonyl Acetate 2.00E - 11 e1 2,A CH 3 CH 2 CH(CH 2 CH(CH 3 )CH 2 CH 2 OC(O)CH 3 )CH(CH 3 )CH 2 CH(CH 3 )CH 3 Dibutyl phthalate 8.59E - 12 e11 11 2,2,4 - trimethyl - 1,3 - pentanediol diisobutyrate 1.15E - 11 e1 2 CH 3 CH(CH 3 )C(O)OCH 2 C(CH 3 )(CH 3 )CH(OC(O)CH(CH 3 )C H 3 )CH(CH 3 )CH 3 methyl linolenate; methyl cis,cis,cis - 9,12,15 - octadecatrienoate 2.02E - 10 e1 2 CH 3 CH 2 ^CH=CHvCH 2 ^CH=CHvCH 2 ^CH=CHvCH 2 CH 2 C H 2 CH 2 CH 2 CH 2 CH 2 C(O)OCH 3 methyl linoelate; methyl cis,cis - 9,12 - octadecadienoate 1.42E - 10 e1 2 CH 3 CH 2 CH 2 CH 2 CH 2 ^CH=CHvCH 2 ^CH=CHvCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 C( O)OCH 3 Methylamine 1.97E - 11 38 3,12 CH 3 NH 2 Methyl Chloride 4.48E - 14 6 3 CH 3 Cl Methyl nitrite 1.20E - 13 20 13 nitromethane 1.30E - 13 6 26 Carbon disulfide 2.76E - 12 48 19 Dichloromethane 1.45E - 13 20 3 ClCH 2 Cl Methyl Bromide 4.12E - 14 20 17 Chloroform 1.06E - 13 20 3 ClCH(Cl)Cl methyl iodide 1.03E - 13 29 20 CH 3 I Chloropicrin 0 51 18 Acetylene 7.56E - 13 6 1 Dimethyl Amine 6.52E - 11 38 3,12 CH 3 NHCH 3

### Table B -4 (continued)

227

Com pound kOH [a] Mec Structure [c] k(300) Ref [b] Ethyl Amine 2.58E - 11 38 3,12 CH 3 CH 2NH 2 Ethanolamine 4.41E - 11 e14 3,12 NH 2 CH 2 CH 2 OH Vinyl Chloride 6.90 E - 12 6 3 CH 2 =CHCl Ethyl Chloride 4.18E - 13 6 3 CH 3 CH 2 Cl 1,1 - difluoroethane; HFC - 152a 3.47E - 14 55 28 Methyl isothiocyanate 1.72E - 12 49 19 nitroethane 1.50E - 13 6 27 Dimethyl Sulfoxide 6.20E - 11 20 19 Chloroacetaldehyde 3.10E - 12 47 1 1,1 - Dichloroethene 1.09E - 11 2 3 CH 2 =C(Cl)Cl Trans - 1,2 - Dichloroethene 2.32E - 12 6 3 ClCH=CH^Cl 1,1 - Dichloroethane 2.60E - 13 20 3 CH 3 CH(Cl)Cl 1,2 - Dichloroethane 2.53E - 13 6 3 ClCH 2 CH 2 Cl 1,1,1,2 - tetrafluoroethane; HFC - 134a 4.59E - 15 55 29 Ethyl Bromide 3.08E - 13 20 17 Trichloroethylene 2.34E - 12 6 3 ClCH=C(Cl)Cl 1,1,1 - Trichloroethane 1.24E - 14 20 3 CH 3 C(Cl)(Cl)Cl 1,1,2 - Trichloroethane 2.00E - 13 6 3 ClCH 2 CH(Cl)Cl Perchloroethylene 1.71E - 13 6 3 ClC(Cl)=C(Cl)Cl 1,2 - Dibromoethane 2.27E - 13 6 17 Methyl Acetylene 5.90E - 12 6 2 HC#CCH 3 Acrylonitrile 4.90E - 12 42 14 Trimethyl Amine 4.84E - 11 38 3,12 CH 3 N(CH 3 )CH 3 isopropylamine 3.78E - 11 e14 3,12 CH 3 CH(CH 3 )NH 2 1 - amino - 2 -propanol 4.85E - 11 e1 3,12 CH 3 CH(OH)CH 2NH 2 3 - Chloropropene 3.20E - 11 e1 3 CH 2 =CHCH 2 Cl 1 -nitropropane 1.33E - 12 e1 3 CH 3 CH 2 CH 2NO 2 2 -nitropropane 2.57E - 13 58 27 chloroacetone 0 51 1 trans - 1,3 - dichloropropene 1.44E - 11 45 3 Cl^CH=CH^CH 2 Cl cis - 1,3 - dichloropropene 8.45E - 12 45 3 Cl^CH=CHvCH 2 Cl 1,2 - Dichloropropane 4.50E - 13 e1 3 CH 3 CH(Cl)CH 2 Cl trans 1,3,3,3 - tetrafluoropropene 9.25E - 13 52 21 2,3,3,3 - tetrafluoropropene 1.05E - 12 53 22 n - Propyl Bromide 1.18E - 12 44 17 1,1,1,3,3 -pentafluoropropane 7.24E - 15 55 30 3,3 - dichloro - 1,1,1,2,2 - pentafluoropropane;HCFC 225ca 2.57E - 14 55 31 1,3 - dichloro - 1,1,2,2,3 - pentafluo ropropane;HCFC 225cb 9.11E - 15 55 31 1,3 -butadiyne 2.13E - 11 e7 36 2 - Butyne 2.72E - 11 6 2 CH 3 C#CCH 3 Ethyl Acetylene 8.00E - 12 6 2 HC#CCH 2 CH 3 t -butyl amine 1.18E - 11 39 3,12 CH 3 C(CH 3 )(CH 3 )NH 2

### Table B -4 (continued)

228

Com pound kOH [a] Mec Structure [c] k(300) Ref [b] mo rpholine 1.12E - 10 e1 2 CH 2 *CH 2 OCH 2 CH 2NH* ethyl methyl ketone oxime 5.14E - 12 e15 15 CH 3 CH 2 C(CH 3 )=NOH Dimethylaminoethanol 6.85E - 11 40 3,12 CH 3 N(CH 3 )CH 2 CH 2 OH 2 - amino - 1 -butanol 5.32E - 11 e14 3,12 CH 3 CH 2 CH(NH 2 )CH 2 OH 2 - Amino - 2 - Methyl - 1 - Propanol 2.80E - 11 41 3,12 CH 3 C(CH 3 )(NH 2 )CH 2 OH 1 - Chlorobutane 2.19E - 12 e1 3 CH 3 CH 2 C H 2 CH 2 Cl Diethanol Amine 1.01E - 10 e14 3,12 HOCH 2 CH 2NHCH 2 CH 2 OH 2 - (Cl - me thyl) - 3 - Cl - Propene 3.16E - 11 2 3 CH 2 =C(CH 2 Cl)CH 2 Cl n - Butyl Bromide 2.46E - 12 44 17 1,1,1,3,3 -pentafluorobutane; HFC - 365mfc 7.12E - 15 55 32 2 - amino - 2 - ethyl - 1,3 - propanediol 2.70E - 11 e1 3,12 CH 3 CH 2 C(NH 2 )(CH 2 OH)CH 2 OH N - Methyl - 2 - Py

rrolidone 2.15E - 11 43 16 methyl nonafluorobutyl ether 1.15E - 12 e1 3 CH 3 OC(F)(F)C(F)(F)C(F)(F)C(F)(F)F methoxy -perfluoro - n -butane 1.20E - 14 57 35 1,1,1,2,2,3,4,5,5,5 - decafluoropentane; HFC - 43 - 10mee 3.50E - 15 55 33 Triethyl Amine 5.57E - 11 e14 3,12 CH 3 CH 2N(CH 2 CH 3 )CH 2 CH 3 Monochlorobenzene 7.70E - 13 20 11 Nitrobenzene 1.41E - 13 5 11 p - Dichlorobenzene 5.55E - 13 e16 11 Triethanolamine 8.04E - 11 e14 3,12 HOCH 2 CH 2N(CH 2 CH 2 OH)CH 2 CH 2 OH Hexamethyldisiloxane 1.38E - 12 2 0 11 Hydroxymethyldisiloxane 1.89E - 12 20 11 Hexafluorobenzene 1.74E - 13 6 11 ethoxy -perfluoro -n -butane 6.40E - 14 56 34 ethoxy -perfluoro - isobutane 7.70E - 14 56 34 ethyl nonafluorobutyl ether 7.97E - 12 e1 3 CH 3 CH 2 OC(F)(F)C(F)(F)C(F)(F)C(F)(F)F m -Nitro toluene 1.24E - 12 5 11 Benzotrifluoride 4.60E - 13 46 11 p - Trifluoromethyl - Cl - Benzene 2.40E - 13 46 11 Para Toluene Isocyanate 5.90E - 12 36 6 D4 Cyclosiloxane 1.00E - 12 20 11 2,4 - Toluene Diisocyanate 7.40E - 12 37 6 Molinate 2.42E - 11 e17 19 Ethyl di - n - Propyl Thiolcarbamate 2.12E - 11 50 19 triisopropanolamine 9.37E - 11 e14 3,12 CH 3 CH(OH)CH 2N(CH 2 CH(CH 3 )OH)CH 2 CH(CH 3 )OH Pebulate 2.26E - 11 e17 19 D5 Cyclosiloxane 1.55E - 12 20 11 thiobencarb 1.87E - 11 e17 19 Methylene Diphenylene Diisocyanate 1.18E - 11 e 13 6 PROD2 Species #1 9.63E - 12 e1 8 CH 3 C(O)CH 2 CH 2 CH 2 OH PROD2 Species #2 1.45E - 11 e1 8 CH 3 C(O)CH 2 CH(CH 3 )CH 2 OH

### Table B -4 (continued)

229

Com pound kOH [a] Mec Structure [c] k(300) Ref [b] PROD2 Species #3 1.52E - 11 e1 8 CH 3 CH 2 C(O)CH 2 CH 2 CH(CH 3 )OH PROD2 Species #4 1.83E - 11 e1 8 CH 3 CH 2 C(O)CH 2 CH 2 CH(OH)CH 2 CH 3 PROD2 Species #5 1.97E - 1 1 e1 8 CH 3 CH 2 CH 2 CH(OH)CH 2 CH 2 C(O)CH 2 CH 3 RNO3 Species #1 1.60E - 12 e1 8 CH 3 CH 2 CH(CH 3 )ONO 2 RNO3 Species #2 1.15E - 11 e1 8 CH 3 CH(OH)CH 2 CH 2 CH 2 ONO 2 RNO3 Species #3 4.70E - 12 e1 8 CH 3 CH 2 CH(CH 3 )CH(CH 3 )ONO 2 RNO3 Species #4 9.89E - 12 e1 8 CH 3 CH 2 CH 2 CH 2 CH 2 CH(ONO 2 )CH 2 O H RNO3 Species #5 5.64E - 12 e1 8 CH 3 CH 2 C(CH 3 )(ONO 2 )CH 2 CH(CH 3 )CH 3 RNO3 Species #6 9.87E - 12 e1 8 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH(ONO 2 )CH 2 CH 3 [a] Rate constant for reaction with OH radicals at 300 o K in units of cm3 molec - 1 s - 1

. See the complete mechanism listing in the electronic version of the report for the temperature dependences, where available. Footnotes for measured rate constants are as follows: 1 As recommended or tabulated by Atkinson and Arey (2003) 2 Atkinson (1997) Recommendation 3 Carter et al (2 000a) 4 298K Rate constant as recommended by C alvert et al (2000). Tem perature dependence estimated from k(T)=A exp(500/T), where A is adjusted to yield the recommended 298K rate constant, based on data for those alkenes for which temperature dependence data are available. 5 As recommended or tabulated by Calvert et al (2002) 6 Rate constant expression recommended by Atkinson (1994) 7 Carter et al (2000b). 8 Aschmann and Atkinson (1998). 9 Bethel et al, (2001). 10 Dagaut et al (1989) 11 Rate constant used i s average of various measurements tabulated by Sidebottom et al (1997). 12 Wallington et al (1990). 13 Bennett and Kerr (1989). 14 Wallington et al (1988a). 15 Average of values of Porter et al (1995) and Aschmann and Atkinson (1998) 16 Rate constant of Da gaut et al (1988a) used. Value of Hartmann et al (1986) is not consistent with cham ber data (Carter et al, 1993) 17 Average of values of Dagaut et al (1988a), Stemmler et al (1996) and Aschmann and Atkinson (1998). 18 Carter et al (1993). 19 Wallington et al (1988b). 20 Rate constant expression recommended by Atkinson (1989). Recommendation not changed in evaluation updates. 21 Wyatt et al. (1999). 22 Wallington et al (2001) 23 Smith et al (1992). Average of values relative to propane and n-butane 24 Carter et al (1996b). 25 Atkinson and Carter (1995). 26 Carter et al (2000c) 27 Carter et al (1997c). 28 Wallington et al (1988c). 29 IUPAC (2006) Recommendation 30 Rudich et al (1995), as recommended by Atkinson (personal communication, 2000). Good agreement with data of Ferronato et al (1998). 31 Bierbach et al (1992) 32 Atkinson et al (1989) 33 Atkinson et al (1983). 34 As tabulated by Atkinson (1989) (Cited reference not available).

### Table B -4 (continued)

230

35 Wang et al (2006). 36 Carter et al (1999a) 37 Becker et al (1988). 38 Average of values tabulated by Carl and Crowley (1998). 39 Koch et al (1996) 40 Average of values of Harris and Pitts (1983) and Anderson and Stephens (1988), as tabulated by Atkinson (1989). 41 Harris and Pitts (1983) 42 Harris et al (1981). Rate constant is pressure dependent and wa s measured at lower than atmospheric pressures, and extrapolated to atmospheric pressure. 43 Aschmann and Atkinson (1999). 44 Donaghy et al. (1993). 45 Tuazon et al (1988). 46 Atkinson et al (1985). 47 Rate constants from Scollard et al (1993) 48 Mechanism is com

plex and depends on pressure, tem perature, and O2 content. Rate constant given is for 1 atm air and 298oK only, and derived from the IUPAC (2006) rate constants recommended for CS2 and HOCS2 (the species assumed to be initially formed in the reaction). See Carter and Malkina (2007). 49 Rate constant from Carter and Malkina (2007). 50 Rate constant from Carter and Malkina (2007). This is somewhat higher than the value determined by Kwok et al (1992), but is used as the basi s for evaluating the mechanism against chamber data. 51 Reaction expected to be slow and is neglected. 52 Søndergaard et al (2007) 53 Nielsen et al (2007) 54 Carter et al (2010) 55 NASA (2006) recommendation. 56 Christensen et al (1998) 57 Wallington et al (1997). Rate constant for mixture of isomers, which couldn't be separated. 58 Liu et al (1990) Footnotes for estimated rate constants are as follows: e1 Estimated using the group - additivity estimation assignments im plemented in the current mechanism generation system. See Carter (2000a) and Table 3 . e2 Assumed to have the same rate constant as the cis isomer. e3 Rate constant estimated using rate constant for ring addition for toluene, derived based on the observed benzaldehyde + belzyl nitrate yields, and estimated rate constants for abstraction reactions for additions at various positions of the mo lecules of the mi xture of alkylbenzenes used to repres ent those with this carbon number. Partial rate constant for reaction at the - CH2 - group next to the aromatic derived from the rate constant for ethylbenzene and the ring addition rate constant for toluene. Partial rate constants for reactions at other pos itions based on standard structure -reactivity methods used in the mechanism generation system. (Carter, 2000a). The compounds used to represent the lumped mo noalkylbenzenes are given with the aromatics mechanism documentation. e4 Rate constant estimated us ing the estimated rate constants for ring addition for the xylene isomers, derived based on the observed tolualdenyde yields and estimated nitrate yields, and based on estimated rate constants for abstraction reactions for additions at various positions of the mo lecules of the mixture of alkylbenzenes used to represent those with this carbon number. Separate ring addition estimates are made for o - , m - , and p - configurations. Partial rate constant for reaction at the - CH2 - or - CH - groups next to the aromatic derived from the rate constants for ethylbenzene or isopropyl benzene, respectively and the ring addition rate constant for toluene. Partial rate constants for reactions at other positions based on standard structure -reactivity methods used in the mechanis m generation system. (Carter, 2000a). T he compounds used to represent the lumped dialkylbenzenes are given in Table 10 . e5 Rate constant estimated using the estimated rate constants for ring addition for the trimethylbenzene isomers, derived based on the observed aromatic aldehyde yields and estimated nitrate yields, and based on estimated rate constants for abstraction reactions for additions at variou s positions of the mo lecules of the mixture of alkylbenzenes used to represent those wi th this carbon number. Separate estimates are made for 1,2,3 (3CnnBEN3), 1,3,4 (4CnnBEN3) and 1,3,5 (5CnnBEN3) substituent configurations, based on the

### Table B -4 (continued)

231 trimethylbenzenes . (Aromatic aldehyde yields for 1,2,3 - trimethylbenzene are not available. The ring addition rate constant for this com pound is estimated to be the same as that for 1,2,4 - trimethylbenzene.) Partial rate constant for reaction at the - CH2 - or - CH - groups next to the aromatic derived from the rate constants for ethylbenzene or isopropyl benzene, respectively, and the ring addition rate constant for toluene. Partial rate constants for reactions at other positions based on standard structure -reactivity methods us ed in the mechanism generation system (Carter, 2000a). T he compounds used to represent the lum ped trialkylbenzenes are given in are given in Table 10 . e6 Average of rate constants for 1 - methyl and 2 - methyl naphthalenes e7 Estimated to have a similar rate constant as 2 -butyne, on the basis of the fact that the rate constant for 1,3 - butadiene is similar to that for the 2 -butenes. This estimate is highly uncertain. e8 Rate constant estimated by Carter and Atkinson (1996). e9 Rate constant for reaction at the aromatic ring assumed to be the same as that for anisole. Rate constant for reaction at the anisole aromatic ring estimated from the total OH rate constant and the rate constant for reaction at me thoxy group estimated using the structure -reactivity estimation methods used in the mechanism generation system (Carter, 2000). Rate constants f or reactions at other positions in this mo lecule also estimated using the structure -reactivity estimation methods used in the mechanism generation system (Carter, 2000). e10 Estimated to have the same rate constant as 1,2 - diacetyl pthallate on the basis of similar substitution around the aromatic ring, and the expectation that for both compound the reaction would be primarily at the aromatic ring. e11 Rate constant for reaction at the aromatic ring assumed to be the same as measured for 1,2 - diacetyl phthalate. Rate constant for reaction at groups of f the aromatic ring estimated using the group - additivity methods incorporated in the mechanism generation system (Carter, 2000). e12 Rate constant for reaction at the aromatic ring estimated to be the same as the total rate constant for acetophenone (Atkinson, 1989), assuming that ring addition is the major reaction for that com pound. The rate constant for reaction at groups off the aromatic ring based on those estimated for 2 - ethyl hexyl acetate, since reaction at the acetate group is estimated to be negligible for that compound. e13 Estimated to have a rate constant that it twice that of pare - toluene isocyanate, based on the structure of the mo lecule (Carter et al, 1999a). e14 Derived from structure -reactivity methods, where group rate constants for reactions at HN, NH2, at groups adjacent to the amino group were derived based on rate constants for the simple amines for which rate constant data are available. e15 The rate constant for addition of OH to the C=N doub le bond is estimated by the rate constant for OH + isobutene x the average of the ratio of the rate constants for CH2=NOH / Ethene and CH3CH=NOH / Propene, with abstractions from the methyl group subtracted off. The CH2=NOH and CH3CH=NOH rate constants are from the tabulation of Atkinson (1989). The rate constants for addition to the methyl groups were estimated using the structure -reactivity methods incorporated in the mechanism generation system. e16 Average of values for o - , m - and p - isomers tabulated b y Atkinson (1989). e17 Rate constant as estimated by Carter and Malkina (2007). e18 Assumed to have the same rate constant as acetaldehyde. [b] Codes for types of mechanisms that were derived are as follows. See the com plete mechanism listing Table B - 2 of this report for the mechanisms. 1 Reactions in the base mechanism or the base chlorine mechanism. See Table A - 2 or Ta ble A - 5 for documentation. 2 Mechanism derived using the mechanism generation s ystem. Rate constants and branching ratios may have been assigned based on available data or estimates for individual cases. See documentation of the mechanism generation system. In most cases these mechanisms should be the same as or similar to those in S APRC - 99. 3 Mechanism derived using the mechanism generation system using enhanced capabilities and additional assignments that were developed for this project. Rate constants and branching ratios may have been assigned based on available data or estimates for individual cases. See documentation of the mechanism generation system. Note that these mechanisms could not be generated using the SAPRC - 99 version of the mechanism generation system.

### Table B -4 (continued)

232

4 The styrene mechanism is based on that derived by C arter et al, (1999b) except for some rate constants updates and re - adjustment of the nitrate yields based on the chamber data. Mechanisms for other styrenes were estimated based on that developed for styrene. 5 The mechanisms for alkylbenzenes were derived as discussed in the documentation of the updated aromatics mechanism. The general ring opening mechanism is as shown on Figure 2 . 6 The mechanism for this aromati c com pound is a simplified and parameterized representation that was either adjusted to fit cham ber data or wa s derived based on mechanism(s) adjusted to fit cham ber data. See Table 14 on non - alkylbenzene aromatics for further information. 7 The furans are assumed to react primarily to form the mo nounsaturated 1,4 - dicarbonyl resulting from OH addition adjacent to the oxygen, followed by ring opening. T hese were represented by the AFG1 and AFG2 mo del species with their relative yields adjusted to fit available chamber data wh ere such data are available, as used in the general aromatic hydrocarbon mechanism discussed in the text. 8 Portions of the mechani sm fo r this photoreactive com pound were derived using the mechanism generation system, with appropriate assignments for rate constants and branching ratios as applicable. The photolysis reactions were estimated, with absorption cross - sections and quantum yields derived as indicated on Table A - 3 or A - 6. The mechanism generation system is described by Carter (2000a), with updates and extensions as described by in the text. 9 Photolysis reactions of C 9+ ketones are assumed to be negligible, based on the apparent decline in overall quantum yields with carbon num ber in mechanisms that give the best fits to environmental chamber data. The mechanisms for the other reactions are estimated using the mechanism generation system. 10 The benzyl alcohol mechanism is based on that derived by Carter et al (2005a). The measured benzaldehyde in the cham ber experiments are consistent with a fraction reacted by abstraction from the - CH 2 OH of

30%, and the products formed following the addition to the aromatic ring are assumed to be the same as used for ethylbenzene. The nitrate yield factor derived for toluene for the peroxy reactions involved in the ring addition mechanism gives results in reasonably good fits to the data and wa s not adjusted. 11 The mechanism for this aromatic com pound wa s derived by analogy to the reactions of benzene or the alkylbenzenes. See text for more details. 12 See Carter (2008a) for a discussion of the mechanisms for the amines and the associate d uncertainties and evaluation problems. The ma gnitudes of the calculated atmospheric reactivities must be considered to be upper limits because of the possibility of removal of the amines by reaction with atmospheric nitric acid is assumed to be negligibl e in the calculations, which might not be the case. The evaluations against chamber data is uncertain because the amount of amine present in the gas phase at the beginning of the cham ber experiments could not be determined, and are expected to be lower than the calculated amounts reacted because of the tendency of the amines to go to surfaces. The amount of initially present amine in the experiments had to be adjusted to fit the initial rates of NO oxidation in the experiments, and the adjusted amounts were always less than the calculated amount injected. 13 The reaction with OH is assumed to proceed by abstraction from the methyl group, followed by decomposition to form NO and formaldehyde. The photolysis absorption cross sections are from Calvert and Pitts (1966). The major reaction pathway is photolysis, which is assumed to form methyl radicals and NO with unit quantum yields. 14 The data of Hashimoto et al (1984) indicate that the products are formaldehyde and HCO - CN after an NO to NO 2 conversion. HCO - CN is assumed to be relatively unreactive, which is supported by the concentration- time profiles reported by Hashimoto et al (1984). Reactions wi th NO 3 and O 3 are assumed to be relatively slow , though no data are available concerning these reactions. 15 An es timated mechanism wa s derived explicitly for this com pound. About 24% of the reaction is assumed to occur at the methyl or CH2 groups, with the subsequent reactions estimated using the procedures in the mechanism generation system. The remainder of the reaction is assumed to be addition of OH to the C=N double bond, which is assumed to form primarily C2H2C(CH3)(OH)N(.)OH, which is assumed to react with O 2 to form C 2 H 5 C(CH 3 )(OH)NO + HO 2 . The rate constant is estimated by the rate constant for OH + isobutene x the average of the ratio of the rate constants for CH 2 =NOH / Ethene and CH 3 CH=NOH / Propene, with abstractions from the methyl group subtracted off. The CH2=NOH and CH3CH=NOH rate constants are from the tabulation of Atkinson (1989). The C 2 H 5 C(CH 3 )(OH)NO is assumed to photolyze rapidly, forming NO + an alpha - hydroxy radical that reacts with O 2 to form MEK and HO 2 . The absorption

### Table B -4 (continued)

233 cross - sections and quantum yields are unknown, but photolysis is assumed to be relatively rapid, and estimated to be comparable to that of methyl nitrite. 16 The N - methyl 2 -py

rrolidone mechanism is based on that derived by Carter et al (1996b). 17 The mechanism for bromine - containing com pound were derived based on that estimated using the mechanism generation system for the corresponding chlorine - containing com pound, but using the appropriate rate constant for the individual com pound. The mechanisms were not optimized to fit the chamber data and no mechanisms were found to simulate the data particularly well (Carter and Tuazo n, 2000). 18 The mechanism for chloropicrin is based on that of Carter et al (1997b), updated as discussed by Carter and Malkina (2007). 19 The mechanisms for these pesticide com pounds were derived as discussed by C arter and Malkina (2007), but updated to the current version of the mechanism. 20 The mechanism used for methyl iodide, including the reactions of the inorganic iodine species formed, is given by Carter (2007). 21 The mechanism, and its evaluation against chamber data, is documented by Carter (20 09a). 22 The mechanism, and its evaluation against chamber data, is documented by Carter (2009b). 23 The mechanism, and its evaluation against chamber data, is documented by Carter et al (2010). 24 Assumed to have an analogous mechanism as that for acetald ehyde, except that the absorption cross sections and quantum yields are those recommended by IUPAC (2006) for glycolaldehyde. 26 Mechanism estimated for this compound based on the following assumptions. Mechanism assumed to involve formation of CH 3 N(OH)(O) O, wh ich thermally decomposes to HNO 3 + CH 3 . Pressure dependence and rate constants for other nitro com pounds suggest that H - abstraction not im portant for alpha - nitro compounds. 27 Mechanism estimated for this com pound based on the following assum ptions. Reaction at group not adjacent to the nitro group, fo llowed by O 2 reaction with the alkoxy radical formed assumed to dominate. Nitrate formation ignored. HCOCH 2NO 2 represented by Acetaldehyde + XN, and CH 3 CH(NO 2 )CHO represented by RCHO + XN. 28 Mechanism es timated for this compound based on the following assumptions. Reaction assumed to occur at the CH 3 group, followed by reaction of the alkoxy radical formed with O 2 , forming CHF 2 CHO. The latter is represented by acetaldehyde (which probably overestimates it s reactivity). 29 Mechanism estimated for this com pound based on the following assum ptions. Decom

position of alkoxy radical, forming CF 3 and inert F 2 CO assumed. CF 3 O assumed to react with other VOCs to form CF 3 OH, which is treated as inert. The effect of the CF3O + VOC reaction is represented by the formation of OH. 30 Mechanism estimated for this com pound based on the following assumptions. Overall nitrate yield estimated by assuming it is the same as the alkyl peroxy radical with the same number of carbo ns. Products formed assumed to be unreactive. Reaction of alkoxy radical with O 2 assumed to dominate. 31 Mechanism estimated for this com pound based on the following assumptions. Overall nitrate yield estimated by assuming it is the same as the alkyl peroxy radical with the same number of carbons. Products formed assumed to be unreactive. Decomposition to form chlorine atoms assumed to dominate. 32 Mechanism estimated for this compound based on the following assumptions. Most of reaction is assumed to occur at CH 2 group, with the alkoxy radical formed assumed to react with O 2 to form a relatively unreactive fluorinated carbonyl product. Overall nitrate yield estimated by assuming it is the same as the alkyl peroxy radical with the same number of carbons. 33 Mechanism estimated for this com pound based on the following assumptions. Alkoxy radical formed following abstraction from either hydrogen is assumed to decompose forming an alpha - hydrogen substituted radical that reacts to form an alkoxy radical that reac ts with O 2 forming HO 2 and an unreactive carbonyl fluoride. Nitrate yields in peroxy radical reactions assumed to be the same as in the corresponding alkylperoxy radical with the same number of carbons. 34 Mechanism estimated for this compound based on the following assumptions. Reaction assumed to occur primarily at the CH 2 group, ultimately giving rise to methyl radicals and C 4 F 9 OCHO, which is assumed to be unreactive. Nitrate yield from peroxy radical formed assumed to be the same as that formed from ethyl propyl ether. 35 Mechanism estimated for this com pound based on the following assumptions. Alkoxy radical formed assumed to react with O 2 forming HO 2 and a perfluoro formate, which is assumed to be unreactive. Nitrate yield from peroxy radical formed as sumed to be the same as that formed from ethyl propyl ether.

### Table B -4 (continued)

234

36 It is assumed that the primary reaction is OH or NO 3 adding to terminal position, forming an allylic stabilized radical. In the case of the OH reaction, the 1,2 - unsaturated alpha - hydroxy radic al reacts with O 2 to form HO2 and 1,2 -butadien - 4 - al, and in the case of the NO 3 reaction the analogous compound reacts unimolecularly to form NO 2 and the same aldehyde. The aldehyde is represented by RCHO, on the basis that this is probably not as bad an approximation as MACR. It is assumed that the reaction with O 3 is slow. A The atmospheric reactivity values were derived using the "Adjusted Products" version of the mechanism, where the major oxidation products are represented explicitly using mechanisms derived using the mechanism generation system. See Carter (2000a, 2009) for more details concerning how adjusted products mechanisms are derived. LM This compound is represented using the "lum ped mo lecule" approach, where the atmospheric reactivity of this com pound is assumed to have the same per - molecule atmospheric impact as another compound. See Table B - 9 for the compounds used to represent other com pounds using the lumped molecule approach. [c] Structures used when deriving the mechanism using the mechanism generation system. If no structure is given then the mechanism generation system wa s not used to derive the mechanisms. "* ", "*1", "* 2" indicate join points for cyclic or bicyclic compounds. "^" and "v" are used to indicate cis/trans isomerization for alkenes (cis/trans isomerization for cyclic compounds isn't recognized by the system). "#" indicates a triple bond.

### 235

Table B - 5 . Listing of compounds for which mechanisms have been derived. 2. Rate constants for

reactions with O 3 

### , NO 3 

### , and O 3 

### P at 300 o

### K, where applicable . Com pound Rate constant at 300 K (cm3 molec - 1 s - 1 ) [a] O 3 NO 3 O 3 P Propene 1.05E - 17 1 9.73E - 15 1 4.01E - 12 2 1 - Butene 9.08E - 18 1 1.38E - 14 1 4.17E - 12 2 Isobutene 1.17E - 17 1 3.44E - 13 1 1.68E - 11 2 cis - 2 - Butene 1.28E - 16 1 3.52E - 13 1 1.75E - 11 2 trans - 2 - Butene 1.95E - 16 1 3.93E - 13 1 1.99E - 11 2 1,3 - Butadiene 6.64E - 18 1 1.00E - 13 1 1.98E - 11 2 1 - Pentene 1.10E - 17 1 1.50E - 14 1 4.69E - 12 2 3 - Methyl - 1 - Butene 9.87E - 18 3 1.39E - 14 e1 4.19E - 12 2 2 - Methyl - 1 - Butene 1.48E - 17 1 3.32E - 13 e1 1.80E - 11 2 2 - Methyl - 2 - Butene 4.11E - 16 1 9.37E - 12 1 5.08E - 11 2 cis - 2 - Pentene 1.31E - 16 1 3.70E - 13 e1 1.70E - 11 2 trans - 2 - Pentene 1.63E - 16 1 3.70E - 13 e1 2.10E - 11 2 Cyclopentene 5.61E - 16 1 4.20E - 13 1 2.10E - 11 2 Trans 1,3 - Pentadiene 1.33E - 17 e2 5.69E - 13 e1 4.76E - 11 e3 1,4 - Pentadiene 1.51E - 17 3 2.76E - 14 e1 1.41E - 11 e3 Isoprene 1.34E - 17 1 6.81E - 13 1 3.50E - 11 2 1 - Hexene 1.17E - 17 1 1.80E - 14 1 5.03E - 12 2 3,3 - Dimethyl - 1 - Butene 4.08E - 18 3 1.38E - 14 e1 4.80E - 12 2 3 - Methyl - 1 - Pentene 3.97E - 18 3 1.39E - 14 e1 5.60E - 12 e1 4 - Methyl - 1 - Pentene 1.04E - 17 3 1.39E - 14 e1 5.60E - 12 e1 2,3 - Dimethyl - 1 - Butene 1.04E - 17 4 3.32E - 13 e1 1.73E - 11 e1 2 - Ethyl - 1 - Butene 1.35E - 17 4 4.52E - 13 1 1.73E - 11 e1 2 - Methyl - 1 - Pentene 1.66E - 17 4 3.32E - 13 e1 2.03E - 11 e1 2,3 - Dimethyl - 2 - Butene 1.14E - 15 1 5.72E - 11 1 7.64E - 11 2 2 - Methyl - 2 - Pentene 3.48E - 16 e1 9.37E - 12 e1 3.86E - 11 e1 Cis - 2 - Hexene 1.08E - 16 1 3.70E - 13 e1 2.05E - 11 e1 Cis - 3 - Hexene 1.43E - 16 6 3.70E - 13 e1 2.05E - 11 e1 Cis - 3 - Methyl - 2 - Pentene 4.58E - 16 7 9.37E - 12 e1 3.71E - 11 e1 Trans 3 - Methyl - 2 - Pentene 5.69E - 16 7 9.37E - 12 e1 3.71E - 11 e1 Trans 4 - Methyl - 2 - Pentene 1.15E - 16 e1 3.70E - 13 e1 1.84E - 11 e1 Trans - 2 - Hexene 1.57E - 16 1 3.70E - 13 e1 2.05E - 11 e1 Trans - 3 - Hexene 1.64E - 16 8 3.70E - 13 e1 2.05E - 11 e1 3 - methylcyclopentene 1.15E - 16 e1 3.70E - 13 e1 2.05E - 11 e1 1 - Methyl cyclopentene 6.81E - 16 10 9.37E - 12 e1 3.71E - 11 e1 Cyclohexene 8.30E - 17 1 5.10E - 13 1 2.00E - 11 2 Trans 1,4 - Hexadiene 1.69E - 16 e4 3.84E - 13 e1 3.91E - 11 e3 1 - Methyl Cyclohexene 1.64E - 16 1 1.00E - 11 1 9.00E - 11 11 4 - Methyl Cyclohexene 9.04E - 17 1 3.70E - 13 e1 2.05E - 11 e1 1 - Heptene 1.21E - 17 1 2.00E - 14 1 8.70E - 12 e1 3,4 - dimethyl - 1 -pentene 1.01E - 17 e1 1.40E - 14 e1 5.60E - 12 e1 3 - methyl - 1 - hexene 1.01E - 17 e1 1.40E - 14 e1 5.60E - 12 e1 2,4 - dimethyl - 1 -pentene 1.18E - 17 e1 3.32E - 13 e1 1.73E - 11 e1 2,3 - dimethyl - 1 -pentene 1.18E - 17 e1 3.32E - 13 e1 1.73E - 11 e1 3,3 - dimethyl - 1 -pentene 1.01E - 17 e1 1.38E - 14 e1 5.60E - 12 e1 2 - methyl - 1 - hexene 1.18E - 17 e1 3.32E - 13 e1 1.73E - 11 e1 2,3,3 - trimethyl - 1 - Butene 8.09E - 18 4 3.32E - 13 e1 1.73E - 11 e1

### Table B - 5 (continued)

236 Com pound Rate constant at 300 K (cm3 molec - 1 s - 1 ) [a] O 3 NO 3 O 3 P 4,4 - dimethyl - cis - 2 -pentene 1.15E - 16 e1 3.70E - 13 e1 1.55E - 11 e1 2,4 - dimethyl - 2 -pentene 3.48E - 16 e1 9.37E - 12 e1 3.71E - 11 e1 2 - methyl - 2 - hexene 3.48E - 16 e1 9.37E - 12 e1 3.71E - 11 e1 3 - ethyl - 2 -pentene 3.48E - 16 e1 9.37E - 12 e1 3.71E - 11 e1 3 - methyl - trans - 3 -hexene 3.48E - 16 e1 9.37E - 12 e1 3.71E - 11 e1 cis - 2 -heptene 1.15E - 16 e1 3.70E - 13 e1 2.05E - 11 e1 2 - Methyl - trans - 3 - Hexene 1.15E - 16 e1 3.70E - 13 e1 2.05E - 11 e1 3 - methyl - cis - 3 - hexene 3.48E - 16 e1 9.37E - 12 e1 3.71E - 11 e1 3,4 - dimethyl - cis - 2 -pentene 3.48E - 16 e1 9.37E - 12 e1 3.71E - 11 e1 2,3 - Dimethyl - 2 - Pentene 6.74E - 16 e1 5.72E - 11 e1 5.07E - 11 e1 Cis - 3 - Heptene 1.15E - 16 e1 3.70E - 13 e1 2.05E - 11 e1 Trans 4,4 - dimethyl - 2 - Pentene 1.15E - 16 e1 3.70E - 13 e1 1.57E - 11 e1 Trans - 2 - Heptene 1.15E - 16 e1 3.70E - 13 e1 2.34E - 11 e1 Trans - 3 - Heptene 1.15E - 16 e1 3.70E - 13 e1 2.05E - 11 e1 cis - 3 - methyl - 2 - hexene 3.48E - 16 e1 9.37E - 12 e1 3.71E - 11 e1 trans - 4 - methyl - 2 -hexene 1.15E - 16 e1 3.70E - 13 e1 2.05E - 11 e1 trans - 3 - methyl - 2 -hexene 3.48E - 16 e1 9.37E - 12 e1 3.71E - 11 e1 1,2 - Dimethyl Cyclohexene 2.11E - 16 12 5.72E - 11 e1 5.29E - 11 e1 1 - Octene 1.45E - 17 3 1.39E - 14 e1 5.60E - 12 e1 2,4,4 - trimethyl - 1 -pentene 1.18E - 17 e1 3.32E - 13 e1 1.73E - 11 e1 3 - Methyl - 2 - Isopropyl - 1 - Butene 3.45E - 18 5 3.32E - 13 e1 1.73E - 11 e1 trans - 2 - octene 1.15E - 16 e1 3.70E - 13 e1 2.05E - 11 e1 2 - Methyl - 2 - heptene 3.48E - 16 e1 9.37E - 12 e1 3.71E - 11 e1 Cis - 4 - Octene 9.22E - 17 6 3.70E - 13 e1 2.05E - 11 e1 Trans 2,2 - Dimethyl 3 - Hexene 4.34E - 17 9 3.70E - 13 e1 2.05E - 11 e1 Trans 2,5 - Dimethyl 3 - Hexene 4.24E - 17 9 3.70E - 13 e1 2.05E - 11 e1 Trans - 3 - Octene 1.15E - 16 e1 3.70E - 13 e1 2.05E - 11 e1 Trans - 4 - Octene 1.34E - 16 8 3.70E - 13 e1 2.40E - 11 e1 2,4,4 - trimethyl - 2 - Pentene 1.44E - 16 10 9.37E - 12 e1 3.71E - 11 e1 2,3 - dimethyl - 2 - hexene 6.74E - 16 e1 5.72E - 11 e1 5.29E - 11 e1 1 -Nonene 1.01E - 17 e1 1.39E - 14 e1 5.60E - 12 e1 4,4 - dimethyl - 1 -pentene 1.01E - 17 e1 1.39E - 14 e1 5.60E - 12 e1 Trans - 4 -Nonene 1.15E - 16 e1 3.70E - 13 e1 2.05E - 11 e1 1 - Decene 9.68E - 18 3 1.40E - 14 e1 5.60E - 12 e1 3,4 - Diethyl - 2 - Hexene 4.28E - 18 7 9.37E - 12 e1 3.71E - 11 e1 Cis - 5 - Decene 1.13E - 16 6 3.70E - 13 e1 2.05E - 11 e1 Trans - 4 - Decene 1.15E - 16 e1 3.70E - 13 e1 2.05E - 11 e1 3 - Carene 3.76E - 17 13 9.10E - 12 1 3.20E - 11 2 a - Pinene 8.55E - 17 1 6.09E - 12 1 3.20E - 11 2 b - Pinene 1.57E - 17 1 2.51E - 12 1 2.70E - 11 2 d - Limonene 2.17E - 16 1 1.22E - 11 1 7.20E - 11 2 Sabinene 8.40E - 17 13 1.00E - 11 1 6.27E - 11 e3 Terpinolene 1.02E - 15 e1 6.66E - 11 e1 1.63E - 10 e1 1 -Undecene 1.01E - 17 e1 1.40E - 14 e1 5.60E - 12 e1 Trans - 5 -Undecene 1.15E - 16 e1 3.70E - 13 e1 2.05E - 11 e1 1 - Dodecene 1.01E - 17 e1 1.40E - 14 e1 5.60E - 12 e1 Trans - 5 - Dodecene 1.15E - 16 e1 3.70E - 13 e1 2.05E - 11 e1 1 - Tridecene 1.01E - 17 e1 1.41E - 14 e1 5.60E - 12 e1

### Table B - 5 (continued)

237 Com pound Rate constant at 300 K (cm3 molec - 1 s - 1 ) [a] O 3 NO 3 O 3 P Trans - 5 - Tridecene 1.15E - 16 e1 3.70E - 13 e1 2.05E - 11 e1 1 - Tetradecene 1.01E - 17 e1 1.41E - 14 e1 5.60E - 12 e1 Trans - 5 - Tetradecene 1.15E - 16 e1 3.70E - 13 e1 2.05E - 11 e1 Trans - 5 - Pentadecene 1.15E - 16 e1 3.70E - 13 e1 2.05E - 11 e1 Styrene 1.76E - 17 3 1.50E - 13 1 1.75E - 11 e5 b - Methyl Styrene 3.25E - 16 e6 3.92E - 13 e7 1.62E - 11 e3 Glyoxal 1.02E - 15 e8 glycolaldehyde 2.84E - 15 e17 Acrolein 3.07E - 19 17 1.18E - 15 18 2.37E - 12 e1 Acrylic Acid 1.01E - 17 e1 2.76E - 18 e1 4.60E - 12 e1 Methyl Glyoxal 2.53E - 15 e8 Crotonaldehyde 1.58E - 18 19 5.12E - 15 20 7.29E - 12 e1 Methacrolein 1.28E - 18 1 3.54E - 15 1 6.34E - 12 e8 Methylvinyl ketone 5.36E - 18 1 4.32E - 12 e8 2 - Methylpropanal 1.15E - 14 1 Butanal 1.15E - 14 1 Methacrylic Acid 1.18E - 17 e1 6.71E - 17 e1 1.42E - 11 e1 Methyl Acrylate 1.01E - 17 e1 2.76E - 18 e1 4.60E - 12 e1 Vinyl Acetate 1.01E - 17 e1 1.38E - 14 e1 5.60E - 12 e1 Hydroxy Methacrolein 1.28E - 18 e9 3.40E - 15 e10 9.95E - 12 e1 2 - Methyl - 3 - Butene - 2 - ol 9.68E - 18 15 1.21E - 14 16 2.01E - 11 e1 2,2 - Dimethylpropanal (pivaldehyde) 2.40E - 14 1 3 - Methylbutanal (Isovaleraldehyde) 1.90E - 14 1 Pentanal (Valeraldehyde) 1.50E - 14 1 Ethyl Acrylate 1.01E - 17 e1 3.70E - 18 e1 4.60E - 12 e1 Methyl Methacrylate 1.18E - 17 e1 6.71E - 17 e1 1.42E - 11 e1 Glutaraldehyde 7.63E - 15 e1 Hexanal 1.60E - 14 1 Ethyl Methacrylate 1.18E - 17 e1 6.80E - 17 e1 1.42E - 11 e1 hydroxypropyl acrylate 1.01E - 17 e1 2.96E - 17 e1 4.60E - 12 e1 Benzaldehyde 2.73E - 15 21 o - Cresol 1.40E - 11 2 Heptanal 1.90E - 14 1 2 - methyl -hexanal 3.90E - 15 e1 n -butyl acrylate 1.01E - 17 e1 5.06E - 17 e1 4.60E - 12 e1 isobutyl acrylate 1.01E - 17 e1 1.14E - 16 e1 4.60E - 12 e1 Octanal 1.70E - 14 1 Butyl Methacrylate 1.18E - 17 e1 1.15E - 16 e1 1.42E - 11 e1 Isobutyl Methacrylate 1.18E - 17 e1 1.79E - 16 e1 1.42E - 11 e1 a - terpineol 3.48E - 16 e1 9.37E - 12 e1 3.71E - 11 e1 Citronellol (3,7 - dimethy - 6 - octen - 1 - ol) 3.48E - 16 e1 9.37E - 12 e1 3.71E - 11 e1 Hydroxycitronellal 4.03E - 15 e1 Linalool 3.58E - 16 e1 9.38E - 12 e1 6.60E - 11 e1 Geraniol 6.96E - 16 e1 1.87E - 11 e1 1.35E - 10 e1 2 - Ethyl - Hexyl Acrylate 1.01E - 17 e1 2.95E - 16 e1 4.60E - 12 e1 methyl cis - 9 -pentadecenoate 1.15E - 16 e1 3.70E - 13 e1 2.05E - 11 e1 methyl linolenate (methyl cis,cis,cis - 9,12,15 - octadecatrienoate) 3.45E - 16 e1 1.11E - 12 e1 1.59E - 10 e1

### Table B - 5 (continued)

238 Com pound Rate constant at 300 K (cm3 molec - 1 s - 1 ) [a] O 3 NO 3 O 3 P methyl linoelate (methyl cis,cis - 9,12 - octadecadienoate) 2.30E - 16 e1 7.40E - 13 e1 7.47E - 11 e1 Methylamine 7.40E - 21 22 9.60E - 14 e11 Acetylene 1.16E - 20 14 Dimethyl Amine 1.67E - 18 22 2.03E - 13 e11 Ethyl Amine 2.09E - 20 e12 1.16E - 13 e11 Ethanolamine 6.86E - 20 e12 1.35E - 13 e11 Dimethyl Sulfoxide 3.00E - 13 27 Trichloroethylene 2.99E - 16 18 4.37E - 14 e1 Trimethyl Amine 7.84E - 18 22 1.56E - 13 e11 isopropylamine 3.48E - 20 e12 1.21E - 13 e11 1 - amino - 2 -propanol 6.58E - 20 e18 1.35E - 13 e1 trans - 1,3 - dichloropropene 7.12E - 19 24 9.13E - 17 e13 1.30E - 12 e14 cis - 1,3 - dichloropropene 1.60E - 19 25 5.57E - 18 e13 4.79E - 13 e14 1,3 -butadiyne 1.00E - 15 e7 t -butyl amine 0 e12 5.88E - 14 e11 mo rpholine 3.77E - 18 e18 3.30E - 13 e1 Dimethylaminoethanol 6.76E - 18 22 1.80E - 13 e11 2 - amino - 1 -butanol 3.74E - 19 e12 1.70E - 13 e11 2 - Amino - 2 - Methyl - 1 - Propanol 0 e12 5.88E - 14 e11 Diethanol Amine 3.78E - 18 e12 3.30E - 13 e11 2 - (Cl - me thyl) - 3 - Cl - Propene 4.14E - 19 26 1.00E - 15 e15 5.60E - 12 e1 2 - amino - 2 - ethyl - 1,3 -propanediol 5.89E - 14 e1 N - Methyl - 2 - Py

rrolidone 1.26E - 13 23 Triethyl Amine 1.20E - 17 e12 1.71E - 13 e11 Triethanolamine 3.94E - 17 e12 2.29E - 13 e11 Molinate 9.20E - 15 e16 EPTC (S - Ethyl Dipropylthiocarbamate) 9.20E - 15 28 triisopropanolamine 3.94E - 17 e12 2.29E - 13 e11 Pebulate 9.20E - 15 e16 Thiobencarb 9.20E - 15 e16 [a] See the complete mechanism listing in the electronic version of the report for the temperature dependences, where available. Footnotes for measured rate constants are as follows: 1 As recommended or tabulated by Atkinson and Arey (2003) 2 As recommended or tabulated by Calvert et al (2002) 3 Rate constant at 298K as recommended or tabulated by Atkinson and Arey (2003). Temperature dependence estimated by assuming that the A factor is the same as that for 1 butene. 4 Rate constant at 298K as recommended or tabulated by Atkinson and Arey (2003). Temperature dep endence estimated by assuming that the A factor is the same as that for 2 methyl - 1 -butene. 5 T=298K rate constant recommended by Atkinson (1997). Temperature dependence estimated by assuming the A factor is the same as for isobutene. 6 Rate constant at 29 8K as recommended or tabulated by Atkinson and Arey (2003). Temperature dependence estimated by assuming that the A factor is the same as that for cis - 2 -butene. 7 Rate constant at 298K as recommended by Atkinson (1997). Temperature dependence estimated by assuming that the A factor is the same as that for 2 - methyl - 1 -butene. 8 Rate constant at 298K as recommended or tabulated by Atkinson and Arey (2003). Temperature dependence estimated by assuming that the A factor is the same as that for trans - 2 -butene.

### Table B - 5 (continued)

239

9 Rate constant at 298K as recommended by Atkinson (1997). Temperature dependence estimated by assuming that the A factor is the same as that for trans - 2 -butene. 10 Rate constant at 298K as recommended or tabulated by Atkinson and Arey (2003). Temperature dependence estimated by assuming that the A factor is the same as that for 2 - methyl - 2 -butene. 11 Atkinson (1997) Recommendation 12 Rate constant at 298K as recommended by Atkinson (1997). Temperature dependence estimated by assuming that the A factor is the same as that for 2,3 - dimethyl - 2 -butene. 13 Rate constant at 298K as recommended or tabulated by Atkinson and Arey (2003). Temperature dependence estimated by assuming that the A factor is the same as that for alpha -pinene. 14 Rate constant at 298K recommended by IUPAC (2006). A factor estimated to be approximately 2 times that for ethene, as assumed by Carter (2000a). 15 Rate constant at 298K is average of 291K rate constant of Grosjean and Grosjean (199 4) and the 298K rate constant of Fantechi et al (1998). Temperature dependence estimated by assuming that the A factor is the same as that for 1 -butene 16 Rate expression of Rudich et al (1996), as recommended by Atkinson (private communication, 2000). Rea sonable agreement with data of Fantechi et al (1998). 17 Rate constant at 298K recommended by Atkinson (1994). Temperature dependence estimated by assuming that the A factor is the same as that for methacrolein. 18 Rate constant relative to ethene from Atkinson et al (1987). Placed on an absolute basis using 300K rate constant for ethene recommended by Atkinson and Arey (2003). 19 Sato et al (2004b). 20 Rate constant relative to propene from Atkinson et al (1987). Placed on an absolute basis using 300K rate constant for propene recommended by Atkinson and Arey (2003). 21 The T=298K rate constant recommended by Atkinson (1994). Temperature dependence estimated by assuming the reaction has the same A factor as the reaction of NO3 with acetaldehyde. This gives the same 298K rate constant but a slightly different temperature dependence than used in SAPRC - 99. 22 Rate constant from Tuazon et al (1994) 23 Rate constant from Aschmann and Atkinson (1999) 24 Rate constant at 298K from Tuazon et al (1984). Temperature d ependence estimated by assuming that the A factor is the same as that for trans - 2 -butene. 25 Rate constant at 298K from Tuazon et al (1984). Temperature dependence estimated by assuming that the A factor is the same as that for cis - 2 -butene. 26 Rate constant at 298K from Atkinson and Carter (1984). Temperature dependence estimated by assuming that the A factor is the same as that for isobutene. 27 Rate constant is geometric mean of measurements of Barnes et al (1989) and Falbe - Hansen et al (2000), as used b y Carter et al (2000). 28 Rate constant from Kwok et al (1992) Footnotes for estimated rate constants are as follows: e1 Estimated using the group - additivity estimation assignments implemented in the current mechanism generation system. See Carter (2000a). e2 Rate constant unknown. Roughly estimate that it is similar to that for isoprene e3 Estimated from correlation between measured OH and O 3 P rate constants (with ethene, allene, and some other outliers excluded) at 300K. e4 Estimated as the sum of the 300 K rate constants for 1 - hexene and trans - 2 - hexene. e5 Assumed to have the same rate constant as cis - 2 -butene on the basis of their having similar OH radical rate constants. e6 Estimated from the 300K styrene, propene, and trans - 2 -butene rate constants by as suming that the styrene/b - methyl styrene ratio is the same as the ratio for propene to trans - 2 -butene. e7 Estimated from the correlation between OH and NO 3 rate constants, using the assigned 300K OH rate constant for this compound. e8 Estimated value used in SAPRC - 99 mechanism. See base mechanism listing and Carter (2000a). e9 Estimated to have the same rate constant and kinetic parameters as methacrolein, as assumed by Carter and Atkinson (1996). e10 Rate constant assumed to be the same as for methacrolein (Carter and Atkinson, 1996)

### Table B - 5 (continued)

240

e11 Estimated based on the NO 3 + NMP rate constant and assuming ratios of rate constants for reactions of NO 3 at various types of amine groups is the same as those estimated for the reactions of OH with those groups. Reaction a ssumed to occur only from NH or NH 2 or from C - H bonds on carbons bonded to the amino group. e12 Estimated from the estimated rate of reaction of OH at the alpha position, and correlations between this and the measured O 3 rate constants of Tuazon et al (199 4) for the methylamines and DMAE. Reaction assumed to be slow

if no abstractable hydrogens in a group adjacent to the amino group. e13 Estimated by Carter and Malkina (2007) based on correlation between O3 and NO3 rate constants. e14 Estimated by Carter and Malkina (2007) based on correlation between O3 and NO3 rate constants. e15 This rate constant estimated by Atkinson (private communication, 1997) based on the rate constant for NO 3 + Allyl chloride (Atkinson, 1991) e16 Estimated by Carter and Malkina (20 07) to have the same rate constant as EPTC. e17 Assumed to have the same rate constant as acetaldehyde. e18 Estimated from estimated rate of reaction of OH at the alpha position, and correlations between this and the measured O 3 rate constants of Tuazon et al (1994) for the methylamines and DMAE.

### 241

Table B - 6 . Listing of compounds for which mechanisms have been derived. 3. Absorption cross sections, quantum yields, and mechanisms for photolysis reactions, where applicable . Com pound Phot Data [a] Mechanism glycolaldehyde HOCCHO 6 GLCLALD + HV = CO + #2 HO2 + HCHO Acrolein MACR - 06 e2 ACROLEIN + HV = #.178 OH + #1.066 HO2 + #.234 MEO2 + #.33 MACO3 + #1.188 CO + #.102 CO2 + #.34 HCHO + #.05 CCOOH + # - .284 XC Hydroxy Acetone MEK- 06 0.175 e3 HOACET + HV = HO2 + MECO3 + HCHO Crotonaldehyde MACR - 06 e2 CROTALD + HV = #2 HO2 + #2 CO + CCHO 2 - Methylpropanal C2CHO e1 2MEC3AL + HV = HO2 + #.96 RO2C + #.04 RO2XC + #.04 zRNO3 + CO + #.96 xHO2 + #.96 xACET + yROOH + # - .12 XC Butanal C2CHO e1 1C4RCHO + HV = HO2 + #.98 RO2C + #.02 RO2XC + #.02 zRNO3 + CO + #.98 xHO2 + #.98 xRCHO + yROOH + # - .06 XC Hydroxy Methacrolein MACR - 06 e2 HOMACR + HV = HO2 + RCO3 + CO + HCHO + # - 1 XC Methoxy Acetone MEK- 06 0.1 e3 MEOACET + HV = MECO3 + RO2C + xHO2 + #.079 xHCHO + yROOH + #1.921 XC 2,2 - Dimethylpropanal (pivaldehyde) C2CHO e1 22DMC3AL + HV = HO2 + #.961 RO2C + #.039 RO2XC + #.039 zRNO3 + CO + #.961 xTBUO + yR6OOH + # - .079 XC 3 - Methylbutanal (Isovaleraldehyde) C2CHO e1 3MC4RCHO + HV = HO2 + #1.294 RO2C + #.053 RO2XC + #.053 zRNO3 + CO + #.947 xHO2 + #.348 xHCHO + #.613 xRCHO + #.334 xACET + yR6OOH + #.492 XC Pentanal (Valeraldehyde) C2CHO e1 1C5RCHO + HV = HO2 + #1.686 RO2C + #.069 RO2XC + #.069 zRNO3 + CO + #.931 xHO2 + #.931 xRCHO + yR6OOH + #.792 XC 2 - Pentanone MEK- 06 0.1 e3 MPK + HV = MECO3 + #.98 RO2C + #.02 RO2XC + #.02 zRNO3 + #.98 xHO2 + #.98 xRCHO + yR6OOH + # - .06 XC 3 - Pentanone MEK- 06 0.1 e3 DEK + HV = RCO3 + RO2C + xHO2 + xCCHO + yR6OOH Methyl Isopropyl Ketone MEK- 06 0.1 e3 MIPRK + HV = MECO3 + #.96 RO2C + #.04 RO2XC + #.04 zRNO3 + #.9 6 xHO2 + #.96 xACET + yR6OOH + # - .12 XC Glutaraldehyde C2CHO e1 GLTRALD + HV = HO2 + #.961 RO2C + #.039 RO2XC + #.039 zRNO3 + CO + #.961 xRCO3 + yR6OOH + #.882 XC 2,4 -pentanedione MEK- 06 0.1 e3 24C5 - K + HV = MECO3 + RO2C + xMECO3 + xHCHO + yR6OOH Hexanal C2CHO e1 1C6RCHO + HV = HO2 + #1.809 RO2C + #.126 RO2XC + #.126 zRNO3 + CO + #.874 xHO2 + #.874 xRCHO + yR6OOH + #1.623 XC 4 - Methyl - 2 - Pentanone MEK- 06 0.02 e3 MIBK + HV = MECO3 + #1.294 RO2C + #.053 RO2XC + #.053 zRNO3 + #.947 xHO2 + #.348 xHCHO + #.613 xRCHO + #.334 xACET + yR6OOH + #.492 XC Methyl n - Butyl Ketone MEK- 06 0.02 e3 MNBK + HV = MECO3 + #1.686 RO2C + #.069 RO2XC + #.069 zRNO3 + #.931 xHO2 + #.931 xRCHO + yR6OOH + #.792 XC Methyl t - Butyl Ketone MEK- 06 0.02 e3 MTBK + HV = MECO3 + #.961 RO2C + #.039 RO2XC + #.039 zRNO3 + #.961 xTBUO + yR6OOH + # - .079 XC Heptanal C2CHO e1 1C7RCHO + HV = HO2 + #1.717 RO2C + #.186 RO2XC + #.186 zRNO3 + CO + #.814 xHO2 + #.814 xRCHO + yR6OOH + #2.443 XC 2 - methyl -hexanal C2CHO e1 2MEXAL + HV = HO2 + #1.60 8 RO2C + #.237 RO2XC + #.237 zRNO3 + CO + #.763 xHO2 + #.763 xPROD2 + yR6OOH

### Table B - 6 (continued)

242

Com pound Phot Data [a] Mechanism 2 - Heptanone MEK- 06 0.004 e3 C7 - KET - 2 + HV = MECO3 + #1.809 RO2C + #.126 RO2XC + #.126 zRNO3 + #.874 xHO2 + #.874 xRCHO + yR6OOH + #1.623 XC 2 - Methyl - 3 - Hexanone MEK- 06 0.004 e3 2M - 3 - HXO + HV = RCO3 + #.98 RO2C + #.02 RO2XC + #.02 zRNO3 + #.98 xHO2 + #.98 xRCHO + yR6OOH + #.94 XC Di - Isopropyl Ketone MEK- 06 0.004 e3 DIPK + HV = RCO3 + #.96 RO2C + #.04 RO2XC + #.04 zRNO3 + #.96 xHO2 + #.96 xACET + yR6OOH + #.88 XC 5 - Methyl - 2 - Hexanone MEK- 06 0.004 e3 5M2HXO + HV = MECO3 + #1.722 RO2C + #.119 RO2XC + #.119 zRNO3 + #.881 xHO2 + #.881 xRCHO + yR6OOH + #1.642 XC 3 - Methyl - 2 - Hexanone MEK- 06 0.004 e3 3M2HXO + HV = MECO3 + #1.612 RO2C + #.165 RO2XC + #.165 zRNO3 + #.835 xHO 2 + #.029 xCCHO + #.029 xRCHO + #.107 xMEK + #.699 xPROD2 + yR6OOH + # - .758 XC Octanal C2CHO e1 1C8RCHO + HV = HO2 + #1.613 RO2C + #.252 RO2XC + #.252 zRNO3 + CO + #.748 xHO2 + #.748 xRCHO + yR6OOH + #3.244 XC 2 - Octanone MEK- 06 0.0001 e3 C8 - KET - 2 + HV = MECO3 + #1.717 RO2C + #.186 RO2XC + #.186 zRNO3 + #.814 xHO2 + #.814 xRCHO + yR6OOH + #2.443 XC Hydroxycitronellal C2CHO e1 HYCITRLL + HV = HO2 + #1.43 RO2C + #.372 RO2XC + #.372 zRNO3 + CO + #.628 xHO2 + #.006 xHCHO + #.622 xRCHO + #.006 xPROD2 + yR6OO H + #4.86 XC Methyl Nitrite CONO 1 ME -NITRT + HV = HCHO + HO2 + NO Carbon Disulfide CS2 0.012 3 CS2 + HV = SO2 + O3P + XC methyl iodide CH3I 5 CH3I + OH = RO2C + xHO2 + xHCHO + I Chloropicrin CLPICER I 0.87 2 CCL3NO2 + HV = NO2 + RO2C + xCL + XC Methyl Isothiocyanate MITC 4 MITC + HV = XC + SO2 + #2 O3P Methyl Isothiocyanate MITC 4 MITC + HV = XC + SO2 + #2 O3P PROD2 Species #1 MEK- 06 0.02 e3 PROD2 - 1 + HV = MECO3 + #1.013 RO2C + xHO2 + #.033 xHCHO + #.002 xCCHO + #.987 xRCHO + yR6OOH PROD2 Species #2 MEK- 06 0.004 e3 PROD2 - 2 + HV = MECO3 + #1.697 RO2C + #.051 RO2XC + #.051 zRNO3 + #.949 xHO2 + #1.484 xHCHO + #.736 xCCHO + #.213 xRCHO + yR6OOH + #.1 XC PROD2 Species #3 MEK- 06 0.0001 e3 PROD2 - 3 + HV = RCO3 + #1.715 RO2C + #.07 RO2XC + #.07 zRNO3 + #.93 xHO2 + #.93 xRCHO + yR6OOH + #.789 XC PROD2 Species #4 MEK- 06 0.0001 e3 PROD2 - 4 + HV = RCO3 + #1.809 RO2C + #.126 RO2XC + #.126 zRNO3 + #.874 xHO2 + #.077 xCCHO + #.874 xRCHO + yR6OOH + #1.469 XC PROD2 Species #5 MEK- 06 0.0001 e3 PROD2 - 5 + HV = RCO3 + #1.717 RO2C + #.186 RO2XC + #.186 zRNO3 + #.814 xHO2 + #.898 xRCHO + yR6OOH + #2.193 XC RNO3 Species #1 IC3ONO2 e4 RNO3 - 1 + HV = NO2 + #.606 HO2 + #.394 RO2C + #.394 CCHO + #.606 MEK + #.394 xHO2 + #.394 xCCHO + #.394 yROOH RNO3 Species #2 I C3ONO2 e4 RNO3 - 2 + HV = NO2 + HO2 + PROD2 + # - 1 XC RNO3 Species #3 IC3ONO2 e4 RNO3 - 3 + HV = NO2 + #.016 HO2 + #1.226 RO2C + #.081 RO2XC + #.081 zRNO3 + #.89 CCHO + #.016 PROD2 + #.904 xHO2 + #.645 xCCHO + #.495 xMEK + #.085 xPROD2 + #.984 yR6OOH + # - .143 XC

### Table B - 6 (continued)

243

Com pound Phot Data [a] Mechanism RNO3 Species #4 IC3ONO2 e4 RNO3 - 4 + HV = NO2 + #.441 HO2 + #.483 RO2C + #.075 RO2XC + #.075 zRNO3 + #.441 HCHO + #.441 RCHO + #.483 xHO2 + #.483 xPROD2 + #.559 yR6OOH + #1.882 XC RNO3 Species #5 IC3ONO2 e4 RNO3 - 5 + HV = NO2 + #1.422 RO2C + #. 215 RO2XC + #.215 zRNO3 + #.137 MEK + #.124 PROD2 + #.785 xHO2 + #.367 xHCHO + #.341 xCCHO + #.379 xRCHO + #.046 xACET + #.236 xPROD2 + yR6OOH + #1.678 XC RNO3 Species #6 IC3ONO2 e4 RNO3 - 6 + HV = NO2 + #.802 RO2C + #.24 RO2XC + #.24 zRNO3 + #.76 xHO2 + #.76 xPROD2 + yR6OOH + #4 XC [a] The first column gives the photolysis set name that refers to the set of absorption cross - sections and (in some cases) quantum yields. The second column gives the overall quantum yield, if quantum yields are not given in the photolysis set. If blank, then unit quantum yields are used. The third column gives the footnote for the measured or estimated absorption cross - sections and quantum yields. Footnotes for measured data are as follows. In all these cases, the ab sorption cross sections are given in Table B - 8 . 1 Absorption cross - sections from Calvert and Pitts (1966). Unit quantum yields assumed. 2 Absorption c ross - sections and quantum yields from Carter et al (1997b). 3 Absorption cross - sections from current IUPAC (2006) recommendation. Quantum yield is IUPAC (2006) upper limit recommendation, but chamber data are best fit is this upper limit is used. See Carter and Malkina (2007). 4 Based on data from Alvarez (1993) and Alvarez and Moore (1994). 5 IUPAC (2006) recommendation. Unit quantum yields assumed. 6 IUPAC (2006) recommendation for absorption cross - sections and overall quantum yield. Footnotes for estimated absorption cross - sections and quantum yields are as follows. In all these cases, the photolysis sets are associated with the base mechanism, and the corresponding absorption cross sections and quantum yields are given in Table A - 3 in Appendix A. See footnotes to Ta ble A - 2 for the documentation for the values used. e1 Assumed to have the same photolysis rate as propionaldehyde (model species RCHO). e2 Assumed to have the same photolysis rate as methacrolein (mo del species MACR) e3 Assumed to have the same absorption cross sections of methyl ethyl ketone, but with overall quantum yields depending on the carbon number, based on quantum yields that give the best simulations of the chamber data for methyl ethyl keto ne, methyl propyl ketone, methyl isopropyl ketone, and 2 -heptanol. Based on these data, overall quantum yields for simple ketones with carbon numbers of 4, 5, 6, 8, and  8 are assumed to be 0.174, 0.1, 0.02, 0.004, and ~0, respectively. For oxygenated keto nes such as hydroxyacetone or the PROD2 species, the effective carbon number is the sum of the carbons + OH groups. For the purpose of computing an average quantum yield and a photolysis mechanism for PROD2, quantum yields of 0.0001 were used for PROD2 spe cies with 8 or more carbons + OH groups. This was necessary in order for the mechanisms for these species to be generated. e4 Assumed to have the same photolysis rate as isopropyl nitrate, as used in the base mechanism for RNO3.

### 244

Table B - 7 . Listing of compounds for which mechanisms have been derived. 4. Rate constants and

mechanisms for reactions with chlorine atoms, where used . Com pound Rate const. [a] Mechanism [b] Ethane 5.95E - 11 1 ETHANE + CL = xHO2 + RO2C + HCL + xCCHO + yROOH Propane 1.37E - 10 2 PROPANE + CL = #.97 xHO2 + #.97 RO2C + #.03 RO2XC + #.03 zRNO3 + HCL + #.482 xRCHO + #.488 xACET + yROOH + # - .09 XC n - Butane 2.05E - 10 1 N - C4 + CL = HCL + #1.418 RO2C + #.077 RO2XC + #.077 zRNO3 + #.923 xHO2 + #.481 xCCHO + #.313 xRCHO + #.37 xMEK + yROOH + #.16 XC n - Pentane 2.80E - 10 2 N - C5 + CL = HCL + #1.577 RO2C + #.143 RO2XC + #.143 zRNO3 + #.857 xHO2 + #.105 xCCHO + #.328 xRCHO + #.177 xMEK + #.352 xPROD2 + yR6OOH + #.127 XC n - Hexane 3.40E - 10 2 N - C6 + CL = HCL + #1.591 RO2C + #.22 RO2XC + #.22 zRNO3 + #.78 xHO2 + #.009 xCCHO + #.215 xRCHO + #.585 xPROD2 + yR6OOH + #.51 XC n - Heptane 3.90E - 10 2 N - C7 + CL = HCL + #1.519 RO2C + #.29 RO2XC + #.29 zRNO3 + #.71 xHO2 + #.143 xRCHO + #.575 xPROD2 + yR6OOH + #1.386 XC n - Octane 4.60E - 10 2 N - C8 + CL = HCL + #1.449 RO2C + #.352 RO2XC + #.352 zRNO3 + #.648 xHO2 + #.088 xRCHO + #.561 xPROD2 + yR6OOH + #2.263 XC n -Nonane 4.80E - 10 2 N - C9 + CL = HCL + #1.393 RO2C + #.398 RO2XC + #.398 zRNO3 + #.602 xHO2 + #.068 xRCHO + #.535 xPROD2 + yR6OOH + #3.203 XC n - Decane 5.50E - 10 2 N - C10 + CL = HCL + #1.355 RO2C + #.428 RO2XC + #.428 zRNO3 + #.572 xHO2 + #.057 xRCHO + #.515 xPROD2 + yR6OOH + #4.17 XC n - Undecane 6.27E - 10 e1 N - C11 + CL = HCL + #1.331 RO2C + #.448 RO2XC + #.448 zRNO3 + #.552 xHO2 + #.049 xRCHO + #.503 xPROD2 + yR6OOH + #5.147 XC n - Dodecane 6.89E - 10 e1 N - C12 + CL = HCL + #1.315 RO2C + #.46 RO2XC + #.46 zR NO3 + #.54 xHO2 + #.044 xRCHO + #.497 xPROD2 + yR6OOH + #6.131 XC n - Tridecane 7.51E - 10 e1 N - C13 + CL = HCL + #1.305 RO2C + #.467 RO2XC + #.467 zRNO3 + #.533 xHO2 + #.039 xRCHO + #.494 xPROD2 + yR6OOH + #7.118 XC Isobutane 1.43E - 10 2 2 - ME - C3 + CL = HCL + #1.19 RO2C + #.049 RO2XC + #.049 zRNO3 + #.651 xHO2 + #.3 xTBUO + #.239 xHCHO + #.422 xRCHO + #.23 xACET + yROOH + #.314 XC Iso - Pentane 2.20E - 10 2 2 - ME - C4 + CL = HCL + #1.734 RO2C + #.123 RO2XC + #.123 zRNO3 + #.869 xHO2 + #.008 xMEO2 + #.044 xHCHO + #.48 2 xCCHO + #.381 xRCHO + #.439 xACET + #.042 xMEK + yR6OOH + #.623 XC 2,2 - Dimethyl Butane 1.96E - 10 e1 22 - DM - C4 + CL = HCL + #2.068 RO2C + #.167 RO2XC + #.167 zRNO3 + #.549 xHO2 + #.016 xMEO2 + #.268 xTBUO + #.409 xHCHO + #.638 xCCHO + #.185 xRCHO + #.363 xACET + #.016 xMEK + yR6OOH + #.513 XC 2,3 - Dimethyl Butane 2.30E - 10 2 23 - DM - C4 + CL = HCL + #1.733 RO2C + #.164 RO2XC + #.164 zRNO3 + #.836 xHO2 + #.047 xHCHO + #.039 xCCHO + #.456 xRCHO + #.734 xACET + #.001 xMEK + yR6OOH + #1.315 XC 2 - Methyl Pentane 2.90E - 10 2 2 - ME - C5 + CL = HCL + #1.661 RO2C + #.193 RO2XC + #.193 zRNO3 + #.807 xHO2 + #.001 xHCHO + #.004 xCCHO + #.625 xRCHO + #.234 xACET + #.006 xMEK + #.183 xPROD2 + yR6OOH + #1.139 XC 3 - Methylpentane 2.80E - 10 2 3 - ME - C5 + CL = HCL + #1.832 RO2C + #.1 91 RO2XC + #.191 zRNO3 + #.809 xHO2 + #.019 xHCHO + #.784 xCCHO + #.282 xRCHO + #.344 xMEK + #.047 xPROD2 + yR6OOH + #.762 XC 2,3 - Dimethyl Pentane 2.79E - 10 e1 23 - DM - C5 + CL = HCL + #1.846 RO2C + #.253 RO2XC + #.253 zRNO3 + #.747 xHO2 + #.038 xHCHO + #.415 xCCHO + #.313 xRCHO + #.41 xACET + #.203 xMEK + #.047 xPROD2 + yR6OOH + #1.351 XC

### Table B - 7 (continued)

245

Com pound Rate const. [a] Mechanism [b] 2,4 - Dimethyl Pentane 2.90E - 10 2 24 - DM - C5 + CL = HCL + #1.857 RO2C + #.234 RO2XC + #.234 zRNO3 + #.766 xHO2 + #.213 xHCHO + #.009 xCCHO + #.661 xRCHO + #.23 xACET + #.008 xM EK + #.082 xPROD2 + yR6OOH + #2.163 XC 2 - Methyl Hexane 3.50E - 10 2 2 - ME - C6 + CL = HCL + #1.585 RO2C + #.267 RO2XC + #.267 zRNO3 + #.733 xHO2 + #.008 xHCHO + #.019 xCCHO + #.362 xRCHO + #.121 xACET + #.378 xPROD2 + yR6OOH + #1.633 XC 3 - Methyl Hexane 3.30E - 10 e1 3 - ME - C6 + CL = HCL + #1.67 RO2C + #.269 RO2XC + #.269 zRNO3 + #.731 xHO2 + #.005 xHCHO + #.171 xCCHO + #.433 xRCHO + #.133 xMEK + #.289 xPROD2 + yR6OOH + #1.479 XC 2,4 - Dimethyl Hexane 3.41E - 10 e1 24 - DM - C6 + CL = HCL + #1.752 RO2C + #.34 RO2XC + #.34 zRNO3 + #.66 xHO2 + #.103 xHCHO + #.212 xCCHO + #.427 xRCHO + #.055 xACET + #.065 xMEK + #.227 xPROD2 + yR6OOH + #2.365 XC 2 - Methyl Heptane 3.91E - 10 e1 2 - ME - C7 + CL = HCL + #1.489 RO2C + #.338 RO2XC + #.338 zRNO3 + #.662 xHO2 + #.006 xHCHO + #.01 xCCHO + #.229 xRCHO + #.021 xACET + #.45 xPROD2 + yR6OOH + #2.494 XC 4 - Methyl Heptane 3.92E - 10 e1 4 - ME - C7 + CL = HCL + #1.542 RO2C + #.338 RO2XC + #.338 zRNO3 + #.662 xHO2 + #.002 xHCHO + #.004 xCCHO + #.326 xRCHO + #.041 xMEK + #.411 xPROD2 + yR6OOH + #2.353 XC 2,4 - Dimethyl Heptane 4.03E - 10 e1 24 - DM - C7 + CL = HCL + #1.588 RO2C + #.396 RO2XC + #.396 zRNO3 + #.604 xHO2 + #.071 xHCHO + #.007 xCCHO + #.387 xRCHO + #.019 xACET + #.014 xMEK + #.339 xPROD2 + yR6OOH + #3.226 XC 2 - Methyl Octane 4.53E - 10 e1 2 - ME - C8 + CL = HCL + #1.447 RO2C + #.4 RO2XC + #.4 zRNO3 + #.6 xHO2 + #.001 xHCHO + #.136 xRCHO + #.013 xACET + #.469 xPROD2 + yR6OOH + #3.336 XC 4 - Methyl Octane 4.54E - 10 e1 4 - ME - C8 + CL = HCL + #1.472 RO2C + #.395 RO2XC + #.395 zRNO3 + #.605 xHO2 + #.001 xHCHO + #.0 12 xCCHO + #.188 xRCHO + #.004 xMEK + #.482 xPROD2 + yR6OOH + #3.132 XC 2,6 - Dimethyl Octane 4.64E - 10 e1 26DM - C8 + CL = HCL + #1.507 RO2C + #.429 RO2XC + #.429 zRNO3 + #.571 xHO2 + #.001 xHCHO + #.071 xCCHO + #.262 xRCHO + #.054 xACET + #.036 xMEK + #.318 xPROD2 + yR6OOH + #4.283 XC 2 - Methyl Nonane 5.14E - 10 e1 2 - ME - C9 + CL = HCL + #1.399 RO2C + #.435 RO2XC + #.435 zRNO3 + #.565 xHO2 + #.106 xRCHO + #.012 xACET + #.46 xPROD2 + yR6OOH + #4.279 XC 4 - Methyl Nonane 5.15E - 10 e1 4 - ME - C9 + CL = HCL + #1.418 RO2C + #.429 RO2XC + #.429 zRNO3 + #.571 xHO2 + #.001 xHCHO + #.007 xCCHO + #.161 xRCHO + #.002 xMEK + #.466 xPROD2 + yR6OOH + #4.121 XC 2,6 - Dimethyl Nonane 5.26E - 10 e1 26DM - C9 + CL = HCL + #1.455 RO2C + #.458 RO2XC + #.458 zRNO3 + #.542 xHO2 + #.001 xHCHO + #.001 xCCHO + #.219 xRCHO + #.049 xACET + #.003 xMEK + #.371 xPROD2 + yR6OOH + #5.21 XC 3 - Methyl Decane 5.77E - 10 e1 3 - ME - C10 + CL = HCL + #1.391 RO2C + #.458 RO2XC + #.458 zRNO3 + #.542 xHO2 + #.001 xHCHO + #.032 xCCHO + #.096 xRCHO + #.01 xMEK + #.449 xPROD2 + yR6OOH + #5.166 XC 4 - Methyl Decane 5.77E - 10 e1 4 - ME - C10 + CL = HCL + #1.396 RO2C + #.458 RO2XC + #.458 zRNO3 + #.542 xHO2 + #.001 xHCHO + #.001 xCCHO + #.118 xRCHO + #.002 xMEK + #.462 xPROD2 + yR6OOH + #5.118 XC 3,6 - Dimethyl Decane 5.89E - 10 e1 36DM - C10 + CL = HCL + #1.46 RO2C + #.482 RO2XC + #.482 zRNO3 + #.518 xHO2 + #.001 xHCHO + #.056 xCCHO + #.165 xRCHO + #.029 xMEK + #.406 xPROD2 + yR 6OOH + #5.955 XC 3 - Methyl Undecane 6.39E - 10 e1 3 - ME - C11 + CL = HCL + #1.367 RO2C + #.469 RO2XC + #.469 zRNO3 + #.531 xHO2 + #.001 xHCHO + #.029 xCCHO + #.084 xRCHO + #.009 xMEK + #.449 xPROD2 + yR6OOH + #6.146 XC

### Table B - 7 (continued)

246

Com pound Rate const. [a] Mechanism [b] 5 - Methyl Undecane 6.39E - 10 e1 5 - ME - C11 + CL = HCL + #1.366 RO2C + #.469 RO2XC + #.469 zRNO3 + #.531 xHO2 + #.003 xCCHO + #.098 xRCHO + #.464 xPROD2 + yR6OOH + #6.098 XC 2,4,6,8 - Tetramethyl Nonane 5.49E - 10 e1 2468TMC9 + CL = #.488 xHO2 + #1.531 RO2C + #.512 RO2XC + #.512 zRNO3 + HCL + #.011 xHCHO + #.001 xCCHO + #.35 xRCHO + #.038 xACET + #.001 xMEK + #.28 xPROD2 + yR6OOH + #7.067 XC 3,6 - Dimethyl Undecane 6.51E - 10 e1 36DM - C11 + CL = HCL + #1.428 RO2C + #.488 RO2XC + #.488 zRNO3 + #.512 xHO2 + #.001 xHCHO + #.046 xCCHO + #.152 xRCHO + #.023 xMEK + #.406 xPROD2 + yR6OOH + #6.993 XC 3 - Methyl Dodecane 7.01E - 10 e1 3 - ME - C12 + CL = HCL + #1.351 RO2C + #.476 RO2XC + #.476 zRNO3 + #.524 xHO2 + #.001 xHCHO + #.026 xCCHO + #.076 xRCHO + #.008 xMEK + #.45 xPROD2 + yR6OOH + #7.13 XC 5 - Methyl Dodecane 7.01E - 1 0 e1 5 - ME - C12 + CL = HCL + #1.352 RO2C + #.478 RO2XC + #.478 zRNO3 + #.522 xHO2 + #.003 xCCHO + #.087 xRCHO + #.461 xPROD2 + yR6OOH + #7.099 XC Cyclopentane 3.09E - 10 e1 CYCC5 + CL = HCL + #2.438 RO2C + #.224 RO2XC + #.224 zRNO3 + #.776 xHO2 + #.054 xCO + #.756 xRCHO + #.02 xMEK + yR6OOH + #1.255 XC Cyclohexane 3.50E - 10 2 CYCC6 + CL = HCL + #1.272 RO2C + #.201 RO2XC + #.201 zRNO3 + #.799 xHO2 + #.203 xRCHO + #.597 xPROD2 + yR6OOH + #.608 XC Methylcyclopentane 3.21E - 10 e1 ME - CYCC5 + CL = HCL + #2.241 RO2C + #.31 RO2XC + #.31 zRNO3 + #.596 xHO2 + #.092 xMECO3 + #.003 xRCO3 + #.028 xCO + #.052 xHCHO + #.679 xRCHO + #.001 xMEK + #.007 xPROD2 + yR6OOH + #1.785 XC 1,2 - dimethylcyclopentane 3.32E - 10 e1 2468TMC9 + CL = #.488 xHO2 + #1.531 RO2C + #.512 RO2XC + #.51 2 zRNO3 + HCL + #.011 xHCHO + #.001 xCCHO + #.35 xRCHO + #.038 xACET + #.001 xMEK + #.28 xPROD2 + yR6OOH + #7.067 XC Ethyl Cyclopentane 3.83E - 10 e1 2468TMC9 + CL = #.488 xHO2 + #1.531 RO2C + #.512 RO2XC + #.512 zRNO3 + HCL + #.011 xHCHO + #.001 xCCHO + #. 35 xRCHO + #.038 xACET + #.001 xMEK + #.28 xPROD2 + yR6OOH + #7.067 XC Methylcyclohexane 3.90E - 10 2 ME - CYCC6 + CL = HCL + #1.6 RO2C + #.318 RO2XC + #.318 zRNO3 + #.682 xHO2 + #.044 xHCHO + #.003 xCCHO + #.377 xRCHO + #.31 xPROD2 + yR6OOH + #2.057 XC Ethylcyclohexane 4.45E - 10 e1 ET - CYCC6 + CL = HCL + #1.528 RO2C + #.365 RO2XC + #.365 zRNO3 + #.634 xHO2 + #.002 xHCHO + #.135 xCCHO + #.298 xRCHO + #.34 xPROD2 + yR6OOH + #2.602 XC Propene 2.67E - 10 3 PROPENE + CL = #.124 HCL + #.971 RO2C + #.029 RO2XC + #.029 zRNO3 + #.971 xHO2 + #.124 xMACR + yROOH + #2.328 XC 1 - Butene 3.39E - 10 4 2468TMC9 + CL = #.488 xHO2 + #1.531 RO2C + #.512 RO2XC + #.512 zRNO3 + HCL + #.011 xHCHO + #.001 xCCHO + #.35 xRCHO + #.038 xACET + #.001 xMEK + #.28 xPROD2 + yR6OOH + #7.067 XC (Me chanism is average of those for propene and 1 -butene) 1 - Pentene 4.05E - 10 4 1 - PENTEN + CL = #.408 HCL + #1.666 RO2C + #.136 RO2XC + #.136 zRNO3 + #.864 xHO2 + #.039 xHCHO + #.225 xCCHO + #.079 xRCHO + #.223 xMACR + #.021 xMVK + #.042 xIPRD + yR6OOH + #2.27 1 XC 3 - Methyl - 1 - Butene 3.52E - 10 5 Use mechanism derived for the 2 -butenes 1 - Hexene Use mechanism and rate constant of 1 -pentene 1 - Heptene Use mechanism and rate constant of 1 -pentene 1 - Octene Use mechanism and rate constant of 1 -pentene 1 -Nonene Use mechanism and rate constant of 1 -pentene 1 - Decene Use mechanism and rate constant of 1 -pentene 1 -Undecene Use mechanism and rate constant of 1 -pentene

### Table B - 7 (continued)

247

Com pound Rate const. [a] Mechanism [b] Isobutene 3.25E - 10 5 2468TMC9 + CL = #.488 xHO2 + #1.531 RO2C + #.512 RO2XC + #.512 zRNO3 + HCL + #.011 xHCHO + #.001 xCCHO + #.35 xRCHO + #.038 xACET + #.001 xMEK + #.28 xPROD2 + yR6OOH + #7.067 XC 2 - Methyl - 1 - Butene 3.82E - 10 5 2468TMC9 + CL = #.488 xHO2 + #1.531 RO2C + #.512 RO2XC + #.512 zRNO3 + HCL + #.011 xHCHO + #.001 xCCHO + #.35 xRCHO + #.038 xACET + #.001 xMEK + #.28 xPROD2 + yR6OOH + #7.067 XC cis - 2 - Butene 3.88E - 10 5 C - 2 - BUTE + CL = #.199 HCL + #.971 RO2C + #.079 RO2XC + #.079 zRNO3 + #.919 xHO2 + #.002 xMEO2 + #.047 xHCHO + #.104 xMVK + #.08 xIPRD + yROOH + #2.66 XC trans - 2 - Butene 3. 55E - 10 3 T - 2 - BUTE + CL = #.199 HCL + #.923 RO2C + #.077 RO2XC + #.077 zRNO3 + #.921 xHO2 + #.002 xMEO2 + #.104 xMVK + #.082 xIPRD + yROOH + #2.709 XC 2 - Methyl - 2 - Butene 3.23E - 10 5 Use mechanism derived for the 2 -butenes cis - 2 - Pentene 3.94E - 10 e1 C - 2 - PENT + CL = #.33 HCL + #1.729 RO2C + #.14 RO2XC + #.14 zRNO3 + #.282 xHO2 + #.001 xMEO2 + #.577 xCL + #.116 xHCHO + #.742 xCCHO + #.577 xRCHO + #.052 xMVK + #.231 xIPRD + yR6OOH + # - .535 XC trans - 2 - Pentene 3.94E - 10 e1 T - 2 - PENT + CL = #.33 HCL + #1.634 RO2C + # .134 RO2XC + #.134 zRNO3 + #.287 xHO2 + #.002 xMEO2 + #.577 xCL + #.078 xHCHO + #.687 xCCHO + #.577 xRCHO + #.052 xMVK + #.237 xIPRD + yR6OOH + # - .381 XC Cis - 2 - Hexene Use mechanism and rate constant derived for the 2 -pentenes Trans - 2 - Hexene Use mechanism and rate constant derived for the 2 -pentenes Trans - 2 - Heptene Use mechanism and rate constant derived for the 2 -pentenes Trans - 3 - Heptene Use mechanism and rate constant derived for the 2 -pentenes Trans - 4 - Octene Use mechanism and rate constant derived for the 2 -pentenes Trans - 4 -Nonene Use mechanism and rate constant derived for the 2 -pentenes 3,4 - Diethyl - 2 - Hexene Use mechanism and rate constant derived for the 2 -pentenes Trans - 4 - Decene Use mechanism and rate constant derived for the 2 -p entenes Trans - 5 -Undecene Use mechanism and rate constant derived for the 2 -pentenes Cyclohexene Use mechanism and rate constant derived for the 2 -pentenes 1,3 - Butadiene 4.90E - 10 2 13 - BUTDE + CL = #.39 xHO2 + #.541 xCL + #1.884 RO2C + #.069 RO2XC + # .069 zRNO3 + #.863 xHCHO + #.457 xMACR + #.473 xIPRD + yROOH + # - 1.47 XC alpha Pinene 5.46E - 10 e1 A - PINENE + CL = #.548 HCL + #2.258 RO2C + #.582 RO2XC + #.582 zRNO3 + #.252 xHO2 + #.034 xMECO3 + #.05 xRCO3 + #.016 xMACO3 + #.068 xCL + #.035 xCO + #.158 xHCHO + #.185 xRCHO + #.274 xACET + #.007 xGLY + #.003 xBACL + #.006 xAFG1 + #.006 xAFG2 + #.003 xMVK + #.158 xIPRD + yROOH + # - 6.231 XC Toluene 6.20E - 11 6 TOLUENE + CL = #.894 RO2C + #.106 RO2XC + #.106 zRNO3 + #.894 xHO2 + #.894 xBALD + yR6OOH + #.106 XC Ethyl Benzene 1.70E - 10 e1 C2 - BENZ + CL = #.864 RO2C + #.136 RO2XC + #.136 zRNO3 + #.864 xHO2 + #.864 xPROD2 + yR6OOH + #2 XC n - Propyl Benzene 2.28E - 10 e1 N - C3 - BEN + CL = #.838 RO2C + #.162 RO2XC + #.162 zRNO3 + #.838 xHO2 + #.838 xPROD2 + yR6OOH + #3 XC Isopropyl Benzene (cumene) 1.56E - 10 e1 I - C3 - BEN + CL = #.838 RO2C + #.162 RO2XC + #.162 zRNO3 + #.838 xHO2 + #.838 xPROD2 + yR6OOH + #3 XC C10 Monosubstituted Benzenes 2.48E - 10 e1 C10 - BEN1 + CL = #.82 RO2C + #.18 RO2XC + #.18 zRNO3 + #.82 xHO2 + #.82 xP ROD2 + yR6OOH + #4 XC t - Butyl Benzene 9.82E - 11 e1 T - C4 - BEN + CL = #.82 RO2C + #.18 RO2XC + #.18 zRNO3 + #.82 xHO2 + #.82 xPROD2 + yR6OOH + #4 XC

### Table B - 7 (continued)

248

Com pound Rate const. [a] Mechanism [b] C11 Monosubstituted Benzenes 3.10E - 10 e1 C11 - BEN1 + CL = #.808 RO2C + #.192 RO2XC + #.192 zRNO3 + #.808 xHO2 + #.808 xPROD2 + yR6OOH + #5 XC C12 Monosubstituted Benzenes 3.72E - 10 e1 C12 - BEN1 + CL = #.8 RO2C + #.2 RO2XC + #.2 zRNO3 + #.8 xHO2 + #.8 xPROD2 + yR6OOH + #6 XC C13 Monosubstituted Benzenes 4.33E - 10 e1 C13 - BEN1 + CL = #.795 RO2C + #.205 RO2XC + #.205 zRNO3 + #.795 xHO2 + #.795 xPROD2 + yR6OOH + #7 XC C14 Monosubstituted Benzenes 4.95E - 10 e1 C14 - BEN1 + CL = #.792 RO2C + #.208 RO2XC + #.208 zRNO3 + #.792 xHO2 + #.792 xPROD2 + yR6OOH + #8 XC C15 Monosubstituted Benzenes 5.57E - 10 e1 C15 - BEN1 + CL = #.791 RO2C + #.209 RO2XC + #.209 zRNO3 + #.791 xHO2 + #.791 xPROD2 + yR6OOH + #9 XC C16 Monosubstituted Benzenes 6.19E - 10 e1 C16 - BEN1 + CL = #.789 RO2C + #.211 RO2XC + #.211 zRNO3 + #.789 xHO2 + #.789 xPROD2 + yR6OOH + #10 XC m - Xylene 1.35E - 10 6 M - XYLENE + CL = #.864 RO2C + #.136 RO2XC + #.136 zRNO3 + #.864 xHO2 + #.864 xBALD + yR6OOH + #1.136 XC o - Xylene 1.40E - 10 6 O - XYLENE + CL = #.864 RO2C + #.136 RO2XC + #.136 zRNO3 + #.864 xHO2 + #.864 xBALD + yR6OOH + #1.136 XC p - Xylene 1.44E - 10 6 P - XYLENE + CL = #.864 RO2C + #.136 RO2XC + #.136 zRNO3 + #.864 xHO2 + #.864 xBALD + yR6OOH + #1.136 XC m - Ethyl Toluene 2.39E - 10 e1 M - ET - TOL + CL = #.838 RO2C + #.162 RO2XC + #.162 zRNO3 + #.838 xHO2 + #.243 xBALD + #.595 xPROD2 + yR6OOH + #2.757 XC o - Ethyl Toluene 2.39E - 10 e1 O - ET - TOL + CL = #.838 RO2C + #.162 RO2XC + #.162 zRNO3 + #.838 xHO2 + #.243 xBALD + #.595 xPROD2 + yR6OOH + #2.757 XC p - Ethyl Toluene 2.39E - 10 e1 P - ET - TOL + CL = #.838 RO2C + #.162 RO2XC + #.162 zRNO3 + #.838 xHO2 + #.243 xBALD + #.595 xPROD2 + yR6OOH + #2.757 XC m - c10 disubstituted benzenes 3.02E - 10 e1 MC10BEN2 + CL = #.82 RO2C + #.18 RO2XC + #.18 zRNO3 + #.82 xHO2 + #.094 xBALD + #.725 xPROD2 + yR6OOH + #3.906 XC o - c10 disubstituted benzenes 3.02E - 10 e1 OC10BEN2 + CL = #.82 RO2C + #.18 RO2XC + #.18 zR NO3 + #.82 xHO2 + #.094 xBALD + #.725 xPROD2 + yR6OOH + #3.906 XC p - c10 disubstituted benzenes 3.02E - 10 e1 PC10BEN2 + CL = #.82 RO2C + #.18 RO2XC + #.18 zRNO3 + #.82 xHO2 + #.094 xBALD + #.725 xPROD2 + yR6OOH + #3.906 XC 1 - methyl - 4 - isopropylbenzene (p cyme ne) 2.25E - 10 e1 P - CYMENE + CL = #.82 RO2C + #.18 RO2XC + #.18 zRNO3 + #.82 xHO2 + #.253 xBALD + #.567 xPROD2 + yR6OOH + #3.747 XC m - c11 disubstituted benzenes 3.53E - 10 e1 MC11BEN2 + CL = #.808 RO2C + #.192 RO2XC + #.192 zRNO3 + #.808 xHO2 + #.054 xBALD + #.754 xPROD2 + yR6OOH + #4.946 XC o - c11 disubstituted benzenes 3.53E - 10 e1 OC11BEN2 + CL = #.808 RO2C + #.192 RO2XC + #.192 zRNO3 + #.808 xHO2 + #.054 xBALD + #.754 xPROD2 + yR6OOH + #4.946 XC p - c11 disubstituted benzenes 3.53E - 10 e1 PC11BEN2 + CL = #. 808 RO2C + #.192 RO2XC + #.192 zRNO3 + #.808 xHO2 + #.054 xBALD + #.754 xPROD2 + yR6OOH + #4.946 XC m - c12 disubstituted benzenes 4.00E - 10 e1 MC12BEN2 + CL = #.8 RO2C + #.2 RO2XC + #.2 zRNO3 + #.8 xHO2 + #.035 xBALD + #.765 xPROD2 + yR6OOH + #5.965 XC o - c 12 disubstituted benzenes 4.00E - 10 e1 OC12BEN2 + CL = #.8 RO2C + #.2 RO2XC + #.2 zRNO3 + #.8 xHO2 + #.035 xBALD + #.765 xPROD2 + yR6OOH + #5.965 XC p - c12 disubstituted benzenes 4.00E - 10 e1 PC12BEN2 + CL = #.8 RO2C + #.2 RO2XC + #.2 zRNO3 + #.8 xHO2 + #.03 5 xBALD + #.765 xPROD2 + yR6OOH + #5.965 XC m - c13 disubstituted benzenes 4.58E - 10 e1 MC13BEN2 + CL = #.795 RO2C + #.205 RO2XC + #.205 zRNO3 + #.795 xHO2 + #.795 xPROD2 + yR6OOH + #7 XC o - c13 disubstituted benzenes 4.58E - 10 e1 OC13BEN2 + CL = #.795 RO2C + #.205 RO2XC + #.205 zRNO3 + #.795 xHO2 + #.795 xPROD2 + yR6OOH + #7 XC p - c13 disubstituted benzenes 4.58E - 10 e1 PC13BEN2 + CL = #.795 RO2C + #.205 RO2XC + #.205 zRNO3 + #.795 xHO2 + #.795 xPROD2 + yR6OOH + #7 XC

### Table B - 7 (continued)

249

Com pound Rate const. [a] Mechanism [b] m - c14 disubstituted benzenes 5.20E - 10 e1 MC14BEN2 + CL = #.792 RO2C + #.208 RO2XC + #.208 zRNO3 + #.792 xHO2 + #.792 xPROD2 + yR6OOH + #8 XC o - c14 disubstituted benzenes 5.20E - 10 e1 OC14BEN2 + CL = #.792 RO2C + #.208 RO2XC + #.208 zRNO3 + #.792 xHO2 + #.792 xPROD2 + yR6OOH + #8 XC p - c14 disubstituted benzenes 5.20E - 10 e1 PC14BEN2 + CL = #.792 RO2C + #.208 RO2XC + #.208 zRNO3 + #.792 xHO2 + #.792 xPROD2 + yR6OOH + #8 XC m - c15 disubstituted benzenes 5.81E - 10 e1 MC15BEN2 + CL = #.791 RO2C + #.209 RO2XC + #.209 zRNO3 + #.791 xHO2 + #.791 xPROD2 + yR6OOH + #9 XC o - c15 disubstituted benzenes 5.81E - 10 e1 OC15BEN2 + CL = #.791 RO2C + #.209 RO2XC + #.209 zRNO3 + #.791 xHO2 + #.791 xPROD2 + yR6OOH + #9 XC p - c15 disubstituted benzenes 5.81E - 10 e1 PC15BEN2 + CL = #.791 RO2C + #.209 RO2XC + #.209 zRNO3 + # .791 xHO2 + #.791 xPROD2 + yR6OOH + #9 XC m - c16 disubstituted benzenes 6.43E - 10 e1 MC16BEN2 + CL = #.789 RO2C + #.211 RO2XC + #.211 zRNO3 + #.789 xHO2 + #.789 xPROD2 + yR6OOH + #10 XC o - c16 disubstituted benzenes 6.43E - 10 e1 OC16BEN2 + CL = #.789 RO2C + #.211 RO2XC + #.211 zRNO3 + #.789 xHO2 + #.789 xPROD2 + yR6OOH + #10 XC p - c16 disubstituted benzenes 6.43E - 10 e1 PC16BEN2 + CL = #.789 RO2C + #.211 RO2XC + #.211 zRNO3 + #.789 xHO2 + #.789 xPROD2 + yR6OOH + #10 XC 1,2,3 - Trimethyl Benzene 2.42E - 10 e2 123 - TMB + CL = #.838 RO2C + #.162 RO2XC + #.162 zRNO3 + #.838 xHO2 + #.838 xBALD + yR6OOH + #2.162 XC 1,2,4 - Trimethyl Benzene 2.42E - 10 e2 124 - TMB + CL = #.838 RO2C + #.162 RO2XC + #.162 zRNO3 + #.838 xHO2 + #.838 xBALD + yR6OOH + #2.162 XC 1,3,5 - Trimethyl Benzene 2.42E - 10 7 135 - TMB + CL = #.838 RO2C + #.162 RO2XC + #.162 zRNO3 + #.838 xHO2 + #.838 xBALD + yR6OOH + #2.162 XC 1,2,3 - c10 trisubstituted benzenes 3.09E - 10 e1 3C10BEN3 + CL = #.808 RO2C + #.192 RO2XC + #.192 zRNO3 + #.808 xHO2 + #.363 xBALD + #.445 xPROD2 + yR6OOH + #3.637 XC 1,2,4 - c10 trisubstituted benzenes 3.09E - 10 e1 4C10BEN3 + CL = #.808 RO2C + #.192 RO2XC + #.192 zRNO3 + #.808 xHO2 + #.363 xBALD + #.445 xPROD2 + yR6OOH + #3.637 XC 1,3,5 - c10 trisubstituted benzenes 3.09E - 10 e1 5C10BEN3 + CL = #.808 RO2C + #.192 RO2XC + #.192 zRNO3 + #.808 xHO2 + #.363 xBALD + #.445 xPROD2 + yR6OOH + #3.637 XC 1,2,3 - c11 trisubstituted benzenes 3.88E - 10 e1 3C11BEN3 + CL = #.8 RO2C + #.2 RO2XC + #.2 zRNO3 + #.8 xHO2 + #.215 xBALD + #.585 xPROD2 + yR6OOH + #4.785 XC 1,2,4 - c11 trisubstituted benzenes 3.88E - 10 e1 4C11BEN3 + CL = #.8 RO2C + #.2 RO2XC + #.2 zRNO3 + #.8 xHO2 + #.215 xBALD + #.585 xPROD2 + yR6OOH + #4.785 XC 1,3,5 - c11 trisubstituted benzenes 3.88E - 10 e1 5C11BEN3 + CL = #.8 RO2C + #.2 RO2XC + #.2 zRNO3 + #.8 xHO2 + #.215 xBALD + #.585 xPROD2 + yR6OOH + #4.785 XC 1,2,3 - c12 trisubstituted benzenes 4.13E - 10 e1 3C12BEN3 + CL = #.795 RO2C + #.205 RO2XC + #.205 zRNO3 + #.795 xHO2 + #.179 xBALD + #.616 xPROD2 + yR6OOH + #5.821 XC 1,2,4 - c12 trisubstituted benz enes 4.13E - 10 e1 4C12BEN3 + CL = #.795 RO2C + #.205 RO2XC + #.205 zRNO3 + #.795 xHO2 + #.179 xBALD + #.616 xPROD2 + yR6OOH + #5.821 XC 1,3,5 - c12 trisubstituted benzenes 4.13E - 10 e1 5C12BEN3 + CL = #.795 RO2C + #.205 RO2XC + #.205 zRNO3 + #.795 xHO2 + #.17 9 xBALD + #.616 xPROD2 + yR6OOH + #5.821 XC 1,2,3 - c13 trisubstituted benzenes 4.87E - 10 e1 3C13BEN3 + CL = #.792 RO2C + #.208 RO2XC + #.208 zRNO3 + #.792 xHO2 + #.113 xBALD + #.679 xPROD2 + yR6OOH + #6.887 XC 1,2,4 - c13 trisubstituted benzenes 4.87E - 10 e1 4C13BEN3 + CL = #.792 RO2C + #.208 RO2XC + #.208 zRNO3 + #.792 xHO2 + #.113 xBALD + #.679 xPROD2 + yR6OOH + #6.887 XC 1,3,5 - c13 trisubstituted benzenes 4.87E - 10 e1 5C13BEN3 + CL = #.792 RO2C + #.208 RO2XC + #.208 zRNO3 + #.792 xHO2 + #.113 xBALD + #.679 xPROD2 + yR6OOH + #6.887 XC 1,2,3 - c14 trisubstituted benzenes 5.50E - 10 e1 3C14BEN3 + CL = #.792 RO2C + #.208 RO2XC + #.208 zRNO3 + #.792 xHO2 + #.075 xBALD + #.717 xPROD2 + yR6OOH + #7.925 XC

### Table B - 7 (continued)

250

Com pound Rate const. [a] Mechanism [b] 1,2,4 - c14 trisubstituted benzenes 5.50E - 10 e1 4C14BEN3 + CL = # .792 RO2C + #.208 RO2XC + #.208 zRNO3 + #.792 xHO2 + #.075 xBALD + #.717 xPROD2 + yR6OOH + #7.925 XC 1,3,5 - c14 trisubstituted benzenes 5.50E - 10 e1 5C14BEN3 + CL = #.792 RO2C + #.208 RO2XC + #.208 zRNO3 + #.792 xHO2 + #.075 xBALD + #.717 xPROD2 + yR6OOH + #7.925 XC 1,2,3 - c15 trisubstituted benzenes 5.88E - 10 e1 3C15BEN3 + CL = #.791 RO2C + #.209 RO2XC + #.209 zRNO3 + #.791 xHO2 + #.047 xBALD + #.744 xPROD2 + yR6OOH + #8.953 XC 1,2,4 - c15 trisubstituted benzenes 5.88E - 10 e1 4C15BEN3 + CL = #.791 RO2C + #.209 RO2XC + #.209 zRNO3 + #.791 xHO2 + #.047 xBALD + #.744 xPROD2 + yR6OOH + #8.953 XC 1,3,5 - c15 trisubstituted benzenes 5.88E - 10 e1 5C15BEN3 + CL = #.791 RO2C + #.209 RO2XC + #.209 zRNO3 + #.791 xHO2 + #.047 xBALD + #.744 xPROD2 + yR6OOH + #8.953 XC 1,2,3 - c16 trisubstituted benzenes 6.49E - 10 e1 3C16BEN3 + CL = #.789 RO2C + #.211 RO2XC + #.211 zRNO3 + #.789 xHO2 + #.021 xBALD + #.768 xPROD2 + yR6OOH + #9.979 XC 1,2,4 - c16 trisubstituted benzenes 6.49E - 10 e1 4C16BEN3 + CL = #.789 RO2C + #.211 RO2XC + #.211 zR NO3 + #.789 xHO2 + #.021 xBALD + #.768 xPROD2 + yR6OOH + #9.979 XC 1,3,5 - c16 trisubstituted benzenes 6.49E - 10 e1 5C16BEN3 + CL = #.789 RO2C + #.211 RO2XC + #.211 zRNO3 + #.789 xHO2 + #.021 xBALD + #.768 xPROD2 + yR6OOH + #9.979 XC PROD2 Species #1 1.35E - 10 e1 PROD2 - 1 + CL = HCL + #.512 HO2 + #.456 RO2C + #.032 RO2XC + #.032 zRNO3 + #.512 RCHO + #.429 xHO2 + #.018 xMECO3 + #.009 xRCO3 + #.438 xHCHO + #.447 xRCHO + #.488 yR6OOH + #1.431 XC PROD2 Species #2 1.46E - 10 e1 PROD2 - 2 + CL = HCL + #.476 HO2 + #.651 RO2C + #.063 RO2XC + #.063 zRNO3 + #.476 RCHO + #.445 xHO2 + #.016 xMECO3 + #.621 xHCHO + #.208 xRCHO + #.253 xMEK + #.524 yR6OOH + #1.904 XC PROD2 Species #3 1.78E - 10 e1 PROD2 - 3 + CL = HCL + #.255 HO2 + #.687 RO2C + #.107 RO2XC + #.107 zRNO3 + #.255 PRO D2 + #.568 xHO2 + #.069 xRCO3 + #.124 xHCHO + #.313 xCCHO + #.624 xRCHO + #.745 yR6OOH + #1.994 XC PROD2 Species #4 2.41E - 10 e1 PROD2 - 4 + CL = HCL + #.18 HO2 + #.782 RO2C + #.164 RO2XC + #.164 zRNO3 + #.18 PROD2 + #.629 xHO2 + #.027 xRCO3 + #.231 xCCHO + #.882 xRCHO + #.002 xPROD2 + #.82 yR6OOH + #2.73 XC PROD2 Species #5 3.02E - 10 e1 PROD2 - 5 + CL = HCL + #.146 HO2 + #.821 RO2C + #.214 RO2XC + #.214 zRNO3 + #.146 PROD2 + #.634 xHO2 + #.007 xRCO3 + #.796 xRCHO + #.2 xPROD2 + #.854 yR6OOH + #3.237 XC RNO3 S pecies #1 5.05E - 11 e1 RNO3 - 1 + CL = HCL + #.105 NO2 + #1.408 RO2C + #.065 RO2XC + #.065 zRNO3 + #.105 MEK + #.115 xNO2 + #.715 xHO2 + #.23 xCCHO + #.715 xRNO3 + #.895 yROOH + #.065 XN + # - 1.559 XC RNO3 Species #2 1.56E - 10 e1 RNO3 - 2 + CL = HCL + #.052 NO2 + #.291 HO2 + #.837 RO2C + #.058 RO2XC + #.058 zRNO3 + #.052 RCHO + #.291 RNO3 + #.599 xHO2 + #.003 xHCHO + #.373 xCCHO + #.599 xRNO3 + #.657 yR6OOH + #.058 XN + # - 1.594 XC RNO3 Species #3 1.45E - 10 e1 RNO3 - 3 + CL = HCL + #.037 NO2 + #1.511 RO2C + #.185 RO 2XC + #.185 zRNO3 + #.037 PROD2 + #.405 xNO2 + #.373 xHO2 + #.077 xHCHO + #.991 xCCHO + #.05 xRCHO + #.031 xMEK + #.06 xPROD2 + #.373 xRNO3 + #.963 yR6OOH + #.185 XN + # - .261 XC RNO3 Species #4 2.43E - 10 e1 RNO3 - 4 + CL = HCL + #.021 NO2 + #.036 HO2 + #1.15 8 RO2C + #.178 RO2XC + #.178 zRNO3 + #.021 PROD2 + #.036 RNO3 + #.159 xNO2 + #.605 xHO2 + #.008 xCCHO + #.011 xRCHO + #.159 xPROD2 + #.605 xRNO3 + #.943 yR6OOH + #.178 XN + #.952 XC RNO3 Species #5 1.61E - 10 e1 RNO3 - 5 + CL = HCL + #1.449 RO2C + #.304 RO2XC + #.304 zRNO3 + #.27 xNO2 + #.426 xHO2 + #.188 xHCHO + #.197 xCCHO + #.058 xRCHO + #.016 xACET + #.216 xMEK + #.054 xPROD2 + #.426 xRNO3 + yR6OOH + #.304 XN + #1.625 XC

### Table B - 7 (continued)

251

Com pound Rate const. [a] Mechanism [b] RNO3 Species #6 3.99E - 10 e1 RNO3 - 6 + CL = HCL + #.013 NO2 + #1.33 RO2C + #.42 RO2XC + #.42 zRNO3 + #.013 PROD2 + #.003 xNO2 + #.564 xHO2 + #.003 xPROD2 + #.564 xRNO3 + #.987 yR6OOH + #.42 XN + #4 XC [a] Rate constant for the reaction with Cl atoms in cm 3 mo lec - 1 s - 1 . The temperature dependences are unknown, so they are assumed to be temperature independent. Footnotes for measured rate constants are as follows: 1 IUPAC (2006) Recommendation 2 Atkinson (1997) Recommendation 3 Average of values tabulated by Wang et al (2002). Value of Wang et al (2002) placed on an absolute basis using the Atkinson (1997) -recommended rate constant for n - heptane. 4 Average of value of Coquet et al (2000), placed on an absolute basis using the Atkinson (1997) - recommended n - hexane rate constant, and the value of Wang et al (2002), placed on an absolute basis usin g the Atkinson (1997) -recommended rate constant for n -heptane. 5 Value of Wang et al (2002), placed on an absolute basis using the Atkinson (1997) -recommended rate constant for n - heptane. 6 Average of values tabulated by Wang et al (2005). 7 Wang et al (20 05) Footnotes for estimated rate constants are as follows: e1 Estimated using the group - additivity estimation assignments as indicated on Table 3 . e2 Estimated to have the same rate constant as 1,3,5 - trimethylbenzene. [b] Mechanisms derived for the mechanism generation system except for the aromatics, whose mechanisms were derived as discussed in the "Updated Aromatics Mechanisms" section.

### 252

Table B - 8 . Absorption cross sections used for the photolysis reactions for represented photoreactive

VOCs that are not in the base mechanism .

a) Phot set HOCCHO : Glycolaldehyde photolysis Note: Quantum yield of 0.75 is used for all wavelengths (not shown below) wl abs wl abs wl abs wl abs wl abs wl abs 205 3.91E - 19 228 6.37E - 21 251 2.50E - 20 274 5.40E - 20 297 3.29E - 20 320 3.29E - 21 206 3.37E - 19 229 6.37E - 21 252 2.65E - 20 275 5.41E - 20 298 3.17E - 20 321 2.85E - 21 207 2.87E - 19 230 6.49E - 21 253 2.82E - 20 276 5.39E - 20 299 3.02E - 20 322 2.49E - 21 208 2.46E - 19 231 6.44E - 21 254 2.97E - 20 277 5.42E - 20 300 2.90E - 20 323 2.13E - 21 209 2.12E - 19 232 6.80E - 21 255 3.09E - 20 278 5.37E - 20 301 2.74E - 20 324 1.85E - 21 210 1.81E - 19 233 7.23E - 21 256 3.21E - 20 279 5.34E - 20 302 2.51E - 20 325 1.47E - 21 211 1.53E - 19 234 7.85E - 21 257 3.39E - 20 280 5.34E - 20 303 2.26E - 20 326 1.28E - 21 212 1.30E - 19 235 8.33E - 21 258 3.59E - 20 281 5.37E - 20 304 2.07E - 20 327 1.05E - 21 213 1.12E - 19 236 8.80E - 21 259 3.75E - 20 282 5.37E - 20 305 1.91E - 20 328 8.70E - 22 214 9.40E - 20 237 9.39E - 21 260 3.89E - 20 283 5.25E - 20 306 1.77E - 20 329 8.40E - 22 215 7.84E - 20 238 1.03E - 20 261 4.02E - 20 284 5.12E - 20 307 1.64E - 20 330 6.80E - 22 216 6.49E - 20 239 1.11E - 20 262 4.13E - 20 285 5.01E - 20 308 1.50E - 20 331 5.80E - 22 217 5.30E - 20 240 1.20E - 20 263 4.24E - 20 286 4.93E - 20 309 1.36E - 20 332 4.30E - 22 218 4.26E - 20 241 1.28E - 20 264 4.40E - 20 287 4.80E - 20 310 1.25E - 20 333 4.00E - 22 219 3.37E - 20 242 1.38E - 20 265 4.60E - 20 288 4.67E - 20 311 1.15E - 20 334 4.00E - 22 220 2.65E - 20 243 1.50E - 20 266 4.75E - 20 289 4.58E - 20 312 1.03E - 20 335 3.90E - 22 221 2.13E - 20 244 1.59E - 20 267 4.85E - 20 290 4.50E - 20 313 8.84E - 21 336 0.00E+00 222 1.65E - 20 245 1.71E - 20 268 4.92E - 20 291 4.41E - 20 314 7.71E - 21 223 1.36E - 20 246 1.83E - 20 269 4.99E - 20 292 4.19E - 20 315 6.89E - 21 224 1.12E - 20 247 1.95E - 20 270 5.05E - 20 293 3.96E - 20 316 5.97E - 21 225 9.33E - 21 248 2.09E - 20 271 5.14E - 20 294 3.76E - 20 317 5.16E - 21 226 7.83E - 21 249 2.22E - 20 272 5.23E - 20 295 3.59E - 20 318 4.55E - 21 227 6.91E - 21 250 2.36E - 20 273 5.36E - 20 296 3.46E - 20 319 3.96E - 21 

### Wavelengths in nm and absorption cross - sections in cm- 2 

### . IUPAC (2006) recommendation (including 0.75 overall quantum yield)

b) Phot set CONO: Absorption cross - sections for methyl nitrite wl abs wl abs wl abs wl abs wl abs wl abs 250 1.55e - 18 295 8.60e - 20 320 1.45e - 19 345 1.45e - 19 370 1.24e - 19 395 2.70e - 20 260 1.00e - 18 300 7.00e - 20 325 9.70e - 20 350 2.91e - 19 375 9.70e - 20 400 1.10e - 20 280 1.83e - 19 305 6.50e - 20 330 2.37e - 19 355 1.78e - 19 380 4.90e - 20 405 1.40e - 20 285 1.49e - 19 310 9.10e - 20 335 1.19e - 19 360 1.62e - 19 385 4.30e - 20 410 - 290 1.08e - 19 315 8.10e - 20 340 3.07e - 19 365 1.67e - 19 390 4.30e - 20 

### Wavelengths in nm and absorption cross - sections in cm- 2 

### . Absorption cross - sections from Calvert and Pitts (1966). Unit quantum yields assumed.

### Table B - 8 (continued)

253 c) Phot set CS2 : Absorption cross - sections for carbon disulfide wl abs wl abs wl abs wl abs wl abs wl abs 280 5.30e - 22 296 1.13e - 20 312 6.69e - 20 328 2.85e - 20 344 5.56e - 21 360 1.19e - 21 281 6.20e - 22 297 1.86e - 20 313 8.15e - 20 329 2.85e - 20 345 3.53e - 21 361 4.20e - 22 282 8.00e - 22 298 2.29e - 20 314 7.84e - 20 330 3.80e - 20 346 3.50e - 21 362 4.80e - 22 283 1.03e - 21 299 2.02e - 20 315 9.44e - 20 331 1.30e - 20 347 3.28e - 21 363 2.10e - 22 284 1.22e - 21 300 1.88e - 20 316 7.04e - 20 332 3.06e - 20 348 1.09e - 21 364 3.70e - 22 285 1.58e - 21 301 3.27e - 20 317 9.46e - 20 333 1.55e - 20 349 3.68e - 21 365 1.20e - 22 286 2.09e - 21 302 3.17e - 20 318 7.16e - 20 334 1.51e - 20 350 2.39e - 21 366 3.60e - 22 287 2.54e - 21 303 3.13e - 20 319 9.80e - 20 335 1.38e - 20 351 1.27e - 21 367 2.30e - 22 288 3.09e - 21 304 4.44e - 20 320 4.52e - 20 336 8.61e - 21 352 2.55e - 21 368 2.00e - 22 289 4.45e - 21 305 4.46e - 20 321 6.12e - 20 337 1.38e - 20 353 6.60e - 22 369 1.10e - 22 290 4.38e - 21 306 3.66e - 20 322 4.22e - 20 338 5.91e - 21 354 1.72e - 21 370 1.80e - 22 291 6.35e - 21 307 5.12e - 20 323 5.18e - 20 339 1.12e - 20 355 2.47e - 21 371 292 6.40e - 21 308 7.10e - 20 324 3.52e - 20 340 4.89e - 21 356 5.20e - 22 293 8.78e - 21 309 4.93e - 20 325 8.63e - 20 341 3.86e - 21 357 1.33e - 21 294 8.01e - 21 310 8.84e - 20 326 5.02e - 20 342 5.73e - 21 358 5.50e - 22 295 1.14e - 20 311 5.61e - 20 327 3.48e - 20 343 3.87e - 21 359 5.90e - 22 

### Wavelengths in nm and absorption cross - sections in cm- 2 

### . IUPAC (2006) recommendation for absorption cross - sections. Unit quantum yields assumed.

d) Phot set CH3I: Absorption cross - sections for methyl iodide wl Abs wl Abs wl abs wl abs wl abs 280 2.80e - 19 300 2.03e - 20 320 2.15e - 21 340 2.30e - 22 360 1.30e - 23 285 1.52e - 19 305 1.09e - 20 325 1.24e - 21 345 1.27e - 22 365 4.00e - 24 290 7.79e - 20 310 6.19e - 21 330 7.00e - 22 350 6.70e - 23 370 - 295 3.92e - 20 315 3.56e - 21 335 3.30e - 22 355 2.60e - 23 

### Wavelengths in nm and absorption cross - sections in cm- 2 

### . IUPAC (2006) recommendation. e) Phot set BRNO2: Absorption cross - sections for BrNO2 used in the methyl iodide mechanism for INO2 wl Abs wl Abs wl abs wl abs wl abs wl abs 280 8.80e - 19 310 1.10e - 19 340 1.60e - 19 370 1.70e - 19 400 1.40e - 19 430 9.00e - 20 285 6.30e - 19 315 1.10e - 19 345 1.50e - 19 375 1.80e - 19 405 1.40e - 19 435 8.00e - 20 290 4.40e - 19 320 1.00e - 19 350 1.60e - 19 380 1.70e - 19 410 1.30e - 19 440 7.00e - 20 295 3.00e - 19 325 1.20e - 19 355 1.60e - 19 385 1.70e - 19 415 1.20e - 19 445 7.00e - 20 300 2.00e - 19 330 1.30e - 19 360 1.80e - 19 390 1.60e - 19 420 1.10e - 19 450 6.00e - 20 305 1.50e - 19 335 1.40e - 19 365 1.90e - 19 395 1.50e - 19 425 1.00e - 19 480 - 

### Wavelengths in nm and absorption cross - sections in cm- 2 

### . IUPAC (2006) recommendation.

f) Phot set HI: Absorption cross - sections for HI used in the methyl iodide mechanism. wl Abs wl Abs wl abs wl abs wl abs 280 8.94e - 20 295 3.17e - 20 310 1.01e - 20 325 2.47e - 21 340 4.70e - 22 285 6.37e - 20 300 2.23e - 20 315 6.53e - 21 330 1.45e - 21 347 - 290 4.51e - 20 305 1.52e - 20 320 4.09e - 21 335 8.30e - 22 

### Wavelengths in nm and absorption cross - sections in cm- 2 

### . IUPAC (2006) recommendation.

### Table B - 8 (continued)

254

g) Phot set HOI: Absorption cross - sections for HOI used in the methyl iodide mechanism. wl Abs wl Abs wl abs wl abs wl abs wl abs 280 7.70e - 21 320 2.07e - 18 360 2.58e - 18 400 3.22e - 18 440 1.13e - 18 480 2.96e - 20 285 2.26e - 20 325 2.72e - 18 365 2.21e - 18 405 3.32e - 18 445 8.13e - 19 485 1.61e - 20 290 5.89e - 20 330 3.29e - 18 370 1.98e - 18 410 3.27e - 18 450 5.63e - 19 490 8.60e - 21 295 1.37e - 19 335 3.70e - 18 375 1.94e - 18 415 3.07e - 18 455 3.76e - 19 496 - 300 2.86e - 19 340 3.85e - 18 380 2.07e - 18 420 2.75e - 18 460 2.42e - 19 305 5.41e - 19 345 3.77e - 18 385 2.33e - 18 425 2.35e - 18 465 1.50e - 19 310 9.26e - 19 350 3.47e - 18 390 2.66e - 18 430 1.92e - 18 470 9.04e - 20 315 1.45e - 18 355 3.04e - 18 395 2.98e - 18 435 1.50e - 18 475 5.25e - 20 

### Wavelengths in nm and absorption cross - sections in cm- 2 

### . IUPAC (2006) recommendation.

h) Phot set CLPICERI : Absorption cross - sections for chloropicrin wl abs wl abs wl abs wl abs wl abs wl abs 280 1.67e - 19 300 6.44e - 20 320 1.38e - 20 340 5.20e - 21 360 1.54e - 21 380 5.57e - 22 282 1.62e - 19 302 5.47e - 20 322 1.23e - 20 342 4.80e - 21 362 2.13e - 21 382 4.66e - 22 284 1.54e - 19 304 4.68e - 20 324 1.10e - 20 344 4.36e - 21 364 1.78e - 21 384 4.68e - 22 286 1.44e - 19 306 3.97e - 20 326 9.94e - 21 346 4.00e - 21 366 1.25e - 21 386 1.70e - 22 288 1.34e - 19 308 3.33e - 20 328 8.98e - 21 348 3.68e - 21 368 1.28e - 21 388 5.02e - 22 290 1.23e - 19 310 2.79e - 20 330 8.18e - 21 350 3.34e - 21 370 1.04e - 21 390 3.50e - 22 292 1.10e - 19 312 2.36e - 20 332 7.54e - 21 352 3.05e - 21 372 1.08e - 21 392 - 294 9.82e - 20 314 2.03e - 20 334 6.82e - 21 354 2.70e - 21 374 7.13e - 22 296 8.71e - 20 316 1.77e - 20 336 6.27e - 21 356 2.51e - 21 376 6.96e - 22 298 7.57e - 20 318 1.55e - 20 338 5.69e - 21 358 2.30e - 21 378 5.85e - 22 

### Wavelengths in nm and absorption cross - sections in cm- 2 

### . Absorption cross - sections from Carter et al (1997b). Unit quantum yields assumed.

i) Phot set MITC : Absorption cross - sections for methyl isothiocyanate. wl abs wl abs wl abs wl abs 285.6 3.44e - 20 302.5 1.23e - 20 317.5 3.48e - 21 332.5 4.00e - 22 290.0 2.66e - 20 307.5 8.52e - 21 322.5 1.96e - 21 337.5 1.70e - 22 297.5 1.70e - 20 312.5 5.63e - 21 327.5 9.60e - 22 340.0 - 

### Wavelengths in nm and absorption cross - sections in cm- 2 

### . Absorption cross - sections from Alvarez and Moore (1994). Unit quantum yields assumed.

### Table B - 8 (continued)

255 j) Phot set PAA : Peroxy acetic acid absorption cross - sections wl abs wl abs wl abs wl abs wl abs wl abs 210 3.81E - 19 234 7.03E - 20 258 1.93E - 20 282 4.44E - 21 306 7.80E - 22 330 9.00E - 23 212 3.31E - 19 236 6.31E - 20 260 1.71E - 20 284 3.86E - 21 308 6.90E - 22 332 1.10E - 22 214 2.95E - 19 238 5.61E - 20 262 1.53E - 20 286 3.34E - 21 310 6.20E - 22 334 1.10E - 22 216 2.54E - 19 240 5.03E - 20 264 1.35E - 20 288 2.97E - 21 312 4.50E - 22 336 9.00E - 23 218 2.17E - 19 242 4.83E - 20 266 1.21E - 20 290 2.56E - 21 314 4.40E - 22 338 9.00E - 23 220 1.89E - 19 244 4.31E - 20 268 1.06E - 20 292 2.26E - 21 316 4.00E - 22 340 6.00E - 23 222 1.60E - 19 246 3.82E - 20 270 9.45E - 21 294 1.93E - 21 318 3.50E - 22 342 3.00E - 23 224 1.39E - 19 248 3.41E - 20 272 8.35E - 21 296 1.70E - 21 320 2.50E - 22 344 0.00E+00 226 1.20E - 19 250 3.05E - 20 274 7.42E - 21 298 1.41E - 21 322 2.00E - 22 228 1.05E - 19 252 2.71E - 20 276 6.51E - 21 300 1.23E - 21 324 2.00E - 22 230 9.10E - 20 254 2.42E - 20 278 5.74E - 21 302 1.07E - 21 326 1.70E - 22 232 8.01E - 20 256 2.16E - 20 280 5.06E - 21 304 9.40E - 22 328 1.40E - 22 

### Wavelengths in nm and absorption cross - sections in cm- 2 

### . Orlando and Tyldall (2003)

### 256

Table B - 9 . Lumped molecule representations used in the SAPRC - 07 mechanism . Com pound or Mixture Representation Mol Com

pound Mol Com pound Mol Com pound Branched C5 Alkanes 1 Iso - Pentane Branched C6 Alkanes 0.5 2,3 - Dimethyl Butane 0.25 3 - Methylpentane 0.25 2 - Methyl Pentane C6 Cycloalkanes 1 Cyclohexane Branched C7 Alkanes 0.5 2,4 - Dimethyl Pentane 0.25 3 - Methyl Hexane 0.25 2 - Methyl Hexane C7 Cycloalkanes 1 Methylcyclohexane Branched C8 Alkanes 0.5 2,4 - Dimethyl Hexane 0.25 4 - Methyl Heptane 0.25 2 - Methyl Heptane C8 Bicycloalkanes 1 Methylcyclohexane C8 Cycloalkanes 1 Ethylcyclohexane Branched C9 Alkanes 0.5 2,4 - Dimethyl Heptane 0.25 4 - Methyl Octane 0.25 2 - Methyl Octane C9 Bicycloalkanes 0.5 Propyl Cyclohexane 0.5 1 - Ethyl - 4 - Methyl Cyclohexane C9 Cycloalkanes 0.5 Propyl Cyclohexane 0.5 1 - Ethyl - 4 - Methyl Cyclohexane Branched C10 Alkanes 0.5 2,6 - Dimethyl Octane 0.25 4 - Methyl Nonane 0.25 2 - Methyl Nonane C10 Bicycloalkanes 0.34 Butyl Cyclohexane 0.33 1 - Methyl - 3 - Isopropyl Cyclohexane 0.33 1,4 - Diethyl - Cyclohexane isobutylclohexane; (2 - methylpropyl) cyclohexane 1 Butyl Cyclohexane sec -butylcyclohexane 1 Butyl Cyclohexane C10 Cycloalkanes 0.34 Butyl Cyclohexane 0.33 1 - Methyl - 3 - Isopropyl Cyclohexane 0.33 1,4 - Diethyl - Cyclohexane Branched C11 alkanes 0.5 2,6 - Dimethyl Nonane 0.25 4 - Methyl Decane 0.25 3 - Methyl Decane C11 Bicycloalkanes 0.34 Pentyl Cyclohexane 0.33 1,3 - Diethyl - 5 - Methyl Cyclohexane 0.33 1 - Ethyl - 2 - Propyl Cyclohexane C11 Cycloalkanes 0.34 Pentyl Cyclohexane 0.33 1,3 - Diethyl - 5 - Methyl Cyclohexane 0.33 1 - Ethyl - 2 - Propyl Cyclohexane Branched C12 Alkanes 0.5 3,6 - Dimethyl Decane 0.25 5 - Methyl Undecane 0.25 3 - Methyl Undecane C12 Tricycloalkanes 0.34 Hexyl Cyclohexane 0.33 1,3,5 - Triethyl Cyclohexane 0.33 1 - Methyl - 4 - Pentyl Cyclohexane C12 Bicycloalkanes 0.34 Hexyl Cyclohexane 0.33 1,3,5 - Triethyl Cyclohexane 0.33 1 - Methyl - 4 - Pentyl Cyclohexane C12 Cycloalkanes 0.34 Hexyl Cyclohexane 0.33 1,3,5 - Triethyl Cyclohexane 0.33 1 - Methyl - 4 - Pentyl Cyclohexane

### Table B - 9 (continued)

257

Com pound or Mixture Representation Mol Com

pound Mol Com pound Mol Com pound Branched C13 Alkanes 0.5 3,6 - Dimethyl Undecane 0.25 5 - Methyl Dodecane 0.25 3 - Methyl Dodecane C13 Tricycloalkanes 0.34 Heptyl Cyclohexane 0.33 1,3 - Diethyl - 5 - Propyl Cyclohexane 0.33 1 - Methyl - 2 - Hexyl Cyclohexane C13 Bicycloalkanes 0.34 Heptyl Cyclohexane 0.33 1,3 - Diethyl - 5 - Propyl Cyclohexane 0.33 1 - Methyl - 2 - Hexyl Cyclohexane C13 Cycloalkanes 0.34 Heptyl Cyclohexane 0.33 1,3 - Diethyl - 5 - Propyl Cyclohexane 0.33 1 - Methyl - 2 - Hexyl Cyclohexane Branched C14 Alkanes 0.5 3,7 - Dimethyl Dodecane 0.25 6 - Methyl Tridecane 0.25 3 - Methyl Tridecane C14 Tricycloalkanes 0.34 Octyl Cyclohexane 0.33 1,3 - Dipropyl - 5 - Ethyl Cyclohexane 0.33 trans 1 - Methyl - 4 - Heptyl Cyclohexane C14 Bicycloalkanes 0.34 Octyl Cyclohexane 0.33 1,3 - Dipropyl - 5 - Ethyl Cyclohexane 0.33 trans 1 - Methyl - 4 - Heptyl Cyclohexane C14 Cycloalkanes 0.34 Octyl Cyclohexane 0.33 1,3 - Dipropyl - 5 - Ethyl Cyclohexane 0.33 trans 1 - Methyl - 4 - Heptyl Cyclohexane Branched C15 Alkanes 0.5 3,7 - Dimethyl Tridecane 0.25 6 - Methyl Tetradecane 0.25 3 - Methyl Tetradecane C15 Tricycloalkanes 0.34 Nonyl Cyclohexane 0.33 1,3,5 - Tripropyl Cyclohexane 0.33 1 - Methyl - 2 - Octyl Cyclohexane C15 Bicycloalkanes 0.34 Nonyl Cyclohexane 0.33 1,3,5 - Tripropyl Cyclohexane 0.33 1 - Methyl - 2 - Octyl Cyclohexane C15 Cycloalkanes 0.34 Nonyl Cyclohexane 0.33 1,3,5 - Tripropyl Cyclohexane 0.33 1 - Methyl - 2 - Octyl Cyclohexane Branched C16 Alkanes 0.5 4,8 - Dimethyl Tetradecane 0.25 7 - Methyl Pentadecane 0.25 3 - Methyl Pentadecane C16 Tricycloalkanes 0.34 Nonyl Cyclohexane 0.33 1,3,5 - Tripropyl Cyclohexane 0.33 1 - Methyl - 2 - Octyl Cyclohexane C16 Bicycloalkanes 0.34 Nonyl Cyclohexane 0.33 1,3,5 - Tripropyl Cyclohexane 0.33 1 - Methyl - 2 - Octyl Cyclohexane C16 Cycloalkanes 0.34 Decyl Cyclohexane 0.33 1,3 - Propyl - 5 - Butyl Cyclohexane 0.33 1 - Methyl - 4 -Nonyl Cyclohexane n - C17 1 n - C16 Branched C17 Alkanes 0.5 4,8 - Dimethyl Tetradecane 0.25 7 - Methyl Pentadecane 0.25 3 - Methyl Pentadecane C17 Tricycloalkanes 0.34 Nonyl Cyclohexane 0.33 1,3,5 - Tripropyl Cyclohexane 0.33 1 - Methyl - 2 - Octyl Cyclohexane C17 Bicycloalkanes 0.34 Nonyl Cyclohexane 0.33 1,3,5 - Tripropyl Cyclohexane 0.33 1 - Methyl - 2 - Octyl Cyclohexane

### Table B - 9 (continued)

258

Com pound or Mixture Representation Mol Com

pound Mol Com pound Mol Com pound C17 Cycloalkanes 0.34 Decyl Cyclohexane 0.33 1,3 - Propyl - 5 - Butyl Cyclohexane 0.33 1 - Methyl - 4 -Nonyl Cyclohexane n - C18 1 n - C16 Branched C18 Alkanes 0.5 4,8 - Dimethyl Tetradecane 0.25 7 - Methyl Pentadecane 0.25 3 - Methyl Pentadecane C18 Tricycloalkanes 0.34 Nonyl Cyclohexane 0.33 1,3,5 - Tripropyl Cyclohexane 0.33 1 - Methyl - 2 - Octyl Cyclohexane C18 Bicycloalkanes 0.34 Nonyl Cyclohexane 0.33 1,3,5 - Tripropyl Cyclohexane 0.33 1 - Methyl - 2 - Octyl Cyclohexane C18 Cycloalkanes 0.34 Decyl Cyclohexane 0.33 1,3 - Propyl - 5 - Butyl Cyclohexane 0.33 1 - Methyl - 4 -Nonyl Cyclohexane n - C19 1 n - C16 Branched C19 Alkanes 0.5 4,8 - Dimethyl Tetradecane 0.25 7 - Methyl Pentadecane 0.25 3 - Methyl Pentadecane C19 Tricycloalkanes 0.34 Nonyl Cyclohexane 0.33 1,3,5 - Tripropyl Cyclohexane 0.33 1 - Methyl - 2 - Octyl Cyclohexane C19 Bicycloalkanes 0.34 Nonyl Cyclohexane 0.33 1,3,5 - Tripropyl Cyclohexane 0.33 1 - Methyl - 2 - Octyl Cyclohexane C19 Cycloalkanes 0.34 Decyl Cyclohexane 0.33 1,3 - Propyl - 5 - Butyl Cyclohexane 0.33 1 - Methyl - 4 -Nonyl Cyclohexane n - C20 1 n - C16 Branched C20 Alkanes 0.5 4,8 - Dimethyl Tetradecane 0.25 7 - Methyl Pentadecane 0.25 3 - Methyl Pentadecane C20 Tricycloalkanes 0.34 Nonyl Cyclohexane 0.33 1,3,5 - Tripropyl Cyclohexane 0.33 1 - Methyl - 2 - Octyl Cyclohexane C20 Bicycloalkanes 0.34 Nonyl Cyclohexane 0.33 1,3,5 - Tripropyl Cyclohexane 0.33 1 - Methyl - 2 - Octyl Cyclohexane C20 Cycloalkanes 0.34 Decyl Cyclohexane 0.33 1,3 - Propyl - 5 - Butyl Cyclohexane 0.33 1 - Methyl - 4 -Nonyl Cyclohexane n - C21 1 n - C16 Branched C21 Alkanes 0.5 4,8 - Dimethyl Tetradecane 0.25 7 - Methyl Pentadecane 0.25 3 - Methyl Pentadecane C21 Tricycloalkanes 0.34 Nonyl Cyclohexane 0.33 1,3,5 - Tripropyl Cyclohexane 0.33 1 - Methyl - 2 - Octyl Cyclohexane C21 Bicycloalkanes 0.34 Nonyl Cyclohexane 0.33 1,3,5 - Tripropyl Cyclohexane 0.33 1 - Methyl - 2 - Octyl Cyclohexane C21 Cycloalkanes 0.34 Decyl Cyclohexane 0.33 1,3 - Propyl - 5 - Butyl Cyclohexane 0.33 1 - Methyl - 4 -Nonyl Cyclohexane n - C22 1 n - C16

### Table B - 9 (continued)

259

Com pound or Mixture Representation Mol Com

pound Mol Com pound Mol Com pound Branched C22 Alkanes 0.5 4,8 - Dimethyl Tetradecane 0.25 7 - Methyl Pentadecane 0.25 3 - Methyl Pentadecane C22 Tricycloalkanes 0.34 Nonyl Cyclohexane 0.33 1,3,5 - Tripropyl Cyclohexane 0.33 1 - Methyl - 2 - Octyl Cyclohexane C22 Bicycloalkanes 0.34 Nonyl Cyclohexane 0.33 1,3,5 - Tripropyl Cyclohexane 0.33 1 - Methyl - 2 - Octyl Cyclohexane C22 Cycloalkanes 0.34 Decyl Cyclohexane 0.33 1,3 - Propyl - 5 - Butyl Cyclohexane 0.33 1 - Methyl - 4 -Nonyl Cyclohexane C4 Terminal Alkenes 1 1 - Butene C4 Internal Alkenes 0.5 trans - 2 - Butene 0.5 cis - 2 - Butene C4 Alkenes 0.5 1 - Butene 0.25 trans - 2 - Butene 0.25 cis - 2 - Butene C5 Terminal Alkenes 1 1 - Pentene 2 - Pentenes 0.5 cis - 2 - Pentene 0.5 trans - 2 - Pentene C5 Internal Alkenes 0.5 cis - 2 - Pentene 0.5 trans - 2 - Pentene Cis 1,3 - Pentadiene 1 Trans 1,3 - Pentadiene Cyclopentadiene 1 Cyclopentene C5 Alkenes 0.5 1 - Pentene 0.25 cis - 2 - Pentene 0.25 trans - 2 - Pentene C6 Terminal Alkenes 1 1 - Hexene Cis 4 - Methyl - 2 - Pentene 1 Trans 4 - Methyl - 2 - Pentene 2 - Hexenes 0.5 Cis - 2 - Hexene 0.5 Trans - 2 - Hexene C6 Internal Alkenes 0.5 Cis - 2 - Hexene 0.5 Trans - 2 - Hexene trans,trans - 2,4 -hexadiene 1 Trans - 2 - Hexene Trans 1,3 - Hexadiene 1 Trans 1,3 - Pentadiene C6 Cyclic or di - olefins 0.5 Cis - 2 - Hexene 0.5 Trans - 2 - Hexene C6 Alkenes 0.5 1 - Heptene 0.25 Cis - 2 - Hexene 0.25 Trans - 2 - Hexene C7 Cyclic or di - olefins 1 Trans - 2 - Heptene 2 - Heptenes 0.5 Trans - 3 - Heptene 0.5 Cis - 3 - Heptene C7 Terminal Alkenes 1 1 - Heptene C7 Internal Alkenes 1 Trans - 3 - Heptene C7 Alkenes 0.5 1 - Heptene 0.5 Trans - 3 - Heptene C8 Cyclic or di - olefins 1 Trans - 4 - Octene 3 - Octenes 1 Trans - 3 - Octene C8 Terminal Alkenes 1 1 - Octene C8 Internal Alkenes 1 Trans - 4 - Octene C8 Alkenes 0.5 1 - Octene 0.5 Trans - 4 - Octene

### Table B - 9 (continued)

260

Com pound or Mixture Representation Mol Com

pound Mol Com pound Mol Com pound C9 Terminal Alkenes 1 1 -Nonene 4 -Nonene 1 Trans - 4 -Nonene 3 -Nonenes 1 Trans - 4 -Nonene C9 Internal Alkenes 1 Trans - 4 -Nonene C9 Cyclic or di - olefins 1 Trans - 4 -Nonene C9 Alkenes 0.5 1 -Nonene 0.5 Trans - 4 -Nonene C10 Terminal Alkenes 1 1 - Decene C10 3 - Alkenes 1 Trans - 4 - Decene C10 Internal Alkenes 1 Trans - 4 - Decene C10 Cyclic or di - olefins 1 Trans - 4 - Decene Camphene 1 a -pinene Terpene 0.4 a - Pinene 0.25 b - Pinene 0.1 d - Limonene 0.15 3 - Carene 0.1 Sabinene C10 Alkenes 0.333 1 - Decene 0.667 Trans - 4 - Decene C11 Terminal Alkenes 1 1 -Undecene C11 3 - Alkenes 1 Trans - 5 -Undecene C11 Internal Alkenes 1 Trans - 5 -Undecene C11 Cyclic or di - olefins 1 Trans - 5 -Undecene C11 Alkenes 0.5 1 -Undecene 0.5 Trans - 5 -Undecene C12 Terminal Alkenes 1 1 - Dodecene C12 2 - Alkenes 1 Trans - 5 - Dodecene C12 3 - Alkenes 1 Trans - 5 - Dodecene C12 Internal Alkenes 1 Trans - 5 - Dodecene C12 Cyclic or di - olefins 1 Trans - 5 - Dodecene C12 Alkenes 0.5 1 - Dodecene 0.5 Trans - 5 - Dodecene C13 Terminal Alkenes 1 1 - Tridecene C13 3 - Alkenes 1 Trans - 5 - Tridecene C13 Internal Alkenes 1 Trans - 5 - Tridecene C13 Cyclic or di - olefins 1 Trans - 5 - Tridecene C13 Alkenes 0.5 1 - Tridecene 0.5 Trans - 5 - Tridecene C14 Terminal Alkenes 1 1 - Tetradecene C14 3 - Alkenes 1 Trans - 5 - Tetradecene C14 Internal Alkenes 1 Trans - 5 - Tetradecene C14 Cyclic or di - olefins 1 Trans - 5 - Tetradecene

### Table B - 9 (continued)

261

Com pound or Mixture Representation Mol Com

pound Mol Com pound Mol Com pound C14 Alkenes 0.5 1 - Tetradecene 0.5 Trans - 5 - Tetradecene 1 -pentadecene 1 1 - Tetradecene C15 Terminal Alkenes 1 1 - Tetradecene C15 3 - Alkenes 1 Trans - 5 - Pentadecene C15 Internal Alkenes 1 Trans - 5 - Pentadecene C15 Cyclic or di - olefins 1 Trans - 5 - Pentadecene C15 Alkenes 0.5 1 - Tetradecene 0.5 Trans - 5 - Pentadecene C8 Disubstituted Benzenes 0.34 m - Xylene 0.33 o - Xylene 0.33 p - Xylene Isomers of Ethylbenzene 0.25 m - Xylene 0.25 o - Xylene 0.25 p - Xylene 0.25 Ethyl Benzene C9 Monosubstituted Benzenes 1 n - Propyl Benzene C9 Disubstituted Benzenes 0.334 m - Ethyl Toluene 0.333 o - Ethyl Toluene 0.333 p - Ethyl Toluene C9 Trisubstituted Benzenes 0.334 1,2,4 - Trimethyl Benzene 0.333 1,2,3 - Trimethyl Benzene 0.333 1,3,5 - Trimethyl Benzene Isomers of Propylbenzene 0.111 1,3,5 - Trimethyl Benzene 0.111 1,2,3 - Trimethyl Benzene 0.111 1,2,4 - Trimethyl Benzene 0.334 n - Propyl Benzene 0.111 m - Ethyl Toluene 0.111 o - Ethyl Toluene 0.111 p - Ethyl Toluene Indene 1 Styrene Indan 1 Tetralin Allylbenzene 1 Styrene a - Methyl Styrene 1 Styrene C9 Styrenes 1 Styrene n - Butyl Benzene 1 C10 Monosubstituted Benzenes s - Butyl Benzene 1 C10 Monosubstituted Benzenes o - cymene; 1 - methyl - 2 - (1 - methylethyl)benzene 1 o - c10 disubstituted benzenes 1 - methyl - 2 - n -propylbenzene 1 o - c10 disubstituted benzenes m - cymene; 1 - methyl - 3 - (1 - methylethyl)benzene 1 m - c10 disubstituted benzenes 1 - methyl - 3 - n -propylbenzene 1 m - c10 disubstituted benzenes 1 - methyl - 4 - n -propylbenzene 1 p - c10 disubstituted benzenes C10 Disubstituted Benzenes 0.334 m - c10 disubstituted benzenes 0.333 o - c10 disubstituted benzenes 0.333 p - c10 disubstituted benzenes m - Diethyl Benzene 1 m - c10 disubstituted benzenes o - Diethyl Benzene 1 o - c10 disubstituted benzenes p - Diethyl Benzene 1 p - c10 disubstituted benzenes

### Table B - 9 (continued)

262

Com pound or Mixture Representation Mol Com

pound Mol Com pound Mol Com pound 1,2,3,4 - tetramethylbenzene 0.334 1,2,4 - c10 trisubstituted benzenes 0.333 1,2,3 - c10 trisubstituted benzenes 0.333 1,3,5 - c10 trisubstituted benzenes 1,2,4,5 - tetramethylbenzene 0.334 1,2,4 - c10 trisubstituted benzenes 0.333 1,2,3 - c10 trisubstituted benzenes 0.333 1,3,5 - c10 trisubstituted benzenes 1,2 - dimethyl - 3 - ethylbenzene 1 1,2,3 - c10 trisubstituted benzenes 1,2 - dimethyl - 4 - ethylbenzene 1 1,2,4 - c10 trisubstituted benzenes 1,3 - dimethyl - 2 - ethylbenzene 1 1,2,3 - c10 trisubstituted benzenes 1,3 - dimethyl - 4 - ethylbenze ne 1 1,2,4 - c10 trisubstituted benzenes 1,3 - dimethyl - 5 - ethylbenzene 1 1,3,5 - c10 trisubstituted benzenes 1,4 - dimethyl - 2 - ethylbenzene 1 1,2,4 - c10 trisubstituted benzenes 1,2,3,5 Tetramethyl Benzene 0.334 1,2,4 - c10 trisubstituted benzenes 0.333 1,2,3 - c10 trisubstituted benzenes 0.333 1,3,5 - c10 trisubstituted benzenes C10 Trisubstituted Benzenes 0.334 1,2,4 - c10 trisubstituted benzenes 0.333 1,2,3 - c10 trisubstituted benzenes 0.333 1,3,5 - c10 trisubstituted benzenes C10 Tetrasubstituted Benzenes 0. 334 1,2,4 - c10 trisubstituted benzenes 0.333 1,2,3 - c10 trisubstituted benzenes 0.333 1,3,5 - c10 trisubstituted benzenes Isomers of Butylbenzene 0.334 C10 Monosubstituted Benzenes 0.111 o - c10 disubstituted benzenes 0.111 m - c10 disubstituted benzenes 0.111 p - c10 disubstituted benzenes 0.111 1,2,3 - c10 trisubstituted benzenes 0.111 1,2,4 - c10 trisubstituted benzenes 0.111 1,3,5 - c10 trisubstituted benzenes Methyl Indans 1 Tetralin C10 Styrenes 1 Styrene n -pentylbenzene 1 C11 Monosubstituted Benz enes 1 -butyl - 2 - methylbenzene 1 o - c11 disubstituted benzenes 1 - ethyl - 2 - n -propylbenzene 1 o - c11 disubstituted benzenes o - t -butyl toluene; 1 - (1,1 - dimethylethyl) - 2 - methylbenzene 1 o - c11 disubstituted benzenes 1 - methyl - 3 - n -butyl -benzene 1 m - c11 disubstituted benzenes p - Isobutyl toluene; 1 - methyl - 4(2 - methylpropyl) benzene 1 p - c11 disubstituted benzenes C11 Disubstituted Benzenes 0.334 m - c11 disubstituted benzenes 0.333 o - c11 disubstituted benzenes 0.333 p - c11 disubstituted benzenes Pentamethylbenzene 0.334 1,2,4 - c11 trisubstituted benzenes 0.333 1,2,3 - c11 trisubstituted benzenes 0.333 1,3,5 - c11 trisubstituted benzenes 1 - methyl - 3,5 - diethylbenzene 1 1,3,5 - c11 trisubstituted benzenes

### Table B - 9 (continued)

263

Com pound or Mixture Representation Mol Com

pound Mol Com pound Mol Com pound C11 Trisubstituted Benzenes 0.334 1,2,4 - c11 tri substituted benzenes 0.333 1,2,3 - c11 trisubstituted benzenes 0.333 1,3,5 - c11 trisubstituted benzenes C11 Tetrasubstituted Benzenes 0.334 1,2,4 - c11 trisubstituted benzenes 0.333 1,2,3 - c11 trisubstituted benzenes 0.333 1,3,5 - c11 trisubstituted benzenes C11 Pentasubstituted Benzenes 0.334 1,2,4 - c11 trisubstituted benzenes 0.333 1,2,3 - c11 trisubstituted benzenes 0.333 1,3,5 - c11 trisubstituted benzenes Isomers of Pentylbenzene 0.334 C10 Monosubstituted Benzenes 0.111 o - c11 disubstituted benzenes 0.111 o - c11 disubstituted benzenes 0.111 p - c11 disubstituted benzenes 0.111 1,2,3 - c11 trisubstituted benzenes 0.111 1,2,4 - c11 trisubstituted benzenes 0.111 1,3,5 - c11 trisubstituted benzenes C11 Tetralin or Indan 1 Tetralin 1 - Methyl Naphthalene 1 Methyl Naphthalenes 2 - Methyl Naphthalene 1 Methyl Naphthalenes 1,3 - di -n -propylbenzene 1 o - c12 disubstituted benzenes 1,4 diisopropyl benzene 1 p - c12 disubstituted benzenes 3 - Isopropyl Cumene; 1,3 - diisopropyl benzene 1 m - c12 disubstituted benzene s C12 Disubstituted Benzenes 0.334 m - c12 disubstituted benzenes 0.333 o - c12 disubstituted benzenes 0.333 p - c12 disubstituted benzenes 1 - (1,1 - dimethylethyl) - 3,5 - dimethylbenzene 1 1,3,5 - c12 trisubstituted benzenes C12 Trisubstituted Benzenes 0.334 1,2,4 - c12 trisubstituted benzenes 0.333 1,2,3 - c12 trisubstituted benzenes 0.333 1,3,5 - c12 trisubstituted benzenes C12 Tetrasubstituted Benzenes 0.334 1,2,4 - c12 trisubstituted benzenes 0.333 1,2,3 - c12 trisubstituted benzenes 0.333 1,3,5 - c12 trisubstituted benzenes C12 Pentasubstituted Benzenes 0.334 1,2,4 - c12 trisubstituted benzenes 0.333 1,2,3 - c12 trisubstituted benzenes 0.333 1,3,5 - c12 trisubstituted benzenes C12 Hexasubstituted Benzenes 0.334 1,2,4 - c12 trisubstituted benzenes 0.333 1,2,3 - c12 trisubstituted benzenes 0.333 1,3,5 - c12 trisubstituted benzenes Isomers of Hexylbenzene 0.334 C10 Monosubstituted Benzenes 0.111 o - c12 disubstituted benzenes 0.111 o - c12 disubstituted benzenes 0.111 p - c12 disubstituted benzenes 0.111 1,2,3 - c12 trisubstituted benzenes 0.111 1,2,4 - c12 trisubstituted benzenes 0.111 1,3,5 - c12 trisubstituted benzenes C12 Tetralin or Indan 1 Tetralin 1 - Ethylnaphthalene 1 Methyl Naphthalenes C12 Naphthalenes 0.5 Methyl Naphthalenes 0.5 2,3 - Dimethyl Naphthalene

### Table B - 9 (continued)

264

Com pound or Mixture Representation Mol Com

pound Mol Com pound Mol Com pound C12 Mo nosubstituted Naphthalene 1 Methyl Naphthalenes C12 Disubstituted Naphthalenes 1 2,3 - Dimethyl Naphthalene Dimethyl Naphthalenes 1 2,3 - Dimethyl Naphthalene C13 Disubstituted Benzenes 0.334 m - c13 disubstituted benzenes 0.333 o - c13 disubstitute d benzenes 0.333 p - c13 disubstituted benzenes C13 Trisubstituted Benzenes 0.334 1,2,4 - c13 trisubstituted benzenes 0.333 1,2,3 - c13 trisubstituted benzenes 0.333 1,3,5 - c13 trisubstituted benzenes C13 Tetralin or Indan 1 Tetralin C13 Naphthalenes 0.5 M ethyl Naphthalenes 0.5 2,3 - Dimethyl Naphthalene C13 Monosubstituted Naphthalene 1 Methyl Naphthalenes C13 Disubstituted Naphthalenes 1 2,3 - Dimethyl Naphthalene C13 Trisubstituted Naphthalenes 1 2,3 - Dimethyl Naphthalene C14 Disubstituted B enzenes 0.334 m - c14 disubstituted benzenes 0.333 o - c14 disubstituted benzenes 0.333 p - c14 disubstituted benzenes C14 Trisubstituted Benzenes 0.334 1,2,4 - c14 trisubstituted benzenes 0.333 1,2,3 - c14 trisubstituted benzenes 0.333 1,3,5 - c14 trisubstituted benzenes C14 Tetralin or Indan 1 Tetralin C14 Naphthalenes 0.5 Methyl Naphthalenes 0.5 2,3 - Dimethyl Naphthalene C15 Disubstituted Benzenes 0.334 m - c15 disubstituted benzenes 0.333 o - c15 disubstituted benzenes 0.333 p - c15 disubstituted benzenes C15 Trisubstituted Benzenes 0.334 1,2,4 - c15 trisubstituted benzenes 0.333 1,2,3 - c15 trisubstituted benzenes 0.333 1,3,5 - c15 trisubstituted benzenes C15 Tetralin or Indan 1 Tetralin C15 Naphthalenes 0.5 Methyl Naphthalenes 0.5 2,3 - Dimethyl Naphthalene C 16 Disubstituted Benzenes 0.334 m - c16 disubstituted benzenes 0.333 o - c16 disubstituted benzenes 0.333 p - c16 disubstituted benzenes C16 Trisubstituted Benzenes 0.334 1,2,4 - c16 trisubstituted benzenes 0.333 1,2,3 - c16 trisubstituted benzenes 0.333 1,3,5 - c16 trisubstituted benzenes C16 Tetralin or Indan 1 Tetralin C16 Naphthalenes 0.5 Methyl Naphthalenes 0.5 2,3 - Dimethyl Naphthalene C17 Monosubstituted Benzenes 1 C16 Monosubstituted Benzenes C17 Disubstituted Benzenes 0.334 m - c16 disubstituted benzenes 0.333 o - c16 disubstituted benzenes 0.333 p - c16 disubstituted benzenes C17 Trisubstituted Benzenes 0.334 1,2,4 - c16 trisubstituted benzenes 0.333 1,2,3 - c16 trisubstituted benzenes 0.333 1,3,5 - c16 trisubstituted benzenes C17 Tetralin or Indan 1 Tetralin C17 Naphthalenes 0.5 Methyl Naphthalenes 0.5 2,3 - Dimethyl Naphthalene C18 Monosubstituted Benzenes 1 C16 Monosubstituted Benzenes C18 Disubstituted Benzenes 0.334 m - c16 disubstituted benzenes 0.333 o - c16 disubstituted benzenes 0.333 p - c16 disubstituted benzenes

### Table B - 9 (continued)

265

Com pound or Mixture Representation Mol Com

pound Mol Com pound Mol Com pound C18 Trisubstituted Benzenes 0.334 1,2,4 - c16 trisubstituted benzenes 0.333 1,2,3 - c16 trisubstituted benzenes 0.333 1,3,5 - c16 trisubstituted benzenes C18 Tetralin or Indan 1 Tetralin C18 Naphthalenes 0.5 Methyl Naphthalenes 0.5 2,3 - Dimethyl Naphthalene C19 Monosubstituted Benzenes 1 C16 Monosubstituted Benzenes C19 Disubstituted Benzenes 0.334 m - c16 disubstituted benzenes 0.333 o - c16 disubstituted benzenes 0.333 p - c16 disubstituted benzenes C19 Trisubstituted Benzenes 0. 334 1,2,4 - c16 trisubstituted benzenes 0.333 1,2,3 - c16 trisubstituted benzenes 0.333 1,3,5 - c16 trisubstituted benzenes C19 Tetralin or Indan 1 Tetralin C19 Naphthalenes 0.5 Methyl Naphthalenes 0.5 2,3 - Dimethyl Naphthalene C20 Monosubstituted Benzen es 1 C16 Monosubstituted Benzenes C20 Disubstituted Benzenes 0.334 m - c16 disubstituted benzenes 0.333 o - c16 disubstituted benzenes 0.333 p - c16 disubstituted benzenes C20 Trisubstituted Benzenes 0.334 1,2,4 - c16 trisubstituted benzenes 0.333 1,2,3 - c16 trisubstituted benzenes 0.333 1,3,5 - c16 trisubstituted benzenes C20 Tetralin or Indan 1 Tetralin C20 Naphthalenes 0.5 Methyl Naphthalenes 0.5 2,3 - Dimethyl Naphthalene C21 Monosubstituted Benzenes 1 C16 Monosubstituted Benzenes C21 Disubstituted Benzenes 0.334 m - c16 disubstituted benzenes 0.333 o - c16 disubstituted benzenes 0.333 p - c16 disubstituted benzenes C21 Trisubstituted Benzenes 0.334 1,2,4 - c16 trisubstituted benzenes 0.333 1,2,3 - c16 trisubstituted benzenes 0.333 1,3,5 - c16 trisubstituted benzenes C21 Tetralin or Indan 1 Tetralin C21 Naphthalenes 0.5 Methyl Naphthalenes 0.5 2,3 - Dimethyl Naphthalene C22 Monosubstituted Benzenes 1 C16 Monosubstituted Benzenes C22 Disubstituted Benzenes 0.334 m - c16 disubstituted benzenes 0.333 o - c16 disubstituted benzenes 0.333 p - c16 disubstituted benzenes C22 Trisubstituted Benzenes 0.334 1,2,4 - c16 trisubstituted benzenes 0.333 1,2,3 - c16 trisubstituted benzenes 0.333 1,3,5 - c16 trisubstituted benzenes C22 Tetralin or Indan 1 Tetralin C22 N aphthalenes 0.5 Methyl Naphthalenes 0.5 2,3 - Dimethyl Naphthalene Peroxyacetic Acid 1 Acetic Acid C4 aldehydes 1 Butanal C5 Cyclic Ketones 1 Cyclopentanone C5 Aldehydes 1 Pentanal (Valeraldehyde) C5 Ketones 1 2 - Pentanone Phenol 1 o - Cresol

### Table B - 9 (continued)

266

Com pound or Mixture Representation Mol Com

pound Mol Com pound Mol Com pound 2 - Ethyl furan 1 2 - methyl furan C6 Cyclic Ketones 1 Cyclohexanone mesityl oxide (2 - methyl - 2 -penten 4 - one) 1 Lumped product model species ISO - PROD C6 Aldehydes 1 Hexanal C6 Ketones 1 Methyl n - Butyl Ketone C7 Alkyl Phenols 1 o - Cresol m - Cresol 1 o - Cresol p - Cresol 1 o - Cresol C7 Cyclic Ketones 1 Cyclohexanone C7 Aldehydes 1 Heptanal C7 Ketones 1 2 - Heptanone Tolualdehyde 1 Benzaldehyde 4 - vinylphenol 1 styrene 2,4 - Dimethyl Phenol 1 o - Cresol 2,5 - Dimethyl Phenol 1 o - Cresol 3,4 - Dimethyl Phenol 1 o - Cresol 2,3 - Dimethyl Phenol 1 o - Cresol 2,6 - Dimethyl Phenol 1 o - Cresol C8 Alkyl Phenols 1 o - Cresol beta -phenethyl alcohol 1 benzyl alcohol C8 Cyclic Ketones 1 Cyclohexanone C8 Aldehydes 1 Octanal C8 Ketones 1 2 - Octanone Hexyl Acetates 0.5 n - Hexyl Acetate 0.125 2 - Methylpentyl Acetate 0.125 3 - Methylpentyl Acetate 0.125 4 - Methylpentyl Acetate 0.125 2,3 - Dimethylbutyl Acetate methylparaben (4 - Hydroxybenzoic acid, methyl ester) 1 o - cresol Cinnamic aldehyde 1 lumped c5+ unsaturated carbonyl species Cinnamic alcohol 1 b - methyl styrene 2,3,5 - Trimethyl Phenol 1 o - Cresol 2,3,6 - Trimethyl Phenol 1 o - Cresol C9 Alkyl Phenols 1 o - Cresol

### Table B - 9 (continued)

267

Com pound or Mixture Representation Mol Com

pound Mol Com pound Mol Com pound isophorone {3,5,5 - trimethyl - 2 - cyclohexenone} 1 Lumped product model species ISO - PROD C9 Cyclic Ketones 1 Cyclohexanone C9 Ketones 1 2 -Nonanone 1 -phenoxy - 2 -propanol 1 n - Propyl Benzene Dipropylene glycol methyl ether acetate isomers 0.5 Dipropylene glycol methyl ether acetate isomer #1 0.5 Dipropylene glycol methyl ether acetate isomer #2 anethol 1 b - methyl styrene C10 Alkyl Phenols 1 o - Cresol C10 Cyclic Ketones 1 Cyclohexanone C10 Ketones 1 2 - Decanone propylp araben 1 o - cresol C11 Alkyl Phenols 1 o - Cresol C12 Alkyl Phenols 1 o - Cresol Texanol isomers 0.67 3 - Hydroxy - 2,2,4 - Trimethylpentyl - 1 - Isobutyrate 0.33 1 - Hydroxy - 2,2,4 - Trimethylpentyl - 3 - Isobutyrate Substituted C7 ester (C12) 0.67 3 - Hydroxy - 2 ,2,4 - Trimethylpentyl - 1 - Isobutyrate 0.33 1 - Hydroxy - 2,2,4 - Trimethylpentyl - 3 - Isobutyrate Substituted C9 Ester (C12) 0.67 3 - Hydroxy - 2,2,4 - Trimethylpentyl - 1 - Isobutyrate 0.33 1 - Hydroxy - 2,2,4 - Trimethylpentyl - 3 - Isobutyrate Amyl cinnamal 1 lumped c5+ unsaturated carbonyl species isobornyl methacrylate 1 isobutyl methacrylate Hexyl cinnamal 1 lumped c5+ unsaturated carbonyl species 2,6 - di - tert -butyl -p - cresol 1 o - cresol methyl cis - 9 - hexadecenoate (methyl palmitoleate) 1 methyl cis - 9 -pentadec enoate methyl hexadecanoate; methyl palmitate 1 methyl pentadecanoate Methyl cis - 9 - heptadecenoate 1 methyl cis - 9 -pentadecenoate

### Table B - 9 (continued)

268

Com pound or Mixture Representation Mol Com

pound Mol Com pound Mol Com pound methyl heptadecanoate; methyl margarate 1 methyl pentadecanoate methyl cis - 9 - octadecenoate; methyl oleate 1 methyl cis - 9 -pentadecenoate methyl octadecanoate; methyl stearate 1 methyl pentadecanoate Carbon Tetrachloride 1 Represented as inert Methylene Bromide 1 Represented as inert Cis - 1,2 - Dichloroethene 1 Trans - 1,2 - Dichloroethene 1,3 - di chloropropene mixture 0.56 cis - 1,3 - dichloropropene 0.44 trans - 1,3 - dichloropropene 1 -buten - 3 - yne (vinyl acetylene) 1 1 - Butene methyl nonafluoroisobutyl ether 1 methyl nonafluorobutyl ether Methoxy perfluoro isobutane 1 Methoxy perfluoro n -butane triethylene diamine 1 triethyl amine o - dichlorobenzene 1 p - dichlorobenzene ethyl nonafluoroisobutyl ether 1 ethyl nonafluorobutyl ether Perfluorohexane 1 Represented as inert 2 - chlorotoluene 1 toluene 3 - (Chloromethyl) - Heptane 1 3 - Methyl Heptane 2,6 - Toluene Diisocyanate 1 2,4 - Toluene Diisocyanate Toluene Diisocyanate (mixed isomers) 1 2,4 - Toluene Diisocyanate lauryl pyrrolidone 1 n - methyl - 2 -py rrolidone

### 269

Table B - 10 . Listing of components of complex mixtures for which atmospheric reactivities have been

calculated. (Available in electronic form only) **Because of the size of this table, it is only available in as supplementary material in electronic form. See Appendix D.** 

Table B - 1 1 . Assignments of e xplicitly represented compounds to lumped model species in the fixed

parameter mechanism. (Available in electronic form only) **Because of the size of this table, it is only available in as s**  **upplementary material in electronic form. See Appendix D.**

### 270



### APPENDIX C. MECHANIS **M EVALUATION TABULAT IONS AND PLOTS**  This appendix contains the plots of the results of the model simulations of the environmental chamber experiments. Th e data presented in these plots are described in the "Data Presented" subsection of the "Mechanism Evaluation" section of the report. Reference is made to Table C - 1 , which contains the list of environmental chamber experiments used in this mechanism evaluation. Because of its size, this table is available only as supplementary material in the Excel file that also contains the tabulations in the other appendices to this report. This is described in Appendix D . Table C - 1 . List of environmental chamber experiments used in the mechanism evaluation. .

(Available in electronic for m only) **Because of the size of this table, it is only available in as supplementary material in electronic form. See Appendix D.** 

### 271

Figure C - 1 . Plots of experimental and calculated environmental chamber reactivity results for c arbon

monoxide. **CTC105B ETC418**  **CTC123A DTC014A**  **DTC015B DTC016A**  **CO CO**  **CO CO**  **CO CO**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC020B DTC029A**  **ETC483 ETC487**  **EPA 282A**  **EPA283A CO**  **CO CO**  **CO CO**  **CO IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-E MIR1**  **IR Surg-E MIR1 IR Surg-8 vary**  **IR Surg-8 vary**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90

0 1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40

0 1 2 3 4 5 6

0.00 0.00 0.00 0.00 0.00 0.00

1 2 3 4 5 6 0.00 0.00 0.00 0.00 0.00 0.01 0.01

1 2 3 4 5 6 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20

0 1 2 3 4 5 6

0.00 0.00 0.00 0.00 0.00 0.01 0.01

1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60 1.80

0 1 2 3 4 5 6

0.00 0.00 0.00 0.00 0.00 0.01 0.01

1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60 1.80

0 1 2 3 4 5 6

-0.1 -0.1 0.0 0.0 0.0 0.0 1 2 3 4 5 6

0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0

1 2 3 4 5 6

-0.1 -0.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0

1 2 3 4 5 6

-0.1 -0.1 -0.1 -0.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1 2 3 4 5 6

-0.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0

1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40

0 1 2 3 4 5 6

0.00 0.20 0.40 0.60 0.80 1.00

0 1 2 3 4 5 6 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01

1 2 3 4 5 6

0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01

1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40

0 1 2 3 4 5 6

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

1 2 3 4 5 6 0.00 0.00 0.00 0.00 0.00 0.01

1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60 1.80

0 1 2 3 4 5 6

0.00 0.00 0.00 0.00 0.00 0.01 0.01

1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60 1.80

0 1 2 3 4 5 6 -0.1 -0.1 0.0 0.0 0.0 0.0 0.0

1 2 3 4 5 6

-0.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0

1 2 3 4 5 6

-0.2 -0.2 -0.1 -0.1 -0.1 -0.1 -0.1 0.0 0.0 0.0 1 2 3 4 5 6

-0.1 -0.1 -0.1 0.0 0.0 0.0 0.0 0.0

1 2 3 4 5 6

-0.1 -0.1 -0.1 0.0 0.0 0.0 0.0 0.0 0.1

1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

0.00 0.00 0.00 0.00 0.00 0.00 0.00

0 1 2 3 4 5 6

-0.1 -0.1 0.0 0.0 0.0 0.0 0 1 2 3 4 5 6 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14

0 1 2 3 4 5 6

0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01

0 1 2 3 4 5 6

-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

### 272

Figure C - 2 . Plots of experimental and calculated environmental chamber reactivity results for ethane

and propane **DTC242A ETC092**  **ETC099 ETC235**  **ETC506 ETHANE**  **ETHANE ETHA** **NE ETHA** **NE ETHA** **NE IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-E MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**EPA292A EPA297B**  **ETC226 ETC230**  **ETC305 ETHANE**  **ETHANE PROPA** **NE PROPA** **NE PROPA** **NE IR Surg-8 vary**  **IR Surg-8 vary IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.20 0.40 0.60 0.80 1.00

0 1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70

0 1 2 3 4 5 6

0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01

1 2 3 4 5 6 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.01

1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70

0 1 2 3 4 5 6

0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.01

1 2 3 4 5 6 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01

1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20

0 1 2 3 4 5 6

0.00 0.00 0.00 0.01 0.01 0.01

1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40

0 1 2 3 4 5 6

-0.01 0.00 0.01 0.01 0.02 0.02 0.03 0.03

1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20

0 1 2 3 4 5 6 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6

1 2 3 4 5 6 -0.3 -0.2 -0.2 -0.1 -0.1 0.0 0.1 0.1 0.2

1 2 3 4 5 6

-0.2 -0.2 -0.1 -0.1 0.0 0.1 0.1

1 2 3 4 5 6

-0.2 -0.2 -0.1 -0.1 0.0 0.1 0.1

1 2 3 4 5 6

-0.4 -0.4 -0.3 -0.3 -0.2 -0.2 -0.1 -0.1 0.0 0.1 0.1 1 2 3 4 5 6

-1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40

0 1 2 3 4 5 6

0.00 0.01 0.01 0.02 0.02 0.03

1 2 3 4 5 6 0.00 0.01 0.01 0.02 0.02 0.03

1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20

0 1 2 3 4 5 6

-0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1 1 2 3 4 5 6

-0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

0.00 0.02 0.04 0.06 0.08 0.10

0 1 2 3 4 5 6

0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01

0 1 2 3 4 5 6

-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2

0 1 2 3 4 5 6 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18

0 1 2 3 4 5 6

0.00 0.00 0.00 0.00 0.00 0.00 0.00

0 1 2 3 4 5 6

-0.3 -0.3 -0.2 -0.2 -0.1 -0.1 0.0 0.1 0.1 0 1 2 3 4 5 6

### 273

Figure C - 3 . Plots of experimental and calculated environmental ch amber reactivity results for n butane **ETC094 ETC097**  **ETC135 ETC224**  **DTC019B DTC031A**  **N-C4 N-C4**  **N-C4 N-C4**  **N-C4 N-C4**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**ETC389 ETC393**  **ETC484 ETC488**  **N-C4 N-C4**  **N-C4 N-C4**  **IR Surg-3 LN1 IR Surg-3 LN1**  **IR Surg-E MIR1 IR Surg-E MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

0.000 0.005 0.010 0.015 0.020 0.025

1 2 3 4 5 6 0.00 0.01 0.02 0.03 0.04

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03

1 2 3 4 5 6 0.00 0.01 0.02 0.03

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.04 0.08 0.12

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03 0.04 0.05

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-2.0 -1.6 -1.2 -0.8 -0.4 0.0 0.4 1 2 3 4 5 6

-2.0 -1.5 -1.0 -0.5 0.0 0.5 1 2 3 4 5 6

-1.6 -1.2 -0.8 -0.4 0.0 0.4 1 2 3 4 5 6

-2.0 -1.5 -1.0 -0.5 0.0 0.5 1 2 3 4 5 6

-2.5 -2.0 -1.5 -1.0 -0.5 0.0 1 2 3 4 5 6

-5 -4 -3 -2 -1 0 1 2 3 4 5 6

0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6 2.0

0 1 2 3 4 5 6

-0.04 -0.02 0.00 0.02 0.04 0.06

1 2 3 4 5 6 -0.04 -0.02 0.00 0.02 0.04 0.06

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06

1 2 3 4 5 6 0.00 0.02 0.04 0.06

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

-6 -4 -2 0 1 2 3 4 5 6

-8 -6 -4 -2 0 2 1 2 3 4 5 6

-3 -2 -1 0 1 1 2 3 4 5 6

-2.0 -1.5 -1.0 -0.5 0.0 0.5 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 274

Figure C -4 . Plots of experimental and calculated environmental chamber reactivity results for n hexane and the Surg - 3 MIR1 experiments for n - octane. **ETC201 ETC209**  **DTC072A CTC110B**  **ETC237 ETC239**  **N-C6 N-C6**  **N-C6 N-C8**  **N-C8 N-C8**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-E MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70

0 1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40

0 1 2 3 4 5 6

-0.14 -0.12 -0.10 -0.08 -0.06 -0.04 -0.02 0.00 0.02 1 2 3 4 5 6

-0.16 -0.14 -0.12 -0.10 -0.08 -0.06 -0.04 -0.02 0.00 1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70

0 1 2 3 4 5 6

-0.18 -0.16 -0.14 -0.12 -0.10 -0.08 -0.06 -0.04 -0.02 0.00 1 2 3 4 5 6

-0.50 -0.40 -0.30 -0.20 -0.10 0.00 1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70

0 1 2 3 4 5 6

-0.30 -0.25 -0.20 -0.15 -0.10 -0.05 0.00 1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70

0 1 2 3 4 5 6

-0.30 -0.25 -0.20 -0.15 -0.10 -0.05 0.00 1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70

0 1 2 3 4 5 6

-16.0 -14.0 -12.0 -10.0 -8.0 -6.0 -4.0 -2.0 0.0 1 2 3 4 5 6

-12.0 -10.0 -8.0 -6.0 -4.0 -2.0 0.0 2.0 1 2 3 4 5 6

-16.0 -14.0 -12.0 -10.0 -8.0 -6.0 -4.0 -2.0 0.0 2.0 1 2 3 4 5 6

-30.0 -25.0 -20.0 -15.0 -10.0 -5.0 0.0 5.0 10.0 1 2 3 4 5 6

-14.0 -12.0 -10.0 -8.0 -6.0 -4.0 -2.0 0.0 2.0 1 2 3 4 5 6

-14.0 -12.0 -10.0 -8.0 -6.0 -4.0 -2.0 0.0 2.0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 275

Figure C - 5 . Plots of experimental and calculated environmental chamber reactivity results for n octane (excluding the Surg - 3 MIR1 experiments, which are on Figure C -4 ). **CTC131A DTC024B**  **DTC070A DTC037B**  **DTC071B N-C8**  **N-C8 N-C8**  **N-C8 N-C8**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 MIR1 IR Surg-8 LN1**  **IR Surg-8 LN1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**EPA 114B**  **EPA095A EPA083B**  **EPA 085B**  **EPA 113B**  **N-C8 N-C8**  **N-C8 N-C8**  **N-C8 IR Surg-8 MIR2**  **IR Surg-8 LN2 IR Surg-8 vary**  **IR Surg-8 vary IR Surg-8 vary**  0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90

0 1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20

0 1 2 3 4 5 6

-0.10 -0.05 0.00 0.05 0.10 0.15

1 2 3 4 5 6 -0.10 -0.05 0.00 0.05 0.10 0.15 0.20 0.25

1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20

0 1 2 3 4 5 6

-0.10 -0.05 0.00 0.05 0.10 0.15 0.20 0.25

1 2 3 4 5 6 -0.06 -0.04 -0.02 0.00 0.02 0.04 0.06 0.08 0.10 0.12

1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90

0 1 2 3 4 5 6

-0.10 -0.05 0.00 0.05 0.10 0.15

1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80

0 1 2 3 4 5 6

-12.0 -10.0 -8.0 -6.0 -4.0 -2.0 0.0 1 2 3 4 5 6

-16.0 -14.0 -12.0 -10.0 -8.0 -6.0 -4.0 -2.0 0.0 1 2 3 4 5 6

-20.0 -15.0 -10.0 -5.0 0.0 1 2 3 4 5 6

-25.0 -20.0 -15.0 -10.0 -5.0 0.0 1 2 3 4 5 6

-35.0 -30.0 -25.0 -20.0 -15.0 -10.0 -5.0 0.0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.30 -0.25 -0.20 -0.15 -0.10 -0.05 0.00 0 1 2 3 4 5 6

-300.0 -250.0 -200.0 -150.0 -100.0 -50.0 0.0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.15 -0.10 -0.05 0.00 0.05 0 1 2 3 4 5 6

-140.0 -120.0 -100.0 -80.0 -60.0 -40.0 -20.0 0.0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25 0.30

0 1 2 3 4 5 6

-0.15 -0.10 -0.05 0.00 0.05 0.10

0 1 2 3 4 5 6

-140.0 -120.0 -100.0 -80.0 -60.0 -40.0 -20.0 0.0 0 1 2 3 4 5 6 0.00 0.02 0.04 0.06 0.08 0.10 0.12

0 1 2 3 4 5 6

-0.10 -0.08 -0.06 -0.04 -0.02 0.00 0 1 2 3 4 5 6

-60.0 -50.0 -40.0 -30.0 -20.0 -10.0 0.0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35

0 1 2 3 4 5 6

-0.200 -0.150 -0.100 -0.050 0.000 0 1 2 3 4 5 6

-160.0 -140.0 -120.0 -100.0 -80.0 -60.0 -40.0 -20.0 0.0 0 1 2 3 4 5 6

**Base Experiment Test Experiment**  **Base M odel (SAPRC-07)**  **SAPRC-07 Test Model SAPRC-99 Test Model** 

### 276

Figure C - 6 . Plots of experimental and calculated environmental chamber reactivity results for n dodecane.

**DTC271B DTC273A**  **DTC283B N-C12**  **N-C12 N-C12**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**CTC150B CTC154A**  **DTC272A DTC274B**  **DTC284A DTC293A**  **N-C12 N-C12**  **N-C12 N-C12**  **N-C12 N-C12**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 MIR1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90

0 1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90

0 1 2 3 4 5 6

-1.40 -1.20 -1.00 -0.80 -0.60 -0.40 -0.20 0.00 1 2 3 4 5 6

-0.16 -0.14 -0.12 -0.10 -0.08 -0.06 -0.04 -0.02 0.00 1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90

0 1 2 3 4 5 6

-1.60 -1.40 -1.20 -1.00 -0.80 -0.60 -0.40 -0.20 0.00 1 2 3 4 5 6

-0.40 -0.30 -0.20 -0.10 0.00 0.10 0.20

1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90

0 1 2 3 4 5 6

-0.25 -0.20 -0.15 -0.10 -0.05 0.00 0.05 0.10 0.15

1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90

0 1 2 3 4 5 6

-0.40 -0.30 -0.20 -0.10 0.00 0.10 0.20

1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60

0 1 2 3 4 5 6 -70.0 -60.0 -50.0 -40.0 -30.0 -20.0 -10.0 0.0 10.0 1 2 3 4 5 6

-8.0 -6.0 -4.0 -2.0 0.0 2.0 1 2 3 4 5 6

-70.0 -60.0 -50.0 -40.0 -30.0 -20.0 -10.0 0.0 1 2 3 4 5 6

-35.0 -30.0 -25.0 -20.0 -15.0 -10.0 -5.0 0.0 5.0 10.0 1 2 3 4 5 6

-25.0 -20.0 -15.0 -10.0 -5.0 0.0 1 2 3 4 5 6

-60.0 -50.0 -40.0 -30.0 -20.0 -10.0 0.0 10.0 20.0 1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60

0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35

0 1 2 3 4 5 6

-0.50 -0.40 -0.30 -0.20 -0.10 0.00 0.10 0.20 0.30

1 2 3 4 5 6

-0.40 -0.30 -0.20 -0.10 0.00 0.10 0.20

1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60

0 1 2 3 4 5 6

-0.35 -0.30 -0.25 -0.20 -0.15 -0.10 -0.05 0.00 0.05 0.10 1 2 3 4 5 6

-100.0 -80.0 -60.0 -40.0 -20.0 0.0 1 2 3 4 5 6

-70.0 -60.0 -50.0 -40.0 -30.0 -20.0 -10.0 0.0 1 2 3 4 5 6

-35.0 -30.0 -25.0 -20.0 -15.0 -10.0 -5.0 0.0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 277

Figure C - 7 . Plots of experimental and calculated environmental chamber reactivity results f or n tetradecane

**DTC275A DTC277B**  **DTC289B N-C14**  **N-C14 N-C14**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1**

 **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**CTC151A CTC158A**  **DTC276B DTC278A**  **DTC290A N-C14**  **N-C14 N-C14**  **N-C14 N-C14**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 MIR1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90

0 1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90

0 1 2 3 4 5 6

-2.00 -1.50 -1.00 -0.50 0.00 1 2 3 4 5 6

-2.50 -2.00 -1.50 -1.00 -0.50 0.00 1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00

0 1 2 3 4 5 6

-1.80 -1.60 -1.40 -1.20 -1.00 -0.80 -0.60 -0.40 -0.20 0.00 1 2 3 4 5 6

-0.30 -0.20 -0.10 0.00 0.10 0.20 0.30

1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80

0 1 2 3 4 5 6

-0.40 -0.35 -0.30 -0.25 -0.20 -0.15 -0.10 -0.05 0.00 0.05 0.10 1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90

0 1 2 3 4 5 6

-0.50 -0.40 -0.30 -0.20 -0.10 0.00 0.10 0.20

1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60

0 1 2 3 4 5 6 -80.0 -60.0 -40.0 -20.0 0.0 20.0 1 2 3 4 5 6

-120.0 -100.0 -80.0 -60.0 -40.0 -20.0 0.0 20.0 1 2 3 4 5 6

-70.0 -60.0 -50.0 -40.0 -30.0 -20.0 -10.0 0.0 10.0 1 2 3 4 5 6

-35.0 -30.0 -25.0 -20.0 -15.0 -10.0 -5.0 0.0 1 2 3 4 5 6

-30.0 -25.0 -20.0 -15.0 -10.0 -5.0 0.0 1 2 3 4 5 6

-80.0 -70.0 -60.0 -50.0 -40.0 -30.0 -20.0 -10.0 0.0 10.0 1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60

0 1 2 3 4 5 6

-1.00 -0.80 -0.60 -0.40 -0.20 0.00 0.20 0.40

1 2 3 4 5 6

-0.60 -0.50 -0.40 -0.30 -0.20 -0.10 0.00 0.10 0.20 1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60

0 1 2 3 4 5 6

-120.0 -100.0 -80.0 -60.0 -40.0 -20.0 0.0 20.0 1 2 3 4 5 6

-100.0 -80.0 -60.0 -40.0 -20.0 0.0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 278

Figure C - 8 . Plots of experimental and calculated environmental chamber reactivity results for n pentadecane and n -hexadecane. **DTC279B DTC280A**  **N-C15 N-C15**  **IR Surg-3 MIR1 IR Surg-8 MIR1** 

 **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC281B DTC282A**  **DTC291B CTC152B**  **CTC156B N-C16**  **N-C16 N-C16**  **N-C16 N-C16**  **IR Surg-8 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-8 MIR1**  **IR Surg-8 MIR1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90

0 1 2 3 4 5 6

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90

0 1 2 3 4 5 6 -2.50 -2.00 -1.50 -1.00 -0.50 0.00 1 2 3 4 5 6

-1.00 -0.80 -0.60 -0.40 -0.20 0.00 0.20 1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60

0 1 2 3 4 5 6

-4.00 -3.50 -3.00 -2.50 -2.00 -1.50 -1.00 -0.50 0.00 1 2 3 4 5 6

-2.00 -1.50 -1.00 -0.50 0.00 1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90

0 1 2 3 4 5 6

-0.40 -0.30 -0.20 -0.10 0.00 0.10 0.20 0.30 0.40 0.50

1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70

0 1 2 3 4 5 6

-0.40 -0.30 -0.20 -0.10 0.00 0.10 0.20

1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90

0 1 2 3 4 5 6 -120.0 -100.0 -80.0 -60.0 -40.0 -20.0 0.0 20.0 1 2 3 4 5 6

-140.0 -120.0 -100.0 -80.0 -60.0 -40.0 -20.0 0.0 1 2 3 4 5 6

-100.0 -80.0 -60.0 -40.0 -20.0 0.0 20.0 1 2 3 4 5 6

-80.0 -70.0 -60.0 -50.0 -40.0 -30.0 -20.0 -10.0 0.0 10.0 1 2 3 4 5 6

-35.0 -30.0 -25.0 -20.0 -15.0 -10.0 -5.0 0.0 1 2 3 4 5 6

-35.0 -30.0 -25.0 -20.0 -15.0 -10.0 -5.0 0.0 1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60

0 1 2 3 4 5 6

-0.80 -0.60 -0.40 -0.20 0.00 0.20 0.40

1 2 3 4 5 6

-100.0 -80.0 -60.0 -40.0 -20.0 0.0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 279

Figure C - 9 . Plots of experimental and calculated environmental chamber reactivity results for

isobutane, 2,2,4 -trimethyl pentane, and 2,6 - dimethyl octane. **ETC228 ETC232**  **ETC241 ETC303**  **ETC291 ETC293**  **2-ME-C3 2-ME-C3**  **2-ME-C3 2-ME-C3**  **224TM-C5 224TM-C5**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC738B DTC747A**  **DTC739A DTC733A**  **DTC749A 26DM-C8**  **26DM-C8 26DM-C8**  **26DM-C8 26DM-C8**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-x MIR1**  **IR Surg-x MIR1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.20 0.40 0.60 0.80 1.00

0 1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40

0 1 2 3 4 5 6

-0.02 0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 0.00 0.01 0.01 0.02 0.02 0.03 0.03 0.04 0.04

1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07

1 2 3 4 5 6 -0.01 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08

1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20

0 1 2 3 4 5 6

-0.02 -0.01 -0.01 0.00 0.01 0.01 0.02 0.02 0.03

1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20

0 1 2 3 4 5 6

-0.02 -0.01 -0.01 0.00 0.01 0.01 0.02 0.02 0.03

1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20

0 1 2 3 4 5 6

-4.0 -3.0 -2.0 -1.0 0.0 1.0 1 2 3 4 5 6

-0.8 -0.6 -0.4 -0.2 0.0 0.2 1 2 3 4 5 6

-1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 1 2 3 4 5 6

-2.0 -1.5 -1.0 -0.5 0.0 0.5 1 2 3 4 5 6

-2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1 2 3 4 5 6

-2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1 2 3 4 5 6

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70

0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40

0 1 2 3 4 5 6

-0.25 -0.20 -0.15 -0.10 -0.05 0.00 0.05 0.10

1 2 3 4 5 6

-0.20 -0.15 -0.10 -0.05 0.00 0.05 0.10 0.15

1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80

0 1 2 3 4 5 6

-0.15 -0.10 -0.05 0.00 0.05 0.10

1 2 3 4 5 6

-0.45 -0.40 -0.35 -0.30 -0.25 -0.20 -0.15 -0.10 -0.05 0.00 1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70

0 1 2 3 4 5 6

-0.60 -0.50 -0.40 -0.30 -0.20 -0.10 0.00 1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70

0 1 2 3 4 5 6

-25.0 -20.0 -15.0 -10.0 -5.0 0.0 5.0 1 2 3 4 5 6

-20.0 -15.0 -10.0 -5.0 0.0 1 2 3 4 5 6

-30.0 -25.0 -20.0 -15.0 -10.0 -5.0 0.0 1 2 3 4 5 6

-16.0 -14.0 -12.0 -10.0 -8.0 -6.0 -4.0 -2.0 0.0 1 2 3 4 5 6

-25.0 -20.0 -15.0 -10.0 -5.0 0.0 5.0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 280

Figure C - 10 . Plots of experimental and calculated environmental chamber reactivity results for 2 -

methyl nonane and 3,4 - di ethyl hexane. **DTC734B DTC741A**  **DTC737A DTC746B**  **DTC740B 2-ME-C9**  **2-ME-C9 2-ME-C9**  **2-ME-C9 2-ME-C9**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC726B DTC729B**  **DTC732B DTC748B**  **DTC725A DTC730A**  **34-DE-C6 34-DE-C6**  **34-DE-C6 34-DE-C6**  **34-DE-C6 34-DE-C6**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-8 LN1**  **IR Surg-x MIR1 IR Surg-x MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.4 -0.3 -0.2 -0.1 0.0 1 2 3 4 5 6

-0.5 -0.4 -0.3 -0.2 -0.1 0.0 1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-0.4 -0.2 0.0 0.2 0.4

1 2 3 4 5 6

-0.2 -0.1 0.0 0.1

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.2 -0.1 0.0 0.1

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4

0 1 2 3 4 5 6

-0.2 -0.1 0.0 0.1

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 -16 -12 -8 -4 0 4 1 2 3 4 5 6

-25 -20 -15 -10 -5 0 5 1 2 3 4 5 6

-25 -20 -15 -10 -5 0 1 2 3 4 5 6

-20 -16 -12 -8 -4 0 1 2 3 4 5 6

-25 -20 -15 -10 -5 0 1 2 3 4 5 6

-30 -20 -10 0 10 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4

0 1 2 3 4 5 6

-0.15 -0.10 -0.05 0.00 0.05 0.10

1 2 3 4 5 6

-0.06 -0.04 -0.02 0.00 0.02 0.04 0.06

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4

0 1 2 3 4 5 6

-0.04 -0.02 0.00 0.02 0.04

1 2 3 4 5 6

-0.2 -0.1 0.0 0.1

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-0.3 -0.2 -0.1 0.0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-16 -12 -8 -4 0 1 2 3 4 5 6

-16 -12 -8 -4 0 1 2 3 4 5 6

-8 -6 -4 -2 0 1 2 3 4 5 6

-12 -8 -4 0 4 1 2 3 4 5 6

-12 -8 -4 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 281

Figure C - 11 . Plots of experimental and calculated environmental chamber reactivity results for

cyclohexane and hexyl cyclohexane. **DTC541A DTC551A**  **DTC543B DTC552B**  **DTC544A DTC553A**  **CYCC6 CYCC6**  **CYCC6 CYCC6**  **CYCC6 CYCC6**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC315B DTC318B**  **CTC167A DTC317A**  **DTC319B CTC233A**  **C6-CYCC6 C6-CYCC6**  **C6-CYCC6 C6-CYCC6**  **C6-CYCC6 C6-CYCC6**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 MIR1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.20 -0.15 -0.10 -0.05 0.00 0.05 1 2 3 4 5 6

-0.16 -0.12 -0.08 -0.04 0.00 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.04 0.00 0.04 0.08 0.12 0.16

1 2 3 4 5 6 -0.04 0.00 0.04 0.08 0.12 0.16

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.04 0.08 0.12

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06 0.08 0.10

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-12 -8 -4 0 4 1 2 3 4 5 6

-10 -8 -6 -4 -2 0 1 2 3 4 5 6

-10 -8 -6 -4 -2 0 1 2 3 4 5 6

-16 -12 -8 -4 0 1 2 3 4 5 6

-16 -12 -8 -4 0 1 2 3 4 5 6

-16 -12 -8 -4 0 1 2 3 4 5 6

0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-1.6 -1.2 -0.8 -0.4 0.0 1 2 3 4 5 6

-2.0 -1.6 -1.2 -0.8 -0.4 0.0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.4 -0.2 0.0 0.2

1 2 3 4 5 6

-0.4 -0.2 0.0 0.2

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-0.4 -0.2 0.0 0.2 0.4

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.3 -0.2 -0.1 0.0 0.1 0.2

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-80 -60 -40 -20 0 1 2 3 4 5 6

-120 -80 -40 0 40 1 2 3 4 5 6

-30 -20 -10 0 1 2 3 4 5 6

-80 -60 -40 -20 0 1 2 3 4 5 6

-80 -60 -40 -20 0 1 2 3 4 5 6

-30 -20 -10 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 282

Figure C - 12 . Plots of experimental and calculated environmental chamber reactivity results for octyl

cyclohexane. **CTC231A DTC324A**  **CTC168B CTC232B**  **CTC239B C8-CYCC6**  **C8-CYCC6 C8-CYCC6**  **C8-CYCC6 C8-CYCC6**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 MIR1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**CTC240A DTC325B**  **C8-CYCC6 C8-CYCC6**  **IR Surg-8 LN1 IR Surg-8 LN1** 

 **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-1.6 -1.2 -0.8 -0.4 0.0 1 2 3 4 5 6

-2.5 -2.0 -1.5 -1.0 -0.5 0.0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.4 -0.2 0.0 0.2

1 2 3 4 5 6

-0.6 -0.4 -0.2 0.0 0.2 0.4

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.4 -0.2 0.0 0.2 0.4

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.4 -0.2 0.0 0.2

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6 -60 -40 -20 0 20 1 2 3 4 5 6

-80 -60 -40 -20 0 20 1 2 3 4 5 6

-40 -30 -20 -10 0 1 2 3 4 5 6

-40 -30 -20 -10 0 10 1 2 3 4 5 6

-30 -20 -10 0 10 1 2 3 4 5 6

-30 -20 -10 0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.6 -0.4 -0.2 0.0 0.2 1 2 3 4 5 6

-40 -30 -20 -10 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 283

Figure C - 13 . Plots of model errors in simulations of the ethene - NO x 

### environmental chamber

experiments. Ethene - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final UCR Arc Light 10 -3% -2% -6% -5% UCR Blacklight 29 24% 9% 22% 10% TVA chamber 3 -6% 4% -16% -4% OTC Chamber 7 -30% -22% -28% -23%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 UCR Arc Light UCR Blacklight TVA chamber OTC Chamber

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 284

Figure C - 14 . Plots of experimental and calculated environmental chamber reactivity results for ethene.

**ETC199 ETC203**  **DTC017A DTC038A**  **ETHENE ETHENE**  **ETHENE ETHENE**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0.0 0.4 0.8 1.2 1.6

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0.0 0.2 0.4 0.6 0.8 1.0

1 2 3 4 5 6 0.0 0.1 0.2 0.3

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-10 0 10 20 30 40

1 2 3 4 5 6 -20 0 20 40 60

1 2 3 4 5 6 -10 0 10 20 30 40

1 2 3 4 5 6 -12 -8 -4 0 4 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 285

Figure C - 15 . Plots of model errors in simulations of the propene - NO x 

### environmental chamber

experiments. Propene - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final UCR Arc Light 74 -9% -1% -8% 2% UCR Blacklight 84 -5% -1% 5% 3% TVA chamber 4 8% 13% 2% 6% OTC Chamber 6 -19% 1% -3% 1% UNC Chamber 20 58% 19% 61% 22% Added CO 2 3% -12% 23% -5%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 UCR Arc Light UCR Blacklight TV A chamber OTC Chamber UNC Chamber Added CO

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 286

Figure C - 16 . Plots of experimental and calculated environmental chamber reactivity results for

propene. **CTC142B ETC106**  **ETC108 ETC110**  **ETC118 PROPENE**  **PROPENE PROPENE**  **PROPENE PROPENE**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**CTC130B DTC018A**  **DTC032B ETC496**  **ETC500 PROPENE**  **PROPENE PROPENE**  **PROPENE PROPENE**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-E MIR1**  **IR Surg-E MIR1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.0 0.4 0.8 1.2 1.6

1 2 3 4 5 6 0 1 2 3

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.0 0.5 1.0 1.5 2.0 2.5

1 2 3 4 5 6 0 1 2 3

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0 1 2 3

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.0 0.2 0.4 0.6 0.8 1.0

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 -10 0 10 20 30

1 2 3 4 5 6 -40 -20 0 20 40 60

1 2 3 4 5 6 -20 0 20 40 60

1 2 3 4 5 6 -80 -40 0 40 80

1 2 3 4 5 6

-20 0 20 40 60 80

1 2 3 4 5 6

-5 0 5 10 15 20

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0.0 0.4 0.8 1.2 1.6 2.0

1 2 3 4 5 6 -0.2 0.0 0.2 0.4 0.6 0.8

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-1 0 1 2 3

1 2 3 4 5 6 -1 0 1 2 3

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

-10 0 10 20 30 40

1 2 3 4 5 6 -40 -30 -20 -10 0 10 1 2 3 4 5 6

-20 0 20 40 60

1 2 3 4 5 6 -40 0 40 80

1 2 3 4 5 6 Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 287

Figure C - 17 . Plots of model errors in simulations of the 1 -buteme and 1 -hexene - NO x 

### environmental

chamber experiments.

1-Butene - NOx and 1-Hexene - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final 1-Butene, Black 3 18% -1% 7% -9% 1-Butene, Arc 3 -11% -8% -34% -22% 1-Hexene, Black 3 1% 15% 16% 17%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 1-Butene, Black 1-Butene, Arc 1-Hexene, Black

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 288

Figure C - 18 . Plots of model errors in simulations of the trans - 2 -butene and isobutene - NO x



### environmental chamber experiments.

Trans-2-Butene - NOx and Isobutene - NOx Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Isobutene, Black 2 0% 13% -7% 9% Trans-2-Butene, TVA 3 1% 8% 0% 3% Trans-2-Butene, EC 3 5% 1% 8% 0% SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 Isobutene, Black Trans-2-Butene, TVA Trans-2-Butene, EC

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 289

Figure C - 19 . Plots of experimental and calculated environmental chamber re activity results for

isobutene and trans - 2 -butene. **ETC253 ETC255**  **ETC257 ETC307**  **ETC309 DTC021B**  **ISOBUTEN ISOBUTEN**  **ISOBUTEN T-2-BUTE**  **T-2-BUTE T-2-BUTE**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-8 MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC069A DTC033A**  **DTC041A DTC043B**  **ETC493 ETC501**  **T-2-BUTE T-2-BUTE**  **T-2-BUTE T-2-BUTE**  **T-2-BUTE T-2-BUTE**  **IR Surg-8 MIR1 IR Surg-8 LN1**  **IR Surg-E LN1 IR Surg-E MIR1**  **IR Surg-E MIR1 IR Surg-E MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0 1 2 3

1 2 3 4 5 6 0 1 2 3

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0 1 2 3 4

1 2 3 4 5 6 0 2 4 6 8

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0 2 4 6 8

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0.0 0.5 1.0 1.5 2.0

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0 20 40 60 80 100

1 2 3 4 5 6 -40 0 40 80 120

1 2 3 4 5 6 -40 0 40 80 120

1 2 3 4 5 6 0 50 100 150 200 250

1 2 3 4 5 6 0 50 100 150 200 250

1 2 3 4 5 6 0 10 20 30 40

1 2 3 4 5 6

0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0.0 0.5 1.0 1.5 2.0 2.5

1 2 3 4 5 6 -0.8 -0.4 0.0 0.4 0.8 1.2

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-4 -2 0 2 4 6 8

1 2 3 4 5 6 0 2 4 6 8 10

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

-2 0 2 4 6 8

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

-4 0 4 8 12

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0 20 40 60

1 2 3 4 5 6 -60 -40 -20 0 20 40

1 2 3 4 5 6

-100 0 100 200

1 2 3 4 5 6 0 100 200 300

1 2 3 4 5 6 0 50 100 150 200

1 2 3 4 5 6 -100 0 100 200 300 400

1 2 3 4 5 6 Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 290

Figure C - 20 . Plots of model errors in simulations of the isoprene - NO x 

### environmental chamber

experiments. Isoprene - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Arc Light 3 -4% -5% -9% -8% Blacklight 6 -6% -7% -11% -11% EC Chamber 5 8% 19% -7% 12% OTC Chamber 4 -3% -1% -4% -2% UNC Chamber 10 -2% 1% -1% 4%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 Arc Light Blacklight EC Chamber OTC Chamber UNC Chamber

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 291

Figure C - 21 . Plots of experimental and calculated environmental chamber reactivity results for

isoprene **ETC271 ETC273**  **ETC275 ETC277**  **DTC046A DTC050B**  **ISOPRENE ISOPRENE**  **ISOPRENE ISOPRENE**  **ISOPRENE ISOPRENE**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-E LN1 IR Surg-E LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC047B ETC495**  **ETC503 ETC510**  **ISOPRENE ISOPRENE**  **ISOPRENE ISOPRENE**  **IR Surg-E MIR1 IR Surg-E MIR1**  **IR Surg-E MIR1 IR Surg-E MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0 1 2 3 4

1 2 3 4 5 6 0 1 2 3 4

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0 1 2 3 4 5

1 2 3 4 5 6 0 2 4 6

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

-2 -1 0 1 2

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-2 -1 0 1 2

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-20 0 20 40 60 80

1 2 3 4 5 6 -20 0 20 40 60 80

1 2 3 4 5 6 -40 0 40 80 120

1 2 3 4 5 6 -40 0 40 80 120

1 2 3 4 5 6 -80 -40 0 40 80

1 2 3 4 5 6

-120 -80 -40 0 40 1 2 3 4 5 6

0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0 2 4 6

1 2 3 4 5 6 -1 0 1 2 3 4

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

-1 0 1 2 3

1 2 3 4 5 6 -1 0 1 2 3

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

-100 -50 0 50 100 150

1 2 3 4 5 6 -40 -20 0 20 40 60

1 2 3 4 5 6 -40 0 40 80 120

1 2 3 4 5 6 -40 -20 0 20 40 60

1 2 3 4 5 6 Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 292

Figure C - 22 . Plots of model errors in simulations of the terpene - NO x 

### environmental chamber

experiments. Terpene - NOx Experiments Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final a-Pinene 6 6% 2% 1% -1% b-Pinene 6 -8% 44% -13% 41% d-Limonene 7 -7% -6% -2% -4% Sabinene 3 54% 3% 6% 4% 3-Carene 4 -12% -15% -9% -22%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Runs Group

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 a-Pinene b-Pinene d-Limonene Sabinene 3-Carene

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 293

Figure C - 23 . Plo ts of experimental and calculated environmental chamber reactivity results for  - and

 -pinene and d- limonene. **DTC034B DTC044A**  **DTC045B ETC508**  **DTC048A DTC051B**  **A- PINENE**  **A-PINENE A-PINENE**  **A- PINENE**  **B-PINENE B-PINENE**  **IR Surg-8 LN1 IR Surg-E LN1**  **IR Surg-E MIR1 IR Surg-E MIR1**  **IR Surg-E LN1 IR Surg-E MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

-0.8 -0.4 0.0 0.4 0.8

1 2 3 4 5 6

-4 -2 0 2 4

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0 2 4 6

1 2 3 4 5 6 -2 0 2 4 6

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

-2.5 -2.0 -1.5 -1.0 -0.5 0.0 1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

-1.0 -0.5 0.0 0.5 1.0 1.5

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6 2.0

0 1 2 3 4 5 6

-80 -60 -40 -20 0 20 1 2 3 4 5 6

-150 -100 -50 0 50 100

1 2 3 4 5 6

-50 0 50 100 150 200

1 2 3 4 5 6 -40 0 40 80 120

1 2 3 4 5 6 -200 -150 -100 -50 0 50 1 2 3 4 5 6

-120 -80 -40 0 40 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

**EPA793A EPA** **797A EPA**  **804A D-LIMONE**  **D-LIMONE D-LIMONE**  **IR Surg-7 MIR2 IR Surg-7 MIR2**  **IR Surg-7 LN2**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14

0 1 2 3 4 5 6

-0.50 0.00 0.50 1.00 1.50 2.00

0 1 2 3 4 5 6

-150.0 -100.0 -50.0 0.0 50.0 100.0

0 1 2 3 4 5 6 0.00 0.02 0.04 0.06 0.08 0.10 0.12

0 1 2 3 4 5 6

-0.40 -0.20 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40

0 1 2 3 4 5 6

-600.0 -500.0 -400.0 -300.0 -200.0 -100.0 0.0 100.0 0 1 2 3 4 5 6 0.00 0.02 0.04 0.06 0.08 0.10 0.12

0 1 2 3 4 5 6

-0.60 -0.40 -0.20 0.00 0.20 0.40 0.60 0.80

0 1 2 3 4 5 6

-500.0 -400.0 -300.0 -200.0 -100.0 0.0 100.0 200.0

0 1 2 3 4 5 6

**Base Experiment Test Experiment**  **Base Calc (SAPRC-07) SA** **PRC-07 Test Calc SAPRC-99 Test Calc** 

### 294

Figure C - 24 . Plots of experimental and calculated environmental chamber reactivity results for

cyclohexene.

Figure C - 25 . Plots of experimental and calculated environmental chamber reactivity results for styrene. **EPA408B CYC-HEXE**  **NA surg**   **(O 3**  **-NO) (ppm) IR**   **(O 3**  **-NO) (mole basis) IR IntOH (ppt-min/ppm)**  **Cyclohexene (ppm)**

0.00 0.04 0.08 0.12

0 1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6 -200 -100 0 100 200

0 1 2 3 4 5 6 **Base Experiment Test Experiment**  **Base Calc (SAPRC-07) SA** **PRC-07 Test Calc SAPRC-99 Test Calc**  0.00 0.02 0.04 0.06

0 1 2 3 4 5 6

**CTC246A CTC250B**  **CTC248B CTC251A**  **CTC249A CTC253B**  **STYRENE STYRENE**  **STYRENE STYRENE**  **STYRENE STYRENE**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.6 -0.4 -0.2 0.0 1 2 3 4 5 6

-1.0 -0.8 -0.6 -0.4 -0.2 0.0 1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-0.2 -0.1 0.0 0.1 0.2

1 2 3 4 5 6

-0.2 -0.1 0.0 0.1 0.2 0.3

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.4 -0.3 -0.2 -0.1 0.0 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-0.4 -0.3 -0.2 -0.1 0.0 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-30 -20 -10 0 10 1 2 3 4 5 6

-60 -40 -20 0 20 1 2 3 4 5 6

-30 -20 -10 0 10 1 2 3 4 5 6

-20 -15 -10 -5 0 5 1 2 3 4 5 6

-25 -20 -15 -10 -5 0 1 2 3 4 5 6

-40 -30 -20 -10 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 295

Figure C - 26 . Plots of model errors in simulations of the benzene and benzene + CO - NO x



### environmental chamber experiments. Benzene - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Arc Light 4 58% 12% 42% 6% Blacklight 4 -30% 18% -31% 3% Added CO 1 -68% -29% -60% -32%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-75% -50% -25% 0% 25% 50% 75%

1 2 3 4 5 6 -75% -50% -25% 0% 25% 50% 75%

1 2 3 4 5 6 Arc Light Blacklight Added CO

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 29 6

Figure C - 27 . Plots of experimental and calculated environmental chamber reactivity results for

benzene. **ETC263 ETC265**  **DTC039B EPA**  **421B BENZENE**  **BENZENE BENZENE**  **BENZENE IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-8 LN1**  **IR Surg-NA vary**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

-0.04 -0.02 0.00 0.02 0.04

1 2 3 4 5 6

-0.5 0.0 0.5 1.0 1.5 2.0

1 2 3 4 5 6 -1 0 1 2 3

1 2 3 4 5 6 -4 -3 -2 -1 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model 0.00 0.04 0.08 0.12 0.16

0 1 2 3 4 5 6

0.00 0.04 0.08 0.12

0 1 2 3 4 5 6

-10 0 10 20 30

0 1 2 3 4 5 6

### 297

Figure C - 28 . Plots of model errors in simulations of the to luene and toluene + CO - NO x



### environmental chamber experiments. Toluene - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Arc Light 22 3% 11% -13% 7% Blacklight 19 -7% -3% 28% 2% TVA chamber 3 -3% -2% -5% 1% OTC Chamber 4 -4% 7% -11% 15% UNC Chamber 5 53% 68% 27% 88% Added CO 7 -20% -19% -18% -13%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50% 75%

1 2 3 4 5 6 -50% -25% 0% 25% 50% 75%

1 2 3 4 5 6 Arc Light Blacklight TVA chamber OTC Chamber UNC Chamber Added CO

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 298

Figure C - 29 . Plots of model errors in simulations of the ethylbenzene - NO x 

### environmental chamber

experiments. Ethylbenzene - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Arc Light 4 5% 5% -18% 14% Blacklight 4 16% -10% -3% -10%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 Arc Light Blacklight

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 299

Figure C - 30 . Plot s of experimental and calculated environmental chamber reactivity results for toluene

and ethylbenzene. **CTC108B ETC101**  **ETC103 CTC127B**  **DTC023A DTC030B**  **TOLUENE TOLUENE**  **TOLUENE TOLUENE**  **TOLUENE TOLUENE**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-8 MIR1**  **IR Surg-8 MIR1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**ETC311 ETC313**  **ETC315 C2-BENZ**  **C2-BENZ C2-BENZ**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.0 0.2 0.4 0.6 0.8

1 2 3 4 5 6 -0.4 0.0 0.4 0.8 1.2 1.6

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.0 0.4 0.8 1.2 1.6

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.0 0.2 0.4 0.6 0.8 1.0

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

-0.2 -0.1 0.0 0.1 0.2

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-10 0 10 20 30

1 2 3 4 5 6 -20 0 20 40 60

1 2 3 4 5 6 -20 0 20 40 60

1 2 3 4 5 6 0 4 8 12 16

1 2 3 4 5 6 0 10 20 30 40

1 2 3 4 5 6 -20 -15 -10 -5 0 5 1 2 3 4 5 6

0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.4 0.0 0.4 0.8 1.2

1 2 3 4 5 6 -0.4 0.0 0.4 0.8 1.2 1.6

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.4 0.0 0.4 0.8 1.2

1 2 3 4 5 6

-40 -20 0 20 40 60

1 2 3 4 5 6 -60 -40 -20 0 20 40

1 2 3 4 5 6

-20 -10 0 10 20

1 2 3 4 5 6 Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 300

Figure C - 31 . Plots of model errors in simulations of the m -xylene and m -xylene + CO - NO x



### environmental chamber experiments. M-Xylene - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Arc Light 20 24% 7% -2% -6% Blacklight 36 4% 5% 4% -6% TVA chamber 2 -7% -1% -14% -9% Added CO 6 -24% -23% -2% -17%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 Arc Light Blacklight TVA chamber Added CO

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 301

Figure C - 32 . Plots of model errors in simulations of the o -xylene - NO x 

### environmental chamber

experiments. O-Xylene - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Arc Light 6 15% 4% -2% -6% Blacklight 6 10% -3% -3% -12% EC Chamber 2 -1% 7% -15% 1% UNC Chamber 4 54% 16% 45% 24%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 Arc Light Blacklight EC Chamber UNC Chamber

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 302

Figure C - 33 . Plots of model errors in simulations of the p -xylene - NO x 

### environmental chamber

experiments. P-Xylene - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Arc Light 6 52% -10% 6% 6% Blacklight 7 10% -15% -3% -4% Added CO 1 -38% -30% -54% -27%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 Arc Light Blacklight Added CO

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 303

Figure C - 34 . Plots of experimental and calculated environmental chamber reactivity results for m xylene (additional experiments shown on Figure C - 35 ). **CTC109A ETC196**  **ETC207 ETC301**  **CTC128A DTC025A**  **M-XYLENE M-XYLENE**  **M-XYLENE M-XYLENE**  **M-XYLENE M-XYLENE**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC068B DTC035A**  **DTC067B EPA**  **110A EPA**  **123B M-XYLENE**  **M-XYLENE M-XYLENE**  **M-XYLENE M-XYLENE**  **IR Surg-8 MIR1 IR Surg-8 LN1**  **IR Surg-8 LN1 IR Surg-8 MIR2**  **IR Surg-8 LN2**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0 1 2 3 4

1 2 3 4 5 6 -2 0 2 4 6 8

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0 2 4 6 8

1 2 3 4 5 6 -2 0 2 4 6 8

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0.0 0.5 1.0 1.5 2.0 2.5

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0 1 2 3 4 5

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

-40 0 40 80 120

1 2 3 4 5 6 -100 0 100 200 300

1 2 3 4 5 6 0 50 100 150 200 250

1 2 3 4 5 6 -100 0 100 200 300

1 2 3 4 5 6 -20 0 20 40 60 80 100

1 2 3 4 5 6 0 50 100 150 200

1 2 3 4 5 6

0.0 0.4 0.8 1.2

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0 2 4 6

1 2 3 4 5 6 -1.0 -0.5 0.0 0.5 1.0 1.5

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.8 -0.4 0.0 0.4 0.8 1.2

1 2 3 4 5 6

-40 0 40 80 120 160

1 2 3 4 5 6 -120 -80 -40 0 40 80

1 2 3 4 5 6

-120 -80 -40 0 40 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

-2 0 2 4 6

0 1 2 3 4 5 6

-800 -400 0 400 800

0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-1.5 -1.0 -0.5 0.0 0.5 1.0

0 1 2 3 4 5 6

-400 -300 -200 -100 0 100 0 1 2 3 4 5 6

### 304

Figure C - 35 . Plots of experimental and calculated environmental chamber reactivity results for m xylene (with variable surrogate conditions), o -xylene , and p -xylene. **EPA084A EPA086B**  **EPA100B EPA**  **108A EPA**  **128B EPA**  **406B M-XYLENE**  **M-XYLENE M-XYLENE**  **M-XYLENE M-XYLENE**  **M-XYLENE IR Surg-8 vary**  **IR Surg-8 vary IR Surg-8 vary**  **IR Surg-8 vary IR Surg-8 vary**  **IR Surg-NA vary**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**ETC259 ETC261**  **ETC348 EPA**  **422A O-XYLENE**  **O-XYLENE P-XYLENE**  **P-XYLENE IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **VOC - CO - NOx**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0 2 4 6

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0 2 4 6

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

-1 0 1 2 3 4

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

-50 0 50 100 150 200

1 2 3 4 5 6 -50 0 50 100 150 200

1 2 3 4 5 6 -40 0 40 80 120

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4

0 1 2 3 4 5 6

-1 0 1 2 3

0 1 2 3 4 5 6

-400 -300 -200 -100 0 100 200

0 1 2 3 4 5 6 0.00 0.04 0.08 0.12

0 1 2 3 4 5 6

-0.8 -0.4 0.0 0.4

0 1 2 3 4 5 6

-300 -200 -100 0 100 0 1 2 3 4 5 6 0.00 0.02 0.04 0.06 0.08

0 1 2 3 4 5 6

-1.5 -1.0 -0.5 0.0 0.5 1.0

0 1 2 3 4 5 6

-1200 -800 -400 0 400 0 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4

0 1 2 3 4 5 6

0 2 4 6 8

0 1 2 3 4 5 6

-400 0 400 800 1200

0 1 2 3 4 5 6 0.0 0.1 0.2 0.3

0 1 2 3 4 5 6

-2 0 2 4 6

0 1 2 3 4 5 6

-500 0 500 1000 1500 2000

0 1 2 3 4 5 6 0.00 0.04 0.08 0.12 0.16

0 1 2 3 4 5 6

-2 0 2 4 6

0 1 2 3 4 5 6

-400 0 400 800 1200

0 1 2 3 4 5 6

0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03 0.04

0 1 2 3 4 5 6

-16 -12 -8 -4 0 0 1 2 3 4 5 6

**Base Experiment Test Experiment**  **Base Model (SA PRC-07)**  **SA PRC-07 Test Model**  **SA PRC-99 Test Model**  **Base Experiment Test Experiment**  **Base Model (SA PRC-07)**  **SA PRC-07 Test Model**  **SA PRC-99 Test Model** 

### 305

Figure C - 36 . Plots of model errors in simulations of the 1,2,3 -trimethylbenzene - NO x 

### environmental

chamber experiments. 123-TMB - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Arc Light 4 1% -1% 9% 1% Blacklight 5 2% -8% 6% -5%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 Arc Light Blacklight

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 306

Figure C - 37 . Plots of model errors in simulations of the 1,2,4 -trimethylbenzene - NO x 

### environmental

chamber experiments. 124-TMB - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Arc Light 4 23% -2% 5% 14% Blacklight 6 17% -9% -5% -8% Added CO 1 -8% -19% -36% -21%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 Arc Light Blacklight Added CO

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 307

Figure C - 38 . Plots of model errors in simulations of the 1,3,5 -trimethylbenzene and 1,3,5 -

trimethylbenzene + CO - NO x 

### environmental chamber experiments. 135-TMB - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Arc Light 5 0% 3% 1% 5% Blacklight 12 0% 0% -2% 1% EC Chamber 2 21% 33% 14% 35% Added CO 2 0% -15% -1% -7%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 Arc Light Blacklight EC Chamber Added CO

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 308

Fi gure C - 39 . Plots of experimental and calculated environmental chamber reactivity results for 1,2,3 - ,

1,2,4 - and 1,3,4 -trimethylbenzenes. **ETC297 ETC299**  **ETC267 ETC269**  **ETC249 123-TMB**  **123-TMB 124-TMB**  **124-TMB 135-TMB**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0 4 8 12

1 2 3 4 5 6 0 4 8 12

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0 2 4 6 8 10

1 2 3 4 5 6 0 2 4 6 8

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0 10 20 30

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

-100 0 100 200 300 400 500

1 2 3 4 5 6 -200 0 200 400 600

1 2 3 4 5 6 -100 0 100 200 300

1 2 3 4 5 6 -100 0 100 200 300

1 2 3 4 5 6 -200 0 200 400 600 800

1 2 3 4 5 6 Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 309

Figure C -40 . Plots of model errors in simulations of the nap hthalene, 2,3 - dimethylnaphthalene, and

tetralin - NO x 

### environmental chamber experiments.

Naphtlanenes and Tetralin NOx Experiments Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Naphthalene 5 15% 5% 17% 3% Tetralin 5 -14% 7% 4% 16% 2,3-Dime.naphth. 4 14% 0% 10% -2%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 Naphthalene Tetralin 2,3-Dime.naphth.

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 310

Figure C -41 . Plots of model errors in simulations of the acetylene - NO x 

### environmental chamber

experiments. Acetyllene - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Arc Light 2 25% -5% -35% -23% Blacklight 2 2% 2% -16% -19%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 Arc Light Blacklight

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 311

Figure C -42 . Plots of experimental and calculated environmental chamber reactivity results for

acetylene. **CTC184B CTC185A**  **CTC192A CTC186B**  **CTC193B ACETYLEN**  **ACETYLEN ACE**  **TYLEN ACETYLEN**  **ACETYLEN IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**CTC187A CTC194A**  **ACE TYLEN**  **AC ETYLEN**  **IR Surg-8 LN1 IR Surg-8 LN1** 

 **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03

1 2 3 4 5 6 0.00 0.01 0.02 0.03 0.04

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03 0.04

1 2 3 4 5 6 0.00 0.01 0.02 0.03 0.04

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.002 0.000 0.002 0.004 0.006 0.008

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6 -0.4 0.0 0.4 0.8 1.2

1 2 3 4 5 6 0.0 0.4 0.8 1.2

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6 2.0

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

1 2 3 4 5 6 0.0 0.4 0.8 1.2

1 2 3 4 5 6

-0.4 -0.2 0.0 0.2 0.4

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-0.002 0.000 0.002 0.004 0.006

1 2 3 4 5 6

-0.2 -0.1 0.0 0.1 0.2 0.3

1 2 3 4 5 6 Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 312

Figure C -43 . Plots of experimental and calculated environmental chamber reactivity results for

methanol and ethanol. **ETC285 ETC287**  **ETC289 ETC131**  **ETC133 ETC138**  **MEOH MEOH**  **MEOH ETOH**  **ETOH ETOH**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 -0.04 -0.02 0.00 0.02 0.04 0.06

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.02 0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-0.4 0.0 0.4 0.8 1.2 1.6

1 2 3 4 5 6 -6 -4 -2 0 2 4

1 2 3 4 5 6

-2 -1 0 1 2

1 2 3 4 5 6 -1.2 -0.8 -0.4 0.0 0.4 0.8 1.2

1 2 3 4 5 6

-1.2 -0.8 -0.4 0.0 0.4 0.8

1 2 3 4 5 6

-1.2 -0.8 -0.4 0.0 0.4 0.8

1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 313

Figure C -44 . Plots of experimental and calculated environmental chamber reactivity results for

isopropyl alcohol. **DTC395A DTC398B**  **ETC148 ETC155**  **ETC157 ETC159**  **I-C3-OH I-C3-OH**  **I-C3-OH I-C3-OH**  **I-C3-OH I-C3-OH**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC396B DTC399A**  **DTC397A DTC400B**  **I-C3-OH I-C3-OH**  **I-C3-OH I-C3-OH**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06

1 2 3 4 5 6 0.00 0.04 0.08 0.12

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06 0.08 0.10

1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.05 0.10 0.15 0.20 0.25

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.04 0.00 0.04 0.08 0.12 0.16 0.20

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.8 -0.6 -0.4 -0.2 0.0 0.2 1 2 3 4 5 6

-2 -1 0 1 2

1 2 3 4 5 6 -1.2 -0.8 -0.4 0.0 0.4 0.8 1.2

1 2 3 4 5 6 -2 0 2 4 6

1 2 3 4 5 6 -4 0 4 8

1 2 3 4 5 6 -4 -2 0 2 4 6

1 2 3 4 5 6

0.0 0.4 0.8 1.2

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06

1 2 3 4 5 6 0.00 0.04 0.08 0.12 0.16

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03 0.04

1 2 3 4 5 6 0.00 0.01 0.02 0.03 0.04 0.05

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-1.2 -0.8 -0.4 0.0 0.4 0.8

1 2 3 4 5 6

-6 -4 -2 0 2 1 2 3 4 5 6

-3 -2 -1 0 1 2 3 4 5 6

-6 -4 -2 0 2 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 314

Figure C -45 . Plots of experimental and calculated environmental chamber reactivity results for t -butyl

alcohol. **DTC233A DTC241B**  **DTC249A DTC256A**  **T-C4-OH T-C4-OH**  **T-C4-OH T-C4-OH**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC259A DTC268A**  **DTC269A T-C4-OH**  **T-C4-OH T-C4-OH**  **IR Surg-8 LN1 IR Surg-8 LN1**  **IR Surg-8 LN1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

-0.01 0.00 0.01 0.02 0.03

1 2 3 4 5 6 -0.004 0.000 0.004 0.008 0.012 0.016

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03 0.04

1 2 3 4 5 6 0.00 0.02 0.04 0.06

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.000 0.005 0.010 0.015 0.020 0.025

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.000 0.004 0.008 0.012 0.016

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 -1.2 -0.8 -0.4 0.0 0.4 1 2 3 4 5 6

-0.8 -0.6 -0.4 -0.2 0.0 0.2 1 2 3 4 5 6

-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 1 2 3 4 5 6

-0.8 -0.4 0.0 0.4

1 2 3 4 5 6

-1.6 -1.2 -0.8 -0.4 0.0 0.4 1 2 3 4 5 6

-1.2 -0.8 -0.4 0.0 0.4 0.8

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03

1 2 3 4 5 6

-1.6 -1.2 -0.8 -0.4 0.0 0.4 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 315

Figure C -46 . Plots of experimental and calculated environmental chamber reactivity results for 1 - , 2 - ,

and 3 - octanol.

**DTC508B DTC529A**  **DTC509A DTC519B**  **1-C8-OH 1-C8-OH**  **1-C8-OH 1-C8-OH**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC517A DTC521B**  **DTC524B DTC514B**  **DTC516B DTC520A**  **2-C8-OH 2-C8-OH**  **2-C8-OH 3-C8-OH**  **3-C8-OH 3-C8-OH**  **IR Surg-3 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.6 -0.4 -0.2 0.0 1 2 3 4 5 6

-1.0 -0.8 -0.6 -0.4 -0.2 0.0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.2 0.0 0.2 0.4 0.6

1 2 3 4 5 6 -0.1 0.0 0.1 0.2

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-0.5 -0.4 -0.3 -0.2 -0.1 0.0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.1 0.0 0.1 0.2 0.3 0.4

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 -25 -20 -15 -10 -5 0 1 2 3 4 5 6

-80 -60 -40 -20 0 20 1 2 3 4 5 6

-60 -40 -20 0 20 1 2 3 4 5 6

-40 -30 -20 -10 0 1 2 3 4 5 6

-40 -30 -20 -10 0 10 1 2 3 4 5 6

-25 -20 -15 -10 -5 0 1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.05 0.00 0.05 0.10 0.15 0.20

1 2 3 4 5 6 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.2 0.0 0.2 0.4 0.6

1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-30 -20 -10 0 1 2 3 4 5 6

-60 -40 -20 0 20 1 2 3 4 5 6

-40 -30 -20 -10 0 1 2 3 4 5 6

-40 -30 -20 -10 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 316

Figure C -47 . P lots of experimental and calculated environmental chamber reactivity results for

ethylene glycol. **EPA 278B**  **EPA 250B**  **EPA253A EPA**  **258B EPA**  **415B ET-GLYCL**  **ET-GLYCL ET-GLYCL**  **ET-GLYCL ET-GLYCL**  **IR Surg-7 MIR2 IR Surg-7 LN2**  **IR Surg-7 LN2 IR Surg-8 vary**  **IR Surg-NA vary**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.1 0.2 0.3

0 1 2 3 4 5 6

-0.1 0.0 0.1 0.2 0.3 0.4

0 1 2 3 4 5 6

-120 -80 -40 0 40 0 1 2 3 4 5 6 0.0 0.1 0.2 0.3

0 1 2 3 4 5 6

-0.05 0.00 0.05 0.10 0.15

0 1 2 3 4 5 6

-50 -40 -30 -20 -10 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

0.00 0.04 0.08 0.12 0.16

0 1 2 3 4 5 6

-40 -30 -20 -10 0 10 0 1 2 3 4 5 6 0.0 0.1 0.2 0.3

0 1 2 3 4 5 6

-0.05 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-60 -40 -20 0 20 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

0.0 0.1 0.2 0.3 0.4

0 1 2 3 4 5 6

-40 -20 0 20 40

0 1 2 3 4 5 6 **Base Experiment Test Experiment**  **Base Calc (SA PRC-07)**  **SAPRC-07 Test Calc SAPRC-99 Test Calc** 

### 317

Figure C -48 . Plots of experimental and calculated environmental chamber reactivity results for

propylene glycol. **DTC385A DTC389B**  **DTC386B DTC390A**  **DTC388A DTC391B**  **PR-GLYCL PR-GLYCL**  **PR-GLYCL PR-GLYCL**  **PR-GLYCL PR-GLYCL**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**EPA 257B**  **EPA273A EPA**  **277A EPA**  **245B EPA**  **252A EPA**  **404B PR-GLYCL**  **PR-GLYCL PR-GLYCL**  **PR-GLYCL PR-GLYCL**  **PR-GLYCL IR Surg-7 MIR2**  **IR Surg-7 MIR2 IR Surg-7 MIR2**  **IR Surg-7 LN2 IR Surg-7 LN2**  **IR Surg-NA vary**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.05 0.10 0.15 0.20

1 2 3 4 5 6 0.0 0.1 0.2 0.3

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.0 0.1 0.2 0.3 0.4

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.04 0.08 0.12

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

0.00 0.04 0.08 0.12 0.16 0.20

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-2.0 -1.6 -1.2 -0.8 -0.4 0.0 1 2 3 4 5 6

-2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1 2 3 4 5 6

-4 -2 0 2 4 6

1 2 3 4 5 6 -8 -4 0 4 8

1 2 3 4 5 6

-10 -8 -6 -4 -2 0 1 2 3 4 5 6

-16 -12 -8 -4 0 4 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

0.0 0.1 0.2 0.3

0 1 2 3 4 5 6

-0.1 0.0 0.1 0.2 0.3

0 1 2 3 4 5 6

-120 -80 -40 0 40 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-120 -80 -40 0 40 0 1 2 3 4 5 6 0.0 0.1 0.2 0.3

0 1 2 3 4 5 6

-0.1 0.0 0.1 0.2 0.3 0.4

0 1 2 3 4 5 6

-300 -200 -100 0 100 0 1 2 3 4 5 6 0.0 0.1 0.2 0.3

0 1 2 3 4 5 6

-0.05 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-60 -40 -20 0 20 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

0.00 0.04 0.08 0.12 0.16

0 1 2 3 4 5 6

-60 -40 -20 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.2 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-40 -20 0 20 40

0 1 2 3 4 5 6 **Base Experiment Test Experiment**  **Base Model (SAPRC-07) SAPRC-07 Test Model**  **SAPRC-99 Test Model**

### 318

Figure C -49 . Plots of experimental and calculated environmental chamber reactivity results for

dimethyl ether and diethyl ether.

**ETC279 ETC281**  **ETC283 ETC295**  **ME-O-ME ME-O-ME**  **ME-O-ME ME-O-ME**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC510B DTC522A**  **DTC511A DTC515A**  **DTC513A DTC525A**  **ET-O-ET ET-O-ET**  **ET-O-ET ET-O-ET**  **ET-O-ET ET-O-ET**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0.00 0.04 0.08 0.12 0.16

1 2 3 4 5 6 0.00 0.04 0.08 0.12 0.16

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0.00 0.04 0.08 0.12 0.16 0.20

1 2 3 4 5 6 0.00 0.04 0.08 0.12 0.16

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0.0 0.1 0.2 0.3 0.4 0.5

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0.0 0.1 0.2 0.3 0.4

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6 -1.2 -0.8 -0.4 0.0 0.4 0.8

1 2 3 4 5 6

-1.5 -1.0 -0.5 0.0 0.5 1.0

1 2 3 4 5 6

-3 -2 -1 0 1 1 2 3 4 5 6

-3 -2 -1 0 1 1 2 3 4 5 6

-16 -12 -8 -4 0 4 1 2 3 4 5 6

-6 -4 -2 0 2 1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.0 0.1 0.2 0.3 0.4 0.5

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0.0 0.1 0.2 0.3

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-8 -6 -4 -2 0 2 1 2 3 4 5 6

-15 -10 -5 0 5 10

1 2 3 4 5 6

-20 -15 -10 -5 0 1 2 3 4 5 6

-30 -20 -10 0 10 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 319

Figure C - 50 . Plots of experimental and calculated environmental chamber reactivity results for methyl

t -butyl ether.

**ETC120 ETC123**  **ETC125 ETC127**  **MTBE MTBE**  **MTBE MTBE**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 0.00 0.04 0.08 0.12

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.02 0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-3 -2 -1 0 1 1 2 3 4 5 6

-2 -1 0 1

1 2 3 4 5 6

-3 -2 -1 0 1 1 2 3 4 5 6

-3 -2 -1 0 1 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 320

Figure C - 51 . Plots of experimental and calculated environmental chamber reactivity results for 1 -

methoxy - 2 -propanol. **DTC489A DTC495A**  **DTC492A DTC500A**  **DTC496B DTC501B**  **MEOC3OH MEOC3OH**  **MEOC3OH MEOC3OH**  **MEOC3OH MEOC3OH**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0.00 0.05 0.10 0.15 0.20 0.25

1 2 3 4 5 6 0.0 0.1 0.2 0.3

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0.0 0.1 0.2 0.3 0.4 0.5

1 2 3 4 5 6 0.0 0.2 0.4 0.6

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.04 0.08 0.12 0.16 0.20

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.00 0.05 0.10 0.15 0.20 0.25

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-8 -6 -4 -2 0 2 1 2 3 4 5 6

-12 -8 -4 0 4 8

1 2 3 4 5 6

-16 -12 -8 -4 0 4 1 2 3 4 5 6

-20 -15 -10 -5 0 5 1 2 3 4 5 6

-25 -20 -15 -10 -5 0 1 2 3 4 5 6

-30 -20 -10 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 321

Figure C - 52 . Plots of experimental and calculated environmental chamber reactivity results for 2 -

ethoxyethanol and 2 - (2 - ethoxyethoxy) ethanol (DGEE). **ETC163 ETC171**  **ETC175 ETC166**  **ETC169 ETC173**  **ETO-ETOH ETO-ETOH**  **ETO-ETOH DGEE**  **DGEE DGEE**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0.0 0.2 0.4 0.6 0.8 1.0

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0.0 0.2 0.4 0.6 0.8 1.0

1 2 3 4 5 6 -0.2 0.0 0.2 0.4 0.6 0.8

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

-0.2 0.0 0.2 0.4 0.6

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.2 0.0 0.2 0.4 0.6

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

-6 -4 -2 0 2 4

1 2 3 4 5 6

-8 -4 0 4 8

1 2 3 4 5 6 -15 -10 -5 0 5 1 2 3 4 5 6

-40 -30 -20 -10 0 10 1 2 3 4 5 6

-40 -30 -20 -10 0 10 1 2 3 4 5 6

-20 -15 -10 -5 0 5 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 322

Figure C - 53 . Plots of experimental and calculated environmental chamber reactivity results for 2 -

butoxyethanol. **DTC491B DTC498B**  **DTC505B DTC493B**  **DTC502A BUO-ETOH**  **BUO-ETOH BUO-ETOH**  **BUO-ETOH BUO-ETOH**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-8 MIR1**  **IR Surg-8 MIR1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC497A DTC506A**  **BUO-ETOH BUO-ETOH**  **IR Surg-8 LN1 IR Surg-8 LN1** 

 **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.08 -0.04 0.00 0.04 0.08

1 2 3 4 5 6

-0.04 0.00 0.04 0.08 0.12

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-0.10 -0.05 0.00 0.05 0.10 0.15

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0.0 0.2 0.4 0.6 0.8

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.05 0.10 0.15 0.20 0.25

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 -12 -8 -4 0 1 2 3 4 5 6

-12 -8 -4 0 4 1 2 3 4 5 6

-16 -12 -8 -4 0 4 1 2 3 4 5 6

-16 -12 -8 -4 0 1 2 3 4 5 6

-20 -16 -12 -8 -4 0 1 2 3 4 5 6

-25 -20 -15 -10 -5 0 1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

0.0 0.1 0.2 0.3

1 2 3 4 5 6

-30 -20 -10 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 323

Figure C - 54 . Plots of experimental and calculated environmental chamber reactivity results for 2 - (2 -

butoxyethoxy) - ethanol.

**EPA352B EPA**  **335A EPA**  **353B DGBE**  **DGBE DGBE**  **IR Surg-7 MIR2 IR Surg-7 LN2**  **IR Surg-7 LN2**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.6 -0.4 -0.2 0.0 0.2 0.4

0 1 2 3 4 5 6

-800 -600 -400 -200 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.6 -0.4 -0.2 0.0 0.2 0.4

0 1 2 3 4 5 6

-400 -300 -200 -100 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

-0.6 -0.4 -0.2 0.0 0.2 0.4

0 1 2 3 4 5 6

-400 -300 -200 -100 0 0 1 2 3 4 5 6

**Base Experiment Test Experiment**  **Base Calc (SAPRC-07) SA** **PRC-07 Test Calc SAPRC-99 Test Calc** 

### 324

Figure C - 55 . Plots of experimental and calculat ed environmental chamber reactivity results for methyl

acetate.

**DTC327A DTC328B**  **DTC336A ME-A** **CET ME-A** **CET ME-A** **CET IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1** 

 **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC332A DTC335B**  **DTC329A DTC330B**  **ME-A CET**  **ME-A CET**  **ME-A CET**  **ME-ACET IR Surg-8 MIR1**  **IR Surg-8 MIR1 IR Surg-8 LN1**  **IR Surg-8 LN1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.004 0.000 0.004 0.008 0.012

1 2 3 4 5 6 0.000 0.004 0.008 0.012

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0.000 0.002 0.004 0.006 0.008

1 2 3 4 5 6

0.000 0.002 0.004 0.006 0.008 0.010

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

0.000 0.005 0.010 0.015 0.020

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.000 0.002 0.004 0.006 0.008 0.010

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 -0.4 -0.2 0.0 0.2 0.4 0.6

1 2 3 4 5 6 -0.4 -0.2 0.0 0.2

1 2 3 4 5 6

-0.20 -0.15 -0.10 -0.05 0.00 0.05 0.10

1 2 3 4 5 6

-0.3 -0.2 -0.1 0.0 0.1 0.2

1 2 3 4 5 6

-0.4 -0.2 0.0 0.2 0.4

1 2 3 4 5 6

-0.3 -0.2 -0.1 0.0 0.1 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.000 0.004 0.008 0.012

1 2 3 4 5 6

-0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4

1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 325

Figure C - 56 . Plots of experimental and calculated environmental chamber reactivity results for ethyl

acetate. **DTC358A DTC362B**  **DTC364B DTC359B**  **DTC408B ET-A** **CET ET-A** **CET ET-ACET**  **ET-A CET**  **ET-A CET**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-8 MIR1**  **IR Surg-8 MIR1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**CTC195B DTC394A**  **DTC409A DTC415B**  **ET-A CET**  **ET-ACET ET-ACET**  **ET-A CET**  **IR Surg-8 LN1 IR Surg-8 LN1**  **IR Surg-8 LN1 IR Surg-3 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.06 -0.04 -0.02 0.00 0.02 1 2 3 4 5 6

-0.08 -0.06 -0.04 -0.02 0.00 0.02 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.08 -0.06 -0.04 -0.02 0.00 0.02 1 2 3 4 5 6

-0.012 -0.008 -0.004 0.000 0.004 0.008

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.008 -0.004 0.000 0.004 0.008

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.016 -0.012 -0.008 -0.004 0.000 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6 -4 -3 -2 -1 0 1 1 2 3 4 5 6

-4 -3 -2 -1 0 1 1 2 3 4 5 6

-4 -3 -2 -1 0 1 1 2 3 4 5 6

-4 -3 -2 -1 0 1 1 2 3 4 5 6

-2.0 -1.5 -1.0 -0.5 0.0 0.5 1 2 3 4 5 6

-3 -2 -1 0 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.012 -0.008 -0.004 0.000 0.004 1 2 3 4 5 6

-0.008 -0.006 -0.004 -0.002 0.000 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-0.10 -0.08 -0.06 -0.04 -0.02 0.00 1 2 3 4 5 6

-5 -4 -3 -2 -1 0 1 2 3 4 5 6

-2.0 -1.5 -1.0 -0.5 0.0 0.5 1 2 3 4 5 6

-6 -4 -2 0 2 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 326

Figure C - 57 . Plots o f experimental and calculated environmental chamber reactivity results for

isopropyl and t -butyl acetates.

**DTC688B DTC689A**  **DTC697A IPR-A** **CET IPR-ACET**  **IPR-ACET IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**CTC216B CTC221A**  **CTC217A CTC222B**  **CTC220B CTC223A**  **TBU-A CET**  **TBU-ACET TBU-A** **CET TBU-A** **CET TBU-A** **CET TBU-A** **CET IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-8 MIR1**  **IR Surg-8 MIR1 IR Surg-8 LN1**  **IR Surg-8 LN1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 0.00 0.04 0.08 0.12 0.16

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0.00 0.05 0.10 0.15 0.20 0.25

1 2 3 4 5 6

-0.004 -0.002 0.000 0.002 0.004

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.004 -0.002 0.000 0.002

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

0.000 0.005 0.010 0.015 0.020 0.025

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6 -1.6 -1.2 -0.8 -0.4 0.0 0.4 1 2 3 4 5 6

-3 -2 -1 0 1 1 2 3 4 5 6

-2 -1 0 1 2

1 2 3 4 5 6

-0.8 -0.6 -0.4 -0.2 0.0 0.2 1 2 3 4 5 6

-0.6 -0.4 -0.2 0.0 0.2 1 2 3 4 5 6

-0.4 -0.3 -0.2 -0.1 0.0 0.1 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03 0.04

1 2 3 4 5 6 0.000 0.002 0.004 0.006 0.008

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.000 0.002 0.004 0.006 0.008

1 2 3 4 5 6

-0.6 -0.4 -0.2 0.0 0.2 1 2 3 4 5 6

-0.6 -0.4 -0.2 0.0 0.2 1 2 3 4 5 6

-0.6 -0.4 -0.2 0.0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 327

Figure C - 58 . Plots of experimental and calculated environmental chamber reactivity results for methyl

isobutyrate. **DTC528B DTC533A**  **DTC530B DTC534B**  **ME-IBUA**

**T ME-IBUAT**  **ME-IBUA T**  **ME-IBUA T**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1** 

 **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC531A DTC539A**  **DTC548A ME-IBUAT**  **ME-IBUAT ME-IBUA**  **T IR Surg-8 LN1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.06 -0.04 -0.02 0.00 0.02 1 2 3 4 5 6

-0.08 -0.06 -0.04 -0.02 0.00 0.02 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03

1 2 3 4 5 6 -0.01 0.00 0.01 0.02 0.03

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.010 -0.005 0.000 0.005 0.010 0.015

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-0.008 -0.004 0.000 0.004 0.008 0.012

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6 -4 -3 -2 -1 0 1 2 3 4 5 6

-4 -3 -2 -1 0 1 1 2 3 4 5 6

-3 -2 -1 0 1 2 3 4 5 6

-3 -2 -1 0 1 1 2 3 4 5 6

-4 -3 -2 -1 0 1 2 3 4 5 6

-2.5 -2.0 -1.5 -1.0 -0.5 0.0 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-0.008 -0.004 0.000 0.004 0.008

1 2 3 4 5 6

-2.0 -1.5 -1.0 -0.5 0.0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 328

Figure C - 59 . Plots of experimental and calculated environmental chamber reactivity results for methyl

pivalate. **DTC694A DTC701B**  **DTC695B DTC702A**  **DTC700A DTC707B**  **ME-PVA T**  **ME-PVAT ME-PVAT**  **ME-PVA T**  **ME-PVA T**  **ME-PVA T**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.03 -0.02 -0.01 0.00 0.01 1 2 3 4 5 6

-0.020 -0.016 -0.012 -0.008 -0.004 0.000 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.004 0.000 0.004 0.008 0.012

1 2 3 4 5 6 -0.004 0.000 0.004 0.008 0.012

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.004 -0.002 0.000 0.002 0.004 0.006

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-0.004 -0.002 0.000 0.002 0.004

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-1.6 -1.2 -0.8 -0.4 0.0 0.4 1 2 3 4 5 6

-0.8 -0.6 -0.4 -0.2 0.0 0.2 1 2 3 4 5 6

-2.0 -1.6 -1.2 -0.8 -0.4 0.0 1 2 3 4 5 6

-1.2 -0.8 -0.4 0.0 0.4 1 2 3 4 5 6

-1.0 -0.8 -0.6 -0.4 -0.2 0.0 1 2 3 4 5 6

-0.8 -0.6 -0.4 -0.2 0.0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 329

Figure C - 60 . Plots of experimental and calculated environmental chamber reactivity re sults for n -butyl

acetate.

**CTC196A DTC365A**  **DTC368B DTC402B**  **BU-A CET**  **BU-A CET**  **BU-ACET BU-ACET**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC403A DTC410B**  **DTC406A DTC411A**  **BU-A CET**  **BU-A CET**  **BU-ACET BU-ACET**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.08 -0.06 -0.04 -0.02 0.00 1 2 3 4 5 6

-0.08 -0.06 -0.04 -0.02 0.00 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.06 -0.04 -0.02 0.00 1 2 3 4 5 6

-0.10 -0.08 -0.06 -0.04 -0.02 0.00 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03 0.04

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 -4 -3 -2 -1 0 1 1 2 3 4 5 6

-4 -3 -2 -1 0 1 1 2 3 4 5 6

-3 -2 -1 0 1 2 3 4 5 6

-6 -4 -2 0 2 1 2 3 4 5 6

-5 -4 -3 -2 -1 0 1 2 3 4 5 6

-3 -2 -1 0 1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03

1 2 3 4 5 6 0.000 0.004 0.008 0.012 0.016 0.020

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-6 -4 -2 0 1 2 3 4 5 6

-3 -2 -1 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 330

Figure C - 61 . Plots of experimental and calculated environmental chamber reactivity results for

dimethyl carbonate and methyl isopropyl carbonate. **DTC692B DTC703B**  **DTC693A DTC705A**  **DTC698B DMC**  **DMC DMC**  **DMC DMC**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC750B DTC759A**  **DTC755A DTC762A**  **DTC758B DTC763B**  **MIPR-CB MIPR-CB**  **MIPR-CB MIPR-CB**  **MIPR-CB MIPR-CB**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.000 0.002 0.004 0.006 0.008

1 2 3 4 5 6 0.000 0.002 0.004 0.006 0.008 0.010

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.000 0.004 0.008 0.012 0.016

1 2 3 4 5 6 0.000 0.004 0.008 0.012 0.016 0.020

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.000 0.002 0.004 0.006

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 -0.2 -0.1 0.0 0.1

1 2 3 4 5 6

-0.12 -0.08 -0.04 0.00 0.04 1 2 3 4 5 6

-0.3 -0.2 -0.1 0.0 0.1 1 2 3 4 5 6

-0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2

1 2 3 4 5 6

-0.4 -0.3 -0.2 -0.1 0.0 1 2 3 4 5 6

-2.0 -1.5 -1.0 -0.5 0.0 0.5 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 0.00 0.04 0.08 0.12 0.16

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.04 0.08 0.12 0.16 0.20

1 2 3 4 5 6 0.00 0.01 0.02 0.03 0.04 0.05

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03 0.04 0.05

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4

0 1 2 3 4 5 6

-2.0 -1.5 -1.0 -0.5 0.0 0.5 1 2 3 4 5 6

-4 -3 -2 -1 0 1 1 2 3 4 5 6

-4 -3 -2 -1 0 1 1 2 3 4 5 6

-4 -3 -2 -1 0 1 2 3 4 5 6

-6 -4 -2 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 331

Figure C - 62 . Plots of experimental and calculated environmental chamber reactivity results for

propylene carbonate.

**DTC235B DTC239B**  **DTC243A DTC264B**  **PC PC**  **PC PC**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC250B DTC260B**  **DTC266A PC**  **PC PC**  **IR Surg-8 MIR1 IR Surg-8 LN1**  **IR Surg-8 LN1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.03 -0.02 -0.01 0.00 0.01 0.02

1 2 3 4 5 6

-0.016 -0.012 -0.008 -0.004 0.000 0.004 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.008 -0.004 0.000 0.004 0.008

1 2 3 4 5 6

-0.012 -0.008 -0.004 0.000 0.004 0.008

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.0 0.1 0.2 0.3 0.4

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.000 0.005 0.010 0.015 0.020

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 -12 -8 -4 0 4 1 2 3 4 5 6

-1.5 -1.0 -0.5 0.0 0.5 1.0

1 2 3 4 5 6

-0.8 -0.6 -0.4 -0.2 0.0 0.2 1 2 3 4 5 6

-2.0 -1.5 -1.0 -0.5 0.0 0.5 1 2 3 4 5 6

-20 -16 -12 -8 -4 0 1 2 3 4 5 6

-3 -2 -1 0 1 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.000 0.004 0.008 0.012 0.016

1 2 3 4 5 6

-1.6 -1.2 -0.8 -0.4 0.0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 332

Figure C - 63 . Plots of experimental and calculated environmental chamber reactivity results for 1 -

methoxy - 2 -propyl acetate. **DTC532B DTC537A**  **DTC549B DTC538B**  **DTC547B DTC540B**  **PGME-A CT**  **PGME-A CT**  **PGME-A CT**  **PGME-A CT**  **PGME-ACT PGME-A** **CT IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.4 -0.3 -0.2 -0.1 0.0 0.1 1 2 3 4 5 6

-0.6 -0.4 -0.2 0.0 0.2 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.3 -0.2 -0.1 0.0 0.1 1 2 3 4 5 6

0.00 0.05 0.10 0.15 0.20 0.25

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.04 0.08 0.12 0.16 0.20

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.04 0.00 0.04 0.08

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-30 -20 -10 0 10 1 2 3 4 5 6

-30 -20 -10 0 10 1 2 3 4 5 6

-20 -15 -10 -5 0 5 1 2 3 4 5 6

-25 -20 -15 -10 -5 0 1 2 3 4 5 6

-16 -12 -8 -4 0 1 2 3 4 5 6

-25 -20 -15 -10 -5 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 333

Figure C - 64 . Plots of experimental and calculated environmental chamber reactivity results for

dimethyl succinate and dimethyl glutarate. **CTC197B CTC211B**  **CTC198A CTC208A**  **CTC199B CTC210A**  **DBE-4 DBE-4**  **DBE-4 DBE-4**  **DBE-4 DBE-4**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**CTC201A CTC209B**  **CTC204A CTC212B**  **CTC205B CTC215A**  **DBE-5 DBE-5**  **DBE-5 DBE-5**  **DBE-5 DBE-5**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

-0.006 -0.004 -0.002 0.000 0.002 1 2 3 4 5 6

-0.010 -0.008 -0.006 -0.004 -0.002 0.000 0.002 1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03

1 2 3 4 5 6 0.00 0.01 0.02 0.03 0.04

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

0.000 0.004 0.008 0.012 0.016 0.020

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

0.000 0.004 0.008 0.012 0.016

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-1.2 -0.8 -0.4 0.0 0.4 1 2 3 4 5 6

-1.6 -1.2 -0.8 -0.4 0.0 1 2 3 4 5 6

-1.2 -0.8 -0.4 0.0 0.4 1 2 3 4 5 6

-1.2 -0.8 -0.4 0.0 0.4 1 2 3 4 5 6

-1.6 -1.2 -0.8 -0.4 0.0 1 2 3 4 5 6

-1.2 -0.8 -0.4 0.0 1 2 3 4 5 6

0.0 0.2 0.4 0.6

0 1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

-0.04 -0.03 -0.02 -0.01 0.00 1 2 3 4 5 6

-0.08 -0.06 -0.04 -0.02 0.00 1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-0.02 0.00 0.02 0.04 0.06

1 2 3 4 5 6 -0.02 0.00 0.02 0.04 0.06

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.01 0.00 0.01 0.02 0.03

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

0.000 0.005 0.010 0.015 0.020

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-2.0 -1.6 -1.2 -0.8 -0.4 0.0 1 2 3 4 5 6

-4 -3 -2 -1 0 1 2 3 4 5 6

-2.0 -1.5 -1.0 -0.5 0.0 0.5 1 2 3 4 5 6

-2.0 -1.5 -1.0 -0.5 0.0 1 2 3 4 5 6

-3 -2 -1 0 1 2 3 4 5 6

-2.5 -2.0 -1.5 -1.0 -0.5 0.0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 334

Figure C - 65 . Plots of experimental and calculated environmental chamber reactivity results for the

Texanol® 1 

### isomers.

1 

### Texanol is a trademark of Eastman Chemical Company. **EPA 229A**  **EPA 230B**  **EPA 231B**  **EPA232A TEXANOL**  **TEXANOL TEXANOL**  **TEXANOL IR Surg-7 MIR2**  **IR Surg-7 MIR2 IR Surg-7 LN2**  **IR Surg-7 LN2**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

-0.2 -0.1 0.0 0.1 0.2

0 1 2 3 4 5 6

-400 -300 -200 -100 0 100 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

-0.2 -0.1 0.0 0.1 0.2

0 1 2 3 4 5 6

-400 -300 -200 -100 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.2 -0.1 0.0 0.1

0 1 2 3 4 5 6

-160 -120 -80 -40 0 40 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

-0.2 -0.1 0.0 0.1 0.2

0 1 2 3 4 5 6

-160 -120 -80 -40 0 0 1 2 3 4 5 6

**Base Experiment Test Experiment**  **Base Calc (SA PRC-07)**  **SAPRC-07 Test Calc SAPRC-99 Test Calc** 

### 335

Figure C - 66 . Plots of model errors in simulations of the furan - NO x 

### environmental chamber

experiments. Furan - NOx Experiments Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final EPA Chm., Arc 2 -29% 1% -28% -25% EPA Chm, Black 2 -55% -26% 12% -26% ITC Chamber 4 -20% 47% -15% 1%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 EPA Chm., Arc EPA Chm, Black ITC Chamber

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 336

Figure C - 67 . Plots of model error s in simulations of the methyl furan - NO x 

### environmental chamber

experiments. Methylfuran - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07

2-Hr Final 2-Methyl, Arc 2 (Not represented) -13% -12% 3-Methyl, Arc 4 -15% -23% 3-Methyl, Black 2 -3% -21% 2,5-Dimethyl, Arc 2 -19% -24% SAPRC-07 Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 2-Methyl, Arc 3-Methyl, Arc 3-Methyl, Black 2,5-Dimethyl, Arc

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 337

Figure C - 68 . Plots of model errors in simulations of the benzyl alcohol and benzyl alcohol + CO - NO x



### environmental chamber experiments. Benzyl Alcohol - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Arc Light 3 7% 18% -1% 10% Blacklight 2 -17% 11% 20% 7% Added CO 1 -11% 3% -14% 19%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 Arc Light Blacklight Added CO

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 338

Figure C - 69 . Plots of experimental and calculated environmental chamber reactivity results for benzyl

alcohol.

**EPA319A EPA323B**  **EPA 320B**  **BZ-CH2OH BZ-CH2OH**  **BZ-CH2OH IR Surg-7 MIR2**  **IR Surg-7 MIR2 IR Surg-7 LN2**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-1.0 -0.5 0.0 0.5 1.0

0 1 2 3 4 5 6

-400 -200 0 200

0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.5 0.0 0.5 1.0 1.5

0 1 2 3 4 5 6

-600 -400 -200 0 200 0 1 2 3 4 5 6 0.00 0.04 0.08 0.12 0.16

0 1 2 3

-0.1 0.0 0.1 0.2 0.3

0 1 2 3

-160 -120 -80 -40 0 40 0 1 2 3

**Base Experiment Test Experiment**  **Base Calc (SAPRC-07) SA** **PRC-07 Test Calc SAPRC-99 Test Calc** 

### 339

Figure C - 70 . Plots of model errors in simulations of the formaldehyde - NO x 

### environmental chamber

experiments. Formaldehyde - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final UCR Arc Light 14 -3% -5% -8% -8% UCR Blacklight 9 -6% -7% -7% -6% TVA chamber 3 -1% -4% -3% -4% Added CO 7 -10% -11% -6% -7%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 UCR Arc Light UCR Blacklight TVA chamber Added CO

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 340

Figure C - 71 . Plots of experimental and calculated environmental chamber reactivity results for

formaldehyde. **ETC352 ETC357**  **ETC470 ETC489**  **FORMA LD**  **FORMA LD**  **FORMALD FORMA** **LD IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-E MIR1**  **IR Surg-E MIR1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**CTC138B CTC140A**  **DTC022B DTC036A**  **FORMA LD**  **FORMALD FORMALD**  **FORMA LD**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 MIR1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 0 1 2 3 4 5

1 2 3 4 5 6 0 1 2 3

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0.0 0.2 0.4 0.6

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.0 0.4 0.8 1.2

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

-0.2 0.0 0.2 0.4 0.6

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 0 50 100 150 200

1 2 3 4 5 6 0 40 80 120 160

1 2 3 4 5 6

0 5 10 15 20 25

1 2 3 4 5 6 -10 0 10 20 30

1 2 3 4 5 6 0 20 40 60

1 2 3 4 5 6 0 4 8 12 16 20

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0 1 2 3 4

1 2 3 4 5 6 0 1 2 3

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0 40 80 120

1 2 3 4 5 6 -40 0 40 80 120

1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 341

Figure C - 72 . Plots of model errors in simulations of the acetaldehyde - NO x 

### environmental chamber

experiments. Acetaldehyde - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Arc Light 8 17% 16% 5% 5% Blacklight 5 8% 4% 2% -1% OTC Chamber 4 -2% 1% -5% -1% Added CO 1 6% -5% 6% -5%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 Arc Light Blacklight OTC Chamber Added CO

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 342

Figure C - 73 . Plots of experimental and calculated environmental chamber reactivity results for

acetaldehyde. **CTC107A ETC335**  **ETC338 DTC065A**  **DTC066B ACETALD**  **AC ETAL**  **D ACETALD**  **ACETALD ACETALD**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70

0 1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20

0 1 2 3 4 5 6

-0.50 -0.40 -0.30 -0.20 -0.10 0.00 0.10 0.20

1 2 3 4 5 6

0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45

1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20

0 1 2 3 4 5 6

0.00 0.05 0.10 0.15 0.20 0.25 0.30

1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25

1 2 3 4 5 6 0.00 0.20 0.40 0.60 0.80 1.00 1.20

0 1 2 3 4 5 6

-0.08 -0.07 -0.06 -0.05 -0.04 -0.03 -0.02 -0.01 0.00 1 2 3 4 5 6 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80

0 1 2 3 4 5 6

-25.0 -20.0 -15.0 -10.0 -5.0 0.0 5.0 1 2 3 4 5 6

-20.0 -15.0 -10.0 -5.0 0.0 5.0 1 2 3 4 5 6

-14.0 -12.0 -10.0 -8.0 -6.0 -4.0 -2.0 0.0 2.0 4.0 1 2 3 4 5 6

-14.0 -12.0 -10.0 -8.0 -6.0 -4.0 -2.0 0.0 1 2 3 4 5 6

-25.0 -20.0 -15.0 -10.0 -5.0 0.0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 343

Figure C - 74 . Plots of model er rors in simulations of the acrolein and methacrolein (MA) - NO x 

### environmental chamber experiments. Acrolein, Methacrolein - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Acrolein 3 -16% 0% -5% 2% MA, XTC Chamber 2 -16% -11% -19% -13% MA, EC Chamber 4 3% 30% -8% 18% MA, Blacklights 6 17% -8% 1% -11%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 Acrolein MA, XTC Chamber MA, EC Chamber MA, Blacklights

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 344

Figure C - 75 . Plots of experimental and calculated environmental chamber reactivity results for

benzaldehyde.

**CTC267B CTC266A**  **EPA 380B**  **BENZA LD**  **BENZA LD**  **BENZA LD**  **IR Surg-8 LN1 IR Surg-x MIR1**  **IR Surg-7 MIR2**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-1.0 -0.8 -0.6 -0.4 -0.2 0.0 1 2 3 4 5 6

-2.0 -1.5 -1.0 -0.5 0.0 1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-50 -40 -30 -20 -10 0 1 2 3 4 5 6

-120 -80 -40 0 40 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model 0.00 0.04 0.08 0.12 0.16

0 1 2 3 4 5 6

-1.2 -0.8 -0.4 0.0 0.4 0 1 2 3 4 5 6

-300 -200 -100 0 0 1 2 3 4 5 6

### 345

Figure C - 76 . Plots of model errors in simulations of the acetone - NO x 

### environmental chamber

experiments. Acetone - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Arc Light 2 -16% -16% -34% -31% Blacklight 3 23% 27% -4% 6% OTC Chamber 2 -13% -3% -29% -14%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 Arc Light Blacklight OTC Chamber

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 346

Figure C - 77 . Plots of experimental and calculated environmental chamber reactivity results for

acetone. **ETC243 ETC245**  **ETC247 DTC028A**  **DTC064B ACETONE**  **ACETONE ACE**  **TONE ACETONE**  **ACETONE IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**OTC275A OTC276B**  **ETC480 ETC481**  **ETC490 ACETONE**  **ACETONE AC**  **ETONE ACETONE**  **ACETONE IR Surg-8 LN1**  **IR Surg-8 LN1 IR Surg-E MIR1**  **IR Surg-E MIR1 IR Surg-E MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.04 0.08 0.12 0.16 0.20

1 2 3 4 5 6 0.00 0.04 0.08 0.12

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06 0.08 0.10

1 2 3 4 5 6 0.00 0.01 0.02 0.03 0.04

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03 0.04

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06

1 2 3 4 5 6 0.0 0.5 1.0 1.5 2.0

0 1 2 3 4 5 6 -4 0 4 8 12

1 2 3 4 5 6 -2 0 2 4 6

1 2 3 4 5 6 0 1 2 3

1 2 3 4 5 6 -0.2 0.0 0.2 0.4 0.6 0.8

1 2 3 4 5 6 -0.2 0.0 0.2 0.4

1 2 3 4 5 6

-0.8 -0.4 0.0 0.4 0.8 1.2

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6 2.0

0 1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06

1 2 3 4 5 6 0.00 0.02 0.04 0.06

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03 0.04 0.05

1 2 3 4 5 6 0.00 0.01 0.02 0.03 0.04 0.05

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

-1.0 -0.5 0.0 0.5 1.0 1.5

1 2 3 4 5 6 -1 0 1 2

1 2 3 4 5 6 -0.5 0.0 0.5 1.0 1.5 2.0

1 2 3 4 5 6 -0.8 -0.4 0.0 0.4 0.8 1.2

1 2 3 4 5 6 Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 347

Figure C - 78 . Plots of model errors in simulations of the methyl ethyl ketone (MEK), 2 -pentanone

(MPK) and 2 -heptanone - NO x 

### environmental chamber experiments. Ketone - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final MEK, Arc 2 -6% -6% -5% -7% MEK, Black 4 6% 7% 8% 7% MPK 1 13% 2% 6% -2% 2-Heptanone 1 9% -1% -43% -39%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 MEK, Arc MEK, Black MPK 2-Heptanone

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 348

Figure C - 79 . Plots of experimental and calculated environmental chamber reactivity results for methyl

ethyl ketone. **CTC181A DTC363A**  **CTC180B DTC338A**  **DTC345B MEK**  **MEK MEK**  **MEK MEK**  **IR Surg-3 MIR1 IR Surg-x MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-x MIR1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.02 0.00 0.02 0.04 0.06

1 2 3 4 5 6 0.00 0.01 0.02 0.03 0.04

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03 0.04 0.05

1 2 3 4 5 6 0.00 0.02 0.04 0.06 0.08 0.10

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06 0.08 0.10

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-3 -2 -1 0 1 1 2 3 4 5 6

-3 -2 -1 0 1 1 2 3 4 5 6

-1.5 -1.0 -0.5 0.0 0.5 1.0

1 2 3 4 5 6

-2 -1 0 1 2

1 2 3 4 5 6

-2 -1 0 1 2

1 2 3 4 5 6 Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 349

Figure C - 80 . Plots of experimental and calculated environmental chamber reactivity results for 2 -

pentanone.

**CTC255A CTC260B**  **CTC263B CTC258B**  **MPK MPK**  **MPK MPK**  **IR Surg-3 MIR1 IR Surg-8 MIR1**  **IR Surg-8 MIR1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-0.12 -0.08 -0.04 0.00 0.04 1 2 3 4 5 6

0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.020 -0.015 -0.010 -0.005 0.000 0.005 1 2 3 4 5 6

-0.03 -0.02 -0.01 0.00 0.01 0.02

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-8 -6 -4 -2 0 2 1 2 3 4 5 6

-6 -4 -2 0 2 1 2 3 4 5 6

-5 -4 -3 -2 -1 0 1 2 3 4 5 6

-8 -6 -4 -2 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 350

Figure C - 81 . Plots of experimental and calculated environmental chamber reactivity results for 4 -

methyl - 2 -pentanone and 2 - heptanone. **CTC183A DTC366B**  **DTC369A CTC182B**  **DTC370B DTC414A**  **MIBK MIBK**  **MIBK MIBK**  **MIBK MIBK**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-8 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC412B DTC418A**  **CTC257A CTC262A**  **CTC259A MIBK**  **MIBK C7-KET-2**  **C7-KET-2 C7-KET-2**  **IR Surg-8 LN1 IR Surg-8 LN1**  **IR Surg-3 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.20 -0.15 -0.10 -0.05 0.00 0.05 1 2 3 4 5 6

-0.12 -0.08 -0.04 0.00 0.04 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.08 -0.06 -0.04 -0.02 0.00 0.02 0.04

1 2 3 4 5 6

0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.00 0.01 0.02 0.03 0.04

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-12 -8 -4 0 1 2 3 4 5 6

-8 -6 -4 -2 0 1 2 3 4 5 6

-6 -4 -2 0 2 1 2 3 4 5 6

-12 -8 -4 0 1 2 3 4 5 6

-8 -6 -4 -2 0 1 2 3 4 5 6

-8 -6 -4 -2 0 1 2 3 4 5 6

0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-0.025 -0.020 -0.015 -0.010 -0.005 0.000 1 2 3 4 5 6

-0.04 -0.02 0.00 0.02

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-0.16 -0.12 -0.08 -0.04 0.00 1 2 3 4 5 6

-0.04 0.00 0.04 0.08 0.12 0.16

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.04 -0.02 0.00 0.02 0.04

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-6 -4 -2 0 1 2 3 4 5 6

-16 -12 -8 -4 0 1 2 3 4 5 6

-8 -6 -4 -2 0 2 1 2 3 4 5 6

-12 -8 -4 0 4 1 2 3 4 5 6

-8 -6 -4 -2 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 351

Figure C - 82 . Plots of experimental and calculated environmental chamber reactivity results for

cyclohexanone. **CTC227A DTC554B**  **DTC558A CTC229B**  **DTC556A CC6-KET**  **CC6-KET CC6-KET**  **CC6-KET CC6-KET**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-8 MIR1**  **IR Surg-8 MIR1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC559B CTC235A**  **CTC238A DTC557B**  **CC6-KET CC6-KET**  **CC6-KET CC6-KET**  **IR Surg-8 MIR1 IR Surg-8 LN1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.25 -0.20 -0.15 -0.10 -0.05 0.00 1 2 3 4 5 6

-0.20 -0.15 -0.10 -0.05 0.00 0.05 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.3 -0.2 -0.1 0.0 0.1 1 2 3 4 5 6

-0.08 -0.04 0.00 0.04

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.04 -0.02 0.00 0.02

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.06 -0.04 -0.02 0.00 0.02 0.04

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 -16 -12 -8 -4 0 4 1 2 3 4 5 6

-10 -8 -6 -4 -2 0 1 2 3 4 5 6

-12 -8 -4 0 4 1 2 3 4 5 6

-8 -6 -4 -2 0 1 2 3 4 5 6

-12 -8 -4 0 1 2 3 4 5 6

-12 -8 -4 0 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-0.06 -0.04 -0.02 0.00 0.02 1 2 3 4 5 6

-0.12 -0.08 -0.04 0.00 0.04 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-0.05 -0.04 -0.03 -0.02 -0.01 0.00 0.01 1 2 3 4 5 6

-10 -8 -6 -4 -2 0 1 2 3 4 5 6

-16 -12 -8 -4 0 1 2 3 4 5 6

-10 -8 -6 -4 -2 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 352

Figure C - 83 . Plots of model errors in simulations of the methyl vinyl ketone - NO x 

### environmental

chamber experiments. MVK - NOx Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final EC Chamber 3 -3% 17% -10% 11% Blacklight 3 0% -6% -15% -11%

SAPRC-99 SAPRC-07

Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range)

Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 -50% -25% 0% 25% 50%

1 2 3 4 5 6 EC Chamber Blacklight

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 353

Figure C - 84 . Plots of experimental and calculated  ([O 3 

### ] - [NO]), cresol, and PAN concentrations in the

cresol - NO x 

### environmental chamber experiments.

Figure C - 85 . Plots of experimental and calculated environmental chamber reactivity results for m cresol. **EC281**

**o-Cresol EC289**  **m-Cresol EC290**  **p-Cresol**  **([O 3**  **]-[NO]) (ppm)**

**Cresol (ppm)**

**PAN (ppm)**

**Irradiation time (minutes)** 0.0 0.2 0.4 0.6

0 120 240 360 0.0 0.2 0.4 0.6

0 120 240 360 0.0 0.1 0.2 0.3 0.4 0.5

0 120 240 360

0.0 0.1 0.2 0.3 0.4 0.5

0 120 240 360 0.0 0.1 0.2 0.3 0.4

0 120 240 360 0.0 0.1 0.2 0.3 0.4

0 120 240 360

0.000 0.002 0.004 0.006 0.008

0 120 240 360 0.000 0.002 0.004 0.006 0.008

0 120 240 360 0.000 0.002 0.004 0.006 0.008

0 120 240 360

**EPA383B M-CRESOL**  **IR Surg-7 LN2**  **(O 3**  **-NO) (ppm) IR**   **(O 3**  **-NO) (mole basis)**  **IR IntOH (ppt-min/ppm) m-Cresol (ppm)** 

0.00 0.05 0.10 0.15

0 1 2 3 4 5 6 -0.6 -0.4 -0.2 0.0 0.2 0.4

0 1 2 3 4 5 6

-200 -150 -100 -50 0 50 0 1 2 3 4 5 6

**Base Experiment Test Experiment**  **Base Calc (SAPRC-07) SAPRC-07 Test Calc**  **SAPRC-99 Test Calc** 0.00 0.02 0.04 0.06 0.08 0.10

0 1 2 3 4 5 6

### 354

Figure C - 86 . Plots of experimental and calculated environmental chamber reactivity results for para

toluene isocyanate. **DTC601A DTC602A**  **DTC618A DTC610A**  **DTC604B DTC608A**  **P-TI P-TI**  **P-TI P-TI**  **P-TI P-TI**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

0.00 0.05 0.10 0.15 0.20

1 2 3 4 5 6 -0.04 -0.03 -0.02 -0.01 0.00 0.01 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.012 -0.008 -0.004 0.000 0.004 1 2 3 4 5 6

-0.02 -0.01 0.00 0.01 0.02

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.04 -0.03 -0.02 -0.01 0.00 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-0.020 -0.016 -0.012 -0.008 -0.004 0.000 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-4 0 4 8 12

1 2 3 4 5 6 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1 2 3 4 5 6

-1.2 -0.8 -0.4 0.0 0.4 1 2 3 4 5 6

-2.0 -1.5 -1.0 -0.5 0.0 1 2 3 4 5 6

-6 -4 -2 0 1 2 3 4 5 6

-3 -2 -1 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 355

Figure C - 87 . Plots of experimental and calculated environmental chamber reactivity results for 2,4 -

toluene diisocyanate (TDI1) and 2,6 -toluene diisocyanate (TDI2). **DTC447A DTC450A**  **DTC456A DTC459A**  **TDI TDI**  **TDI TDI**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC453A DTC454A**  **DTC462B DTC467A**  **DTC466A TDI**  **TDI TDI**  **TDI2 TDI2**  **IR Surg-8 LN1 IR Surg-8 LN1**  **IR Surg-8 LN1 IR Surg-3 MIR1**  **IR Surg-8 LN1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.25 -0.20 -0.15 -0.10 -0.05 0.00 1 2 3 4 5 6

-0.5 -0.4 -0.3 -0.2 -0.1 0.0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.4 -0.3 -0.2 -0.1 0.0 1 2 3 4 5 6

-0.6 -0.4 -0.2 0.0 0.2 1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-0.16 -0.12 -0.08 -0.04 0.00 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-0.3 -0.2 -0.1 0.0 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4

0 1 2 3 4 5 6 -8 -6 -4 -2 0 2 1 2 3 4 5 6

-20 -15 -10 -5 0 5 1 2 3 4 5 6

-20 -16 -12 -8 -4 0 1 2 3 4 5 6

-30 -20 -10 0 10 20

1 2 3 4 5 6

-12 -8 -4 0 1 2 3 4 5 6

-25 -20 -15 -10 -5 0 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4

0 1 2 3 4 5 6

-0.3 -0.2 -0.1 0.0 1 2 3 4 5 6

-0.5 -0.4 -0.3 -0.2 -0.1 0.0 1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-0.4 -0.3 -0.2 -0.1 0.0 1 2 3 4 5 6

-25 -20 -15 -10 -5 0 1 2 3 4 5 6

-20 -15 -10 -5 0 5 1 2 3 4 5 6

-40 -30 -20 -10 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 356

Figure C - 88 . Plots of experimental and calculated environmental chamber reactivity results for n methyl - 2 -pyrrolidone. **DTC240A DTC244B**  **DTC252A DTC255B**  **DTC261A DTC267B**  **NMP NMP**  **NMP NMP**  **NMP NMP**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.2 -0.1 0.0 0.1

1 2 3 4 5 6

-0.08 -0.04 0.00 0.04 0.08

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.04 0.08 0.12 0.16

1 2 3 4 5 6 0.0 0.2 0.4 0.6

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.2 -0.1 0.0 0.1 0.2 0.3 0.4

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-0.1 0.0 0.1 0.2

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-12 -8 -4 0 1 2 3 4 5 6

-5 -4 -3 -2 -1 0 1 2 3 4 5 6

-10 -8 -6 -4 -2 0 1 2 3 4 5 6

-30 -20 -10 0 10 1 2 3 4 5 6

-50 -40 -30 -20 -10 0 1 2 3 4 5 6

-30 -20 -10 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 357

Figure C - 89 . Plots of experimental and calculated environmental chamber reactivity results for n propyl bromide and n -butyl bromide. **DTC421A DTC433A**  **DTC423B DTC427A**  **DTC424A DTC428B**  **C3-BR C3-BR**  **C3-BR C3-BR**  **C3-BR C3-BR**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC401A DTC426B**  **DTC419B DTC430A**  **DTC420B DTC432B**  **C4-BR C4-BR**  **C4-BR C4-BR**  **C4-BR C4-BR**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.02 0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 -0.04 0.00 0.04 0.08 0.12

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.02 0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 -0.04 -0.02 0.00 0.02 0.04

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.04 -0.02 0.00 0.02 0.04

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4

0 1 2 3 4 5 6

-0.02 -0.01 0.00 0.01 0.02

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-1.2 -0.8 -0.4 0.0 0.4 1 2 3 4 5 6

-1 0 1 2 3

1 2 3 4 5 6 -4 -2 0 2 4

1 2 3 4 5 6 -4 -3 -2 -1 0 1 1 2 3 4 5 6

-8 -6 -4 -2 0 1 2 3 4 5 6

-2.5 -2.0 -1.5 -1.0 -0.5 0.0 1 2 3 4 5 6

0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.02 0.00 0.02 0.04 0.06

1 2 3 4 5 6 -0.02 0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.04 -0.02 0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 -0.04 -0.02 0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.02 -0.01 0.00 0.01 0.02 0.03

1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-0.02 -0.01 0.00 0.01 0.02 0.03

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-1.2 -0.8 -0.4 0.0 0.4 1 2 3 4 5 6

-2 -1 0 1

1 2 3 4 5 6

-3 -2 -1 0 1 1 2 3 4 5 6

-4 -3 -2 -1 0 1 1 2 3 4 5 6

-2.5 -2.0 -1.5 -1.0 -0.5 0.0 1 2 3 4 5 6

-2.0 -1.5 -1.0 -0.5 0.0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 358

Figure C - 90 . Plots of experimental and calculated environmental chamber reactivity results for

trichloroethylene. **DTC303B DTC305A**  **DTC308B DTC311B**  **DTC320A CL3-ETHE**  **CL3-ETHE CL3-ETHE**  **CL3-ETHE CL3-ETHE**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 MIR1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC309A DTC321B**  **DTC312A CL3-ETHE**  **CL3-ETHE CL3-ETHE**  **IR Surg-8 LN1 IR Surg-8 LN1**  **IR Surg-X LN1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 -0.04 0.00 0.04 0.08 0.12

1 2 3 4 5 6 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6

-0.08 -0.04 0.00 0.04 0.08 0.12

1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.00 0.05 0.10 0.15 0.20

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.04 0.00 0.04 0.08

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 -1.6 -1.2 -0.8 -0.4 0.0 0.4 1 2 3 4 5 6

-3 -2 -1 0 1 2

1 2 3 4 5 6

-12 -8 -4 0 4 1 2 3 4 5 6

-2 0 2 4 6

1 2 3 4 5 6 -4 0 4 8 12

1 2 3 4 5 6

-6 -4 -2 0 2 1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-0.02 0.00 0.02 0.04 0.06 0.08

1 2 3 4 5 6 -0.08 -0.04 0.00 0.04 0.08

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-10 -8 -6 -4 -2 0 1 2 3 4 5 6

-4 0 4 8 12

1 2 3 4 5 6 Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 359

Figure C - 91 . Plots of model errors in simulations of the 1,3 - dichloropropene and 1,3 - dichloropropene

+ n -butane - NO x 

### environmental chamber experiments. 1,3-Dichloropropene Runs Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final 13-DCP - NOx 4 0% 0% -18% -9% DCP + n-C4 - NOx 2 0% 0% -24% -13% SAPRC-07 Average Model Error vs Hour of Run Group Runs

Distribution of Final Hour Model Errors (Fraction of

runs vs error range) Distribution of Hour 2 Model Errors (Fraction of runs vs error range) -75% -50% -25% 0% 25% 50% 75%

1 2 3 4 5 6 13-DCP - NOx DCP + n-C4 - NOx

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 360

Figure C - 92 . Plots of experimental and calculated environmental chamber reactivity results for the 1,3 -

dichloropropenes.

Figure C - 93 . Plots of experimental and calculated environmental chamber reactivity results for 2 -

(chloromethyl) - 3 - chloro -propene.

**EPA550A EPA554B**  **EPA 555B**  **13-DCP 13-DCP**  **13-DCP IR Surg-7 MIR2**  **IR Surg-7 LN2 IR Surg-8 vary**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70

0 1 2 3 4 5 6

-200.0 -150.0 -100.0 -50.0 0.0 50.0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.05 0.00 0.05 0.10 0.15 0.20 0.25 0.30

0 1 2 3 4 5 6

-80.0 -60.0 -40.0 -20.0 0.0 20.0 0 1 2 3 4 5 6 0.00 0.02 0.04 0.06 0.08 0.10 0.12

0 1 2 3 4 5 6

-0.10 -0.05 0.00 0.05 0.10 0.15 0.20 0.25 0.30

0 1 2 3 4 5 6

-150.0 -100.0 -50.0 0.0 50.0 0 1 2 3 4 5 6

**Base Experiment Test Experiment**  **Base Calc (SAPRC-07) SAPRC-07 Test Calc** 

**ETC342 CL2IBUTE**  **IR Surg-3 MIR1**  **(O 3**  **-NO) (ppm) vs Hour IR**   **(O 3**  **-NO) (mole basis) vs Hour**  **IR IntOH (ppt-min/ppm) vs Hour** 

0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60

0 1 2 3 4 5 6 0.00 1.00 2.00 3.00 4.00 5.00 6.00

1 2 3 4 5 6 -50.0 0.0 50.0 100.0 150.0

1 2 3 4 5 6 Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 361

Figure C - 94 Plots of model errors in simulations of the chloropicrin (CP)

– alkane - NO x 

### and the

chlorine + alkane - NO x 

### experiments. Chlorine and Chloropicrin Average  ([O3]-[NO]) Model Error SAPRC-99 SAPRC-07 2-Hr Final 2-Hr Final Cl2 + n-C4 - NOx 2 4% 5% CP + n-C4 - NOx 2 14% 8% CP + C2 + NOx 2 1% 2% CP + n-C4 - Air 2 -1% -6% SAPRC-07 Average Model Error vs Hour of Run

Distribution of Final Hour Model Errors (Fraction of runs vs error range) Distribution of Hour 2 Model Errors (Fraction of runs vs error range) Group Runs

-50% -25% 0% 25% 50%

1 2 3 4 5 6 Cl2 + n-C4 - NOx CP + n-C4 - NOx CP + C2 + NOx CP + n-C4 - Air

0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80% 0% 20% 40% 60% 80% 100%<-80%-80%--60%-60%--40%-40%--20%-20%-0%0%-20%20%-40%40%-60%60%-80%>-80%

### 362

Figure C - 95 . Plots of experimental and calculated environmental chamber reactivity results for

chloropicrin.

(IntCl is integrated chlorine calculated from the consumption rate for n - octane relative to the consumption rate of m - xylene) 

### Figure C - 96 . Plots of experimental and calculated environmental chamber reactivity results for

chlorine. Note that chlorine was added to the "base case" experiment after four hours of irradiation. **CTC112A CTC119B**  **CTC121A CTC124B**  **CTC126A CCL3NO2**  **CCL3NO2 CCL3NO2**  **CCL3NO2 CCL3NO2**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-3 MIR1 IR Surg-8 MIR2**  **IR Surg-8 MIR2**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.4 0.8 1.2 1.6

0 1 2 3 4 5 6

0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

0 5 10 15 20

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.0 0.5 1.0 1.5 2.0 2.5

0 1 2 3 4 5 6

0 20 40 60 80

0 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4

0.0 0.5 1.0 1.5 2.0

0 1 2 3 4

0 20 40 60 80

0 1 2 3 4 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-20 -10 0 10 20 30

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0 10 20 30 40

0 1 2 3 4 5 6 **Base Experiment Test Experiment**  **Base Calc (SA PRC-07)**  **SAPRC-07 Test Calc SAPRC-99 Test Calc** 

**DTC323: Effect of Cl 2** **Additions**  **(O 3**  **-NO) (ppm)**   **(O 3**  **-NO) change / Cl 2** 

**added (mole basis) n-Octane**  **(ppm) m-Xylene (ppm)**  **IntOH change / Cl 2**  **added (ppb-min/ppm) IntCL**  **(ppt-min)**

0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6 -1 0 1 2 3 4

0 1 2 3 4 5 6 -200 -100 0 100 200

0 1 2 3 4 5 6

**Side A (59 ppb Cl2 added at start)**  **Side B (57 ppb Cl2 added at hour 4) Side A Calc**  **Side B Calc** 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6 0.00 0.04 0.08 0.12

0 1 2 3 4 5 6 0.00 0.04 0.08 0.12

0 1 2 3 4 5 6

### 363

Figure C - 97 . Plots of experimental and c alculated environmental chamber reactivity results for

hexamethyldisiloxane, d4 cyclosiloxane, and hydroxymethyldisiloxane. **ETC179 ETC391**  **ETC396 ETC398**  **ETC402 ETC406**  **SI2OME6 SI2OME6**  **SI2OME6 (SIOME)4**  **(SIOME)4 (SIOME)4**  **IR Surg-3 MIR1 IR Surg-X LN1**  **IR Surg-X LN1 IR Surg-X LN1**  **IR Surg-X LN1 IR Surg-X LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**ETC409 ETC412**  **ETC400 ETC404**  **SI2OMEOH SI2OMEOH**  **SI2OMEOH SI2OMEOH**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-X LN1 IR Surg-X LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.06 -0.04 -0.02 0.00 0.02 1 2 3 4 5 6

-0.12 -0.08 -0.04 0.00 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.16 -0.12 -0.08 -0.04 0.00 1 2 3 4 5 6

-0.20 -0.16 -0.12 -0.08 -0.04 0.00 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.25 -0.20 -0.15 -0.10 -0.05 0.00 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.3 -0.2 -0.1 0.0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-2.5 -2.0 -1.5 -1.0 -0.5 0.0 1 2 3 4 5 6

-8 -6 -4 -2 0 2 1 2 3 4 5 6

-8 -6 -4 -2 0 2 1 2 3 4 5 6

-12 -8 -4 0 1 2 3 4 5 6

-12 -8 -4 0 4 1 2 3 4 5 6

-16 -12 -8 -4 0 4 1 2 3 4 5 6

0.0 0.2 0.4 0.6

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.16 -0.12 -0.08 -0.04 0.00 1 2 3 4 5 6

-0.3 -0.2 -0.1 0.0 0.1 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.25 -0.20 -0.15 -0.10 -0.05 0.00 1 2 3 4 5 6

-0.4 -0.3 -0.2 -0.1 0.0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-8 -6 -4 -2 0 2 1 2 3 4 5 6

-12 -8 -4 0 4 8

1 2 3 4 5 6

-16 -12 -8 -4 0 1 2 3 4 5 6

-30 -20 -10 0 10 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 364

Figure C - 98 . Plots of experimental and calculated environmental chamber reactivity results for carbon

disulfide and methyl isothiocyanate. **EPA591A EPA592B**  **EPA 597B**  **EPA 598A**  **CS2 CS2**  **CS2 CS2**  **IR Surg-7 MIR2 IR Surg-7 MIR2**  **IR Surg-7 LN2 IR Surg-7 LN2**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**EPA587A EPA588B**  **EPA 589A**  **EPA 599A**  **MITC MITC**  **MITC MITC**  **IR Surg-7 MIR2 IR Surg-7 MIR2**  **IR Surg-7 LN2 IR Surg-7 LN2**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

-0.02 0.00 0.02 0.04 0.06 0.08

0 1 2 3 4 5 6

-20 -15 -10 -5 0 5 0 1 2 3 4 5 6 0.00 0.04 0.08 0.12 0.16

0 1 2

0.00 0.01 0.02 0.03 0.04 0.05

0 1 2

-4 -2 0 2 4

0 1 2 0.00 0.04 0.08 0.12 0.16

0 1 2 3 4 5 6

-0.01 0.00 0.01 0.02 0.03 0.04

0 1 2 3 4 5 6

-12 -8 -4 0 4 8

0 1 2 3 4 5 6 0.00 0.04 0.08 0.12 0.16

0 1 2 3 4 5 6

-0.02 0.00 0.02 0.04 0.06 0.08

0 1 2 3 4 5 6

-15 -10 -5 0 5 10

0 1 2 3 4 5 6

0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.05 0.00 0.05 0.10 0.15

0 1 2 3 4 5 6

-60 -40 -20 0 20 40

0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

0.00 0.04 0.08

0 1 2 3 4 5 6

-20 -10 0 10

0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

0.00 0.04 0.08

0 1 2 3 4 5 6

-8 -4 0 4

0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

0.00 0.02 0.04 0.06 0.08

0 1 2 3 4 5 6

-8 -4 0 4 8

0 1 2 3 4 5 6 **Base Experiment Test Experiment**  **Base Calc (SAPRC-07) SAPRC-07 Test Calc**  **Base Experiment Test Experiment**  **Base Calc (SAPRC-07) SAPRC-07 Test Calc** 

### 365

Figure C - 99 . Plots of experimental and calculated O 3 

### , NO, DMSO and formaldehyde in the dimethyl

sulfoxide - NO x 

### environmental chamber experiments.

Figure C - 100 . Plots of experimental and calculated environmental chamber reactivity results for

dimethyl sulfoxide.

**O3 NO**  **DMSO Formaldehyde** **D T** **C 7** **8 5** **B D** **T C** **7 8** **5 A** 

Time (minutes) 0.00 0.10 0.20 0.30 0.40 0.50

0 120 240 360

0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40

0 120 240 360 0.00 0.05 0.10 0.15 0.20 0.25

0 120 240 360

0.00 0.02 0.04 0.06 0.08 0.10 0.12

0 120 240 360 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35

0 120 240 360

0.00 0.05 0.10 0.15 0.20 0.25 0.30

0 120 240 360 0.00 0.05 0.10 0.15 0.20 0.25 0.30

0 120 240 360

0.00 0.05 0.10 0.15 0.20 0.25

0 120 240 360 Experimental SAPRC-07 SAPRC-99

**DTC766A DTC783B**  **DTC780B DTC786A**  **DTC782A DTC787B**  **DMSO DMSO**  **DMSO DMSO**  **DMSO DMSO**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.4 0.8 1.2

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

0.0 0.4 0.8 1.2 1.6

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0 1 2 3

1 2 3 4 5 6 0.0 0.4 0.8 1.2 1.6 2.0

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

0.0 0.2 0.4 0.6 0.8

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

0.0 0.2 0.4 0.6 0.8 1.0

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4

0 1 2 3 4 5 6

-5 0 5 10 15 20

1 2 3 4 5 6 -10 0 10 20 30

1 2 3 4 5 6 -60 -40 -20 0 20 40

1 2 3 4 5 6

-10 -5 0 5 10 15

1 2 3 4 5 6 -80 -60 -40 -20 0 1 2 3 4 5 6

-120 -80 -40 0 40 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 366

Figure C - 101 . Plots of experimental and calculated environmental chamber reactivity results for s - ethyl

dipropylthi ocarbamate (EPTC). **EPA 581A**  **EPA 586A**  **EPA 583B**  **EPA 584B**  **EPA 590B**  **EPTC EPTC**  **EPTC EPTC**  **EPTC IR Surg-7 MIR2**  **IR Surg-7 MIR2 IR Surg-7 LN2**  **IR Surg-7 LN2 IR Surg-7 LN2**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.3 -0.2 -0.1 0.0 0.1 0 1 2 3 4 5 6

-500 -400 -300 -200 -100 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5

-0.1 0.0 0.1

0 1 2 3 4 5

-400 -300 -200 -100 0 0 1 2 3 4 5 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.4 -0.2 0.0 0.2 0.4

0 1 2 3 4 5 6

-400 -300 -200 -100 0 100 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.3 -0.2 -0.1 0.0 0.1 0 1 2 3 4 5 6

-150 -100 -50 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.2 -0.1 0.0 0.1

0 1 2 3 4 5 6

-120 -80 -40 0 0 1 2 3 4 5 6

**Base Experiment Test Experiment**  **Base Calc (SAPRC-07) SAPRC-07 Test Calc** 

### 367

Figure C - 102 . Plots of experimental and calculated environmental chamber reactivity results for the

mineral spirits samples studied for Safety- Kleen (Carter et al, 1997e). **DTC442A DTC486A**  **DTC487B DTC441B**  **DTC480A DTC481B**  **MS-A MS-A**  **MS-A MS-B**  **MS-B MS-B**  **IR Surg-3 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC440A DTC478A**  **DTC479B DTC439B**  **DTC476A DTC477B**  **MS-C MS-C**  **MS-C MS-D**  **MS-D MS-D**  **IR Surg-3 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-0.10 -0.08 -0.06 -0.04 -0.02 0.00 1 2 3 4 5 6

-0.02 -0.01 0.00 0.01 0.02 0.03 0.04

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.015 -0.010 -0.005 0.000 0.005 0.010

1 2 3 4 5 6

-0.10 -0.08 -0.06 -0.04 -0.02 0.00 1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-0.03 -0.02 -0.01 0.00 0.01 0.02

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.02 -0.01 0.00 0.01

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-5 -4 -3 -2 -1 0 1 1 2 3 4 5 6

-4 -3 -2 -1 0 1 2 3 4 5 6

-5 -4 -3 -2 -1 0 1 2 3 4 5 6

-6 -4 -2 0 2 1 2 3 4 5 6

-5 -4 -3 -2 -1 0 1 2 3 4 5 6

-5 -4 -3 -2 -1 0 1 2 3 4 5 6

0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-0.12 -0.08 -0.04 0.00 1 2 3 4 5 6

-0.03 -0.02 -0.01 0.00 0.01 0.02

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4 5 6

-0.02 -0.01 0.00 0.01 0.02

1 2 3 4 5 6

-0.12 -0.08 -0.04 0.00 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.03 -0.02 -0.01 0.00 0.01 0.02

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.02 -0.01 0.00 0.01

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-6 -4 -2 0 1 2 3 4 5 6

-5 -4 -3 -2 -1 0 1 2 3 4 5 6

-5 -4 -3 -2 -1 0 1 2 3 4 5 6

-6 -4 -2 0 2 1 2 3 4 5 6

-5 -4 -3 -2 -1 0 1 2 3 4 5 6

-5 -4 -3 -2 -1 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 368

Figure C - 103 . Plots of experimental and calculated environmental chamber reactivity results for Exxon

Exxol® D95 Fluid and Exxon Isopar® M Fluid studied for ExxonMobil (Carter et al, 2000e) 1



### .

1 

### Exxol and Is opar are trademarks of ExxonMobil Chemical Company. **DTC753A DTC757A**  **DTC754B DTC772B**  **DTC756B DTC778A**  **D95 D95**  **D95 D95**  **D95 D95**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**DTC724B DTC720B**  **DTC771A DTC723A**  **DTC775B ISOPA** **RM ISOPA** **RM ISOPARM**  **ISOPARM ISOPA** **RM IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1 IR Surg-8 LN1**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.25 -0.20 -0.15 -0.10 -0.05 0.00 1 2 3 4 5 6

-0.20 -0.16 -0.12 -0.08 -0.04 0.00 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.12 -0.08 -0.04 0.00 1 2 3 4 5 6

-0.15 -0.10 -0.05 0.00 0.05 0.10

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.12 -0.08 -0.04 0.00 0.04 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4 0.5

0 1 2 3 4 5 6

-0.06 -0.04 -0.02 0.00 0.02 0.04

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4

0 1 2 3 4 5 6

-12 -8 -4 0 4 1 2 3 4 5 6

-12 -8 -4 0 4 1 2 3 4 5 6

-16 -12 -8 -4 0 1 2 3 4 5 6

-20 -16 -12 -8 -4 0 1 2 3 4 5 6

-20 -16 -12 -8 -4 0 1 2 3 4 5 6

-12 -8 -4 0 1 2 3 4 5 6

0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.4 -0.3 -0.2 -0.1 0.0 1 2 3 4 5 6

-0.12 -0.08 -0.04 0.00 0.04 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.15 -0.10 -0.05 0.00 0.05 0.10

1 2 3 4 5 6

-0.06 -0.04 -0.02 0.00 0.02 0.04

1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4

0 1 2 3 4 5 6

-0.06 -0.04 -0.02 0.00 0.02 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4

0 1 2 3 4 5 6

-12 -8 -4 0 4 1 2 3 4 5 6

-12 -8 -4 0 4 1 2 3 4 5 6

-16 -12 -8 -4 0 1 2 3 4 5 6

-12 -8 -4 0 1 2 3 4 5 6

-10 -8 -6 -4 -2 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 369

Figure C - 10 4 . Plots of experimental and calculated environmental chamber reactivity results for oxo decyl Acetate fluid studied for ExxonMobil (Carter et al, 2000e). **DTC760B DTC773A**  **DTC769A DTC776A**  **DTC770B OC10A** **CET OC10A** **CET OC10ACET**  **OC10A CET**  **OC10A CET**  **IR Surg-3 MIR1 IR Surg-3 MIR1**  **IR Surg-8 MIR1 IR Surg-8 MIR1**  **IR Surg-8 LN1**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.25 -0.20 -0.15 -0.10 -0.05 0.00 1 2 3 4 5 6

-0.3 -0.2 -0.1 0.0 1 2 3 4 5 6 0.0 0.2 0.4 0.6

0 1 2 3 4 5 6

-0.08 -0.04 0.00 0.04 0.08

1 2 3 4 5 6

-0.08 -0.04 0.00 0.04 0.08

1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4 5 6

-0.06 -0.04 -0.02 0.00 0.02 1 2 3 4 5 6 0.0 0.1 0.2 0.3 0.4

0 1 2 3 4 5 6

-12 -8 -4 0 4 1 2 3 4 5 6

-12 -8 -4 0 1 2 3 4 5 6

-12 -8 -4 0 4 1 2 3 4 5 6

-16 -12 -8 -4 0 4 1 2 3 4 5 6

-12 -8 -4 0 1 2 3 4 5 6

Base Experiment Test Experiment Base Model (SAPRC-07) SAPRC-07 Test Model SAPRC-99 Test Model

### 370

Figure C - 105 . Plots of experimental and calculated environmental chamber reactivity results for VMP

Naphtha sample studied by Carter and Malkina (2005) and the Kerosene sample studied by Carter and Malkina (2007).

**EPA137B EPA**  **238A EPA**  **126B EPA**  **243B VMPNA** **PH VMPNAPH**  **VMPNAPH VMPNA** **PH IR Surg-8 MIR2**  **IR Surg-7 MIR2 IR Surg-8 LN2**  **IR Surg-7 LN2**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**EPA600B EPA** **607A EPA** **602A EPA** **603B KEROSENE**  **KEROSENE KEROSENE**  **KEROSENE IR Surg-7 MIR2**  **IR Surg-7 MIR2 IR Surg-7 LN2**  **IR Surg-7 LN2**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.04 -0.03 -0.02 -0.01 0.00 0 1 2 3 4 5 6

-40 -30 -20 -10 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

-0.06 -0.04 -0.02 0.00 0.02 0 1 2 3 4 5 6

-30 -20 -10 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.04 -0.03 -0.02 -0.01 0.00 0 1 2 3 4 5 6

-20 -15 -10 -5 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

-0.04 -0.03 -0.02 -0.01 0.00 0.01 0 1 2 3 4 5 6

-40 -30 -20 -10 0 0 1 2 3 4 5 6

0.00 0.04 0.08 0.12 0.16

0 1 2 3 4 5 6

-0.03 -0.02 -0.01 0.00 0.01 0 1 2 3 4 5 6

-30 -20 -10 0 0 1 2 3 4 5 6 0.00 0.04 0.08 0.12

0 1 2 3 4 5 6

-0.03 -0.02 -0.01 0.00 0.01 0 1 2 3 4 5 6

-25 -20 -15 -10 -5 0 0 1 2 3 4 5 6 0.00 0.04 0.08 0.12 0.16

0 1 2 3 4 5 6

-0.02 -0.01 0.00 0 1 2 3 4 5 6

-12 -8 -4 0 0 1 2 3 4 5 6 0.00 0.04 0.08 0.12 0.16

0 1 2 3 4 5 6

-0.04 -0.02 0.00 0.02

0 1 2 3 4 5 6

-25 -20 -15 -10 -5 0 0 1 2 3 4 5 6

**Base Experiment Test Experiment**  **Base Calc (SAPRC-07) SA** **PRC-07 Test Calc SAPRC-99 Test Calc**  **Base Experiment Test Experiment**  **Base Calc (SAPRC-07) SA** **PRC-07 Test Calc SAPRC-99 Test Calc** 

### 371

Figure C - 106 . Plots of experimental and calculated environmental chamber reactivity results for the

dearomatized alkanes mixed, predominately C 10 

### - C 12 

### (ASTM - 1C), synthetic isoparaffinic alkane mixture, predominately C 10 

### - C 12 

### (ASTM - 3C1), Reduced Aromatics Mineral Spirits (ASTM - 1B), and Regular mineral spirits (ASTM - 1A) solvents studied by Carter and Malkina (2 005). **EPA168A EPA152B**  **EPA 163A**  **EPA 138B**  **EPA 150B**  **EPA 237B**  **AS TM-1C**  **AS TM-1C**  **AS TM-3C1**  **AS TM-3C1**  **ASTM-3C1 ASTM-3C1**  **IR Surg-8 MIR2 IR Surg-8 LN2**  **IR Surg-8 MIR2 IR Surg-8 LN2**  **IR Surg-8 LN2 IR Surg-7 LN2**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**EPA151A EPA242B**  **EPA139B EPA**  **167B EPA**  **153A EPA240A**  **AS TM-1B**  **AS TM-1B**  **AS TM-1B**  **AS TM-1A**  **AS TM-1A**  **AS TM-1A**  **IR Surg-8 MIR2 IR Surg-7 LN2**  **IR Surg-8 vary IR Surg-8 MIR2**  **IR Surg-8 LN2 IR Surg-7 LN2**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

-0.16 -0.12 -0.08 -0.04 0.00 0 1 2 3 4 5 6

-60 -40 -20 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.05 -0.04 -0.03 -0.02 -0.01 0.00 0 1 2 3 4 5 6

-25 -20 -15 -10 -5 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.05 -0.04 -0.03 -0.02 -0.01 0.00 0 1 2 3 4 5 6

-50 -40 -30 -20 -10 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.04 -0.02 0.00 0.02 0.04

0 1 2 3 4 5 6

-20 -15 -10 -5 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.06 -0.04 -0.02 0.00 0.02 0 1 2 3 4 5 6

-20 -15 -10 -5 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

-0.04 -0.03 -0.02 -0.01 0.00 0.01 0 1 2 3 4 5 6

-16 -12 -8 -4 0 0 1 2 3 4 5 6

0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

-0.04 -0.03 -0.02 -0.01 0.00 0 1 2 3 4 5 6

-60 -40 -20 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

-0.04 -0.03 -0.02 -0.01 0.00 0 1 2 3 4 5 6

-25 -20 -15 -10 -5 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.08 -0.06 -0.04 -0.02 0.00 0 1 2 3 4 5 6

-30 -20 -10 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

-0.02 -0.01 0.00 0.01 0.02 0.03

0 1 2 3 4 5 6

-40 -30 -20 -10 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.04 -0.03 -0.02 -0.01 0.00 0.01 0 1 2 3 4 5 6

-30 -20 -10 0 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.03 -0.02 -0.01 0.00 0 1 2 3 4 5 6

-20 -15 -10 -5 0 0 1 2 3 4 5 6

**Base Experiment Test Experiment**  **Base Calc (SAPRC-07) SA** **PRC-07 Test Calc SAPRC-99 Test Calc**  **Base Experiment Test Experiment**  **Base Calc (SAPRC-07) SA** **PRC-07 Test Calc SAPRC-99 Test Calc** 

### 372

Figure C - 107 . Plots of experimental and calculated environmental chamber reactivity results for the

aromatic - 100 solvent studied by Carter and Malkina (2005).

Figure C - 108 . Plots of experimental and calculated environmental chamber reactivity results for

ethanolamine and isopropyl amine. In order to obtain the fits shown, the initial amine concentrations had to be adjusted to optimize the model fits to the reactivity data. **EPA 127A**  **EPA 244B**  **EPA124A EPA239A**  **AROM100 AROM100**  **AROM100 AROM100**  **IR Surg-8 MIR2 IR Surg-7 MIR2**  **IR Surg-8 LN2 IR Surg-7 LN2**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.05 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-60 -40 -20 0 20 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

-0.1 0.0 0.1 0.2 0.3

0 1 2 3 4 5 6

-60 -40 -20 0 20 40

0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-0.08 -0.04 0.00 0.04 0.08

0 1 2 3 4 5 6

-30 -20 -10 0 10 0 1 2 3 4 5 6 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

-0.08 -0.04 0.00 0.04 0.08

0 1 2 3 4 5 6

-30 -20 -10 0 10 0 1 2 3 4 5 6

**Base Experiment Test Experiment**  **Base Calc (SA PRC-07)**  **SAPRC-07 Test Calc SAPRC-99 Test Calc** 

**EPA780A EPA790A**  **EPA 791A**  **EPA 798A**  **EPA 805A**  **EPA807A ETOH-NH2**  **ETOH-NH2 ETOH-NH2**  **ETOH-NH2 ETOH-NH2**  **IPR-A MIN**  **IR Surg-7 MIR2 IR Surg-7 MIR2**  **IR Surg-7 LN2 IR Surg-7 LN2**  **IR Surg-7 LN2 IR Surg-7 LN2**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.04 0.08 0.12

0 1 2 3 4

-0.2 0.0 0.2 0.4 0.6 0.8

0 1 2 3 4

-20 0 20 40

0 1 2 3 4 0.00 0.04 0.08 0.12

0 1 2 3 4 5 6

-0.08 -0.04 0.00 0.04 0.08

0 1 2 3 4 5 6

-40 -20 0 20 40

0 1 2 3 4 5 6 0.00 0.04 0.08 0.12 0.16

0 1 2 3 4 5 6

-0.4 -0.2 0.0 0.2

0 1 2 3 4 5 6

-200 -150 -100 -50 0 50 0 1 2 3 4 5 6 0.00 0.04 0.08 0.12

0 1 2 3 4 5 6

-0.14 -0.07 0.00 0.07 0.14

0 1 2 3 4 5 6

-60 -40 -20 0 20 40

0 1 2 3 4 5 6 0.00 0.04 0.08 0.12

0 1 2 3 4 5 6

-0.10 -0.05 0.00 0.05 0.10

0 1 2 3 4 5 6

-60 -40 -20 0 20 0 1 2 3 4 5 6 0.00 0.04 0.08 0.12

0 1 2 3 4 5 6

-0.05 0.00 0.05 0.10 0.15 0.20

0 1 2 3 4 5 6

-60 -40 -20 0 20 0 1 2 3 4 5 6

**Base Experiment Test Experiment**  **Base Calc (SAPRC-07) Adj. Amine Test Calc** 

### 373

Figure C - 109 . Plots of experimental and calculated environmental chamber reactivity results for t -butyl

amine and 2 - amino - 2 - methyl - 1 -propanol. In order to obtain the fits shown, the initial amine concentrations had to be adjusted to optimize the model fits to the reactivity data. **EPA806A EPA** **781A EPA** **782A EPA** **799A TBU-AMIN**  **AMP AMP**  **AM P**  **IR Surg-7 LN2 IR Surg-7 MIR2**  **IR Surg-7 MIR2 IR Surg-7 MIR2**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour**

**EPA783A EPA** **784A EPA** **789B EPA** **792A AM**  **P AMP**  **AMP AM**  **P IR Surg-7 LN2**  **IR Surg-7 LN2 IR Surg-7 LN2**  **IR Surg-7 LN2**  **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.02 0.04 0.06 0.08

0 1 2 3 4 5 6

-0.12 -0.08 -0.04 0.00 0.04 0 1 2 3 4 5 6

-50 -40 -30 -20 -10 0 0 1 2 3 4 5 6 0.00 0.02 0.04 0.06 0.08 0.10

0 1 2 3 4 5 6

-0.15 -0.10 -0.05 0.00 0.05 0 1 2 3 4 5 6

-60 -40 -20 0 20 0 1 2 3 4 5 6 0.00 0.02 0.04 0.06 0.08 0.10

0 1 2 3 4 5 6

-0.8 -0.4 0.0 0.4

0 1 2 3 4 5 6

-500 -400 -300 -200 -100 0 0 1 2 3 4 5 6

0.00 0.04 0.08 0.12 0.16

0 1 2 3 4 5 6

-0.6 -0.4 -0.2 0.0 0 1 2 3 4 5 6

-150 -100 -50 0 50 0 1 2 3 4 5 6 0.00 0.04 0.08 0.12 0.16

0 1 2 3 4 5 6

-0.8 -0.4 0.0 0.4

0 1 2 3 4 5 6

-200 -150 -100 -50 0 50 0 1 2 3 4 5 6 0.00 0.04 0.08 0.12 0.16

0 1 2 3 4 5 6

-1.2 -0.8 -0.4 0.0 0.4 0 1 2 3 4 5 6

-400 -300 -200 -100 0 100 0 1 2 3 4 5 6 0.00 0.02 0.04 0.06 0.08 0.10

0 1 2 3 4 5 6

-1.0 -0.5 0.0 0.5

0 1 2 3 4 5 6

-300 -200 -100 0 100 0 1 2 3 4 5 6 0.00 0.04 0.08 0.12 0.16

0 1 2 3 4 5 6

-0.4 -0.2 0.0 0.2

0 1 2 3 4 5 6

-100 -80 -60 -40 -20 0 0 1 2 3 4 5 6

**Base Experiment Test Experiment**  **Base Calc (SAPRC-07) Ad**  **j. A mine Test Calc**  **Base Experiment Test Experiment**  **Base Calc (SAPRC-07) Ad**  **j. A mine Test Calc** 

### 374

Figure C - 110 . Plots of selected experimental and calculated concentration -time plots for the methyl

iodide - NO x 

### , methyl iodide - CO - NO x 

### , and methyl iodide - O 3 

### experiments. **EPA738A EPA** **743A EPA742B**  **EPA742A CH3I-NOx**  **CH3I-NOx O3-CO**  **O3-CO-CH3I**

**EPA734A EPA734B**  **EPA738B EPA743B**  **CH3I-NOx+CO CH3I-NOx+CO**  **CH3I-NOx+CO CH3I-NOx+CO** 

Time (minutes)**C o** **n c** **e n** **t r** **a t** **i o** **n (** **p p** **m )**  **D(O3-NO)**

0.000 0.005 0.010 0.015 0.020 0.025

0 120 240 360 **D(O3-NO)**

0.00 0.01 0.02 0.03

0 120 240 360

**D(O3-NO)**

0.00 0.04 0.08 0.12 0.16

0 120 240 360 **O3**

0.05 0.06 0.07 0.08 0.09 0.10

0 120 240 360 **CH3I**

0.188 0.192 0.196 0.200 0.204

0 120 240 360 **CH3I**

0.47 0.48 0.49 0.50 0.51

0 120 240 360

**CH3I**

0.184 0.188 0.192 0.196 0.200 0.204

0 120 240 360 **D(O3-NO)**

0.00 0.04 0.08 0.12 0.16

0 120 240 360 **D(O3-NO)**

0.00 0.04 0.08 0.12 0.16

0 120 240 360

**O3**

0.088 0.092 0.096 0.100 0.104

0 120 240 360

**CH3I**

0.184 0.188 0.192 0.196 0.200 0.204

0 120 240 360 **CH3I**

0.18 0.19 0.20 0.21

0 120 240 360 **CH3I**

0.44 0.45 0.46 0.47 0.48 0.49 0.50 0.51

0 120 240 360

**CH3I**

0.30 0.31 0.32 0.33 0.34 0.35

0 120 240 360

**D(O3-NO)**

0.00 0.01 0.02 0.03 0.04

0 120 240 360

Experimental Model

### 375

F igure C - 111 . Plots of experimental and calculated environmental chamber reactivity results for the

methyl iodide experiments of Carter (2007).

**EPA735B EPA736B**  **EPA 737A**  **CH3I CH3I**  **CH3I 0.2011**  **0.3975 0.2129**   **(O 3**  **-NO) (ppm) vs Hour**

**IR**  **(O 3**  **-NO) (mole basis) vs Hour**

**IR IntOH (ppt-min/ppm) vs Hour** 0.00 0.02 0.04 0.06 0.08 0.10

0 1 2 3 4 5 6

-0.20 -0.15 -0.10 -0.05 0.00 0.05 0.10 0.15 0.20 0.25

0 1 2 3 4 5 6

-50.0 0.0 50.0 100.0 150.0 200.0 250.0

0 1 2 3 4 5 6 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14

0 1 2 3 4 5 6

-0.25 -0.20 -0.15 -0.10 -0.05 0.00 0.05 0.10

0 1 2 3 4 5 6

-15.0 -10.0 -5.0 0.0 5.0 10.0 15.0 20.0

0 1 2 3 4 5 6 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14

0 1 2 3 4 5 6

-0.20 -0.15 -0.10 -0.05 0.00 0.05 0.10

0 1 2 3 4 5 6

-50.0 -40.0 -30.0 -20.0 -10.0 0.0 10.0 20.0

0 1 2 3 4 5 6

**Base Experiment Test Experiment**  **Base Calc (SAPRC-07) SA** **PRC-07 Test Calc SAPRC-99 Test Calc** 

### 376 

### APPENDIX D. SUPPLEME **NTARY MATERIAL AVAIL ABLE**  Complete documentation of this mechanism and its evaluation requires several tables that are too extensive to be appropriate for a printed report. These include the following: Table A - 3 Absorption cross - sections and quantum yields for all photolysis reactions in the base

mechanism. Table B - 2 Listing of mechanisms for all VOCs for which mechanism assignments have b een

derived. Table B - 3 Listing of adjustable product mechanisms for all VOCs for which such mechanisms have

been derived. Table B - 10 Listing of components of complex mixtures for which atmospheric reactivities have been

calculated. Table B - 1 1 Assignments of explicitly represented compounds to lumped model species in the fixed

parameter mechanism. Table C - 1 List of environmental chamber experiments used in the mechanism evaluation. These are available in Excel files that can be downloaded using links at the SAPRC mechanism web site at http://www.cert.ucr.edu/~carter/SAPRC. These consist of saprc07.xls, that contains all the tables in Appendix A through Appendix C, and Table -A1.xls, Table - B2.xls, through Table - C1.xls that contain only the tables indicated. Because these files contain documentation information not included in the printable version of this report, these files must be considered to be an integral part of the SAPRC - 07 mechanism documentation. The SAPRC mechanism web site at http://www.cert.ucr.edu/~carter/SAPRC is currently under development. At present it contains this report document (as a Microsoft Word and a PDF file), the files containing the supplementary material as discussed above, and the files to im plement the mechanism and conduct the simulations of the chamber experiments and other test calculations. Additional files will be added as time permits if requested. The web site will cont ain documentation concerning the format and use of the available files.

### 377 

### APPENDIX E. CHANGE L **OG** Inthis Appendix, the changes to the mechanism and the mechanism documentation that was distributed or made available at the SAPRC mechanism web site are listed. If the mechanism needs to be changed or corrected in the future, this report and the supplementary mat erial will be changed accordingly, and the modifications will be listed in this section. 6/15/07 This is the version documented in the final repor t that was submitted as the deliverable for CARB Contract 03 - 318. 

### 12/31/07 This revised version was prepared as part of work on CARB project 06 -408. The

modifications are as follows:  The mechanisms for the amines were revised or added as a result of CARB p roject 06 -408. This resulted in substantial changes in the reactivities for these compounds.  Results of modeling chamber experiments carried out for CARB project 06 -408 was added to the "Mechanism Evaluation Results" section. These were primarily amine exp eriments but included a few other compounds.  A minor error in the representation of the peroxy + HO 2 

### reactions was corrected.  The reactivity scales were re - calculated after these changes were made. The effects of the changes were insignificant except for the amines.. 5/21/08 This revised version was prepared as part of work on documenting the condensed version of

SAPRC - 07 and incorporates corrections of errors or omissions found during the course of the preparation of the condensed mechanism and other work. The reactivity scales were recalculated after these errors were corrected but the changes in the simulations of the chamber experiments were judged to be too small to revise the presentation of the fits of the model simulations to the chamber data. The mo difications to the mechanism and the report were as follows:  This Appendix E, giving the change log, was added to the report.  An error in the rate constant for OH with 1,1 - dichloroethene was corrected. This resulted in a decrease in the MIR of this compound from 2.76 to 1.69.  The reactions of amines with O 3 

### were added. This resulted in changes in MIR's for in certain amines of up to ~30%.  The photolysis reactions for PAN2 and the other high PAN analogues were added, based on analogy with the photolysis of P AN that was already in the mechanism. This shouldn't significantly affect environmental chamber and atmospheric reactivity simulations in this report but may non -negligibly affect regional airshed model predictions under some conditions.  The derivation of the lumped model species whose parameters depend on the base ROG mixture (e.g., ALKn, OLEn, AROn) were re - derived because the original values of the mole fractions of the components used as the weighting factors could not be exactly reproduced. This was ne cessary to derive a standardized spreadsheet to derive weighting factors based on this mixture for mechanisms with other lumping schemes. The changes were small and only affect the fixed parameter version of the mechanism, but may have up to ~10% effects o n MIR's for compounds whose reactivities are highly sensitive to the base mechanism.

### 378  The OLE2 + Cl mechanism was revised to incorporate explicitly generated mechanisms for reactions of chlorine with 1,3 -butadiene and 2 - methyl - 1 -butene. This would not affec t the reactivity results for these compounds.  Minor errors in the zRNO3 yields in the AFGn reactions were corrected. These shouldn't significantly affect model results.  A minor error in the rate constant for the NRAD + HO2 rate constant was corrected. This shouldn't significantly affect model results.  The files implementing the mechanism did not specify yRAOOH as a steady state species as documented, and this was corrected. This shouldn't affect model simulation results but mi ght have a small effect on computer time, depending on how the mechanism is implemented.  The reactivity scales were recalculated after these changes were made. Except for 1,1 - dichloroethene and amines discussed above the changes were relatively minor. The MIR for TDI, changed by about 1 2% and the MIRs for certain higher alkanes changed by as much as 8% but usually less than 5%. For most compounds the change in MIRs were less than 2%. 6/3/08 The CARB hydrocarbon bin reactivities (Kwok et al, 2000; Carter and Malkina, 2005) have

been added to the reactivity tabulation in Table B - 1 and the compositions used to calculate the reactivities of these bins have been added to Table B - 10 ( Table B - 10 available with the supplementary materials only). A footnote was added to Table B - 1 referencing the relevant hydrocarbon bin work. No change was made to the main body of the report text. 6/19/08 Minor editorial corrections made to the documentation in several places, and some updates

made to the references. 7/7/08 An error in the spreadsheet used to derive the aromatics mechanism was found that affected

computation of ratio of BALD and PROD2 yields used to represent aromatic aldehydes and ketones formed from abstractions on alkyl groups on alkylbenzenes. This affected the BALD and PROD2 yields in ARO2 and in alkylbenzenes with groups other than methyl, but had relatively small effects on reactivity and other calculation results. In addition, s everal xPROD species (xHNO3, xHCOOH, xCCOOH, xRCOOH) were found not to be needed in the lumped atmospheric mechanism and were deleted. For reactivity calculations, these are replaced by their corresponding product species. Because of the relatively low reactivity of these species, the effects of this approximation on reactivity calculations, especially for MIR conditions, should be negligible. The mechanism listings were updated and the reactivity scales on Table B - 1 were recomputed using the current versio n of the mechanism. 3/13/09 Several corrections and revisions were made as a result of problems discovered during the

peer review of the mechanism. These are as follows:  An error in the activation energy for the HO 2 

### + O 3 

### reaction was corrected. This result ed in 20% increase in this rate constant at 300 o 

### K.  The reaction of formaldehyde with HO 2 

### was deleted from the mechanism because as formulated in the mechanism it should be negligible under all relevant atmospheric and environmental chamber conditions. This permitted removal of one intermediate species from the mechanism.  The rate constant expression for the reaction of OH radicals with methyl hydroperoxide was changed to that recommended by the NASA (2006) evaluation. This gives a 300 o

### K rate constant that i s 35% higher than that previously used, which was from the IUPAC (2006) evaluation. The IUPAC recommendation has since been changed to an expression that gives an even higher rate constant than the current NASA (2006) recommendation.

### 379 The branching ratios f

or the two competing reactions were also changed slightly to be consistent with the NASA (2006) recommendation.  The group additivity parameters used in the mechanism generation system to estimate rate constants for reactions of OH radicals with organic hydroperoxides were modified to be consistent with the revised rate constant and branching ratio used for OH + methyl hydroperoxide. The methyl hydroperoxide data indicate an unusually large group additivity correction for OOH substitution on alkyl groups, and also indicates a much higher rate constant for reaction at the OOH group in organic hydroperoxides than for H2 

### O 2 

### . The parameters used in the previous version of the mechanism were in error and were not consistent even with the previously used IUPAC (2006 ) rate constant for OH + methyl hydroperoxide. The revised group additivity parameters resulted in changes in the rate constants and the product distributions derived for the reactions of OH with the lumped higher hydroperoxide species ROOH, R6OOH and RAOO H. The products of the CL + RAOOH reaction were also revised, since they were estimated based on those for the OH reaction.  Composition assignments were revised for several mixtures for consistency with the speciation database, resulting in slight changes in reactivities calculated for these mixtures. The affected mixtures, listed in order of reactivity changes, were "isomers of ethylbenzene", "C10 alkenes", and "isomers of butyl benzene", and Table B - 9 has been modified accordingly. The MIR changes caused by these reassignments these were 20%, 9%, and 3%, respectively. The plots and tables in this report giving model performance results in simulating these data have been updated using the current revised mechanism. However, these changes had minor or insignificant effect on model simulations of most of the chamber experiments, and did not require any revisions of parameters adjusted to fit the chamber data. The atmospheric reactivities summarized have been recalculated using the current version of the mechanism and the reactivity tabulations in Table B - 1 and the Supplementary Materials have been updated accordingly. These changes did not have significant affects on any calculated MIR values (changes being less than 4% for all compounds), but did cause changes of up to 25 - 30% for a few compounds in the lower NO x 

### scenarios. This is cons istent with the fact that the HO 2 

### + O 3 

### and the hydroperoxide reactions become more important under low NO x 

### conditions. 6/8/09 Several fluoropropenes were added to the list of compounds with mechanisms and reactivity

estimates based on the results of Carter (2009a,b), and a few minor corrections and additions were made to some of the footnotes in Table B -4 . 6/10/09 Table 22 modified to include the values of all the chamber characterization parameters, not

just RN - I. 6/22/09 The hydrocarbon bin reactivities and uncertainty classifications on Table B - 1 were updated as

discussed by Carter (2009c), which was added to the reference list. Some higher unspeciated aromatics compositions and reactivities on Table B - 1 were also modified. Table B - 10 in the electronic version was updated to give the revised bin and unspeciated aromatic compositions. 1/15/10 Several corrections and revisions were incorporated as a result of problems found with the

mechanism or its documentation to date. These are summarized below.  An error in the mechanism of the acyl peroxy + methyl peroxy reaction (Reaction BR24 in Table A - 2 ) was corrected. The previous version had the alkoxy radical products forming in 10% yields when they should have been 90%. This correction required changing the

### 380 mechanisms for all the peroxy + acyl peroxy reactions to be co nsistent with this. This correction affected the predictions of some low NO x 

### products but had insignificant effects on ozone predictions. Nevertheless, all the reactivity scales were recalculated.  Several other errors in various peroxy + peroxy reactions w ere corrected. These had no significant effect on ozone and had only minor effects for some species under low NO x 

### conditions.  Errors in the calculations of the atmospheric reactivities of the tertiary amines were corrected. The previous atmospheric reactivity calculations did not take into account the NO x 

### loss involved in their mechanisms, though the radical loss was taken into account. This resulted in the MIRs for these compounds becoming positive rather than negative, but low NO x 

### reactivities becoming more negative. This only affects 2 - amino - 2 - methyl - 1 - propanol, t -butyl amine, and 2 - amino - 2 - ethyl - 1,3 -propanediol. This did not affect the simulations of environmental chamber experiments with these compounds.  Numerous errors in Table 1 were corrected.  A number of VOCs were added to the reactivity tabulation in previous revisions but information about their mechanisms was not included in the tables in Appendix B. This information has now been added.  The methods for reactivity values for mixtures was revised to be derived from those given for their components, rather than calculated for each mixture directly, since this approach does not involve the lumping of compounds that can occur when directly computing reactivities of complex mixtures.  The mechanism and reactivity values for 3 - methoxy - 3 - methyl - 1 -butanol were updated based on recent data from our laboratory (Carter et al, 2010).  Several minor errors or omissions found in various tables or the text were corrected. 1/27/10 An error in the files implementing the mechanism, resulting in the rate constant for the

O 1 

### D+H 2 

### O reaction being low by ~18%, was corrected, and all calculations were redone. This had no significant effects on the simulations of the chamber experiments used in the mechanism evaluations, but had small but nonnegligible effects (on the order of ~10%) on ambient simulations and atmospheric reactivity values. Affected tables and plots, including Table B - 1 giving the reactivity vales, werer updated.