REACTIVITY ESTIMATES FOR SELECTED 

CONSUMER PRODUCT COMPOUNDS

Final Report to the 

California Air Resources Board 

Contract No. 06-408 

By 

William P. L. Carter 

February 19, 2008 

Center for Environmental Research and Technology 

College of Engineering 

University of California 

Riverside, California 92521 
ii 

ABSTRACT 

An experimental and modeling study was conducted to assess the ground-level atmospheric 

ozone impacts of several types of consumer product compounds Environmental chamber experiments 

were carried out for the representative amines 2-amino-2-methyl-1-propanol (AMP), ethanolamine, 

isopropyl amine and t-butyl amine and also for d-limonene. AMP and t-butyl amine were found to inhibit 

ozone formation, but the others enhanced ozone, and most were found to significantly enhance formation 

of secondary particle matter (PM). Methods to estimate mechanisms for amines that were qualitatively 

consistent with the chamber data were developed. However, the amine chamber data were not useful for 

quantitative valuation because the amount of amine available for gas-phase reaction could not be 

measured, and appeared to be significantly less than the amount injected. Estimates of atmospheric ozone 

impacts for the amines are also very uncertain because the amount of amines removed by reaction with 

HNO3 in the atmosphere cannot be predicted. The chamber data obtained for d-limonene were well 

simulated by the existing d-limonene mechanism. 

 Representations of the atmospheric reactions of for 15 amines and 30 other types of consumer 

product VOCs were added to the SAPRC-07 mechanism and its MIR and other reactivity scale 

tabulations, which are included with this report. 
iii 

ACKNOWLEDGEMENTS AND DISCLAIMERS 

This work was funded by the California Air Resources Board (CARB) through contract number 

06-408. The compounds studied for this project were determined in discussions with Dr. Dongmin Luo, the 

CARB project officer, and other members of the CARB Research Division and Consumer Products 

Regulation staff, and their helpful input is gratefully acknowledged. 

The environmental chamber experiments were carried out at the College of Engineering Center for 

Environmental Research and Technology (CE-CERT) primarily by Bethany Warren, with assistance from 

Kurt Bumiller, Lindsay D. Yee, Dylan Switzer, and Nicolette A. Ramirez. Mr. Dennis Fitz provided 

assistance in administration of this project. Helpful discussions with Dr. Roger Atkinson and Dr. David 

Cocker are also acknowledged. 

 Although this project was funded by the CARB, the contents of this report reflect only the 

opinions and conclusions of the author. Mention of trade names and commercial products does not 

constitute endorsement or recommendation for use. 
iv 

TABLE OF CONTENTS 

EXECUTIVE SUMMARY .......................................................................................................................... 1

INTRODUCTION ........................................................................................................................................ 6

Background ............................................................................................................................................ 6

Objectives............................................................................................................................................... 7

Overall Approach ................................................................................................................................... 7

EXPERIMENTAL METHODS.................................................................................................................. 10

Chamber Description............................................................................................................................ 10

Analytical Instrumentation ................................................................................................................... 11

Sampling Methods................................................................................................................................ 14

Characterization Methods..................................................................................................................... 14

Experimental Procedures...................................................................................................................... 15

Materials............................................................................................................................................... 16

MODELING METHODS........................................................................................................................... 17

Base Mechanism................................................................................................................................... 17

Representation of Chamber Conditions................................................................................................ 17

Mechanisms for Amines....................................................................................................................... 18

Reaction with OH radicals ............................................................................................................. 18

Reaction with NO3 Radicals .......................................................................................................... 25

Reactions with Ozone .................................................................................................................... 25

Reactions with HNO3..................................................................................................................... 27

Mechanism for d-Limonene ................................................................................................................. 28

Mechanisms for Other VOCs. .............................................................................................................. 28

Atmospheric Reactivity Simulations.................................................................................................... 28

RESULTS AND DISCUSSION ................................................................................................................. 33

Summary of Experiments and Characterization Results ...................................................................... 33

Blacklight Characterization ........................................................................................................... 33

Chamber Effects Characterization ................................................................................................. 34

Background PM Characterization.................................................................................................. 35

Gas-Phase Mechanism Evaluation Results .......................................................................................... 36

Amines ........................................................................................................................................... 38

d-Limonene.................................................................................................................................... 43

PM Impact Results ............................................................................................................................... 44

Atmospheric Reactivity Calculations ................................................................................................... 47

DISCUSSION AND CONCLUSIONS ...................................................................................................... 54

REFERENCES ........................................................................................................................................... 56

APPENDIX A. MECHANISM LISTING .................................................................................................. 60

APPENDIX B. CHAMBER EXPERIMENT LISTING............................................................................. 68

APPENDIX C. UPDATED VOC AND ATMOSPHERIC REACTIVITY LISTING............................... 72
v 

LIST OF TABLES 

Table E-1. Compounds in consumer products inventories for which ozone impact estimates 

were added for this project, and recommended MIR values for regulatory 

applications. ............................................................................................................................. 4

Table 1. List of analytical and characterization instrumentation for the UCR EPA chamber............... 12

Table 2. Experimental and estimated rate constants for the reactions of amines included in 

mechanisms were derived for this project.............................................................................. 19

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

reactions by OH and NO3 radicals and by Cl atoms. ............................................................. 21

Table 4. Assignments made for alkoxy radical intermediates predicted to be formed in the 

photooxidation mechanisms of the amines. ........................................................................... 24

Table 5. List of compounds whose reactivities have been added to the SAPRC-07 reactivity 

tabulation or whose reactivities have been requested by the CARB...................................... 29

Table 6. Summary of initial concentrations and selected gas-phase results of the incremental 

reactivity experiments. ........................................................................................................... 37

Table 7. Summary of conditions and selected results of the d-limonene NOx experiments.................. 45

Table 8. Selected results of PM number and volume measurements made during the 

incremental reactivity experiments carried out for this project.............................................. 48

Table 9. Summary of average 5-hour PM volume incremental reactivities of VOCs studied in 

incremental reactivity experiments in the UCR EPA chamber.............................................. 50

Table 10. Calculated atmospheric reactivity values for amines and other compounds added to 

the atmospheric reactivity tabulations.................................................................................... 51

Table 11. Change in MIR values assigned to amines as a result of this work......................................... 53

Table A-1. Reactions and rate constants used for amines, d-limonene, and the new compounds 

added to the mechanism for this project. ............................................................................... 60

Table A-2. New lumped molecule representations used for atmospheric reactivity estimates of 

compounds added to the reactivity tabulations for this project.............................................. 67

Table B-1. Summary chamber experiments relevant to this project. ....................................................... 68

Table C-1. Listing of VOCs for which atmospheric ozone impact estimates are available, their 

representation in the model, and their calculated atmospheric reactivity values in 

various reactivity scales. This tabulation is current as of December 20, 2007. ..................... 72
vi 

LIST OF FIGURES 

Figure 1. Schematic of the UCR EPA environmental chamber reactors and enclosure......................... 11

Figure 2. Plots of logs of the rate constants for the reactions of the methylamines and DMAE 

with O3 against the logs of the rate constants for reaction of OH radicals at the group 

next to the amino group and also against the total OH rate constant. .................................... 26

Figure 3. Plots of light intensity data used to assign NO2 photolysis rates for the blacklight 

light source............................................................................................................................. 34

Figure 4. Plots of best fit HONO offgasing parameters against UCR EPA run number. ....................... 35

Figure 5. Plots of 5-hour PM volume measurements in pure air experiments the EPA chamber 

against EPA run number. ....................................................................................................... 36

Figure 6. Plots of selected experimental and calculated incremental reactivity results for AMP........... 39

Figure 7. Plots of selected experimental and calculated incremental reactivity results for 

aminoethanol, isopropyl amine, and t-butyl amine. ............................................................... 40

Figure 8. Plots of experimental and selected calculated data for formaldehyde when measured 

in AMP experiments. ............................................................................................................. 41

Figure 9. Plots of experimental and selected calculated data for formaldehyde in the 

ethanolamine experiment with useable formaldehyde data. .................................................. 41

Figure 10. Plots of initial amine concentrations that gave best fits to results of model 

simulations to concentrations calculated from the amount of liquid amine injected. ............ 42

Figure 11. Plots of selected experimental and calculated incremental reactivity results for 

d-limonene. ............................................................................................................................ 44

Figure 12. Plots of selected experimental and calculated data for the d-limonene experiments 

carried out for this program (EPA runs) and previously (ETC runs)..................................... 46

Figure 13. Plot of experimental and calculated formaldehyde data for the d-limonene - NOx

experiments where formaldehyde data are available. ............................................................ 47

Figure 14. Plots of PM volume data from all of the incremental reactivity experiments carried 

out for this project. ................................................................................................................. 49

Figure 15. Plots of incremental reactivities of amines for the various types of atmospheric 

reactivity scenarios calculated assuming rapid and irreversible loss by reaction with 

HNO3 against incremental reactivities calculated assuming no reaction with HNO3. ........... 52
1 

EXECUTIVE SUMMARY 

Background 

Emissions from consumer products are a non-negligible component of the total emissions of 

volatile organic compounds (VOCs) into the atmosphere. VOCs emitted into the atmosphere react in 

sunlight in the presence of oxides of nitrogen (NOx) emitted from other sources to contribute to the 

formation of ground-level ozone (O3), an important air pollution problem in California. Because controls 

from other VOC sources may not be sufficient to achieve air-quality standards for ozone, the California 

Air Resources Board (CARB) has been implementing additional controls for VOC emissions from 

consumer products. In order to achieve the most cost-effective results, the CARB has proposed to utilize 

controls that take into account differences in ozone impacts, or "reactivity", of the many types of 

consumer product VOCs that are in use. 

Reactivity-based VOC controls have already been implemented in regulations for mobile source 

(CARB, 1993) and aerosol coatings (CARB, 2000) emissions in California. These are based on use of the 

Maximum Incremental Reactivity (MIR) scale, which is designed to reflect differences in impacts of 

VOCs on O3 formation in environments where O3 is most sensitive to VOC emissions. However, 

consumer product emissions include many VOCs for which reactivity values are unknown or highly 

uncertain, for which the CARB has had to use "upper limit" estimates of ozone impacts of these 

compounds, based on worst-case considerations of their unknown atmospheric chemistry. This has lead to 

relatively small amounts of some compounds dominating ozone impact estimates of some product 

categories. This is problematical because the actual ozone impacts of these product categories may be 

significantly less, and regulations based on upper limit reactivity estimates may lead inappropriate control 

strategies. 

Objectives 

The overall objective of this project is to reduce uncertainties of ozone impact quantifications of 

selected consumer products compounds of interest to the CARB. The project focused primarily on 

amines, since use of upper limit reactivity estimates for these compounds is problematic for some 

categories. The amines 2-amino-2-methyl-1-propanol (AMP) and ethanolamine were chosen for 

experimental study because of their importance in the consumer product inventories, but atmospheric 

reaction mechanisms and MIR values were also derived for other amines based in part on the results 

obtained for those representative compounds. Amines were not the only types of compounds in consumer 

product inventories where reactivity values are needed, so an additional objective of this project was to 

estimate reactivity values for other compounds for which such values were not previously available. 

Experiments were also needed to verify existing atmospheric reaction mechanisms and reactivity 

estimates for d-limonene, an important consumer product VOC for which mechanism evaluation data 

were inadequate. 
2 

Methods and Results 

Environmental Chamber Experiments 

The major effort in this project was to conduct environmental chamber experiments to test 

estimated mechanisms for the representative amines AMP and ethanolamine, and to test the existing 

mechanism for d-limonene. Experiments using t-butyl isopropyl amine were also carried out to further 

test the general amine mechanisms developed for this project. The chamber experiments were carried out 

in the UCR EPA environmental chamber that was developed for mechanism evaluation at lower and more 

atmospherically representative pollutant levels than previously possible, and that was utilized in recent 

studies of VOCs used in architectural coatings and pesticides. The type of experiments carried out were 

“incremental reactivity” experiments, which involved determining the effect of adding the solvent to 

standard reactive organic gas (ROG) surrogate - NOx experiments designed to simulate the chemical 

conditions of polluted urban atmospheres. Experiments at two different ROG and NOx levels were 

employed to represent different conditions of NOx availability, to provide a more comprehensive test of 

the mechanisms that affect reactivity under differing chemical conditions. The total NOx levels employed 

were in the 25-30 ppb range, which is designed to be representative of urban areas in California and 

which are lower than employed in previous reactivity chamber studies. 

The chamber experiments were useful for quantitative mechanism evaluation for d-limonene and 

for qualitative evaluation of the mechanisms for the amines. The results indicated that d-limonene, 

ethanolamine and isopropyl amine had relatively high and positive impacts on ozone formation, but also 

indicated (somewhat unexpectedly) that AMP and t-butyl amine were ozone inhibitors. Unfortunately, the 

data obtained for the amines were not useful for quantitative mechanism evaluation because of 

uncertainties in the amounts of injected amines that were available for reaction in the gas phase. The 

amount of amine in the gas-phase could not be measured because of lack of suitable analytical methods 

for these compounds, and the chamber results could only be fit by assuming that the amount of amine 

reacting in the gas phase was only 5-60% of the injected amine, with the ratio varying significantly from 

run to run. On the other hand, the results of the limonene experiments were useful for obtaining high 

quality data for mechanism evaluation for this compound. 

Chemical Mechanism Development and Evaluation 

The SAPRC-07 mechanism (Carter, 2007a), which was recently developed under CARB funding 

and utilized to derive an updated MIR scale for use in California reactivity-based regulations was used as 

the starting point. New methods were developed to estimate mechanisms for amines, based on available 

laboratory information and also the results of the experiments for this project. The new estimation 

methods predicted that amines that lack reactive hydrogen atoms vicinal to the amino groups would be 

ozone inhibitors, as indicated by the results of the AMP and t-butyl amine experiments carried out for this 

project. On the other hand, amines such as ethanolamine are predicted and confirmed to have positive and 

relatively high ozone impacts, though not as high as the upper limit estimates that would otherwise be 

used in CARB regulations. Estimated mechanisms were developed for 11 other amines besides the 4 that 

were studied, using an approach that was consistent with the chamber data that were obtained. Estimated 

mechanisms, or methods for estimating atmospheric ozone impacts, were developed for 30 other types of 

VOCs found in consumer products emission inventories. The existing SAPRC-07 mechanism for dlimonene was found to give good simulations of the results of the experiments for this project and was not 

modified. 
3 

An additional consideration in the mechanisms for amines is the fact that they are basic 

compounds that can react with atmospheric nitric acid (HNO3) to form amine nitrate salts, which partition 

into the aerosol phase. The chamber experiments are not sensitive to this reaction because the injected 

amine was in large excess over the HNO3 formed in the experiments, but this could be important under 

atmospheric conditions. However, modeling this under atmospheric conditions is difficult because it 

requires knowledge of unknown equilibrium constants and also requires better knowledge of sources and 

sinks of HNO3, ammonia, and other amines in the atmosphere, which are unknown and probably highly 

variable. Model simulations were carried out based on using two extreme assumptions in this regard – one 

assuming that the amine + HNO3 reaction had a negligible effect on removing amines from ozone 

formation reactions, as would occur if the salt equilibrium favored dissociation in the atmosphere, or if 

there were other significant sinks for HNO3 in the atmosphere, such as reaction with ammonia or other 

amines; and the other assuming that the amine + HNO3 reaction was rapid and irreversible. 

Atmospheric Reactivity Calculations 

Compounds in consumer products inventories for which ozone impact estimates were added for 

this project, and their recommended MIR values for regulatory applications, are listed in Table E-1. The 

values in the "Previous" column were the values given for a few of the amines in previous MIR 

tabulations provided to the CARB for regulatory applications using the SAPRC-99 (Carter, 2003), and 

those in the "Upper Limit" column were derived using the upper limit method (Appendix D of Carter, 

2000a) that would be the probable default values for regulatory MIR's if better estimates were not 

available. The values in parentheses are percent changes in the new values relative to the tabulated values 

shown. It can be seen that in most cases the new values are lower than the previous SAPRC-99 estimates 

for the few cases were they were available, and in all cases the new values were significantly lower than 

the upper limit MIR estimates. Uncertainty codes for the current estimated mechanisms are given in the 

full updated reactivity tabulations included as Appendix C to this report. The uncertainty codes are based 

on those used in previous versions of the mechanism (Carter, 2000a, 2003, 2007a) and are given in 

footnote [b] to Table C-1. 

It should be noted that the MIR values given for the amines on Table E-1 and Appendix C were 

calculated assuming that the removal of the amines by reaction with HNO3 is negligible under 

atmospheric conditions. If the upper limit estimate for removal by this reaction is assumed, the 

magnitudes of the ozone impacts are lower by an order of magnitude or more. However, for regulatory 

purposes, we recommend that values used in the Maximum Incremental Reactivity (MIR) be based on 

conditions where they would have the maximum ozone impact, and those are the conditions where 

removal by reaction with HNO3 is negligible. This is consistent with the general concept of maximum 

incremental reactivity (Carter, 1994a). 

PM Impact Results 

Although the primary focus of this project was reducing uncertainties in ozone impact estimates, 

data were also obtained concerning the relative PM formation potentials for AMP, ethanolamine, and dlimonene. All three of these compounds were found to have very high PM formation potentials compared 

to most of the coatings (Carter et al, 2005b) and pesticide (Carter and Malkina, 2007) VOCs studied 

previously. 
4 

Table E-1. Compounds in consumer products inventories for which ozone impact estimates were 

added for this project, and recommended MIR values for regulatory applications. 

MIR (gm O3 / gm VOC) Compound This Work Previous Upper Limit 

Methylamine 7.25 10.8 (-33%) 

Dimethyl amine 2.65 9.4 (-72%) 14.9 (-82%) 

Ethyl amine 5.45 7.8 (-30%) 14.9 (-63%) 

Trimethyl amine 5.27 7.1 (-25%) 17.1 (-69%) 

Triethyl amine 3.07 16.6 (-81%) 

Triethylene diamine 2.77 15.0 (-81%) 

Ethanolamine 6.59 6.0 (+11%) 11.0 (-40%) 

Dimethylaminoethanol 5.15 4.8 (8%) 15.1 (-66%) 

2-Amino-1-butanol 4.79 15.1 (-68%) 

2-Amino-2-methyl-1-propanol -2.68 4.8 (negative) 15.1 (negative) 

Diethanol amine 2.22 4.0 (-45%) 12.8 (-83%) 

Triethanolamine 3.25 2.8 (+18%) 11.3 (-71%) 

Triisopropanolamine 1.99 8.8 (-77%) 

Terpinolene 6.14 12.3 (-50%) 

Tripropylene glycol 2.07 3.0 (-32%) 

Diethylene glycol mono(2-ethylhexyl) ether 1.45 2.7 (-46%) 

Tripropylene glycol n-butyl ether 1.55 2.4 (-34%) 

Triethyl citrate 0.66 2.9 (-77%) 

2,2,4-Trimethyl-1,3-pentanediol diisobutyrate 0.33 2.8 (-88%) 

Citronellol (3,7-dimethyl-6-octen-1-ol) 5.80 3.8 (53%) 

Linalool 5.44 10.8 (-49%) 

Geraniol 5.10 9.8 (-48%) 

Hexyl cinnamal 2.93 7.8 (-62%) 

Hydroxycitronellal 2.54 10.9 (-77%) 

Cinnamic aldehyde 4.79 12.7 (-62%) 

Amyl cinnamal 3.13 8.3 (-62%) 

4-Vinylphenol 1.44 14.0 (-90%) 

Methylparaben (4-hydroxy benzoic acid, methyl ester) 1.70 11.0 (-85%) 

Propylparaben 1.44 9.3 (-85%) 

2,6-Di-tert-butyl-p-cresol 1.18 7.6 (-85%) 

Beta-phenethyl alcohol 4.49 13.8 (-67%) 

Cinnamic alcohol 0.83 12.5 (-93%) 

Anethol 0.75 11.3 (-93%) 

2-Ethylhexyl benzoate 0.92 7.2 (-87%) 

1-Nitropropane 0.20 11.3 (-98%) 

Ethyl methyl ketone oxime 1.55 15.4 (-90%) 

Lauryl pyrrolidone 0.89 6.6 (-87%) 

o-Dichlorobenzene 0.17 11.4 (-99%) 

2-Chlorotoluene 2.86 13.3 (-78%) 

Methyl nonafluorobutyl ether 0.05 7.2 (-99%) 

Methyl nonafluoroisobutyl ether 0.05 7.2 (-99%) 

Ethyl nonafluorobutyl ether 0.19 6.4 (-97%) 

Ethyl nonafluoroisobutyl ether 0.19 6.4 (-97%) 
5 

Discussion and Recommendations 

This project made significant progress towards achieving its objectives of decreasing 

uncertainties and improving estimates of ozone impacts of consumer product compounds of interest to the 

CARB. Ozone impact estimates and MIR values were derived for a total of 7 amines and 30 other 

compounds present in consumer products inventories for which estimates were not previously available, 

ozone impact estimates and MIR values were significantly improved for 8 amines, and data were obtained 

to support the predictive capabilities of the previously derived mechanism for d-limonene. The major 

contribution of this project concerned the development of improved methods for estimating mechanisms 

for calculating ozone impact estimates for amines, which were previously represented using highly 

approximate "placeholder" mechanisms, or for which only upper limit ozone impact estimates were 

available. As a result of this project, the estimated ozone impacts of amines appropriate for regulatory 

applications were found to be much lower than the upper limit values would indicate. 

However, significant uncertainties still remain concerning the atmospheric reaction mechanisms 

of the amines. The most important concerns the removal of the amines by reaction with HNO3, which 

requires improved values for the equilibrium constants for these reactions, as well as more information 

about sources and sinks of HNO3, amines, and ammonia in the atmosphere. However, there are other 

uncertainties in the amine mechanisms and the available chamber data could not be used to quantitatively 

evaluate mechanism predictions because of the lack of suitable analytical methods for quantitative 

analysis of amines in the gas phase. Methods need to be developed to quantitatively inject and monitor 

these compounds in the gas phase before quantitative data can be obtained to comprehensively evaluate 

the mechanisms for these compounds. 

Mechanisms and reactivity estimates were also derived for a number of other compounds found 

in consumer product inventories for which estimates were not previously available. However, the CARB 

staff had also requested reactivity estimates for a total of 63 other compounds for which reactivity 

estimates are still needed. Of these, 4 are probably of negligible reactivity and 20 are probably nonvolatile, leaving 39 compounds for which reactivity estimates are actually needed. In some of these cases 

the chemical structures could not be determined, but in others the mechanisms are too uncertain to 

estimate; while for others, estimates could be made if more time and resources were available. Additional 

work in this area may be appropriate if the missing estimates remain problematic for the CARB. 

Although the primary focus of this project was reducing uncertainties in ozone impact estimates, 

data were also obtained concerning the relative PM formation potentials for the compounds studied. 

Developing mechanisms for PM impacts was beyond the scope of this project, and it should be 

emphasized that the results are applicable only for the conditions of these experiments, and relative PM 

impacts in the atmosphere may be different. However, the data obtained should be useful for testing 

mechanisms for PM formation of these compounds, and work in this area is needed. 
6 

INTRODUCTION 

Background 

Many different types of volatile organic compounds (VOCs) are emitted into the atmosphere, 

where they can affect photochemical ozone formation and other measures of air quality. Because VOCs 

can react in the atmospheres at different rates and with different mechanisms, the different types of VOCs 

can differ significantly in their effects on air quality. Therefore, VOC control strategies that take these 

“reactivity” differences into account can potentially achieve ozone reductions and other air quality 

benefits in a more cost-effective manner than strategies that treat all non-exempt VOCs equally. 

Reactivity-based control strategies have already been implemented in the California Air Resources Board 

(CARB) Clean Fuel/Low Emissions Vehicle (CF/LEV) regulations (CARB, 1993), aerosol coatings 

regulations (CARB, 2000), and are being considered for architectural coatings (CARB 2007) and other 

stationary source applications. Since California has been successful in implementing reactivity-based 

regulations as a cost-effective way to reduce ozone, it is reasonable to expect that this approach will be 

adopted in other jurisdictions as well. For example, the U.S. EPA recently proposed a national rule on 

aerosol sprays based on reactivity (EPA, 2007). 

Implementation of reactivity-based controls requires some means to measure and quantify 

relative ozone impacts of different VOCs. This is not a simple problem, because the ozone impact of a 

VOC depends on the environment where the VOC is emitted as well as the nature of the VOC (e.g., see 

Carter and Atkinson, 1989). The effect of a VOC on ozone formation in a particular environment can be 

determined from its “incremental reactivity”, which is defined as the amount of additional ozone formed 

when a small amount of the VOC is added to the environment, divided by the amount added. Although 

this can be measured in environmental chamber experiments, such experiment cannot be assumed to be 

the same as incremental reactivities in the atmosphere (Carter and Atkinson, 1989; Carter et al., 1995a). 

This is because it is not currently practical to duplicate in an experiment all the environmental factors that 

affect relative reactivities; and, even if it were, the results would only be applicable to a single type of 

environment. The only practical means to assess atmospheric reactivity, and how it varies among different 

environments, is to estimate its atmospheric ozone impacts using airshed models. However, such model 

calculations are no more reliable than the chemical mechanisms upon which they are based. While the 

initial atmospheric reaction rates for most VOCs are reasonably well known or at least can be estimated, 

for most VOCs the subsequent reactions of the radicals formed are complex and have uncertainties that 

can significantly affect predictions of atmospheric impacts. Laboratory studies can reduce these 

uncertainties, but for most VOCs they will not provide the needed information in the time frame required 

for current regulatory applications. For this reason, environmental chamber experiments and other 

experimental measurements of reactivity are necessary to test and verify the predictive capabilities of the 

chemical mechanisms used to calculate atmospheric reactivities. 

The SAPRC-99 chemical mechanism (Carter, 2000a) has been the most widely used mechanism 

in the United States for calculating relative impacts (reactivities) of VOCs on ozone formation, and is the 

basis of the MIR ozone reactivity scale used in the current CARB reactivity-based regulations. This 

mechanism, and its corresponding reactivity scales, have recently been updated to the SAPRC-07 

mechanism (Carter, 2007a), and it is expected that the current CARB regulatory reactivity scale will be 

updated to the SAPRC-07 version in the next update. The SAPRC-99 and SAPRC-07 mechanisms are 

based on the wide body of available laboratory data, kinetic and mechanistic evaluations, atmospheric 

chemical theories and estimation methods, and environmental chamber data for the many types of 
7 

compounds involved (Carter, 2000a, 2007a and references therein). The most recent SAPRC-07 reactivity 

tabulation has ozone impact estimates for over 1000 types of compounds. However, the number of 

compounds that have been experimentally studied is much more limited, and some of these ozone impacts 

are based on highly uncertain estimated or approximated mechanisms. In addition, there are still many 

compounds in emissions inventories for which mechanisms have not been derived, and therefore ozone 

impact estimates are not available. 

Consumer products are an important component of the total emissions of VOCs into the 

atmosphere, which might make a non-negligible contribution to ozone formation. Because of this, the 

CARB has been implementing additional controls for VOC emissions from consumer products, and is 

considering use of reactivity-based controls for these source categories. However, the uncertainties in 

quantification of ozone impacts (reactivity) of many compounds contained in consumer products are a 

concern. For example, reactivity estimates for several constituents in hairspray and nail care products, 

particularly amines such as 2-amino-2-methyl-1-propanol (AMP) and ethanolamine, are highly uncertain. 

Improved reactivity estimates for these and others are needed. For many such compounds the CARB has 

had to use "upper limit" estimates of ozone impacts of these compounds, based on worst-case 

considerations of reaction rates and mechanisms (see Appendix D of Carter, 2000a). This has led to 

relatively small amounts of some compounds dominating ozone impact estimates of some product 

categories. This is problematical because the actual ozone impacts of these product categories may be 

significantly less, and regulations based on upper-limit reactivity estimates may lead inappropriate control 

strategies. 

Objectives 

The overall objective of this project is to reduce uncertainties of ozone impact quantifications of 

selected consumer products compounds of interest to the CARB. Specific objectives included carrying out 

environmental chamber experiments needed to develop or evaluate mechanisms for a few selected 

representative compounds, derive mechanisms for these and related compounds and other compounds of 

interest based on the data obtained and other available information and estimates, and use the results to 

update or enhance the SAPRC-07 mechanism to include representations and ozone impacts for these 

compounds. 

Based on discussions with the CARB staff, it was decided that this project would focus primarily 

on reducing uncertainties in reactivity estimates for amines, with environmental chamber experiments 

being carried out using the representative amines AMP and aminoethanol. It was also determined that 

experiments were needed to reduce uncertainties in ozone impacts for d-limonene, an important consumer 

product VOC for which mechanism evaluation data were inadequate. The CARB staff also requested that 

the reactivity estimates be made for a number of compounds for which mechanisms reactivity estimates 

were not available, and to accomplish this it was necessary to derive estimated mechanisms or 

approximate representations for the atmospheric reactions of these compounds for the purpose of 

calculating reactivity values. 

Overall Approach 

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. The chamber experiments were 

carried out in the UCR EPA chamber, which was developed under EPA funding for more precise 

mechanism evaluation at lower and more atmospherically representative pollutant levels than previously 

possible (Carter et al, 1999; Carter, 2002; Carter et al 2005a). Results of earlier experiments carried out in 
8 

this chamber, including characterization results that are applicable to this study, are given in previous 

reports or publications (Carter, 2004; Carter and Malkina, 2005; Carter et al, 2005a,b). The approach 

employed followed that used in our previous studies of architectural coating (Carter and Malkina, 2005; 

Carter et al, 2005b) and pesticide (Carter and Malkina, 2007; Carter, 2007b) VOC reactivity. 

The primary objective of these experiments with respect to ozone formation is not to directly 

measure atmospheric ozone reactivity, but to provide data to test the ability of chemical mechanisms used 

in models to predict their ozone impacts in the atmosphere. If the mechanism can be shown to adequately 

simulate the relevant impacts of the VOC in well-characterized environmental chamber experiments with 

a range of chemical conditions representative of the atmosphere, one has increased confidence in the 

predictive capabilities of the model when applied to atmospheric scenarios. If the mechanism 

performance in simulating the experiments is less than satisfactory, then the need to improve the 

mechanism is indicated, and one has decreased confidence in its predictions of atmospheric reactivity. 

The most realistic chemical environment in this regard is one where the test compounds or 

mixtures react in the presence of the other pollutants present in the atmosphere. Therefore, most of the 

environmental chamber experiments for this and the coatings VOC reactivity programs consisted of 

measurements of “incremental reactivity” of the subject compounds or solvents under various conditions. 

These involve two types of irradiations of model photochemical smog mixtures. The first is a “base case” 

experiment where a mixture of reactive organic gases (ROGs) representing those present in polluted 

atmospheres (the “ROG surrogate”) is irradiated in the presence of oxides of nitrogen (NOx) in air. The 

second is the “test” experiment that consists of duplicating the base case irradiation, except that the VOC 

whose reactivity is being assessed is added. The differences between the results of these experiments 

provide a measure of the atmospheric impact of the test compound. These results can be used to test the 

ability of a chemical mechanism to predict the compound's atmospheric impacts under the chemical 

conditions of the experiment. 

Base case experiments to simulate ambient chemical environments require choice of an 

appropriate reactive organic gas (ROG) surrogate mixture to represent the reactive organics that are 

important in affecting ozone formation in the urban atmospheres. For this and the coatings reactivity 

projects, we continued to use a modified version of the 8-component “full surrogate” that was employed 

in our previous reactivity studies for this project. This is because, as discussed previously (Carter et al, 

1995a), use of this surrogate gives a reasonably good representation of ambient anthropogenic VOC 

emissions as represented in current models, and use of more detailed mixtures would not give 

significantly different reactivity results. However, because of experimental problems, for this and many of 

the experiments in the coatings project, the formaldehyde was removed from the surrogate and the initial 

concentrations of the other ROG components were increased by 10% to make up for this reactivity 

change. Model calculations indicate that this surrogate modification should not have significant effects on 

experimental incremental reactivity results (Carter and Malkina, 2005). Target and average measured 

compositions of the ROG surrogates for the reactivity experiments for coatings projects are given by 

Carter and Malkina (2005). The target concentrations used in the experiments for this program were the 

same. 

In order to provide data to test mechanism impacts of the test compounds or mixtures under 

differing atmospheric conditions, the incremental reactivity experiments are generally carried out using 

two different standard conditions of NOx availability relevant to VOC reactivity assessment. Probably the 

most relevant for California regulatory applications is “maximum incremental reactivity” (MIR) 

conditions, which are relatively high NOx conditions where ozone formation is most sensitive to VOC 

emissions. However, it is also necessary to provide data to test mechanism predictions under lower NOx
9 

conditions, since different aspects of the mechanisms are important when NOx is limited. The NOx levels 

that define the boundary line between VOC-sensitive, MIR-like conditions and NOx-limited (and 

therefore NOx-sensitive) conditions is that which yields the maximum ozone concentrations for the given 

level of ROGs, or the conditions of the “maximum ozone incremental reactivity” (MOIR) scale. 

Therefore, experiments with NOx levels that are approximately half that for MOIR conditions might 

provide an appropriate test of the mechanism under NOx-limited conditions. This is referred to as 

“MOIR/2” conditions in the subsequent discussion. If NOx levels are reduced significantly below this, the 

experiment becomes less sensitive to VOC levels and thus less relevant to VOC reactivity assessment. 

The conditions of NOx availability are determined by the ROG/NOx ratios in the base case 

incremental reactivity experiments. In order to completely fix the conditions of these experiments, it is 

also necessary to specify a desired absolute NOx level. We sought input from the CARB staff concerning 

the NOx levels they would consider to be appropriate to use for reactivity studies in the new chamber 

(Carter and Malkina, 2005). Based on their input, and model simulations of reactivity characteristics in 

our chamber, it was determined that the nominal initial concentrations of the MIR base case experiment 

would consist of ~30 ppb NOx and ~0.5 ppmC ROG surrogate, and the MOIR/2 experiment would consist 

of ~25 ppb NOx and ~1 ppmC ROG surrogate (Carter and Malkina, 2005). These were therefore the two 

standard base cases for all the incremental reactivity experiments discussed in this report. 

A number of other control and characterization experiments were also carried out in order to 

adequately characterize the conditions of the chamber for mechanism evaluation and background 

particulate matter (PM). These experiments are discussed where applicable in the results and modeling 

methods sections. 

The SAPRC-07 mechanism, as documented by Carter (2007a), was used as the starting point for 

the mechanism development aspect of the project. The mechanisms for the VOCs studied for this project 

were added to this mechanism, and these VOCs were added to the list of compounds for which reactivity 

values are tabulated. The SAPRC-07 documentation and tabulations (Carter, 2007a, available at 

http://www.cert.ucr.edu/~carter/SAPRC) were updated to include the mechanisms and reactivity 

assignments developed or updated for this project. 
10 

EXPERIMENTAL METHODS 

Chamber Description 

All of the environmental chamber experiments for this project were carried out using the UCR 

EPA environmental chamber. This chamber was constructed under EPA funding to address the needs for 

an improved environmental chamber database for mechanism evaluation (Carter et al, 1999, Carter, 

2002). The objectives, design, construction, and results of the initial evaluation of this chamber facility 

are described in more detail elsewhere (Carter et al, 1999, Carter, 2002; Carter, 2004, Carter et al, 2005a). 

A description of the chamber is also given below. 

The UCR EPA chamber consists of two ~85,000-liter Teflon® reactors located inside a 16,000 

cubic ft temperature-controlled “clean room” that is continuously flushed with purified air. The clean 

room design is employed in order to minimize background contaminants into the reactor due to 

permeation or leaks. Two alternative light sources can be used. The first consists of a 200 KW argon arc 

lamp with specially designed UV filters that give a UV and visible spectrum similar to sunlight. This light 

source could not be used for this project because it was not operational during this period. Banks of 

blacklights are also present to serve as a backup light source for experiments where blacklight irradiation 

is sufficient, and this was used for the experiments for this project because of availability and because use 

of blacklights was judged to be sufficient to satisfy the project objectives. The interior of the enclosure is 

covered with reflective aluminum panels in order to maximize the available light intensity and to attain 

sufficient light uniformity, which is estimated to be ±10% or better in the portion of the enclosure where 

the reactors are located (Carter, 2002). A diagram of the enclosure and reactors is shown in Figure 1. The 

spectrum of the blacklight light source is given by Carter et al (1995b). 

The dual reactors are constructed of flexible 2 mil Teflon® film, which is the same material used 

in the other UCR Teflon chambers used for mechanism evaluation (e.g., Carter et al, 1995b; Carter, 

2000a, 2007a, and references therein). A semi-flexible framework design was developed to minimize 

leakage and simplify the management of large volume reactors. The Teflon film is heat-sealed into 

separate sheets for the top, bottom, and sides (the latter sealed into a cylindrical shape) that are held 

together and in place using bottom frames attached to the floor and moveable top frames. The moveable 

top frame is held to the ceiling by cables that are controlled by motors that raise the top to allow the 

reactors to expand when filled or lower the top to allow the volume to contract when the reactors are 

being emptied or flushed. These motors in turn are controlled by pressure sensors that raise or lower the 

reactors as needed to maintain slight positive pressure. During experiments the top frames are slowly 

lowered to maintain continuous positive pressure as the reactor volumes decrease due to sampling or 

leaks. The experiment is terminated if the volume of one of the reactor reaches about 1/3 the maximum 

value, where the time this took varied depending on the amount of leaks in the reactor, but was greater 

than the duration of most of the experiments discussed in this report. Since at least some leaks are 

unavoidable in large Teflon film reactors, the constant positive pressure is important to minimize the 

introduction of enclosure air into the reactor that may otherwise result. 

As indicated in Figure 1, the floor of the reactors has openings for a high volume mixing system 

for mixing reactants within a reactor and also for exchanging reactants between the reactors to achieve 

equal concentrations in each. This utilizes four 10” Teflon pipes with Teflon-coated blowers and flanges 

to either blow air from one side of a reactor to the other, or to move air between each of the two reactors
11 

20 ft. 20 ft.

20 

 ft. 

This volume kept clear 

to maintain light 

uniformity 

Temperature controlled room flushed 

with purified air and with reflective 

material on all inner surfaces 

Dual Teflon 

Reactors 

Two air Handlers 

are located in the 

corners on each 

side of the light 

(not shown). 

Gas sample lines to 

laboratory below Access 

Door 

200 KW 

Arc Light 

2 Banks of 

Blacklights 

SEMS (PM) 

Instrument 

Floor Frame 

Movable top 

frame allows 

reactors to 

collapse 

under 

pressure 

control 

Mixing System

Under floor 

of reactors 

Figure 1. Schematic of the UCR EPA environmental chamber reactors and enclosure. 

Teflon-coated air-driven metal valves are used to close off the openings to the mixing system when not in 

use, and during the irradiation experiments. 

An AADCO air purification system that provides dry purified air at flow rates up to 1500 liters 

min-1 is used to supply the air to flush the enclosure and to flush and fill the reactors between 

experiments. The air is further purified by passing it through cartridges filled with Purafil® and heated 

Carulite 300® which is a Hopcalite® type catalyst, and also through a filter to remove particulate matter. 

The measured NOx, CO, and non-methane organic concentrations in the purified air were found to be less 

than the detection limits of the instrumentation employed (see Analytical Equipment, below). 

The chamber enclosure is located on the second floor of a two-floor laboratory building that was 

designed and constructed specifically to house this facility (Carter et al, 2002). Most of the analytical 

instrumentation is located on the ground floor beneath the chamber, with sampling lines leading down as 

indicated in Figure 1. 

Analytical Instrumentation 

Table 1 gives a listing of the analytical and characterization instrumentation whose data were 

utilized for this project. Other instrumentation was available and used for some of these experiments, as 

discussed by Carter 2002a and Carter et al, 2005a, but the data obtained were not characterized for 

modeling and thus not used in the mechanism evaluations for this project. The table includes a brief 

description of the equipment, species monitored, and their approximate sensitivities, where applicable. 

These are discussed further in the following sections. 
12 

Table 1. List of analytical and characterization instrumentation for the UCR EPA chamber. 

Type Model or Description Species Sensitivity Comments 

 

Ozone 

Analyzer 

Dasibi Model 1003-AH. UV 

absorption analysis. Also, a 

Monitor Labs 

Chemiluminescence Ozone 

Analyzer Model 8410 was used 

as a backup. 

O3 2 ppb Standard monitoring instrument. 

NO - NOy NO 1 ppb 

Analyzer 

TECO Model 42 C with 

external converter. 

Chemiluminescent analysis for 

NO, NOy by catalytic 

conversion. 

NOy 1 ppb 

Useful for NO and initial NO2

monitoring. Converter close-coupled to 

the reactors so the “NOy” channel should 

include HNO3 as well as NO2, PANs, 

organic nitrates, and other species 

converted to NO by the catalyst. 

CO Analyzer Thermo Environmental 

Instruments Inc. Model 48 C 

CO 50 ppb Standard monitoring instrument 

GC-FID 

Instruments 

Dual HP 6890 Series II GC 

with dual columns, loop 

injectors and FID detectors. 

Controlled by computer 

interfaced to network. 

VOCs ~10 ppbC 30 m x 0.53 mm GS-Alumina column 

used for the analysis of light 

hydrocarbons such as ethylene, 

propylene, n-butane and trans-2-butene 

and 30 m x 0.53 mm DB-5 column used 

for the analysis of C5+ alkanes and 

aromatics, such as toluene and m-xylene. 

Loop injection is suitable for low to 

medium volatility VOCs that are not too 

“sticky” to pass through valves. Two 30 

m x 0.32 mm DB-5 column measure C5+

alkanes and aromatics, such as toluene 

and m-xylene. 

PTR-MS Ionicon Analytik high 

sensitivity proton transfer 

reaction mass spectrometer 

equipped with a quadruple MS. 

Controlled by computer 

interface. 

VOCs ~5ppt Used to measure light VOCs such as 

formaldehyde and some other 

compounds. Used primarily for 

formaldehyde for this project. 

Gas 

Calibrator 

Model 146C Thermo 

Environmental Dynamic Gas 

Calibrator 

N/A N/A Used for calibration of NOx and other 

analyzers. Instrument acquired early in 

project and under continuous use. 

Data 

Acquisition 

Sytem 

Windows PC with custom 

LabView software, 16 analog 

input, 40 I/O, 16 thermocouple, and 8 RS-232 channels. 

N/A N/A Used to collect data from most 

monitoring instruments and control 

sampling solenoids. In-house LabView 

software was developed using software 

developed by Sonoma Technology for 

ARB for the Central California Air 

Quality Study as the starting point. 
Table 1 (continued) 

13 

Type Model or Description Species Sensitivity Comments 

 

Temperature 

sensors 

Various thermocouples, 

radiation shielded 

thermocouple housing 

Tempera

-ture 

~0.1 oC Primary measurement is thermocouples 

inside reactor. However, comparison with 

temperature measurements in the sample 

line suggests that irradiative heating may 

bias these data high by ~2.5o

C. See text. 

Humidity 

Monitor 

General Eastern HYGRO-M1 

Dew Point Monitor 

Humidity Dew point 

range: -40 - 

50o

C 

Instrument performs as expected, but dew 

point below the performance range for 

most of the experiments discussed in this 

report, except for those with added 

humidity. 

QSL 

Spherical 

Irradiance 

Sensor 

Biospherical QSL-2100 PAR 

Irradiance Sensor. Responds to 

400-700 nm light. 

Spherical 

Broadband 

Light 

Intensity

Adequate Provides a measure of absolute intensity 

and light uniformity that is more directly 

related to photolysis rates than light 

intensity on surface. Gives more precise 

measurement of light intensity trends 

than NO2 actinometry, but is relatively 

sensitive to small changes in position. 

Scanning 

Mobility 

Particle 

Spectrometer 

(SMPS) 

TSI 3080L column, TSI 3077 

85Kr neutralizer, and TSI 

3760A CPC. Instrument 

design, control, and operation 

Similar to that described in 

Cocker et al. (2001) 

Aerosol 

number 

and size 

distributions 

Adequate Provides information on size distribution 

of aerosols in the 28-730 nm size range, 

which accounts for most of the aerosol 

mass formed in our experiments. Data 

can be used to assess effects of VOCs on 

secondary PM formation. 

Ozone, CO, NO, and NOy were monitored using commercially available instruments as indicated 

in Table 1. The instruments were spanned for NO, NO2, and CO and zeroed prior to most experiments 

using the gas calibration system indicated in Table 1, and a prepared calibration gas cylinder with known 

amounts of NO and CO. O3 and NO2 spans were conducted by gas phase titration using the calibrator 

during this period. Span and zero corrections were made to the NO, NO2, and CO data as appropriate 

based on the results of these span measurements, and the O3 spans indicated that the UV absorption 

instrument was performing within its specifications. 

Organic reactants other than the amines were measured by gas chromatography with FID 

detection as described elsewhere (Carter et al, 1995b); see also Table 1. The surrogate gaseous 

compounds ethylene, propylene, n-butane and trans-2-butene were monitored by using 30 m megabore 

GS-Alumina column and the loop sampling system. The second signal of the same GC outfitted with FID, 

loop sampling system and 30 m megabore DB-5 column was used to analyze surrogate liquid components 

toluene, n-octane, and m-xylene. The sampling methods employed for injecting the sample with the test 

compounds on the GC column depended on the volatility or “stickiness” of the compounds. 

Both the GC instruments were controlled and their data were analyzed using HPChem software 

installed on a dedicated PC. The GC's were spanned using the prepared calibration cylinder with known 

amounts of ethylene, propane, propylene, n-butane, n-hexane, toluene, n-octane and m-xylene in ultrapure 

nitrogen. Analyses of the span mixture were conducted approximately every day an experiment was run, 

and the results were tracked for consistency. 
14 

The surrogate components analyzed by the above system were calibrated by repeated analysis of 

a standard mixture containing these compounds, and verified by injecting and sampling known amounts 

of the compound in calibration chamber of known volume. The amounts of gaseous compounds injected 

were determined by vacuum methods, using an MKS Baratron precision pressure gauge, and bulbs of 

known volume, determined by weighing when filled with water. The amounts of liquid compounds 

injected were determined by measuring amounts injected using microliter syringes. The volumes of the 

calibration chambers were determined by injecting and analyzing compounds whose analyses have been 

calibrated previously. 

d-Limonene was monitored by the GC with the 30 m megabore DB-5 column. The GC was 

calibrated using the known volume of the reactor and the amount injected for these and previous 

experimental runs with this compound. 

Unfortunately, we were not able to develop a GC or other method to quantitatively analyze the 

amines in the gas phase. Although they give a response on the GC when sampled using the Tenax 

cartridge sampling, this was not found to be quantitative or reproducible in practice. Insufficient 

resources, personnel, or time were available to available to develop a suitable method for this project, and 

a suitable analytical method we could use was not found in the literature. Therefore, most amine 

compound concentrations were determined using the amount injected and the chamber reactors known 

volume. 

Most of the instruments, other than the GCs and aerosol instrument, were interfaced to a PCbased computer data acquisition system under the control of a LabView program written for this purpose. 

These data, and the GC data from the HP ChemStation computer, were collected over the CE-CERT 

computer network and merged into Excel files that were used for applying span, zero, and other 

corrections, and preparation of the data for modeling. 

Sampling Methods 

Samples for analysis by the continuous monitoring instrument were withdrawn alternately from 

the two reactors and zero air, under the control of solenoid valves that were in turn controlled by the data 

acquisition system discussed above. For most experiments the sampling cycle was 5 minutes for each 

reactor, the zero air, or (for control purpose) the chamber enclosure. The program controlling the 

sampling sent data to the data acquisition program to indicate which state was being sampled, so the data 

could be appropriately apportioned when being processed. Data taken less than 3-4 minutes after the 

sample switched were not used for subsequent data processing. The sampling system employed is 

described in more detail by Carter (2002). 

Samples for GC analysis of surrogate compounds were taken at approximately every 20-minute 

directly from each of the reactors through the separate sample lines attached to the bottom of the reactors. 

The GC sample loops were flushed for a desired time with the air from reactors using a pump. 

 Samples from the PTR-MS were conducted from selected reactors for some of the experiments. 

The reactors sampled were selected manually, typically sampling for at least an hour before switching 

sides. The PTR-MS data were used primarily for monitoring formaldehyde in a few of the experiments. 

Characterization Methods 

Use of chamber data for mechanism evaluation requires that the conditions of the experiments be 

adequately characterized. This includes measurements of temperature, humidity, and light, and wall 
15 

effects characterization. Wall effects characterization is discussed in detail by Carter (2004) and updated 

by Carter and Malkina (2005) and Carter (2007a), and most of that discussion is applicable to the 

experiments for this project. The instrumentation used for the other characterization measurements is 

summarized in Table 1, above, and these measurements are discussed further below. 

Temperature was monitored during chamber experiments using calibrated thermocouples 

attached to thermocouple boards on our computer data acquisition system. The temperature in each of the 

reactors was continuously measured using relatively fine gauge thermocouples that were located ~1’ 

above the floor of the reactors. These thermocouples were not shielded from the light, though it was 

expected that irradiative heating would be minimized because of their small size. Experiments where the 

thermocouple for one of the reactors was relocated to inside the sample line indicated that radiative 

heating is probably non-negligible, and that a correction needs to be made for this by subtracting ~2.5o

C 

from the readings of the thermocouples in the reactors. This is discussed by Carter (2004). 

Light Spectrum and Intensity. The spectrum of the light source in the 300-850 nm region has 

been measured using a LiCor LI-1800 spectroradiometer, which is periodically calibrated at the factory 

(e.g., see Carter et al, 2005b). Based on previous extensive measurements the spectrum of the blacklight 

light was assumed to be constant, and was not measured during the time period of this project. The 

method used to derive the light intensity using the blacklight light source was based on that discussed by 

Carter et al (2005b), updated as described by Carter and Malkina (2007). Briefly, the absolute light 

intensity is measured by carrying out NO2 actinometry experiments periodically using the quartz tube 

method of Zafonte et al (1977) modified as discussed by Carter et al (1995b). In most cases the quartz 

tube was located in front of the reactors. Since this location is closer to the light than the centers of the 

reactors, the measurement at this location is expected to be biased high, so the primary utility of these 

data are to assess potential variation of intensity over time. However, several special actinometry 

experiments were previously conducted where the quartz tube was located inside the reactors, to provide a 

direct measurement of the NO2 photolysis rates inside the reactors. The results of these measurements 

were used to derive a correction factor of 0.698 to derive NO2 photolysis rates in the reactor from those 

measured in front of the reactor (Carter et al, 2005b). The trend of in-reactor and corrected in-front-ofreactor actinometry results over blacklight run number (the number of runs conducted using blacklights) 

were then used to derive an assigned NO2 photolysis rate as a function of blacklight run number. Results 

of actinometry measurements carried during the course of this project are given in the "Characterization 

results" section, below. 

Experimental Procedures 

The reaction bags were collapsed to the minimum volume by lowering the top frames, and then 

emptied and refilled at least six times after each experiment, and then were filled with dry purified air on 

the nights before experiments. Span measurements were generally made on the continuous instruments 

prior to injecting the reactants for the experiments. The reactants were then injected through Teflon 

injection lines (that are separate from the sampling lines) leading from the laboratory below to the 

reactors. The common reactants were injected in both reactors simultaneously, and were mixed by using 

the reactor-to-reactor exchange blowers and pipes for 10 minutes. The valves to the exchange system 

were then closed and the other reactants were injected to their respective sides and mixed using the inreactor mixing blowers and pipes for 1 minute. The contents of the chamber were then monitored for at 

least 30 minutes prior to irradiation, and samples were taken from each reactor for GC analysis. 

 Once the initial reactants are injected, stabilized, and sampled, the blacklights are turned on to 

begin the irradiation. During the irradiation the contents of the reactors are kept at a constant positive 

pressure by lowering the top frames as needed, under positive pressure control. The reactor volumes 

therefore decrease during the course of the experiments, in part due to sample withdrawal and in part due 
16 

to small leaks in the reactor. A typical irradiation experiment ended after about 6 hours, by which time the 

reactors are typically down to about half their fully filled volume. Larger leaks are manifested by more 

rapid decline of reactor volumes, and the run is aborted early if the volume declines to about 1/3 the 

maximum. This was not the case for most of the experiments discussed in this report. After the irradiation 

the reactors were emptied and filled six times as indicated above. 

The procedures for injecting the various types of reactants were as follows. The NO, and NO2

were prepared for injection using a vacuum rack. Known pressures of NO, measured with MKS Baratron 

capacitance manometers, were expanded into Pyrex bulbs with known volumes, which were then filled 

with nitrogen (for NO) or purified air (for NO2). In order to maintain constant NO/NO2 ratios the same 

two bulbs of specified volume were utilized in most of experiments. The contents of the bulbs were then 

flushed into the reactor(s) with nitrogen. For experiments with added CO, the CO was purified by passing 

it through an in-line activated charcoal trap and flushing it into the reactor at a known rate for the amount 

of time required to obtain the desired concentration. Measured volumes of volatile liquid reactants were 

injected, using a micro syringe, into a 2 ft long Pyrex injection tube surrounded with heat tape and 

equipped with one port for the injection of the liquid and other ports to attach bulbs with gas reactants. 

For injections into both reactors (e.g, the NOx and base ROG surrogate components in incremental 

reactivity experiments), one end of the injection tube was attached to the “Y”-shape glass tube (equipped 

with stopcocks) that was connected to reactors and the other end of injection tube was connected to a 

nitrogen source. The injections into a single reactor (e.g., for an amine in the reactivity experiments) was 

similar except the “Y” tube was not used. 

The procedures for injection of the hydrocarbon surrogate components were as follows. A 

cylinder containing n-butane, trans-2-butene, propylene and ethylene in nitrogen, was used for injecting 

the gaseous components of the surrogate. The cylinder was attached to the injection system and a gas 

stream was introduced into reactors at controlled flow for certain time to obtain desired concentrations. A 

prepared mixture with the appropriate ratios of toluene, n-octane and m-xylene was utilized for injection 

of these surrogate components, using the procedures as discussed above for pure liquid reactants. All the 

gas and liquid reactants intended to be the same in both reactors were injected at the same time. The 

injection consisted of opening the stopcocks and flushing the contents of the bulbs and the liquid reactants 

with nitrogen, with the liquid reactants being heated slightly using heat that surrounded the injection tube. 

The flushing continued for approximately 10 minutes. 

The amines and d-limonene were injected, using a microsyringe, into a glass injection tube 

leading into the reactor to be employed for the compound. The procedure was similar to that used for the 

liquid hydrocarbon surrogate components. The compounds were flushed into the chamber at least 30 

minutes or longer, until there was no material visible in the injection tube. The amines and sample lines 

leading into the chamber were heated to ~90-100o

C.

Materials 

The sources of the NO, CO and the various base case surrogate compounds came from various 

commercial vendors as employed in previous projects at our laboratory. The AMP was obtained from 

Fluka, the ethanolamine was from Sigma, and the d-limonene was from MP Biochemicals. In all cases the 

stated purities were at least 99%, and no further purification was carried out. 
17 

MODELING METHODS 

Base Mechanism 

The starting point for the chemical mechanism evaluated in this work is the SAPRC-07 

mechanism as documented and listed by Carter (2007a). Files and software implementing this chemical 

mechanism are being prepared and will be available at the SAPRC mechanism web site at 

http://www.cert.ucr.edu/~carter/SAPRC. The changes and additions made to the mechanism as a result of 

work for this project are discussed later in this section. 

As discussed previously (Carter, 2000a,b, 2007a), the SAPRC mechanisms consist of a “base 

mechanism” that represents the reactions of the inorganic species and common organic products and 

lumped organic radical model species and “operators”, and separate mechanisms for the initial reactions 

of the many types other organic compounds that are not in the base mechanism. The compounds, or 

groups of compounds, that are not included in the base mechanism but for which mechanism assignments 

have been made, are referred to as detailed model species. These include all the base ROG surrogate 

constituents and the compounds whose reactions were modeled in this work. These compounds can either 

be represented explicitly, with separate model species with individual reactions or sets of reactions for 

each, or using lumped model species similar to those employed in the “fixed parameter” version of 

SAPRC (Carter, 2000b, 2007a). The latter approach is useful when modeling complex mixtures in 

ambient simulations or simulations of experiments with complex mixtures, but the other approach, 

representing each compound explicitly, is more appropriate when evaluating mechanisms for individual 

compounds or simple mixtures. This is because the purpose of mechanism evaluations against chamber 

data is to assess the performance of the mechanism itself, not to assess the performance lumping 

approaches. The latter is most appropriately assessed by comparing simulations of explicit and condensed 

versions of the same mechanism in ambient simulations. 

In view of this, all of the organic constituents of the base ROG surrogate were represented 

explicitly using separate model species for each compound. In addition, the individual test compounds 

were also represented explicitly when simulating experiments with those compounds. This gives the least 

approximate representation of the atmospheric reactions of these compounds within the framework of the 

SAPRC-07 mechanism. The mechanisms for the individual test compounds are discussed later in this 

section. 

Representation of Chamber Conditions 

The procedures used in the model simulations of the environmental chamber experiments for this 

project were based on those discussed in detail by Carter (2004) and were employed in more recent 

studies (Carter and Malkina, 2007, and references therein), except as indicated below. Carter (2004) 

should be consulted for details of the characterization model and chamber effects parameters employed. 

The temperatures used when modeling were the averages of the temperatures measured in the reactors, 

corrected as discussed by Carter (2004). The light intensity for the black light experiments varied with 

time, and the NO2 photolysis rate for those experiments was derived as discussed in the Characterization 

Results section, below. The blacklight spectral distribution given by Carter et al (1995b) was found to be 

appropriate for the blacklights in this chamber and was therefore used when modeling the blacklight runs 

discussed in this report. 
18 

The chamber effects parameters used when modeling the experiments in this chamber were the 

same as those given by Carter (2004) except for the HONO offgasing parameters, which were derived 

based on results of characterization runs carried out in conjunction with these experiments. As discussed 

by Carter (2004), the chamber effects model currently used for this chamber represents both the chamber 

radical source and background NOx offgasing by HONO offgasing, whose magnitude is determined by 

the chamber effects parameter RN-I, which is the ratio of the HONO offgasing rate to the NO2 photolysis 

rate. The RN-I parameter that best fits the characterization data tends to vary over time depending on the 

conditions of the chamber, and the results of the characterization experiments applicable to modeling the 

experiments discussed in this report, and the assignment of the RN-I values used, are given in the 

Characterization Results section, below. 

The initial reactant concentrations used in the model simulations were based on the measured 

values except for the amines, for which no quantitative analytical method could be found during the 

course of this project. In those cases, an upper limit to the initial concentration can be derived from the 

volume of liquid injected and the volume of the reactors, which were determined in separate experiments 

where known amounts of materials were injected and analyzed in the gas-phase. Although the reactors are 

flexible, their initial volumes were very consistent from run to run because of the use of the pressure 

control system when filling the reactor to its maximum volume prior to the reactant injections (see 

Chamber Description section, above, and Carter, 2004). However, in the case of the amines, the results of 

the reactivity experiments indicate that it is probable that not all of the liquid injected was successfully 

introduced into the gas phase. Therefore, it was necessary to use the initial amine concentrations as an 

adjustable parameter in the model simulations of the added amine experiments. This is discussed in the 

Mechanism Evaluation Results section, below. 

Mechanisms for Amines 

Amines might react in the atmosphere with OH radicals, O3, NO3 radicals, and all these 

possibilities need to be considered when estimating their mechanisms for reactivity assessment. In 

addition, unlike most other VOCs currently represented in the SAPRC mechanisms, amines are basic and 

might also be lost to some extent by reaction with HNO3, forming non-volatile amine salts, potentially 

reducing their availability for ozone formation. Photolysis is not expected to be important based on 

available absorption cross-section data for representative amines. 

The amines for which mechanisms have been derived for the current project are listed on Table 2, 

along with rate constants used for their reactions in the model. The mechanisms in terms of SAPRC-07 

model species are given in Table A-1 in Appendix A. The derivations of these rate constants and 

mechanisms are discussed below. 

Reaction with OH radicals 

Available kinetic information concerning the rate constant for the reactions of amines relevant to 

those modeled in this study with OH radicals is summarized on Table 2. It is assumed that the reaction 

proceeds from H-atom abstraction, since there does not appear to be a chemically reasonable alternative 

mechanism. The rate constants are relatively high compared to H-atom abstractions from alkyl groups. 

This is also the case for tertiary amines, where abstraction from NH cannot occur, which indicates that the 

amino group enhances reaction at adjacent groups when abstracting the alpha-hydrogens. On the other 

hand, the rate constants are also high for reaction of OH with amines, such as AMP, which do not have 

reactive adjacent groups, which indicates that the reaction at the amino group itself is also relatively rapid. 

Therefore, both types of reaction need to be taken into account when deriving group additivity estimates. 
19 

Table 2. Experimental and estimated rate constants for the reactions of amines included in 

mechanisms were derived for this project. 

Rate Constant Compound Measured values [a] Avg. [b] Est'd [c] Diff [d] 

Reaction with OH (10-11 cm3 molec-1 s-1) 

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% 

Ethyl amine 2.38 1 2.77 3 2.58 3.59 28% 

Trimethyl amine 3.58 1 6.09 3 4.84 5.01 4% 

Isopropylamine 3.78 

t-Butyl amine 1.18 6 1.18 1.79 34% 

Triethyl amine 5.57 

Ethanolamine 4.41 

N,N-Dimethylethanolamine (DMAE) 9.00 4 4.70 5 6.85 6.02 -14% 

2-Amino-1-butanol 5.32 

2-Amino-2-methyl-1-propanol (AMP) 2.80 5 2.80 2.19 -28% 

Diethanol amine 10.1 

Triethanol amine 8.04 

Triisopropanol amine 9.37 

Reaction with NO3 (10-13 cm3

 molec-1 s-1) 

Methyl amine 0.96 

Dimethyl amine 2.03 

Ethyl amine 1.16 

Trimethyl amine 1.56 

Isopropylamine 1.21 

t-Butyl amine 0.59 

Triethyl amine 1.71 

Ethanolamine 1.35 

N,N-Dimethylethanolamine (DMAE) 1.80 

2-Amino-1-butanol 1.70 

2-Amino-2-methyl-1-propanol (AMP) 0.59 

Diethanol amine 3.30 

Triethanol amine 2.29 

Triisopropanol amine 2.29 

Reaction with O3 (10-18 cm3

 molec-1 s-1) 

Methyl amine 0.007 7 0.007 0.011 52% 

Dimethyl amine 1.67 7 1.67 0.64 -61% 

Ethyl amine 0.020 

Trimethyl amine 7.84 7 7.84 6.87 -12% 

Isopropylamine 0.033 

t-Butyl amine 0 

Triethyl amine 12.10 

Ethanolamine 0.066 

N,N-Dimethylethanolamine (DMAE) 6.76 7 6.76 13.2 95% 

2-Amino-1-butanol 0.36 

2-Amino-2-methyl-1-propanol (AMP) 0 

Diethanol amine 3.77 
Table 2 (continued) 

20 

Rate Constant Compound Measured values [a] Avg. [b] Est'd [c] Diff [d] 

Triethanol amine 40.2 

Triisopropanol amine 40.2 

Reaction with HNO3 (10-11 cm3

 molec-1 s-1) 

All amines – Lower limit assumption 0 

All amines – Upper limit assumption 4 

[a] References for measured rate constants: 

 1 Carl and Crowley (1998) 2 Atkinson et al. (1977) 

 3 Atkinson et al. (1978) 4 Anderson and Stephens (1988) 

 5 Harris and Pitts (1983) 6 Koch et al (1996) 

 7 Tuazon et al (1994) 

[b] Average of measured values. Used for deriving best-fit structure-reactivity parameters, and for 

environmental chamber and/or atmospheric reactivity modeling. 

[c] Estimated rate constant derived from structure-reactivity estimates as discussed in the text. Used for 

environmental chamber and/or atmospheric reactivity modeling if the entry in the "Used" column is 

blank 

[d] Difference between average experimental and estimated rate constant, where applicable. 

The kinetic data in Table 2 were used to derive parameters for group additivity estimates for the 

rate constants for reactions of OH with amines, using the parameters in the SAPRC-99 and -07 

mechanism generation systems (Carter, 2000a, 2007a) for reactions at the other positions in the 

molecules. Table 3 gives the H-abstraction group-additivity parameters used in the SAPRC-07 

mechanism generation system, to which reactions at the amino groups have been added. For 

completeness, the table shows all the H-atom abstraction parameters used in the system, including those 

for compounds other than amines. Footnotes to the table indicate how these parameters were derived. 

Table 2 indicates that the group-additivity methods can estimate the rate constants for the amines to 

within ±26% on the average. Table 2 also gives the estimated OH radical rate constants for the amines 

represented in the mechanism for which no measured rate constant data are available, which were used in 

the mechanisms derived for these compounds. 

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 α-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·, are not important, 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 4. These assumptions are uncertain, though alternative assumptions 

probably do not yield mechanisms with significantly different reactivities. 

The subsequent reactions of the nitrogen-centered radicals formed after H-abstraction from NH2

or NH groups depends on whether there is an abstractable hydrogen in the α-position to the amine. If 

there is, then it is assumed that the dominant reaction is abstraction of this hydrogen by O2, forming HO2

and the corresponding C=N compound, e.g., 
21 

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

by OH and NO3 radicals and by Cl atoms. 

Table 3a. Abstraction rate constants assigned to groups

OH [a] NO3 Cl Group k(300) A B D Notes [b] k(300) Notes k(300) Notes 

CH3 1.39e-13 4.49e-18 2 320 1,2 7.00e-19 9 3.43e-11 13 

CH2 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) 9.99e-13 1.47e-17 2 85 5 0 10 0 10 

CH3(Bz) [d] 4.92e-13 6 7.00e-19 12 3.43e-11 12 

CH2(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 

CH3(NHx) [e] 1.67e-11 22 ~6.2e-14 24 [f] 

CH2(NHx) [e] 1.84e-11 22 ~4.4e-14 24 [f] 

CH(NHx) [e] 2.01e-11 23 ~9.9e-14 24 [f] 

NH2 1.41e-11 22 ~5.2e-14 24 [f] 

NH 3.17e-11 22 ~5.7e-14 24 [f] 

[a] Temperature dependences for OH rate constants given by k(T) = A BT exp(-D/T), where T is in oK. 

[b] Notes for derivations of the group rate constants and substituent correction factors are given below 

(Note [a] with Table 3b). 

[c] The temperature dependence of 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 3b. Group correction factors for abstraction reactions

Substitutent Correction Factor 

Group OH NO3 Cl 

Factor Note [a] Factor Note Factor Note 

CH3 1 1,2,14 1 17 0 14 

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

CHx(CO) 3.90 1,2 1.34 17 0.95 17 

CHx(CO-O) 1.23 1,2 1.34 17 0.95 17 

CHx(Cl) 0.36 1,2 1.34 17 0.19 19 

CHx(Br) 0.46 1,2 1.34 17 0.95 17 

CHx(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 

CO(OH) 0.74 1,2 0 12 0.04 17 
Table 3b (continued) 

22 

Substitutent Correction Factor 

Group OH NO3 Cl 

Factor Note [a] Factor Note Factor Note 

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) 3.90 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 

ONO2 0.04 1,2 0 12 0.12 

Bz 1 14 1 17 2.03 13 

NH2, NH, N 1 14 1 14 [b] 

[a] Notes for derivations of the group rate constants and group correction factors are as follows. (Note 

that the cited references are given by Carter (2007a) and are not in the reference list for this report 

unless they are relevant for the amines). 

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 IUPAC (2006) recommended rate constant and branching ratio for reaction of OH 

with methyl hydroperoxide. 

6 Average of estimated rate constants per methyl group for the alkylbenzenes for which aromatic 

aldehyde yields have been derived. Reaction 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 ethylbenene. 

8 Derived from the difference for the total rate constants for isopropylbenzene and toluene, and pcymene 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 isopropylbenzene and p-cymene. 

9 From Atkinson (1991). Derived from the correlation between NO3 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 made. By default, the system uses the same assignment as for standard 

CH3, CH2, or CH groups. 

13 Derived by Carter (2007a) from measured chlorine + VOC rate constants. 

14 Assigned. 

15 From Kwok et al (1996). 

16 Adjusted to fit OH + ethyl and propyl formate rate constants (Wallington et al, 1988) 
Table 3b (continued) 

23 

17 No assignment made. This is the default value used by the mechanism generation system, and 

may not be appropriate. 

18 This is the assignment incorporated into the current system. It may not be appropriate. It is not 

used as the basis for estimating NO3 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 amines and alcohol amines for 

which kinetic data are available, as indicated in Table 2. 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 NH2 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 CH3(NHx) and 

CH2(NHx). 

24 The only kinetic data concerning the reactions of NO3 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 HNO3. For lack of other 

data, use the rate constant for NMP as the basis for estimating the group rate constants for 

reaction at the -CH2(N) or CH3(N) groups. The group rate constants for reactions at other amine 

groups, including NH and NH2, are estimated assuming that the ratios of rate constants for 

reactions at the various groups are the same for the NO3 reaction as derived for the OH reaction. 

This is highly uncertain. 

[b] Group rate constants for reactions of chlorine with amines were not derived 

 RCH2NH· + O2 → HO2 + RCH=NH 

This is based on kinetic data obtained by Lindley et al (1979) for reactions of (CH3)2N· with O2, NO, and 

NO2, where the reaction with O2, forming HO2 + CH3-N=CH2, is calculated to dominate under 

atmospheric conditions. 

The subsequent reactions of the C=N products formed in these reactions 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 approximately represented by the 

generic reactive non-aldehyde oxygenated species PROD2. The appropriateness of this representation is 

highly uncertain. 

The above type of reaction cannot occur if the nitrogen-centered radical lacks an abstractable 

hydrogen in the α-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 (AMP). In these cases, the only expected reactions of the 

nitrogen-centered radical is reaction with NO, NO2, or HO2, e.g., 

 (CH3)3CNH· + NO → (CH3)3CNHNO (a) 

 (CH3)3CNH· + NO2 → (CH3)3CNHNO2 (b) 

 (CH3)3CNH· + HO2 → O2 + (CH3)3CNH2 (c) 
24 

Table 4. Assignments made for alkoxy radical intermediates predicted to be formed in the 

photooxidation mechanisms of the amines. 

Radical Reaction Assumed to Dominate 

·OCH2-NH2 + O2 HCO-NH2 + HO2· 

CH3-NH-CH2O· + O2 CH3-NH-CHO + HO2· 

.OCH2CH2-NH2 HCHO + .CH2-NH2

CH3CH(O·)NH2 + O2 CH3C(O)NH2 + HO2· 

CH3-N(CH3)CH2O· + O2 CH3-N(CH3)CHO + HO2· 

NH2CH(O·)CH2OH HCO-NH2 + .CH2OH 

CH3C(O·)(CH3)NH2 CH3C(O)NH2 + CH3· 

CH3C(CH3)(CH2O·)NH2 HCHO + CH3C(·)(CH3)NH2

CH3-N(CH2O·)CH2CH2OH CH3-N(CH2OH)CH2CH(·)OH 

CH3C(CH2O·)(NH2)CH2OH + O2 CH3C(CHO)(NH2)CH2OH + HO2· 

.OCH2CH2CH(NH2)CH2OH NH2CH(CH2CH2OH)CH(·)OH 

CH3-N(CH3)CH(O·)CH2OH CH3-N(CH3)CHO + .CH2OH 

CH3CH(O·)CH(NH2)CH2OH CH3CHO + NH2CH(·)CH2OH 

CH3CH2C(O·)(NH2)CH2OH CH3CH2C(O)NH2 + .CH2OH 

HOCH2CH2-NH-CH(O·)CH2OH HCO-NH-CH2CH2OH + .CH2OH 

CH3CH2-N(CH2CH3)CH2CH2O· CH3CH2-N(CH2CH2OH)CH(·)CH3

CH3CH2-N(CH2CH3)CH(O·)CH3 CH3CH2-N(CH2CH2·)CH(CH3)OH 

CH3CH2-N(CH2CH2O·)CH(CH3)OH CH3CH(·)N(CH2CH2OH)CH(CH3)OH 

CH3CH2-N(CH2CH2OH)CH(O·)CH3 CH3CH2-N(CH2CH(·)OH)CH(CH3)OH 

CH3CH(O·)N(CH2CH2OH)CH(CH3)OH CH3CH(OH)N(CH2CH(·)OH)CH(CH3)OH 

HOCH2CH2-N(CH2CH2OH)CH(O·)CH2OH HCO-N(CH2CH2OH)CH2CH2OH + .CH2OH 

CH3CH(OH)CH2-N(CH2CH(CH3)OH)CH2-

CH(CH2O·)OH 

HCHO + CH3CH(OH)CH2-N(CH2CH(·)OH)CH2CH-

(CH3)OH 

CH3CH(OH)CH2-N(CH2CH(CH3)OH)-

CH(O·)CH(CH3)OH 

CH3CH(OH)CH2-N(CHO)CH2CH(CH3)OH + 

CH3CH(·)OH 

If NOx is present, the major reaction is expected to be process (b), forming the nitramine, since the 

nitrosoamines formed in process (a) are expected to undergo rapid photolysis back to NO and the radical, 

resulting in no net reaction. Since nitramine formation is a radical terminating 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 major 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, as 

discussed in the Mechanism Evaluation Results section, below. 

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 α position. This species is 

representing as reacting with NO2 to form a nitramine, with a rate constant estimated by assuming that it 

is the same as for the reaction of NO2 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 nitrosoamine to reverse the reaction. In the 

absence of NOx, the NRAD is represented as reacting with HO2 to re-form the amine, with a rate constant 
25 

assumed to be the same as used for the reaction of RCO3 with HO2. Because of the way the mechanism is 

implemented it is 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. 

Table A-1 in Appendix A gives the mechanisms that were derived for the reactions of the OH 

radicals with amines based on these assumptions and representations. 

Reaction with NO3 Radicals 

The only kinetic data concerning the reactions of NO3 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 was 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 HNO3. For lack of other data, we use the rate 

constant for NMP as the basis for estimating the group rate constants for reaction at the -CH2(N) or 

CH3(N) groups. The group rate constants for reactions at other amine groups, including NH and NH2, are 

estimated assuming that the ratios of rate constants for reactions at the various groups are the same for the 

NO3 reaction as derived for the OH reaction. This is highly uncertain. 

These assumptions were used as the basis for deriving group-additivity estimates for H-atom 

abstraction reactions of NO3 radicals with amines, as indicated on Table 3, above. For completeness, that 

table also gives group-additivity parameters for other H-atom abstractions by NO3 from other groups as 

implemented in the current mechanism generation system. These were used for deriving rate constants 

and initial branching ratios for the reactions of NO3 with all the amines used in the current study. These 

estimated rate constants are included in Table 2, above. 

The radicals formed in the H-atom abstraction reactions that are assumed to be formed in the 

initial NO3 + amine reactions are the same as those formed in the OH system. The representations of 

those reactions, and of the products formed, have been already discussed above. The mechanisms so 

derived are given in Table A-1 in Appendix A. 

Reactions with Ozone 

The limited available kinetic data concerning the reaction of O3 with amines are given in Table 2, 

above. The rate constant for methylamine is too low to be important under atmospheric conditions, but the 

rate constants for the other compounds are sufficiently high that O3 reaction may be non-negligible, 

though probably not dominant, under atmospheric conditions. Therefore, the possible reactions of O3 with 

amines need to be taken into account when deriving atmospheric mechanisms for these compounds. 

Although some product data were obtained in the study of Tuazon et al (1994), the mechanism is 

uncertain, though the products they observed were similar to those observed or expected from the OH 

reaction. Murphy et al (2007) studied aerosol-phase products of the reactions of trimethyl amine with O3

and observed similar aerosol phase products in the O3 reaction as formed in the NOx-air photooxidations 

of the amine, which are expected to be dominated by the OH reaction. If O-addition reactions occur, the 

adduct formed must eventually decompose to form products similar to those formed in H-abstraction 

reactions, otherwise different types of products would be observed in O3 reactions as formed in OH 

reactions or photooxidations. The relatively high rate constants for the reaction of O3 with trimethyl 

amine and DMAE, and the low rate constant for methylamine, suggests that abstraction from N-H bonds 

is probably not the major process. 
26 

Based on these considerations, for rate constant and mechanism estimation purposes we assume 

that the initial reaction of O3 with amines is at the group next to the amino group, ultimately resulting in 

abstraction from α C-H bonds, forming OH radicals and the same types of radicals as formed in the OH 

reaction, e.g., 

 CH3NH2 + O3 → [adduct?] → O2 + OH + ·CH2NH2

This is consistent with the fact that similar products appear to be formed in the O3 as the OH reaction, and 

is also reasonably consistent with the fact that the O3 + amine rate constant data are well correlated with 

the estimated rate constant for reaction of OH radicals at the group next to the amino group, with the 

correlation being better than the correlation of the O3 rate constant to the total rate constant. This is shown 

on Figure 2, where it can be seen that the O3 rate constants are better correlated to the rate constant for 

OH abstraction from the adjacent group than to the total OH radical rate constant. 

The correlation between the estimated rate constants for reaction of OH with the group next to the 

amino groups and the total O3 rate constants were used as the basis for estimating the rate constants for 

reactions of O3 at these groups, forming OH, O2, and the corresponding H-abstraction radical. The data 

for the methylamines and DMAE were fit by 

 K(group,O3) = 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 was used as the basis for estimating both total O3 rate constants and 

relative rates of reaction at different positions (secondary or tertiary amines) that have non-equivalent 

substituents. The O3 rate constants so derived are given in Table 2, above, where it can be seen that the 

measured values are predicted within a factor better than 2. 

The radicals formed in these O3 reactions are assumed to be the same as formed when OH 

abstracts from the C-H bond in the group adjacent to the amino group, and the representations of their

16.5

17.5

18.5

19.5

20.5

10.0 10.2 10.4 10.6 10.8 11.0

- Log10 k(OH) (cm3

 molec-1 s-1)

- Log 10 k(O3)

Relative to total OH rate

constant

Relative to OH reaction at

alpha position

Best fit line to above

Figure 2. Plots of logs of the rate constants for the reactions of the methylamines and DMAE with 

O3 against the logs of the rate constants for reaction of OH radicals at the group next to 

the amino group and also against the total OH rate constant. 
27 

subsequent reactions, and of the products formed, are the same as used for the OH radical reactions, 

discussed above. The mechanisms so derived are given in Table A-1 in Appendix A. 

Reactions with HNO3

Amines are basic compounds that can react with HNO3 to form amine salts, which are nonvolatile 

and partition into the aerosol phase, making the amine unavailable for reaction in the gas phase. However, 

this reaction is reversible and an equilibrium exists between the salt, and the amine and HNO3. This 

means that under sufficiently low amine or HNO3 concentrations, or if other basic species such as NH3

are present to compete with the HNO3, or there are other important loss processes for the amine or HNO3, 

then the salt formation may be less important in affecting the availability of the amine to react in the gas 

phase. The equilibrium constants for amine salt formation are too uncertain to be useful for estimating 

availability based on theoretical equilibrium considerations (Murphy et al, 2007). Aerosol amine salt 

formation from reactions of amines with HNO3 in environmental chamber experiments under simulated 

atmospheric conditions has been studied by Murphy et al (2007), who found that aerosol amine salt 

formation occurs rapidly when the gas-phase amine and HNO3 are present at concentrations of ~100 ppb. 

However, they also found that the amine salt aerosol formation eventually declined relatively under 

conditions where the amine can undergo gas-phase reactions, such as when O3 is added or photooxidation 

in the presence of NOx. This suggests that revolatilization may be important under atmospheric 

conditions, and because of the relatively high gas phase reactivity of the amines, the amine salt formation 

may not be a permanent sink for the amine under conditions where O3 formation can occur. In addition, if 

excess NH3 is present in the environment, it may compete with the amine for nitrate salt formation, 

making loss of the amine to salt formation less important. 

Model simulations of the environmental chamber experiments carried out for this project were 

found not to be sensitive to assumptions made concerning the loss of amines by reaction with gas-phase 

HNO3. Model calculations assuming rapid (and irreversible) loss of the amine due to reaction with HNO3

gave essentially the same results in terms of calculations of O3 and other measured gas-phase species as 

those assuming no reaction between the amine and HNO3. This is because the amount of HNO3 calculated 

to be formed in the gas-phase reactions of NOx is small compared to the amount of amine injected. 

Therefore, the chamber experiments are not useful for assessing whether loss of amines due to this 

reaction may be important under atmospheric conditions. 

On the other hand, as discussed in the Atmospheric Reactivity Results section, below, in the 

model simulations of the ozone impacts of the amines in the box model, atmospheric scenarios used for 

calculation of the ozone reactivity scales (Carter, 1994a, 2000a, 2007a) are highly sensitive to 

assumptions made concerning the loss of the amine due to reaction with HNO3. The impact in the real 

atmosphere depends on the magnitudes of HNO3 sources and sinks, the amounts of other amines or 

ammonia present to compete with the HNO3, and the amine salt equilibrium constants, which are 

unknown. At present, there is insufficient information available to quantify these impacts, or even to 

assess which of these extremes is most likely to be representative of ozone exceedances in California. 

Because of these uncertainties, atmospheric reactivity assessment calculations are carried out 

assuming either no amine + HNO3 reaction, or assuming that the reaction is rapid and irreversible. The 

latter simulations use an amine + HNO3 rate constant of 4 x 10-11 cm3

 molec-1 s-1, which is a high rate 

constant representative of radical + radical reactions. The product formed is assumed to be unreactive in 

these upper limit calculations. The actual rate constants are unknown but probably less than this value, 

which is considered appropriate for upper limit analyses only. 

As indicated above, the environmental chamber simulations are not sensitive to assumptions 

concerning the rate or reversibility of the amine + HNO3 reaction. However, because the results of the 
28 

model simulations of the added amine experiments indicate that not all the injected amine is available for 

reaction in the gas phase, most of the chamber simulations are based on the assumption that the amine + 

HNO3 reaction is rapid and irreversible. 

Mechanism for d-Limonene 

The mechanism used for d-limonene in this work is the same as that given with the SAPRC-07 

mechanism as documented by Carter (2007a). This was derived using the SAPRC-07 mechanism 

estimation and generation system, incorporating the measured rate constants for its various atmospheric 

reactions. The reactions and rate constants are given in Table A-1 in Appendix A, with footnotes to the 

table indicating the sources of the rate constants used. Because the SAPRC-07 limonene mechanism 

performed reasonably well in simulating the new limonene experiments carried out for this project, this 

mechanism was not changed as a result of this work. 

Mechanisms for Other VOCs. 

The consumer products compounds for which mechanisms and/or ozone reactivity estimates have 

been added as part of this project are summarized on Table 5. In addition to the amines, discussed above, 

these include a number of other compounds found in consumer products speciation surveys for which 

reactivity estimates are needed by the CARB staff. The table indicates how the mechanisms were derived 

or, for compounds represented using the "lumped molecule approach", the compound or model species 

assumed to have the same ozone impact on a per-molecule basis. The reactions and rate constants for the 

compounds that were represented explicitly are given in Table A-1 in Appendix A, and footnotes to the 

table give more information how the mechanisms and/or rate constants were estimated. Table A-2 

summarizes the lumped molecule representations used, for compounds where this is applicable. 

The CARB staff also requested ozone impacts for other compounds found in consumer product 

speciation surveys for which ozone impacts have not yet been derived. These are also listed in Table 5, 

along with the reasons why we were unable to derive mechanisms or assignments for those compounds. 

Atmospheric Reactivity Simulations 

Atmospheric reactivity model simulations were carried out to derive MIR and other atmospheric 

reactivity values for the selected compounds whose ozone impacts were evaluated for this project. The 

scenarios and methods used were the same as those used when calculating the MIR and other atmospheric 

ozone reactivity scales, and were described previously (Carter, 1994a,b 2000a, 2007). The base ROG 

constituents were represented using the lumping procedures incorporated in the condensed version of the 

SAPRC-07 mechanism (Carter, 2007a), and individual compounds whose reactivities were being assessed 

were represented explicitly. The mechanisms used for the compounds studied in this project are discussed 

above and also given in Table A-1 in Appendix A. 

Note that the impact of the reactions of amines with HNO3 under atmospheric conditions is very 

uncertain, and for that reason the atmospheric reactivity calculations were carried out using only upper 

and lower limit assumptions in this regard. The effects of assumptions regarding the importance of amine 

removal are shown in the Atmospheric Reactivity Calculation Results section, below. 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 tabulated atmospheric reactivity values given in the Atmospheric Reactivity 

Calculation Results section were derived based on calculations assuming that loss by reaction with HNO3

is negligible. 
29 

Table 5. List of compounds whose reactivities have been added to the SAPRC-07 reactivity 

tabulation or whose reactivities have been requested by the CARB. 

Compound CAS No. Mechanism Derivation Method or Representation 

Amines for which mechanisms were derived 

Methylamine 74-89-5 

Dimethyl amine 124-40-3 

Ethyl amine 75-04-7 

Trimethyl amine 75-50-3 

Isopropylamine 75-31-0 

t-Butyl amine 75-64-9 

Triethyl amine 121-44-8 

Ethanolamine 141-43-5 

Dimethylaminoethanol 108-01-0 

2-Amino-1-butanol 96-20-8 

2-Amino-2-methyl-1-propanol 124-68-5 

Diethanol amine 111-42-2 

Triethanolamine 102-71-6 

Triisopropanolamine 122-20-3 

The mechanisms were derived based on work for this 

project as discussed in this report. Reactions and rate 

constants as implemented in the SAPRC-07 

mechanism are given in Table A-1 in Appendix A. The 

atmospheric ozone impacts of these compounds 

depend on the extent to which they are removed by 

reaction with HNO3, which is highly uncertain. In 

order to provide an upper limit estimate of the ozone 

impacts of these compounds under conditions where 

they will have their highest impacts, the tabulated 

atmospheric reactivity values were derived based on 

calculations assuming that loss by reaction with HNO3

is negligible. If loss by this process is important, the 

magnitude of the ozone impact may be more than an 

order of magnitude lower. 

Other Compounds whose mechanisms were added 

Tripropylene glycol 24800-44-0 

Diethylene glycol mono(2-

ethylhexyl) ether 

1559-36-0 

Tripropylene glycol n-butyl 

ether 

55934-93-5 

Triethyl citrate 77-93-0 

2,2,4-Trimethyl-1,3-

pentanediol diisobutyrate 

6846-50-0 

Citronellol (3,7-dimethy-6-

octen-1-ol) 

106-22-9 

Linalool 78-70-6 

Geraniol 106-24-1 

Hydroxycitronellal 107-75-5 

The mechanisms were derived using the SAPRC-07 

mechanism generation system without modifications or 

new explicit assignments. The reactions and rate 

constants as implemented in SAPRC-07 are listed in 

Table A-1 in Appendix A. 

 

Terpinolene 586-62-9 

1-Nitropropane 108-03-2 

Methyl nonafluorobutyl ether 163702-07-6 

Ethyl nonafluorobutyl ether 163702-05-4 

The mechanisms were derived using the SAPRC-07 

mechanism generation system without modifications 

except that the dominant reaction pathways for some 

radicals had to be assigned based on mechanism 

generation estimates for similar radicals. The reactions 

and rate constants as implemented in SAPRC-07 are 

listed in Table A-1 in Appendix A. 

2-Ethylhexyl benzoate 5444-75-7 

Ethyl methyl ketone oxime 96-29-7 

Mechanism estimated. The reactions and rate constants 

as implemented in SAPRC-07 are listed in Table A-1 

in Appendix A. Footnotes to the table indicate the 

estimation methods used. 
Table 5 (continued) 

30 

Compound CAS No. Mechanism Derivation Method or Representation 

Methyl iodide 74-88-4 Mechanism of Carter (2007b) used. The reactions and 

rate constants as implemented in SAPRC-07 are also 

listed in Table A-1 in Appendix A. Footnotes to the 

table give the sources of the rate constants and 

estimates. 

Compounds represented using the "Lumped Molecule" approach (assumed to 

have the same ozone impact per molecule emitted as another compound or 

model species) 

Hexyl cinnamal 101-86-0 

Cinnamic aldehyde 104-55-2 

Amyl cinnamal 122-40-7 

Assumed to have the same per-molecule reactivity as 

the lumped c5+ unsaturated carbonyl model species 

(ISOPROD) used to represent these products in the 

isoprene mechanism. 

4-Vinylphenol 2628-17-3 Assumed to have the same per-molecule reactivity as 

styrene 

Methylparaben (4-Hydroxy 

benzoic acid, methyl ester) 

99-76-3 

Propylparaben 94-13-3 

2,6-Di-tert-butyl-p-cresol 128-37-0 

Assumed to have the same per-molecule reactivity as 

o-cresol 

 

Beta-phenethyl alcohol 98-85-1 Assumed to have the same per-molecule reactivity as 

benzyl alcohol 

Cinnamic alcohol 104-54-1 

Anethol 104-46-1 

Assumed to have the same per-molecule reactivity as 

ß-methyl styrene 

Triethylene diamine 280-57-9 Assumed to have the same per-molecule reactivity as 

triethyl amine 

Lauryl pyrrolidone 2687-96-9 Assumed to have the same per-molecule reactivity as 

n-methyl-2-pyrrolidone. 

o-Dichlorobenzene 95-50-1 Assumed to have the same per-molecule reactivity as 

p-dichlorobenzene 

2-Chlorotoluene 95-49-8 Assumed to have the same per-molecule reactivity as 

toluene 

Methyl nonafluoroisobutyl 

ether 

163702-08-7 

Ethyl nonafluoroisobutyl ether 163702-06-5 

Assumed to have the same per-molecule reactivity as 

the corresponding nonafluorobutyl ether. 

Compounds requested by the CARB staff for which mechanisms were not 

derived because the compounds are estimated to have very low ozone impacts. 

HCFC-225ca 422-56-0 

HCFC-225cb 507-55-1 

HFC 43-10mee 138495-42-8 

HFC-245fa 460-73-1 
Table 5 (continued) 

31 

Compound CAS No. Mechanism Derivation Method or Representation 

Compounds requested by the CARB staff for which mechanisms were not 

derived because there was insufficient time and resources available in the project 

to derive estimated mechanisms. (It may be possible to develop estimated 

mechanisms for these compounds, but reactivity estimates would be highly 

uncertain) 

Acetamide MEA (N-acetyl 

monoethanolamine) 

142-26-7 

Benzyl benzoate 120-51-4 

Benzyl salicylate 118-58-1 

Butylphenyl methylpropional 

(Lillac-synthetic fragrance) 

80-54-6 

Compounds requested by the CARB staff for which mechanisms were not 

derived because their mechanisms are too uncertain to estimate 

Acetic acid benzyl ester 140-11-4 

Benzophenone-3 131-57-7 

Benzophenone-4 4065-45-6 

Benzyl nicotinate 94-44-0 

Beta-myrcene 123-35-3 

Biotin (Vitamin H or B7) 58-85-5 

Butetamate (Buteth-3) 14007-64-8 

Butylparaben 94-26-8 

Coumarin 91-64-5 

Ethylparaben 120-47-8 

Eugenol 97-53-0 

Isobutylparaben 4247-02-3 

Isoeugenol 97-54-1 

L-Cysteine (2-amino-3-sulfanylpropanoic acid) 52-90-4 

Musk ketone 81-14-1 

Musk xylene 81-15-2 

Niacinamide (Vitamin B3) 98-92-0 

 

Pantothenic acid (Vitamin B5) 79-83-4 

Phenyl trimethicone (Methyl 

phenyl polysiloxane) 

2116-84-9 

Vanillin 121-33-5 

Compounds requested by the CARB staff that are probably sufficiently low in 

volatility that they may not have significant ozone impacts. They probably 

should not be included in VOC emissions inventories. 

Adenosine triphosphate 56-65-5 

Alpha Olefin sulfonate 68439-57-6 

Ammonium benzoate 1863-63-4 

Ascorbic acid (Vitamin C) 50-81-7 

Di-2-ethylhexyl sebacate 122-62-3 

Di-n-butyltin dilaurate 77-58-7 
Table 5 (continued) 

32 

Compound CAS No. Mechanism Derivation Method or Representation 

Dioctyl Sodium Sulfosuccinate 577-11-7 

Ethylene diamine tetraacetic acid 60-00-4 

Ethylhexyl salicylate (octyl 

salicylate) 

118-60-5 

Lauramide DEA 120-40-1 

Mixed fatty acid methyl esters, 

C16 - C18 

67762-38-3 

Myristic acid (C14 fatty acid) 544-63-8 

Octyl methoxycinnamate 5466-77-3 

Oleic acid 112-80-1 

Palmitic acid (C16 fatty acid) 57-10-3 

Pyridoxine hydrochloride 

(Vitamin B6) 

58-56-0 

Sodium benzoate (Benzoic acid, 

sodium salt) 

532-32-1 

Sodium lauroyl sarcosinate 

(sodium salt (8CI)) 

137-16-6 

Sodium PCA (monosodium salt) 28874-51-3 

Stearic acid 57-11-4 

Compounds or mixtures requested by the CARB staff for which we were unable 

to determine the chemical composition or structure. 

Cedarwood (Cedrus Atlantica) 

Oil 

68990-83-0 

Chlorinated paraffin solvent 63449-39-8 

4,4-(Oxydi-2,1-ethanediyl) 

bismorpholine 

6425-39-4 

Cocamide DEA 68603-42-9 

Diethyltoluenediamine 

(DETDA) 

68479-98-1 

Dimethyl lauramine isostearate 70729-87-2 

HFC-365mfc 406-58-6 

Lauryl lactate 6283-92-7 

MEA borate; monoethanolamine 

borate 

68130-12-1 

MIPA borate; 

monoisopropanolamine borate 

68003-13-4 

Panthenyl ethyl ether (N-(3-

Ethoxypropyl)-2,4-dihydroxy3,3-dimethylbutyramide) 

667-83-4 

Soy methyl esters 

Trimethylolpropane trioleate 68002-79-9 

Trimethylolpropane trioleate 

polyol ester 

57675-44-2 

 
33 

RESULTS AND DISCUSSION 

Summary of Experiments and Characterization Results 

A chronological listing of the environmental chamber experiments carried out for this project is 

given in Table B-1 in Appendix B. These included experiments with the test compounds of interest for 

this study and appropriate characterization and control experiments needed for the data to be useful for 

mechanism evaluation. The results of the mechanism evaluation experiments are discussed in the 

Mechanism Evaluation Results section, below. The characterization results are discussed in the remainder 

of this section. 

The results of the individual characterization experiments that are relevant to the experiments for 

this project are summarized in the “Results” column of Table B-1. The initial characterization 

experiments relevant this chamber are described in detail by Carter (2004) or by Carter and Malkina 

(2005) or Carter et al (2005b), and thus need not be discussed further here. Characterization results 

specific to this project are discussed below. 

Blacklight Characterization 

Because of problems with the arc light source during the period of this project, all of the 

experiments for this project were carried out using the blacklight light source. Methods for characterizing 

the intensity of the blacklight light source were discussed by Carter et al (2005b), though some revisions 

were made as a result of subsequent measurements. As with the arc light source, NO2 actinometry 

measurements were made using the quartz tube method of Zafonte et al (1977), modified as discussed by 

Carter et al (1995b), with the quartz tube both inside the reactors and also in front of the reactors. As 

discussed by Carter et al (2005b), the results of these measurements, and other measures of light intensity, 

indicated a steady decline in light intensity with time, with the results being best correlated with the 

“blacklight run count”, which is the number of experiments carried out in the chamber using the 

blacklights, and is thus an indicator of the ageing of the lights due to use. A plot of the results of the inand out-of-reactor actinometry measurements against run count for UCR EPA experiments carried out 

using the blacklight light source is shown on Figure 3. 

The actinometry measurements made in front of the reactor as shown on Figure 3 are corrected by 

a factor of 0.698 to give an estimate of the corresponding light intensity inside the reactor. As discussed 

by Carter et al (2005b), this was derived from near-simultaneous actinometry measurements made both 

inside and in front of the reactor. Both measurements show similar declines in intensity with time, though 

the measurements in front of the reactor are more comprehensive because of the larger number of 

measurements and the larger period of time for which measurements were made. 

The actinometry measurements using the blacklight lights source are reasonably well fit by the 

following empirical expression, where k1 is the NO2 photolysis rate in min-1: 

 k1 = 0.0958 x [1 + exp(-Blacklight Run Count x 0.003914)] (I) 

The parameters in Equation (I) were derived to minimize sum-of-squares errors in predictions of both the 

in-reactor actinometry measurements and the in-front-of-reactor measurements corrected by a factor of 

0.698. This equation was used to derive the NO2 photolysis rates used when modeling the blacklight 

experiments modeled for this project. Figure 3 indicates the range of blacklight run counts that is 

applicable to the experiments for this project. 
34 

0.10

0.12

0.14

0.16

0.18

0.20

0 100 200 300 400

Blacklight Run Count

NO2 Photolysis Rate (min-1)

In Reactor Measurements

Enclosure Measurements (corrected)

Best fit to data

Runs for this project

Figure 3. Plots of light intensity data used to assign NO2 photolysis rates for the blacklight light 

source. 

The spectrum of the blacklights in this chamber has been measured periodically and continues to 

be essentially the same as the spectrum recommended by Carter et al (1995b) for modeling blacklight 

chamber runs. 

Chamber Effects Characterization 

Except as discussed below, the characterization results for the more recent experiments for this 

project are consistent with those discussed by Carter et al (2005b) and Carter and Malkina (2005, 2007), 

and the same characterization parameters were used for modeling. The most important chamber effect, 

and the only chamber effect parameter that was changed when modeling the experiments for this project, 

concerns the apparent HONO offgasing, which is believed to be responsible for both the chamber radical 

source and NOx offgasing effects (Carter, 2004). This is represented in the chamber effects model by the 

parameter RN-I, which is the HONO offgasing rate used in the simulations divided by the light intensity 

as measured by the NO2 photolysis rate. Figure 4 shows the HONO offgasing parameters that best fit the 

radical or NOx - sensitive characterization experiments carried out in the UCR EPA during the period of 

the last three sets of reactors. Note that the experiments carried out for this project start at run EPA777, so 

the applicable characterization data for this project is for the last set of reactors shown on the figure. 

For the runs carried out for this project, which were all in the newest set of reactors installed after 

run 683, the RN-I value used for both reactors was 15 ppt, the average of the measured values for the 

applicable characterization runs. The values assigned for modeling the runs in the last three sets of 

reactors are indicated on Figure 4. 

Side equivalency test experiments, in which the same mixture is irradiated in both reactors, are 

carried out periodically as controls for the incremental reactivity experiments. Generally good side 

equivalency is observed for the gas-phase results, though sometimes one reactor is more favorable for 

particle formation than the other (Carter et al, 2005b). The results of the side equivalency test 
35 

0

5

10

15

20

25

350 400 450 500 550 600 650 700 750 800

EPA Run Number

HONO Input Parameter (RN-I) (ppt)

Radical sensitive (Side A)

Radical sensitive (Side B)

NOx sensitive (Side A)

NOx sensitive (Side B)

Used in Model (Side A)

Used in Model (Side B)

Replaced Reactors

Figure 4. Plots of best fit HONO offgasing parameters against UCR EPA run number. 

experiment carried out during this project were similar, and are discussed below in conjunction with the 

incremental reactivity experiments with the added test compounds.

Background PM Characterization 

Although the primary objective of this project was to obtain data on ozone impacts, particulate 

matter (PM) volume number measurements were made in conjunction with the experiments that were 

carried out. The results of the initial PM characterization experiments in this chamber were discussed by 

Carter et al (2005a,b). The most useful PM background characterization experiments are pure air 

irradiations, where small but measurable PM formation is generally observed. This is apparently due to 

reaction of OH radicals with some PM precursor, since no PM formation is observed in CO - air or NOx - 

air irradiations, where the presence of the added CO or NOx tend to suppress the OH radical levels. 

Because of this, pure air irradiations continue to be carried out for the purpose of characterizing 

background PM levels, including experiments around the time of the mechanism evaluation experiments 

for this project. 

Plots of the 5-hour PM volume levels measured in this chamber since the time that routine PM 

measurements began are shown on Figure 5. (Data from runs with 5-hour PM volume of greater than 1.5 

μg/m3

, which includes some early runs in the first set of reactors; and run EPA796 carried out during this 

program, which appears to be anomalously contaminated, are not shown.) As discussed by Carter et al 

(2005a,b), for the first two sets of reactors the background PM level was consistently higher in Side A 

than in Side B, with the background in Side B being quite low. However, for the third set of reactors, the 

PM levels were essentially the same on both sides, at about the low range of the level of Side A in the 

previous sets of reactors. For the fourth set of reactors, those used for the runs for this project, the 

background PM levels were lower, being comparable to those found on Side B in the first two reactors, 

though the PM levels were somewhat lower on Side B than on Side A. This background PM level is small 

compared to that formed in the incremental experiments with the added test compounds, and thus should 

not significantly alter conclusions of this study concerning relative PM impacts of the various compounds 

that were studied. 
36 

5-Hour PM volume (ug/m3

)

0.0

0.5

1.0

1.5

150 250 350 450 550 650 750 850

Run Number

Side A Reactors Changed

Side B Runs for this project

Figure 5. Plots of 5-hour PM volume measurements in pure air experiments the EPA chamber 

against EPA run number. 

Gas-Phase Mechanism Evaluation Results 

Table 6 lists the initial concentrations and selected gas-phase results for the incremental reactivity 

experiments carried out for this project. For comparison, the results of the side equivalency test 

experiment, which had no added reactants, are also shown. The measures of gas-phase reactivity used to 

evaluate the mechanisms in the incremental reactivity experiments are the effects of the test compound or 

solvent on ∆([O3]-[NO]), or ([O3]t-[NO]t)-([O3]0-[NO]0), and IntOH, the integrated OH radical levels. As 

discussed elsewhere (e.g., Johnson, 1983; Carter and Atkinson, 1987; Carter and Lurmann, 1991, Carter 

et al, 1993), ∆([O3]-[NO]) gives a direct measure of the amount of conversion of NO to NO2 by peroxy 

radicals formed in the photooxidation reactions, which is the process that is directly responsible for ozone 

formation in the atmosphere. This gives a useful measure of factors affecting O3 reactivity even early in 

the experiments where O3 formation is suppressed by the unreacted NO. Although this is the primary 

measure of the effect of the VOC on O3 formation, the effect on radical levels is also a useful measure for 

mechanism evaluation, because radical levels affect how rapidly all VOCs present, including the base 

ROG components, react to form ozone. 

The integrated OH radical levels are not measured directly, but can be derived from the amounts 

of consumption of reactive VOCs that react only with OH radical levels. In particular, 

tracer

0 t

t kOH

ln([tracer] [tracer] ) Dt IntOH − = (II) 

where [tracer]0 and [tracer]t are the initial and time t concentrations of the compound used as the OH 

tracer, kOHtracer is its OH rate constant, and D is the dilution rate in the experiments. The latter is small in 

our chamber and is neglected in our analysis. For these experiments, the base ROG surrogate component 

m-xylene is the most reactive compound in the experiment that reacts only with OH radicals, and was 

therefore used as the OH tracer to derive the IntOH data. The m-xylene OH radical rate constant used in 

this analysis was 2.36x10-11 cm3

 molec-1 s-1 (Atkinson, 1989). 
37 

Table 6. Summary of initial concentrations and selected gas-phase results of the incremental 

reactivity experiments. 

Test VOC 

Added (ppb) [b] 

Base Run Initial 

Concentrations Final O3 (ppb)

D([O3]-[NO]) 

Change (ppb) 

IntOH 

Change Run Test 

Side 

Type 

[a] Calc Adj NOx

(ppb) 

ROG 

(ppmC)

Hours 

Light 

[c] Test Base 2 Hr Final (ppt-min)

Side Equivalency Test 

785 A MIR - 29 0.55 6 81 79 -2 2 2 

AMP (calculated and adjusted amounts addded) 

799 A MIR 64 20 28 0.56 5 32 64 -19 -35 -17 

782 A MIR 525 30 29 0.60 5 16 61 -21 -51 -24 

781 A MIR 536 25 29 0.50 5 14 48 -18 -42 -23 

792 A MOIR/2 52 10 16 1.05 5 64 69 -31 -5 -6 

789 B MOIR/2 53 25 25 1.15 5 72 104 -47 -32 -15 

783 A MOIR/2 105 35 25 1.21 5 67 100 -53 -33 -12 

784 A MOIR/2 105 40 25 1.08 5 59 100 -57 -40 -15 

Ethanolamine (calculated and adjusted amounts added) 

780 A MIR 100 70 33 0.50 3 71 24 42 50 1 

790 A MIR 101 5 30 0.58 6 81 81 -1 -1 0 

791 A MOIR/2 53 15 25 1.16 5 90 100 1 -11 -5 

798 A MOIR/2 101 20 29 1.34 5 92 96 4 -7 -1 

805 A MOIR/2 250 50 24 1.09 5 81 95 9 -16 -10 

Isopropyl amine (calculated and adjusted amounts added) 

807 A MOIR/2 252 100 22 1.18 6 106 97 34 9 -10 

t-Butyl amine (calculated and adjusted amounts added) 

806 A MOIR/2 251 140 22 1.09 5 13 95 -62 -86 -21 

d-Limonene (measured amounts added) 

797 A MIR 26 25 0.60 5 77 65 22 11 -10 

793 A MIR 35 29 0.58 5 99 62 46 36 -5 

804 A MOIR/2 23 19 1.08 6 83 89 10 -6 -4 

[a] Codes for types of base case experiments for the incremental reactivity experiments are as follows: 

“MIR”: ~30 ppb NOx and ~0.55 ppmC ROG surrogate; “MOIR/2”: ~25 ppb NOx and ~1.1 ppmC 

ROG surrogate. 

[b] For the amines, the initial concentrations calculated from the amount of liquid injected are given in 

the "Calc" column, and the initial concentrations that gave the best fit of model simulations to the 

data are given in the "Adj" column. For d-limonene, the measured initial concentrations, which are 

consistent with the calculated amounts injected, are given. 

[c] Hours of irradiation for which O3 and ∆([O3]-[NO]) data are available. 
38 

A series of d-limonene - NOx experiments were also carried out for the purpose of providing 

additional mechanism evaluation data for that compound. The results of those experiments are discussed 

in conjunction of the mechanism evaluation results for those compounds. 

Amines 

 The amines whose ozone impacts were experimentally studied for this project consisted 

primarily of 2-amino-2-methyl-1-propanol (AMP) and aminoethanol, though one experiment each was 

carried out for t-butyl amine and isopropyl amine. The first two were studied because they are important 

in consumer products inventories, while the latter two were studied to provide additional data to evaluate 

the general mechanism estimation approach. Conditions and selected gas-phase results of the incremental 

reactivity experiments are shown on Table 6 and experimental and calculated concentration-time plots for 

selected species are shown on Figure 6 and Figure 8 for AMP and on Figure 7 and Figure 9 for the other 

amines. 

It was immediately apparent that AMP is a strong inhibitor of the gas-phase reactions, since its 

addition caused a significant slowing of O3 formation, NO oxidation and integrated OH radical levels in 

all experiments. This was also observed with t-butyl amine, but not for aminoethanol and isopropyl 

amine, both of which tended to enhance rates of NO oxidation and O3 formation (at least initially) in most 

experiments. The strong inhibition characteristics of AMP was not expected based on the initially 

estimated mechanisms that assumed that reactions at the amino group were unimportant, but is consistent 

with the mechanism derived in this work, as described above. The inhibiting characteristics of AMP and 

t-butyl amine are attributed to the fact that these compounds lack abstractable hydrogens in the position 

next to the amino group, which means that they have no significant radical propagation pathways 

available following the reactions of OH radicals with the amino group. 

The estimated amine mechanisms developed in this work were qualitatively consistent with the 

results of the reactivity experiments, in that they predicted that AMP and t-butyl amine were strong 

inhibitors; while the other two had a generally positive effect on initial O3 formation and NO oxidation 

rates, and relatively small effects on integrated OH levels. 

However, quantitative mechanism evaluation using the amine experiments was complicated by 

the fact that we were unable to develop a useful quantitative gas-phase analysis method for amines for 

this project, so the amounts of amines injected into the gas phase in these experiments could not be 

determined experimentally, and was therefore uncertain. The amount of compound in the gas phase can 

be estimated from the measured amount of liquid injected, assuming complete injection of all the 

material, and loss of the materials on the wall. This approach has been successfully employed in 

experiments with complex hydrocarbon mixtures such as petroleum distillates used in coatings (Carter 

and Malkina, 2005) and kerosene (Carter and Malkina, 2007). But if this is assumed in the case of the 

amines, then, as shown on Figure 6 and Figure 7, the model significantly overpredicts the effects of the 

amines on NO oxidation and O3 formation in essentially all the amine experiments, both in a negative 

sense for AMP and t-butyl amine, and in a positive sense for aminoethanol and isopropyl amine. 

Although the possibility that this is due to mechanism problems cannot be completely ruled out, the much 

more likely explanation is that only a fraction of the injected amine is making it to the gas phase in the 

experiments, the remainder being lost either to the walls of the reactors or to the injection lines. PM 

formation during injection is probably not playing an important role, since as discussed below no 

significant PM formation occurred in the added amine experiments until the irradiation began. 

In order to obtain at least approximately satisfactory fits of model simulations to the chamber 

data, it is necessary to adjust the initial gas-phase amine concentration for each added amine experiment. 

The best fit concentrations are summarized on Table 6, and the results of the model calculations using 
39 

EPA781A EPA782A EPA799A

MIR MIR MIR

∆(O3-NO) (ppm) vs Hour

IR ∆(O3-NO) (mole basis) vs Hour

IR IntOH (ppt-min/ppm) vs Hour

EPA783A EPA784A EPA789B EPA792A

MOIR/2 MOIR/2 MOIR/2 MOIR/2

∆(O3-NO) (ppm) vs Hour

IR ∆(O3-NO) (mole basis) vs Hour

IR IntOH (ppt-min/ppm) vs Hour

0.00

0.02

0.04

0.06

0.08

0123456

-0.16

-0.12

-0.08

-0.04

0.00

0.04

0123456

-50

-40

-30

-20

-10

0

0123456

0.00

0.02

0.04

0.06

0.08

0.10

0123456

-0.20

-0.15

-0.10

-0.05

0.00

0.05

0123456

-60

-40

-20

0

20

0123456

0.00

0.02

0.04

0.06

0.08

0.10

0123456

-1.2

-0.8

-0.4

0.0

0.4

0123456

-500

-400

-300

-200

-100

0

0123456

0.00

0.04

0.08

0.12

0123456

-1.0

-0.8

-0.6

-0.4

-0.2

0.0

0123456

-160

-120

-80

-40

0

40

0123456

0.00

0.04

0.08

0.12

0123456

-1.2

-0.8

-0.4

0.0

0.4

0123456

-200

-150

-100

-50

0

50

0123456

0.00

0.04

0.08

0.12

0123456

-1.6

-1.2

-0.8

-0.4

0.0

0.4

0123456

-400

-300

-200

-100

0

100

0123456

0.00

0.02

0.04

0.06

0.08

0.10

0123456

-2.0

-1.5

-1.0

-0.5

0.0

0.5

0123456

-400

-300

-200

-100

0

100

0123456

Base

Experiment

Test

Experiment

Base Calc

Test Calc (Adj.

Amine Inj.)

Test Calc (All

Amine Inj.)

Figure 6. Plots of selected experimental and calculated incremental reactivity results for AMP. 
40 

EPA791A EPA798A EPA805A

EtOH-NH2 (MOIR/2) EtOH-NH2 (MOIR/2) EtOH-NH2 (MOIR/2)

∆(O3-NO) (ppm) vs Hour

IR ∆(O3-NO) (mole basis) vs Hour

IR IntOH (ppt-min/ppm) vs Hour

0.00

0.04

0.08

0.12

0123456

-0.4

-0.2

0.0

0.2

0.4

0.6

0123456

-200

-150

-100

-50

0

50

0123456

0.00

0.04

0.08

0.12

0123456

-0.2

0.0

0.2

0.4

0123456

-80

-40

0

40

0123456

0.00

0.04

0.08

0.12

0123456

-0.2

-0.1

0.0

0.1

0.2

0.3

0123456

-60

-40

-20

0

20

0123456

Base

Experiment

Test

Experiment

Base Calc

Test Calc (Adj.

Amine Inj.)

Test Calc (All

Amine Inj.)

EPA780A EPA790A EPA807A EPA806A

EtOH-NH2 (MIR) EtOH-NH2 (MIR) IPR-NH2 (MOIR/2) TBU-NH2 (MOIR/2)

∆(O3-NO) (ppm) vs Hour

IR ∆(O3-NO) (mole basis) vs Hour

IR IntOH (ppt-min/ppm) vs Hour

0.00

0.04

0.08

0.12

01234

-0.4

0.0

0.4

0.8

1.2

01234

-20

0

20

40

01234

0.00

0.04

0.08

0.12

0123456

-0.4

0.0

0.4

0.8

1.2

0123456

-60

-40

-20

0

20

40

0123456

0.00

0.04

0.08

0.12

0123456

-0.2

-0.1

0.0

0.1

0.2

0.3

0123456

-120

-80

-40

0

40

0123456

0.00

0.04

0.08

0.12

0123456

-0.4

-0.3

-0.2

-0.1

0.0

0.1

0123456

-100

-80

-60

-40

-20

0

0123456

Figure 7. Plots of selected experimental and calculated incremental reactivity results for 

aminoethanol, isopropyl amine, and t-butyl amine. 
41 

EPA799 (MIR) EPA792 (MOIR/2)

Formaldehyde (ppm) vs Hour

0.000

0.002

0.004

0.006

0123456

0.000

0.004

0.008

0.012

012345

Base Experiment

Test Experiment

Base Calc

Test Calc (Adj.

Amine Inj.)

Figure 8. Plots of experimental and selected calculated data for formaldehyde when measured in 

AMP experiments. 

EPA791 (MOIR/2)

Formaldehyde (ppm) vs Hour

0.000

0.005

0.010

0.015

0.020

012345

Test Experiment

Test Calc (Adj.

Amine Inj.)

Figure 9. Plots of experimental and selected calculated data for formaldehyde in the ethanolamine 

experiment with useable formaldehyde data. 

these adjusted initial concentrations are shown on Figure 6 through Figure 9. Plots of the best fit initial 

concentrations against the initial concentrations calculated from the amount of liquid injected are shown 

on Figure 10. The apparent amount of amine in the gas phase ranged from 5% to ~60% of the amount 

injected, with the least squares fit ratio being 26%. The fact that there is no systematic trend for this 

fraction based on the compound, amount injected, or type of experiment suggests that this apparent 

incomplete injection is due to experimental variability, and not due to systematic problems with the 

mechanisms used in the model simulations. The higher apparent fractions injected for t-butyl and 

isopropyl amine compared to AMP and aminoethanol can be attributed to the expectation that the latter 

two compounds would be more "sticky" because they have hydroxyl as well as amino groups, which the 

former two compounds lack. 

In any case, the fact that the initial reactant concentrations had to be treated as an adjustable 

parameter in the model simulations in order to obtain even approximately satisfactory fits of the model 

simulations to the data indicates that these data are not very good quantitative tests of the mechanism. The 

only conclusion that can be drawn is that the experiments are qualitatively consistent, or at least not 

inconsistent, with model predictions. 
42 

0.00

0.05

0.10

0.15

0.0 0.2 0.4 0.6

Calculated based on volume liqued injected (ppm)

"Best fit" initial concentration (ppm)

AMP

Ethanolamine

t-Butyl amine

Isopropyl amine

5% line

26% line

60% line

Figure 10. Plots of initial amine concentrations that gave best fits to results of model simulations to 

concentrations calculated from the amount of liquid amine injected. 

Figure 6 shows that if the initial AMP concentrations are adjusted, then the model simulates the 

∆([O3]-[NO]) and IntOH incremental reactivity results reasonably well. The good fits to the ∆([O3]-[NO]) 

at the initial states of the experiments can be attributed to the adjustment, but the ∆([O3]-[NO]) data at the 

later stages of the experiments, and the IntOH data are also fit reasonably well. Similarly good 

simulations are also obtained for the t-butyl amine experiments as well, as shown on Figure 7. 

For ethanolamine, Figure 7 shows that when the initial amine concentration is adjusted so the 

model simulates the initial ∆([O3]-[NO]) levels, the simulations of the ∆([O3]-[NO]) later in the 

experiment and of the IntOH data are reasonably satisfactory in the MIR experiments, but the simulations 

are not quite as good in the more NOx-limited MOIR/2 runs. In those runs, the added amine causes a 

slight reduction in O3 yields at the end of the experiment, while the model predicts the impact is positive, 

and also the model tends to underpredict the IntOH reactivity. A similar result is observed for the 

∆([O3]-[NO]) data for the isopropyl amine experiment, though in that case the IntOH reactivity data are 

reasonably well simulated. The tendency for these amines to reduce peak O3 in NOx-limited experiments 

suggests that their reactions, or more likely the reactions of their oxidation products, have NOx sinks that 

are not adequately represented in the current mechanism. This may be due to the highly approximate 

representation of C=N products predicted to be formed from the reactions of amines with α C-H bonds. 

This discrepancy in the predictions of the effects of ethanolamine and isopropyl amine on peak 

O3 levels suggests that the current mechanism may underpredict the O3 impacts of these compounds, and 

other non-inhibiting amines, under NOx-limited conditions. However, this should not necessarily result in 

biases in predictions of O3 impacts in the MIR scale, which are based on conditions when NOx is in 

excess and are therefore generally insensitive to NOx sinks in the mechanisms for the compounds. 

Figure 8 and Figure 9 show experimental and calculated formaldehyde results for the few added 

amine experiments where formaldehyde measurement data were available. Note that the PTR-MS has not 

yet been quantitatively calibrated for formaldehyde and the response is based on theoretical 

considerations which have some uncertainties. Generally the results are consistent with model predictions 
43 

that the impacts of AMP and aminoethanol on formaldehyde formation are relatively small. However, the 

formaldehyde data in run EPA799 suggests that the model may be somewhat overpredicting the effect of 

AMP on formaldehyde formation. In that experiment, the formaldehyde levels observed in the added 

amine reactor was slightly lower than that in the base case reactor, while the model predicted a slight 

positive effect of AMP on the amine formation. However, the AMP mechanism (shown in Table A-1 in 

Appendix A) does not have formaldehyde as a direct product in any AMP reaction, so the slight 

formaldehyde overprediction is probably due to the approximate representation used for the reactive 

products. 

As discussed above, an uncertainty exists concerning the importance of amine salt formation from 

the amine + HNO3 reaction in removing the amines from availability for gas-phase reaction. To check its 

importance in the environmental chamber simulations, the added amine runs were modeled both by 

assuming that this reaction is negligible, and by using the upper limit rate constant for the reaction and 

assuming it is irreversible. The only significant change caused by using the upper limit rate constant and 

irreversible removal is that the resulting calculation predicted that all the HNO3 forms the salt. The 

changes in final calculated ∆([O3]-[NO]) and IntOH caused by making alternative assumptions 

concerning amine salt formation were less than 3% for all the added amine experiments. This is because 

the amine present was in large excess over the calculated amount of HNO3 formed in the experiments, 

and the model assumes that, other than possible amine salt formation, the gas-phase HNO3 is unreactive. 

d-Limonene 

The conditions and selected results of the incremental reactivity experiments with d-limonene are 

shown on Table 6, and plots of selected experimental and calculated data are shown on Figure 11. The 

model gives reasonably good simulations of ∆([O3]-[NO]), IntOH, and d-limonene results of runs 

EPA793 and EPA804. The simulation of EPA797 is not quite as good, with the model predicting the 

approximate impact on ∆([O3]-[NO]) but at a later time in the experiment, predicting a later time for most 

of the limonene consumption, and a somewhat lower magnitude of ∆([O3]-[NO]) impact. However, these 

discrepancies can be attributed to the mechanism’s underpredictions of the rate of ∆([O3]-[NO]) 

formation, as tends to be the case for the simulations of surrogate experiments at lower ROG/NOx levels 

(Carter, 2007a). If this is taken into account, the simulation of the effects of the d-limonene addition can 

be considered to be reasonably satisfactory. 

In addition to incremental reactivity experiments, several d-limonene - NOx experiments, without 

other added reactants, were also carried out for mechanism evaluation as part of this project. Limonene - 

NOx experiments were also carried out previously at higher concentrations in a smaller chamber (Carter et 

al, 1995b), and these results are also used for mechanism evaluation in this work. The conditions and 

selected results of these and the previous experiments are summarized on Table 7, and experimental and 

calculated results for selected gas-phase species are shown on Figure 12 and Figure 13. 

Figure 12 shows that the model gave very good simulations of the results of the d-limonene - NOx

experiments carried out for this program, and generally good simulations of the experiments carried out 

previously, except perhaps for ETC451. The model predictions of the formaldehyde levels were 

reasonably consistent with the PTR-MS data in the one new experiment with such data, especially 

considering the uncertainty in the calibration of this instrument. The model consistently underpredicted 

the formaldehyde in the earlier d-limonene - NOx experiments, though as discussed by Carter et al 

(1995b), the formaldehyde instrument used at the time tended to be unreliable and subject to biases. 

Despite the uncertainty in the calibration, the more recent PTR-MS formaldehyde data probably should be 

given the greater weight. 
44 

EPA793A EPA797A EPA804A

MIR MIR MOIR/2

∆(O3-NO) (ppm) vs Hour

IR ∆(O3-NO) (mole basis) vs Hour

IR IntOH (ppt-min/ppm) vs Hour

d-Limonene (ppm) vs Hour

0.00

0.04

0.08

0.12

0.16

0123456

-0.5

0.0

0.5

1.0

1.5

2.0

0123456

-200

-100

0

100

0123456

0.00

0.04

0.08

0.12

0123456

-0.4

0.0

0.4

0.8

1.2

1.6

0123456

-600

-400

-200

0

200

0123456

0.00

0.04

0.08

0.12

0123456

-0.8

-0.4

0.0

0.4

0.8

0123456

-400

-200

0

200

0123456

Base

Experiment

Test Experiment

Base Calc

Test Calc

0.00

0.01

0.02

0.03

0.04

0123456

0.00

0.01

0.02

0.03

0123456

0.000

0.005

0.010

0.015

0.020

0.025

0123456

Figure 11. Plots of selected experimental and calculated incremental reactivity results for 

d-limonene. 

In view of the generally satisfactory performance of the existing d-limonene mechanism in 

simulating the current and previous chamber data, no modifications were made to the mechanism for that 

compound as part of this project. 

PM Impact Results 

The PM volume measurement data taken during the incremental reactivity experiments for this 

program are shown on Figure 14, and selected PM results from these experiments, and also the side 

equivalency test experiment, are summarized on Table 8. In addition, the maximum PM volume levels in 

the d-limonene - NOx experiments carried out for this project are included in Table 7, above. 

These results show that, with the possible exception of t-butyl amine, all the compounds studied 

for this project have large, positive impacts on PM formation under simulated atmospheric conditions. 
45 

Table 7. Summary of conditions and selected results of the d-limonene NOx experiments. 

Initial Conc (ppm) Ozone (ppb) Run Limonene NOx 2 Hr. 5 Hr 

Max PM 

(μg/m3

) 

Previous Experiments [a] 

ETC425 0.30 0.25 279 387 

ETC450 0.27 0.24 295 410 

ETC451 0.26 0.57 22 117 

ETC452 0.27 0.16 317 374 

Experiments for this project 

EPA794B 0.15 0.096 140 168 289 

EPA795A 0.32 0.139 144 176 681 

EPA795B 0.15 0.107 131 167 227 

 [a] See Carter et al (1995b) for a discussion of the conditions and modeling methods for these 

experiments, which were carried out in the ETC chamber, which consists of a ~4000-liter collapsible 

Teflon bag with a blacklight light source with a light intensity corresponding to an NO2 photolysis 

rate of 0.35 min-1. These runs were modeled using the chamber effects model for the ETC runs as 

given by Carter et al (1995b) except with a HONO input parameter, RN-I of 40 ppt. No PM data were 

taken during these experiments. 

Note that for the amines, the PM levels at the beginning of the experiments are relatively low (see Figure 

14), indicating that the amine itself is not significantly partitioning into the aerosol phase, and aerosol 

formation does not contribute significantly to the discrepancy between the amount of amines injected and 

the apparent amount of amine reacting in the gas phase. The PM formation must be due to either amine 

salt formation from reaction with the HNO3 formed in the gas-phase reactions, or condensation or 

heterogeneous reactions of oxidation products, or (most likely) both. 

For the purpose of comparing PM impacts of different compounds, it is useful to derive a "PM 

Incremental Reactivity", which is defined as the mass of PM formed (derived from the PM volume 

assuming the PM has the density of water) divided by the mass of VOC initially present in the 

experiments. This normalizes for differences in amounts of VOC injected in the different experiments. In 

the case of the amines, the "initially present" amount in this context was taken as the calculated amount 

injected, since even if all the amount injected did not participate in the gas phase reaction it may possibly 

have contributed somehow to PM formation. These PM incremental reactivity values derived from the 5-

hour PM volume values measured for the various experiments are given in Table 8, and the averages of 

these values for the different compounds are summarized on Table 9. 

For comparison with other VOCs, Table 9 also gives the average 5-hour PM incremental 

reactivities obtained from studies of other compounds and mixtures in this chamber in these types of 

incremental reactivity experiments. These include coatings VOCs studied by Carter et al (2005b) and 

pesticide VOCs studied by Carter and Malkina (2007). The compounds are listed in order of increasing 

PM incremental reactivity. 

Table 9 shows that except for t-butyl amine, which had a moderately low relative PM impact in 

the one experiment with this compound, the compounds studied for this project are among the highest in 
46 

EPA794B EPA795A EPA795B

Ozone (ppm) vs time (minutes)

NO(ppm) vs time (minutes)

d-Limonene (ppm) vs time (minutes)

0.00

0.05

0.10

0.15

0.20

0 120 240 360

0.00

0.05

0.10

0.15

0.20

0 120 240 360

0.00

0.05

0.10

0.15

0.20

0 120 240 360

0.00

0.02

0.04

0.06

0.08

0 120 240 360

0.00

0.04

0.08

0.12

0.16

0 120 240 360

0.00

0.02

0.04

0.06

0.08

0.10

0 120 240 360

0.00

0.04

0.08

0.12

0.16

0 120 240 360

0.0

0.1

0.2

0.3

0.4

0 120 240 360

0.00

0.04

0.08

0.12

0.16

0 120 240 360

Experimental

Calculation

ETC425 ETC450 ETC451 ETC452

Ozone (ppm) vs time (minutes)

NO(ppm) vs time (minutes)

d-Limonene (ppm) vs time (minutes)

O3

0.0

0.1

0.2

0.3

0.4

0 120 240 360

O3

0.0

0.1

0.2

0.3

0.4

0 120 240 360

O3

0.0

0.1

0.2

0.3

0.4

0 120 240 360

NO

0.00

0.05

0.10

0.15

0.20

0.25

0 120 240 360

NO

0.00

0.05

0.10

0.15

0.20

0 120 240 360

NO

0.0

0.1

0.2

0.3

0.4

0.5

0 120 240 360

NO

0.00

0.04

0.08

0.12

0.16

0 120 240 360

O3

0.00

0.04

0.08

0.12

0.16

0 120 240 360

D-LIMONE

0.0

0.1

0.2

0.3

0.4

0 120 240 360

D-LIMONE

0.0

0.1

0.2

0.3

0 120 240 360

D-LIMONE

0.0

0.1

0.2

0.3

0 120 240 360

D-LIMONE

0.0

0.1

0.2

0.3

0 120 240 360

Figure 12. Plots of selected experimental and calculated data for the d-limonene experiments carried 

out for this program (EPA runs) and previously (ETC runs). 
47 

EPA795A

Formaldehyde (ppm) vs time (minutes)

FORMALD

0.00

0.02

0.04

0.06

0 120 240 360

Experimental

Calculation

ETC425 ETC450 ETC451 ETC452

Formaldehyde (ppm) vs time (minutes)

FORMALD

0.00

0.04

0.08

0.12

0.16

0 120 240 360

FORMALD

0.00

0.04

0.08

0.12

0.16

0 120 240 360

FORMALD

0.00

0.04

0.08

0.12

0.16

0 120 240 360

FORMALD

0.00

0.04

0.08

0.12

0.16

0 120 240 360

Figure 13. Plot of experimental and calculated formaldehyde data for the d-limonene - NOx

experiments where formaldehyde data are available. 

terms of PM formation potential of the compounds studied. The highest PM formation was from dlimonene and ethanolamine, which were essentially the same to within the experimental variability. The 

inhibiting amines (AMP and t-butyl amine) were the least reactive of the amines studied, presumably in 

part because they inhibited the overall photooxidation processes, including the rate at which they reacted, 

and were calculated not to react to completion in these experiments. These may have higher relative PM 

formation potentials under more photochemically reactive conditions. 

It should be noted that the relative PM formation potentials summarized in Table 9 are applicable 

only for the conditions of these experiments, and the magnitudes, and even the ordering, of the 

incremental reactivities may be different in atmospheric conditions. The ultimate utility of these data will 

be to provide tests for model predictions of PM formation from these compounds, once mechanisms for 

this purpose have been developed. However, developing mechanisms for predicting quantitative PM 

impacts of these compounds was beyond the scope of this program. 

Atmospheric Reactivity Calculations 

The atmospheric incremental reactivities calculated for the amines and other compounds added to 

the SAPRC-07 mechanism for this project are given on Table 10. Table C-1 in Appendix C gives the 

complete tabulation of VOCs and reactivity values for the SAPRC-07 mechanism, with values for these 

compounds studied for this project added or updated. Table C-1 also gives codes indicating generally how 

these VOCs are represented in the mechanism, the availability of rate constant and experimental data for 

the compounds or mixtures, and uncertainty codes for the mechanisms and atmospheric reactivity 

estimates. The reactivity values and codes Table C-1 replace those given in the initial SAPRC-07 

documentation, dated August 31, 2007 for the compounds studied in this project. [The values for the other 

compounds are unchanged, except that methyl iodide, studied by Carter (2007b), has also been added.]
48 

Table 8. Selected results of PM number and volume measurements made during the incremental 

reactivity experiments carried out for this project. 

5-Hour PM 

Number (103

/m3) 

5-Hour PM Vol. 

(μg/m3 Run ) Test 

Side Type [a] 

Test Cmpd 

added 

(ppb) [b] Test Base Test Base 

5 Hr. PM 

Vol. Incr'l 

Rct'y [c]

Side Equivalency Test 

785 A MIR - 2 2 3.1 0.0 - 

AMP 

799 A MIR 64 6 3 12.9 0.1 55 

782 A MIR 525 16 4 1.3 0.1 1 

781 A MIR 536 17 0 1.6 0.0 1 

792 A MOIR/2 52 13 11 20.0 0.7 103 

789 B MOIR/2 53 6 14 26.4 0.7 133 

783 A MOIR/2 105 12 3 26.5 2.6 63 

784 A MOIR/2 105 9 13 23.3 0.7 59 

Ethanolamine 

780 A MIR 100 No 5 hour data - short run 

790 A MIR 101 7 2 38.4 0.1 153 

791 A MOIR/2 53 15 11 47.5 0.6 356 

798 A MOIR/2 101 12 8 62.9 0.6 248 

805 A MOIR/2 250 23 4 95.7 0.3 154 

Isopropyl amine 

807 A MOIR/2 252 8 9 47.6 0.4 78 

t-Butyl amine 

806 A MOIR/2 251 5 9 5.6 0.6 7 

d-Limonene 

797 A MIR 26 9 7 36.8 0.5 256 

793 A MIR 35 12 1 34.5 0.1 177 

804 A MOIR/2 23 14 6 28.8 0.2 225 

[a] See footnotes to Table 6. 

[b] For amines this is the calculated initial concentration based on the volume of liquid amine injected. 

Note that if the amount injected that gave the best fits of the model simulations to the ozone reactivity 

data were used then the PM volume incremental reactivity would be higher. 

[c] PM volume incremental reactivity is in units of μg PM formed per milligram of VOC added. 

Calculated as the 5-hour PM volume on the test side minus the PM volume in the base case 

experiments, divided by the amount of mg/m3

 test compound added. 
49 

EPA781A EPA782A EPA799A

AMP (MIR) AMP (MIR) AMP (MIR)

PM Volume (μg/m3) vs Hour

EPA783A EPA784A EPA789B EPA792A

AMP (MOIR/2) AMP (MOIR/2) AMP (MOIR/2) AMP (MOIR/2)

0.0

0.5

1.0

1.5

2.0

0123456

0

1

2

3

0123456

0

5

10

15

20

25

0123456

0

10

20

30

0123456

0

10

20

30

0123456

0

10

20

30

0123456

0

5

10

15

20

25

0123456

Base Experiment

Test Experiment

EPA791A EPA798A EPA805A

EtOH-NH2 (MOIR/2) EtOH-NH2 (MOIR/2) EtOH-NH2 (MOIR/2)

0

20

40

60

0123456

0

20

40

60

80

0123456

0

40

80

120

0123456

EPA780A EPA790A EPA807A EPA806A

EtOH-NH2 (MIR) EtOH-NH2 (MIR) IPR-NH2 (MOIR/2) TBU-NH2 (MOIR/2)

0

20

40

60

80

01234

0

10

20

30

40

50

0123456

0

20

40

60

0123456

0

2

4

6

8

10

0123456

EPA793A EPA797A EPA804A

Limonene (MIR) Limonene (MIR) Limonene (MOIR/2)

0

10

20

30

40

50

0123456

0

10

20

30

40

50

0123456

0

10

20

30

40

0123456

Figure 14. Plots of PM volume data from all of the incremental reactivity experiments carried out 

for this project. 
50 

Table 9. Summary of average 5-hour PM volume incremental reactivities of VOCs studied in 

incremental reactivity experiments in the UCR EPA chamber. 

Compound or Mixture Average 5-Hour 

PM IR [a] Project [b] 

1,2-Dichloropropenes Low Pesticide 

Propylene glycol Low Coatings 

Ethylene glycol Low Coatings 

Texanol isomers Low Coatings 

Synthetic isoparaffinic mixture (ASTM-3C1) Low Coatings 

Carbon disulfide 6±1 Pesticide 

t-Butyl amine ~7 This work 

Petroleum distillates (coatings study) 8±3 Coatings 

S-ethyl dipropylthiocarbamate (EPTC) 11±3 Pesticide 

Methyl isothiocyanate 11±5 Pesticide 

2-(2-Butoxyethoxy)-ethanol 34±11 Coatings 

Kerosene 41±9 Pesticide 

2-Amino-2-methyl-1-propanol 59±49 This work 

Isopropyl amine ~78 This work 

Benzyl alcohol 92±7 Coatings 

d-Limonene 219±40 This work 

Ethanolamine 228±97 This work 

[a] PM volume incremental reactivity is in units of μg PM formed per milligram of VOC added. 

Calculated as the 5-hour PM volume on the test side minus the PM volume in the base case 

experiments, divided by the amount of mg/m3

 test compound added. "Low" means the PM volume in 

the added test compound experiment was either lower or not significantly different than in the base 

case experiment. If no standard deviation is given then useful data are available for only a single 

experiment, and the value must be considered to be uncertain by at least ±50%. 

[b] Project for which this compound was studied; consult the project report for details: "Coatings": data 

from Carter et al (2005b); "Pesticide": data from Carter and Malkina (2007); "This work": see Table 

8. 

The online SAPRC-07 mechanism documentation and reactivity scales available at http://www.cert.ucr 

.edu/~carter/SAPRC have been updated accordingly. 

As discussed above, there is a significant uncertainty as to how to represent the possible loss of 

amines due to reaction with HNO3 to form the amine salts in the atmospheric ozone impact simulations. 

Figure 15 shows plots of amine reactivities calculated assuming that this reaction is fast and irreversible, 

against those calculated assuming that the reaction is unimportant. It can be seen that, unlike the 

simulations of the chamber experiment, alternative assumptions in this regard have a significant impact 

on the O3 reactivity results, with the magnitudes of the ozone impacts of the amines generally being at 

least an order of magnitude lower if the reaction is assumed to be fast and irreversible. For some of the 

lower reactivity amines, the low NOx reactivities (reactivities in some base case and EBIR scenarios) go 

from positive to negative, which is probably due to the removal of NOx sources in the mechanism due to 

the reactions of HNO3. The difference between these and the chamber simulations comes from the fact 

that in the chamber simulations, the amine is in large excess, while in these atmospheric reactivity 
51 

Table 10. Calculated atmospheric reactivity values for amines and other compounds added to the 

atmospheric reactivity tabulations. 

Reactivity (gm O3 / gm VOC) Compound CAS No. MIR MOIR EBIR Avg Base ` 

Amines [a] 

Methylamine 74-89-5 7.25 4.04 2.60 3.57±1.09 

Dimethyl amine 124-40-3 2.65 1.84 1.33 1.61±0.56 

Ethyl amine 75-04-7 5.45 2.97 1.91 2.63±0.80 

Trimethyl amine 75-50-3 5.27 2.75 1.81 2.48±0.74 

Isopropylamine 75-31-0 6.97 3.26 2.06 2.97±0.96 

t-Butyl amine 75-64-9 -3.26 -1.06 -0.44 -0.99±0.70 

Triethyl amine 121-44-8 3.07 1.48 0.91 1.31±0.44 

Triethylene diamine 280-57-9 2.77 1.33 0.82 1.18±0.40 

Ethanolamine 141-43-5 6.59 2.99 1.85 2.72±0.92 

Dimethylaminoethanol 108-01-0 5.15 2.21 1.40 2.05±0.69 

2-Amino-1-butanol 96-20-8 4.79 2.14 1.31 1.95±0.67 

2-Amino-2-methyl-1-propanol 124-68-5 -2.68 -0.80 -0.30 -0.76±0.62 

Diethanol amine 111-42-2 2.22 1.08 0.70 0.98±0.32 

Triethanolamine 102-71-6 3.25 1.37 0.81 1.25±0.46 

Triisopropanolamine 122-20-3 1.99 0.96 0.60 0.86±0.29 

Other Compounds

Terpinolene 586-62-9 6.14 2.21 1.17 2.09±1.08 

Tripropylene glycol 24800-44-0 2.07 1.04 0.64 0.92±0.31 

Diethylene glycol mono(2-ethylhexyl) ether 1559-36-0 1.45 0.75 0.42 0.64±0.24 

Tripropylene glycol n-butyl ether 55934-93-5 1.55 0.75 0.43 0.65±0.24 

Triethyl citrate 77-93-0 0.66 0.31 0.16 0.26±0.11 

2,2,4-Trimethyl-1,3-pentanediol 

diisobutyrate 

6846-50-0 0.33 0.20 0.06 0.14±0.09 

Citronellol (3,7-dimethy-6-octen-1-ol) 106-22-9 5.80 2.05 1.12 1.94±0.96 

Linalool 78-70-6 5.44 1.96 1.09 1.85±0.90 

Geraniol 106-24-1 5.10 1.88 1.06 1.78±0.85 

Hexyl cinnamal 101-86-0 2.93 1.08 0.64 1.03±0.41 

Hydroxycitronellal 107-75-5 2.54 1.02 0.61 0.94±0.34 

Cinnamic aldehyde 104-55-2 4.79 1.77 1.05 1.68±0.68 

Amyl cinnamal 122-40-7 3.13 1.16 0.69 1.10±0.44 

4-Vinylphenol 2628-17-3 1.44 0.16 -0.41 -0.01±0.45 

Methylparaben (4-hydroxy-benzoic acid, 

methyl ester) 

99-76-3 1.70 0.10 -0.55 -0.04±0.54 

Propylparaben 94-13-3 1.44 0.08 -0.47 -0.03±0.45 

2,6-Di-tert-butyl-p-cresol 128-37-0 1.18 0.07 -0.38 -0.02±0.37 

Beta-phenethyl alcohol 98-85-1 4.49 1.57 0.76 1.44±0.72 

Cinnamic alcohol 104-54-1 0.83 0.10 -0.29 -0.03±0.27 

Anethol 104-46-1 0.75 0.09 -0.26 -0.03±0.24 

2-Ethylhexyl benzoate 5444-75-7 0.92 0.42 0.18 0.34±0.17 

1-Nitropropane 108-03-2 0.20 0.15 0.11 0.13±0.03 

Ethyl methyl ketone oxime 96-29-7 1.55 1.32 1.45 1.40±0.30 

Lauryl pyrrolidone 2687-96-9 0.89 0.45 0.27 0.40±0.14 
Table 10 (continued) 

52 

Reactivity (gm O3 / gm VOC) Compound CAS No. MIR MOIR EBIR Avg Base ` 

o-Dichlorobenzene 95-50-1 0.17 0.02 -0.04 0.01±0.05 

2-Chlorotoluene 95-49-8 2.86 1.00 0.40 0.88±0.50 

Methyl nonafluorobutyl ether 163702-07-6 0.05 0.04 0.03 0.04±0.01 

Methyl nonafluoroisobutyl ether 163702-08-7 0.05 0.04 0.03 0.04±0.01 

Ethyl nonafluorobutyl ether 163702-05-4 0.19 0.12 0.08 0.11±0.03 

Ethyl nonafluoroisobutyl ether 163702-06-5 0.19 0.12 0.08 0.11±0.03 

[a] Reactivities calculated assuming no loss of amine by reaction with HNO3. See Figure 15 for results of 

calculations assuming rapid and irreversible loss of amines by reaction with HNO3. 

-0.2

0.0

0.2

0.4

0.6

-4 -2 0 2 4 6 8

Reactivity if no HNO3 Reaction (gm O3 / gm amine)

Reactivity if fast HNO3 reaction

Base

MIR

MOIR

EBIR

Slope = 0.064

Figure 15. Plots of incremental reactivities of amines for the various types of atmospheric reactivity 

scenarios calculated assuming rapid and irreversible loss by reaction with HNO3 against 

incremental reactivities calculated assuming no reaction with HNO3. 

scenarios, where the incremental effects of small VOC additions are being calculated, the HNO3 is in 

excess and consumes most of the amine if the amine salt reaction is assumed to be fast and irreversible. 

For regulatory purposes, we recommend that the amine reactivities in the maximum incremental 

reactivity (MIR) scale be calculated based on assuming no significant loss of amines by reaction with 

HNO3, as may occur in environments where there are significant other sinks for HNO3, such as reaction 

with ammonia, other amines, or heterogeneous loss processes, or if the equilibrium favors dissociation of 

the amine salt in the environment under consideration. This would represent the impact of the amines 

under conditions where they would have the maximum ozone impact, which is consistent with the general 

concept of maximum incremental reactivity (Carter, 1994a). Therefore, the amine reactivity values given 

in Table 10 and Table C-1 are based on assuming no loss of the amine by reaction with HNO3. Footnotes 
53 

for the amines in Table C-1 indicate that the tabulated values should be considered upper limits in 

magnitude. 

Table 11 gives the previous estimates of MIR or upper limit MIR values for the amines as a result 

of this work. The values in the middle column were from the most recent update of the SAPRC-99 

tabulation given by Carter (2003) and are based on calculations using highly approximate "placeholder" 

mechanisms as discussed by Carter (2000a). For most amines for which reactivity values were available 

in the previous tabulations the new MIR's are somewhat lower, and in the case of AMP the previous 

estimate was positive, while the current mechanism (and chamber data) indicate it is an ozone inhibitor. 

For most amines, the reactivity values used for regulatory purposes were the upper limit values derived 

using the method given in Appendix D of the SAPRC-99 documentation, which are also shown on Table 

11. It can be seen that these upper limit values are significantly higher than the current estimates, in most 

cases by more than a factor of two. Therefore, ozone impacts estimates for most amines have declined as 

a result of this work. 

Table 11. Change in MIR values assigned to amines as a result of this work. 

Compound MIR (gm O3 / gm VOC) [a] 

This work SAPRC-99 [b] Upper Limit [c] 

Methylamine 7.25 10.8 (-33%) 

Dimethyl amine 2.65 9.4 (-72%) 14.9 (-82%) 

Ethyl amine 5.45 7.8 (-30%) 14.9 (-63%) 

Trimethyl amine 5.27 7.1 (-25%) 17.1 (-69%) 

Isopropylamine 6.97 17.1 (-59%) 

t-Butyl amine -3.26 18.4 (negative) 

Triethyl amine 3.07 16.6 (-81%) 

Triethylene diamine 2.77 15.0 (-81%) 

Ethanolamine 6.59 6.0 (+11%) 11.0 (-40%) 

Dimethylaminoethanol 5.15 4.8 (8%) 15.1 (-66%) 

2-Amino-1-butanol 4.79 15.1 (-68%) 

2-Amino-2-methyl-1-propanol (AMP) -2.68 4.8 (negative) 15.1 (negative) 

Diethanol amine 2.22 4.0 (-45%) 12.8 (-83%) 

Triethanolamine 3.25 2.8 (+18%) 11.3 (-71%) 

Triisopropanolamine 1.99 8.8 (-77%) 

[a] Value in parentheses is change relative to the tabulated value as a result of this work. 

[b] From tabulation of Carter (2003) 

[b] Upper limit MIR calculated using the procedure of Appendix D in the SAPRC-99 

documentation (Carter, 2000a). 
54 

DISCUSSION AND CONCLUSIONS 

This project made significant progress towards achieving its objectives of decreasing 

uncertainties and improving estimates of ozone impacts of consumer product compounds of interest to the 

CARB. Ozone impact estimates and MIR values were derived for a total of 7 amines and 30 other 

compounds present in consumer products inventories for which estimates were not previously available, 

ozone impact estimates and MIR values for 8 amines were significantly improved, and data were obtained 

to support the predictive capabilities of the previously derived mechanism for d-limonene. The major 

contribution of this project concerned the development of improved methods for estimating mechanisms 

for calculating ozone impact estimates for amines, which were previously represented using highly 

approximate "placeholder" mechanisms, or for which only upper limit ozone impact estimates were 

available. As a result of this project, the estimated ozone impacts of amines appropriate for regulatory 

applications are much lower than the upper limit values used previously. 

One unexpected result of this project is that certain types of amines, those that lack abstractable 

hydrogens adjacent to the amino groups, were found to have negative impacts on ozone formation, 

contrary to previous estimates. The most important example of this is AMP, which was one of the priority 

consumer product compounds chosen for study in this project. This inhibition is explainable by the 

current estimated mechanisms, and supported by the environmental chamber experiments with AMP and 

t-butyl amine, another example compound of this type. The chamber experiments with aminoethanol and 

isopropyl amine support the predictions of the current mechanisms that these compounds have positive 

impacts on ozone formation, though their impacts are lower than previous upper limit estimates. 

On the other hand, this project was not totally successful in reducing uncertainties in mechanisms 

and ozone impact estimates of amines to the level obtained for other compounds that have been studied 

previously. Although the experiments carried out for this project were useful in testing mechanisms in a 

qualitative sense, particularly for determining when compounds are inhibitors as opposed to having 

positive impacts of ozone formation, they were not particularly useful for quantitative mechanism 

evaluation. This is because amines are extremely "sticky" compounds that are difficult to reliably inject or 

monitor in the gas phase, and attempts to develop methods to quantitatively monitor these compounds in 

the gas phase were unsuccessful. The results of the experiments could not be satisfactorily simulated 

using reasonable mechanisms unless it is assumed that only a fraction of the injected amines are available 

for reaction in the gas phase, and the amount of amine reacting in the gas phase had to be treated as an 

adjustable parameter. Because this adjustment could mask errors in the mechanism, this means that the 

data obtained cannot fully test the mechanism. Methods need to be developed to quantitatively inject and 

monitor these compounds in the gas phase before quantitative data can be obtained to comprehensively 

evaluate the mechanisms for these compounds. 

On the other hand, the data obtained were sufficient to evaluate the predictive capabilities of the 

mechanisms concerning general reactivity trends, and for the most part the data did not indicate 

systematic problems with the estimated mechanisms. The one exception is that the estimated mechanisms 

did not correctly predict the tendency of the positively reactive amines (aminoethanol and isopropyl 

amine) to cause a slight decrease in O3 formation under NOx-limited conditions. This is attributable to 

uncertainties and approximations in the mechanism concerning the representation of reactive products, 

such as compounds with C=N bonds, in the model. This aspect of the amine mechanisms needs to be 

improved, though how to improve model performance in this respect is presently unclear. However, this 

ozone overprediction bias under NOx-limited conditions should not significantly affect predictions of 

MIR values, which reflect ozone impacts under conditions when NOx is in excess. 
55 

An even more significant problem concerning quantitative predictions of ozone impacts of 

amines concerns its possible removal by reaction with HNO3, forming non-volatile amine salts. HNO3 is 

an important NOx sink species formed under conditions where O3 formation occurs, so its reactions need 

to be taken into account. Amines are basic compounds and are known to rapidly form amine nitrate salts, 

which partition into the aerosol phase, when injected into environmental chambers in the presence of 

HNO3 under atmospheric conditions (Murphy et al, 2007). However, these will also dissociate back to the 

amines and HNO3, and evidence for this dissociation is also observed, though the equilibrium constants 

are highly uncertain (Murphy et al, 2007). If this process is not important in affecting results of the 

chamber experiments carried out for this work because the injected amine is in large excess over the 

HNO3 formed in the photooxidation reactions, it is calculated to be extremely important under 

atmospheric conditions. In particular, if the reactions of HNO3 with amines are rapid and irreversible, 

then the magnitudes of the incremental reactivity values for these compounds are calculated to be an order 

of magnitude or more less than is the case if the reaction is assumed to be negligible. 

It is extremely uncertain how to represent the amine + HNO3 reaction in the atmospheric 

reactivity scenarios because its importance is highly sensitive to atmospheric sources and sinks for 

ammonia, other amines and HNO3, which have highly variable levels that are in most cases unknown. 

For regulatory purposes, we recommend that values used for Maximum Incremental Reactivity (MIR) be 

based on conditions where they would have the maximum ozone impact, which is consistent with the 

general concept of maximum incremental reactivity (Carter, 1994a). For this reason, the tabulated MIR 

and other reactivity values are based on assuming that the reaction with HNO3 is negligible. However, the 

magnitudes of their actual impacts will probably be less than these under real atmospheric conditions. If it 

is desired to derive reactivity values for amines that are more representative to their atmospheric impacts, 

then appropriate methods to represent sources and sinks for basic pollutants (HNO3, ammonia, amines, 

etc.), need to be derived for use in atmospheric reactivity scenarios. This requires a major research effort 

that is beyond the scope of this project. 

In addition to amines, data were also obtained to better evaluate ozone impact mechanisms for dlimonene, an important compound in consumer products emissions. In the case of d-limonene, 

mechanism evaluation experiments were limited to limonene - NOx experiments carried out with 

relatively high reactant concentrations, and the predictive capabilities of the mechanism had not been 

tested under conditions more representative of the atmosphere. The new experiments carried out for this 

project addressed the need for better data to evaluate the mechanism for this important compound, but 

since the mechanism performed well in simulating these data, no need to change the mechanism was 

indicated. 

 Mechanisms and reactivity estimates were also derived for 30 other compounds found in 

consumer product inventories for which estimates were not previously available. However the CARB 

staff had also requested reactivity estimates for a total of 63 other compounds for which reactivity 

estimates are still needed. Of these, 4 are probably of negligible reactivity and 20 are probably nonvolatile, leaving 39 compounds for which reactivity estimates are actually needed. In some of these cases 

the chemical structures could not be determined but in others the mechanisms are too uncertain to 

estimate, while for other estimates could be made if more time and resources were available. Additional 

work in this area may be appropriate if the missing estimates remain problematic for the CARB. 

Although the primary focus of this project was reducing uncertainties in ozone impact estimates, 

data were also obtained concerning the relative PM formation potentials for AMP, ethanolamine, and dlimonene. All three of these compounds were found to have very high PM formation potentials compared 

to most of the coatings VOCs (Carter et al, 2005b) and pesticide VOCs (Carter and Malkina, 2007) 

studied previously. The data obtained should be useful for testing mechanisms for PM formation of these 

compounds, and work in this area is needed. 
56 

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60 

APPENDIX A. MECHANISM LISTING 

Table A-1. Reactions and rate constants used for amines, d-limonene, and the new compounds added 

to the mechanism for this project. 

Reaction Rate [a] Compound Expression Ref Reactions 

 

Methylamine 1.97e-11 1 ME-AMINE + OH = #.458 HO2 + #.542 RO2C + #.458 PROD2 + 

#.542 xHO2 + #.542 xPROD2 + #.542 yROOH + XN + #-5 XC 

 7.40e-21 2 ME-AMINE + O3 = OH + RO2C + xHO2 + xPROD2 + yROOH + 

#-5 XC + XN 

 9.60e-14 e1 ME-AMINE + NO3 = HNO3 + #.458 HO2 + #.542 RO2C + #.458 

PROD2 + #.542 xHO2 + #.542 xPROD2 + #.542 yROOH + #-5 XC 

+ XN 

 4.00e-11 e2 ME-AMINE + HNO3 = XC + XN 

Dimethyl Amine 6.52e-11 1 DM-AMINE + OH = #.243 HO2 + #.514 RO2C + #.243 PROD2 + 

#.514 xHO2 + #.514 xPROD2 + #.514 yROOH + XN + #-2.542 XC

 1.67e-18 2 DM-AMINE + O3 = OH + RO2C + xHO2 + xPROD2 + yROOH + 

#-4 XC + XN 

 2.03e-13 e1 DM-AMINE + NO3 = HNO3 + #.244 HO2 + #.512 RO2C + #.244 

PROD2 + #.512 xHO2 + #.512 xPROD2 + #.512 yROOH + #-2.537 

XC + XN 

 4.00e-11 e2 DM-AMINE + HNO3 = #2 XC + XN 

Ethyl Amine 2.58e-11 1 ET-AMINE + OH = #.485 HO2 + #.515 RO2C + #.485 PROD2 + 

#.515 xHO2 + #.515 xPROD2 + #.515 yROOH + XN + #-4 XC 

 1.98e-20 e3 ET-AMINE + O3 = OH + RO2C + xHO2 + xPROD2 + yROOH + 

#-4 XC + XN 

 1.16e-13 e1 ET-AMINE + NO3 = HNO3 + #.508 HO2 + #.492 RO2C + #.508 

PROD2 + #.492 xHO2 + #.492 xPROD2 + #.492 yROOH + #-4 XC 

+ XN 

 4.00e-11 e2 ET-AMINE + HNO3 = #2 XC + XN 

Trimethyl Amine 4.84e-11 1 TM-AMINE + OH = RO2C + xHO2 + xPROD2 + yROOH + XN + 

#-3 XC 

 7.84e-18 2 TM-AMINE + O3 = OH + RO2C + xHO2 + xPROD2 + yROOH + 

#-3 XC + XN 

 1.56e-13 e1 TM-AMINE + NO3 = HNO3 + RO2C + xHO2 + xPROD2 + 

yROOH + #-3 XC + XN 

 4.00e-11 e2 TM-AMINE + HNO3 = #3 XC + XN 

isopropylamine 3.78e-11 e4 IPR-AMIN + OH = #.463 HO2 + #.537 RO2C + #.463 PROD2 + 

#.537 xMEO2 + #.537 xPROD2 + #.537 yROOH + XN + #-3.537 

XC 

 3.32e-20 e3 IPR-AMIN + O3 = OH + RO2C + xMEO2 + xPROD2 + yROOH + 

#-4 XC + XN 

 1.21e-13 e1 IPR-AMIN + NO3 = HNO3 + #.487 HO2 + #.513 RO2C + #.487 

PROD2 + #.513 xMEO2 + #.513 xPROD2 + #.513 yROOH + #-

3.513 XC + XN 

 4.00e-11 e2 IPR-AMIN + HNO3 = #3 XC + XN 
Table A-1 (continued) 

61 

Reaction Rate [a] Compound Expression Ref Reactions 

 

t-butyl amine 1.18e-11 3 TBU-AMIN + OH = #.971 NRAD + #.055 RO2C + #.001 RO2XC 

+ #.001 zRNO3 + #.028 xMEO2 + #.028 xHCHO + #.028 xPROD2 

+ #.029 yROOH + #.029 XN + #-.113 XC 

 5.88e-14 e1 TBU-AMIN + NO3 = HNO3 + NRAD 

 Same as rxn BR28 e5 NRAD + NO2 = PROD2 + #2 XN + #-2 XC 

 (Neglected) e6 NRAD + NO = nitrosoamine 

 Same as rxn BR31 e7 NRAD + HO2 = #4 XC + XN 

 4.00e-11 e2 TBU-AMIN + HNO3 = #4 XC + XN 

Triethyl Amine 5.57e-11 e4 TE-AMINE + OH = #2.297 RO2C + #.311 RO2XC + #.311 zRNO3 

+ #.689 xHO2 + #.689 xRCHO + yR6OOH + XN + #2.066 XC 

 1.21e-17 e3 TE-AMINE + O3 = OH + #2.297 RO2C + #.311 RO2XC + #.311 

zRNO3 + #.689 xHO2 + #.689 xRCHO + yROOH + #2.066 XC + 

XN 

 1.71e-13 e1 TE-AMINE + NO3 = HNO3 + #2.297 RO2C + #.311 RO2XC + 

#.311 zRNO3 + #.689 xHO2 + #.689 xRCHO + yR6OOH + #2.066 

XC + XN 

 4.00e-11 e2 TE-AMINE + HNO3 = #6 XC + XN 

Ethanolamine 4.41e-11 e4 ETOH-NH2 + OH = #.486 HO2 + #.514 RO2C + #.091 RCHO + 

#.394 PROD2 + #.514 xHO2 + #.514 xHCHO + #.514 xPROD2 + 

#.514 yROOH + XN + #-4.24 XC 

 6.58e-20 e3 ETOH-NH2 + O3 = OH + RO2C + xHO2 + xHCHO + xPROD2 + 

yROOH + #-5 XC + XN 

 1.35e-13 e1 ETOH-NH2 + NO3 = HNO3 + #.436 HO2 + #.564 RO2C + #.436 

PROD2 + #.564 xHO2 + #.564 xHCHO + #.564 xPROD2 + #.564 

yROOH + #-4.564 XC + XN 

 4.00e-11 e2 ETOH-NH2 + HNO3 = #2 XC + XN 

Dimethylaminoethanol 6.85e-11 4 DMAE + OH = #.067 HO2 + #.896 RO2C + #.037 RO2XC + #.037 

zRNO3 + #.067 RCHO + #.896 xHO2 + #.362 xHCHO + #.535 

xRCHO + #.362 xPROD2 + #.933 yROOH + XN + #-.557 XC 

 6.76e-18 2 DMAE + O3 = OH + #.961 RO2C + #.039 RO2XC + #.039 zRNO3 

+ #.961 xHO2 + #.384 xHCHO + #.576 xRCHO + #.384 xPROD2 

+ yROOH + #-0.655 XC + XN 

 1.80e-13 e1 DMAE + NO3 = HNO3 + #.961 RO2C + #.039 RO2XC + #.039 

zRNO3 + #.961 xHO2 + #.406 xHCHO + #.554 xRCHO + #.406 

xPROD2 + yROOH + #-.743 XC + XN 

 4.00e-11 e2 DMAE + HNO3 = #4 XC + XN 

2-amino-1-butanol 5.32e-11 e4 2A1C4OH + OH = #.404 HO2 + #.594 RO2C + #.024 RO2XC + 

#.024 zRNO3 + #.076 RCHO + #.328 PROD2 + #.573 xHO2 + 

#.573 xHCHO + #.021 xCCHO + #.573 xPROD2 + #.596 yROOH 

+ XN + #-2.387 XC 

 3.65e-19 e3 2A1C4OH + O3 = OH + #.961 RO2C + #.039 RO2XC + #.039 

zRNO3 + #.961 xHO2 + #.961 xHCHO + #.961 xPROD2 + 

yROOH + #-2.961 XC + XN 

 1.70e-13 e1 2A1C4OH + NO3 = HNO3 + #.347 HO2 + #.628 RO2C + #.026 

RO2XC + #.026 zRNO3 + #.347 PROD2 + #.628 xHO2 + #.628 

xHCHO + #.628 xPROD2 + #.653 yROOH + #-2.628 XC + XN 

 4.00e-11 e2 2A1C4OH + HNO3 = #4 XC + XN 
Table A-1 (continued) 

62 

Reaction Rate [a] Compound Expression Ref Reactions 

 

2-Amino-2-Methyl-1-

Propanol 

2.80e-11 5 AMP + OH = #.185 HO2 + #.799 NRAD + #.015 RO2C + #.001 

RO2XC + #.001 zRNO3 + #.185 RCHO + #.015 xHO2 + #.015 

xRCHO + #.016 yROOH + #.201 XN + #.199 XC 

 5.88e-14 e1 AMP + NO3 = HNO3 + NRAD 

 Same as rxn BR28 e5 NRAD + NO2 = PROD2 + #2 XN + #-2 XC 

 (Neglected) e6 NRAD + NO = nitrosoamine 

 Same as rxn BR31 NRAD + HO2 = #4 XC + XN 

 4.00e-11 e2 AMP + HNO3 = #4 XC + XN 

Diethanol Amine 1.01e-10 e4 ETOH2-NH + OH = #.316 HO2 + #.43 RO2C + #.018 RO2XC + 

#.018 zRNO3 + #.08 RCHO + #.236 PROD2 + #.43 xHO2 + #.43 

xHCHO + #.43 xPROD2 + #.448 yROOH + XN + #-.774 XC 

 3.77e-18 e3 ETOH2-NH + O3 = OH + #.961 RO2C + #.039 RO2XC + #.039 

zRNO3 + #.961 xHO2 + #.961 xHCHO + #.961 xPROD2 + 

yROOH + #-2.961 XC + XN 

 3.30e-13 e1 ETOH2-NH + NO3 = HNO3 + #.269 HO2 + #.444 RO2C + #.018 

RO2XC + #.018 zRNO3 + #.269 PROD2 + #.444 xHO2 + #.444 

xHCHO + #.444 xPROD2 + #.463 yROOH + #-.832 XC + XN 

 4.00e-11 e2 ETOH2-NH + HNO3 = #4 XC + XN 

Triethanolamine 8.04e-11 e4 ETOH3-N + OH = #.151 HO2 + #.766 RO2C + #.083 RO2XC + 

#.083 zRNO3 + #.151 RCHO + #.766 xHO2 + #.766 xHCHO + 

#.766 xPROD2 + #.849 yR6OOH + XN + #-.314 XC 

 4.02e-17 e3 ETOH3-N + O3 = OH + #.902 RO2C + #.098 RO2XC + #.098 

zRNO3 + #.902 xHO2 + #.902 xHCHO + #.902 xPROD2 + 

yROOH + #-0.902 XC + XN 

 2.29e-13 e1 ETOH3-N + NO3 = HNO3 + #.902 RO2C + #.098 RO2XC + #.098 

zRNO3 + #.902 xHO2 + #.902 xHCHO + #.902 xPROD2 + 

yR6OOH + #-.902 XC + XN 

 4.00e-11 e2 ETOH3-N + HNO3 = #6 XC + XN 

triisopropanol amine 9.37e-11 e4 IC3OH3-N + OH = #.268 HO2 + #.581 RO2C + #.151 RO2XC + 

#.151 zRNO3 + #.268 PROD2 + #.581 xHO2 + #.581 xCCHO + 

#.581 xPROD2 + #.732 yR6OOH + XN + #1.838 XC 

 4.02e-17 e3 IC3OH3-N + O3 = OH + #.794 RO2C + #.206 RO2XC + #.206 

zRNO3 + #.794 xHO2 + #.794 xCCHO + #.794 xPROD2 + yROOH 

+ #1.413 XC + XN 

 2.29e-13 e1 IC3OH3-N + NO3 = HNO3 + #.794 RO2C + #.206 RO2XC + #.206 

zRNO3 + #.794 xHO2 + #.794 xCCHO + #.794 xPROD2 + 

yR6OOH + #1.413 XC + XN 

 4.00e-11 e2 IC3OH3-N + HNO3 = #9 XC + XN 

 
Table A-1 (continued) 

63 

Reaction Rate [a] Compound Expression Ref Reactions 

 

d-Limonene 4.28e-11 x 

exp(-0.797)/RT 

6 D-LIMONE + OH = #.972 RO2C + #.17 RO2XC + #.17 zRNO3 + 

#.827 xHO2 + #.003 xRCO3 + #.288 xHCHO + #.539 xRCHO + 

#.053 xMEK + #.287 xPROD2 + #.019 xMVK + #.012 xIPRD + 

yR6OOH + #5.001 XC 

 2.95e-15 x 

exp(1.556)/RT 

6 D-LIMONE + O3 = #.729 OH + #.009 HO2 + #.619 RO2C + #.177 

RO2XC + #.177 zRNO3 + #.029 CO + #.017 CO2 + #.263 PROD2 

+ #.021 xHO2 + #.482 xMECO3 + #.058 xRCO3 + #.089 xHCHO 

+ #.5 xRCHO + #.015 xMACR + #.007 xIPRD + #.738 yR6OOH + 

#4.497 XC 

 1.22e-11 6 D-LIMONE + NO3 = #1.11 RO2C + #.296 RO2XC + #.296 zRNO3 

+ #.626 xNO2 + #.076 xHO2 + #.002 xRCO3 + #.078 xHCHO + 

#.009 xCCHO + #.641 xRCHO + #.039 xMACR + #.009 xMVK + 

#.028 xIPRD + #.069 xRNO3 + yR6OOH + #5.452 XC + #.304 XN

 7.20e-11 7 D-LIMONE + O3P = PROD2 + #4 XC 

 

Terpinolene 1.96e-10 e8 TRPNOLEN + OH = #.77 RO2C + #.23 RO2XC + #.23 zRNO3 + 

#.77 xHO2 + #.348 xRCHO + #.422 xACET + #.422 xPROD2 + 

yROOH + #3.78 XC 

 1.02e-15 e8 TRPNOLEN + O3 = #.908 OH + #.003 HO2 + #.872 RO2C + #.113 

RO2XC + #.113 zRNO3 + #.01 CO + #.006 CO2 + #.33 ACET + 

#.419 PROD2 + #.056 xHO2 + #.501 xMECO3 + #.241 xRCO3 + 

#.35 xHCHO + #.171 xRCHO + #.055 xAFG3 + #.001 xIPRD + 

#.911 yROOH + #2.825 XC 

 6.66e-11 e8 TRPNOLEN + NO3 = #1.22 RO2C + #.343 RO2XC + #.343 

zRNO3 + #.486 xNO2 + #.17 xHO2 + #.007 xHCHO + #.091 

xRCHO + #.394 xACET + #.394 xPROD2 + #.123 xMVK + #.046 

xIPRD + #.171 xRNO3 + yROOH + #2.368 XC + #.343 XN 

 1.63e-10 e8 TRPNOLEN + O3P = PROD2 + #4 XC 

tripropylene glycol 6.59e-11 e8 TPR-GLCL + OH = #.255 HO2 + #.938 RO2C + #.165 RO2XC + 

#.165 zRNO3 + #.255 PROD2 + #.519 xHO2 + #.061 xMEO2 + 

#.023 xHCHO + #.264 xCCHO + #.92 xPROD2 + #.745 yR6OOH 

+ #.347 XC 

diethylene glycol 

mono(2-ethylhexyl) 

ether 

5.16e-11 e8 DG2EHE + OH = #.079 HO2 + #1.357 RO2C + #.36 RO2XC + 

#.36 zRNO3 + #.079 RCHO + #.562 xHO2 + #.155 xHCHO + #.03 

xCCHO + #.092 xRCHO + #.003 xMEK + #.941 xPROD2 + #.921 

yR6OOH + #3.457 XC 

tripropylene glycol nbutyl ether 9.54e-11 e8 TGLBE + OH = #.042 HO2 + #1.441 RO2C + #.336 RO2XC + 

#.336 zRNO3 + #.042 RCHO + #.492 xHO2 + #.13 xMEO2 + #.172 

xHCHO + #.031 xCCHO + #.091 xRCHO + #.327 xMEK + #.834 

xPROD2 + #.013 xHCOOH + #.958 yR6OOH + #3.895 XC 

triethyl citrate 5.91e-12 e8 TETCITRA + OH = #.026 RCO3 + #.727 RO2C + #.248 RO2XC + 

#.248 zRNO3 + #.026 MEK + #.001 BACL + #.182 xHO2 + #.544 

xMECO3 + #.065 xRCHO + #.027 xMEK + #.183 xPROD2 + #.09 

xMGLY + #.09 xBACL + #.361 xRCOOH + #.974 yROOH + 

#6.125 XC 

2,2,4-trimethyl-1,3-

pentanediol 

diisobutyrate 

1.15e-11 e8 TXIB + OH = #1.976 RO2C + #.53 RO2XC + #.53 zRNO3 + #.443 

xHO2 + #.006 xMEO2 + #.022 xRCO3 + #.186 xCO + #.071 

xHCHO + #.011 xCCHO + #.026 xRCHO + #.659 xACET + #.842 

xMEK + #.004 xPROD2 + #.001 xBACL + #.199 xRCOOH + 

yROOH + #6.427 XC 
Table A-1 (continued) 

64 

Reaction Rate [a] Compound Expression Ref Reactions 

 

Citronellol (3,7-

dimethy-6-octen-1-ol) 

9.87e-11 e8 CITRNLOL + OH = #.041 HO2 + #.792 RO2C + #.226 RO2XC + 

#.226 zRNO3 + #.041 RCHO + #.727 xHO2 + #.006 xMEO2 + 

#.043 xHCHO + #.004 xCCHO + #.7 xRCHO + #.687 xACET + 

#.027 xPROD2 + #.005 xMACR + #.006 xMVK + #.009 xIPRD + 

#.959 yR6OOH + #4.05 XC 

 3.48e-16 e8 CITRNLOL + O3 = #.728 OH + #.009 HO2 + #.765 RO2C + #.007 

RO2XC + #.007 zRNO3 + #.029 CO + #.017 CO2 + #.7 RCHO + 

#.3 ACET + #.263 PROD2 + #.031 xHO2 + #.7 xMECO3 + #.703 

xHCHO + #.001 xCCHO + #.03 xRCHO + #.737 yR6OOH + 

#3.141 XC 

 9.37e-12 e8 CITRNLOL + NO3 = #1.337 RO2C + #.389 RO2XC + #.389 

zRNO3 + #.084 xNO2 + #.527 xHO2 + #.018 xHCHO + #.013 

xCCHO + #.084 xRCHO + #.084 xACET + #.016 xPROD2 + #.528 

xRNO3 + yR6OOH + #3.854 XC + #.388 XN 

 3.71e-11 e8 CITRNLOL + O3P = PROD2 + #4 XC 

Linalool 1.22e-10 e8 LINALOOL + OH = #.775 RO2C + #.232 RO2XC + #.232 zRNO3 

+ #.768 xHO2 + #.064 xHCHO + #.131 xCCHO + #.637 xRCHO + 

#.558 xACET + #.137 xPROD2 + #.009 xMVK + yR6OOH + 

#3.841 XC 

 3.58e-16 e8 LINALOOL + O3 = #.712 OH + #.013 HO2 + #.737 RO2C + #.006 

RO2XC + #.006 zRNO3 + #.036 CO + #.019 CO2 + #.014 HCHO + 

#.694 RCHO + #.292 ACET + #.269 PROD2 + #.005 HCOOH + 

#.03 xHO2 + #.68 xMECO3 + #.704 xHCHO + #.006 xRCHO + 

#.024 xMVK + #.717 yR6OOH + #3.136 XC 

 9.38e-12 e8 LINALOOL + NO3 = #1.298 RO2C + #.388 RO2XC + #.388 

zRNO3 + #.084 xNO2 + #.528 xHO2 + #.084 xRCHO + #.084 

xACET + #.528 xMVK + #.528 xRNO3 + yR6OOH + #1.887 XC + 

#.388 XN 

 6.60e-11 e8 LINALOOL + O3P = PROD2 + #4 XC 

Geraniol 1.80e-10 e8 GERANIOL + OH = #.003 HO2 + #.791 RO2C + #.231 RO2XC + 

#.231 zRNO3 + #.761 xHO2 + #.005 xMEO2 + #.014 xHCHO + 

#.378 xCCHO + #.378 xRCHO + #.378 xACET + #.378 xPROD2 + 

#.003 xMACR + #.005 xMVK + #.013 xIPRD + #.997 yR6OOH + 

#3.205 XC 

 6.96e-16 e8 GERANIOL + O3 = #.728 OH + #.028 HO2 + #.672 RO2C + #.064 

RO2XC + #.064 zRNO3 + #.029 CO + #.017 CO2 + #.019 HCHO + 

#.35 CCHO + #.35 RCHO + #.15 ACET + #.004 MEK + #.281 

PROD2 + #.128 RCOOH + #.015 xHO2 + #.608 xMECO3 + #.031 

xRCO3 + #.413 xHCHO + #.258 xRCHO + #.014 xMACR + #.001 

xIPRD + #.719 yR6OOH + #2.708 XC 

 1.87e-11 e8 GERANIOL + NO3 = #1.096 RO2C + #.319 RO2XC + #.319 

zRNO3 + #.419 xNO2 + #.254 xHO2 + #.008 xMEO2 + #.242 

xHCHO + #.37 xCCHO + #.055 xRCHO + #.055 xACET + #.364 

xPROD2 + #.006 xMACR + #.008 xMVK + #.018 xIPRD + #.266 

xRNO3 + yR6OOH + #2.841 XC + #.315 XN 

 1.35e-10 e8 GERANIOL + O3P = PROD2 + #4 XC 
Table A-1 (continued) 

65 

Reaction Rate [a] Compound Expression Ref Reactions 

 

Hydroxycitronellal 2.80e-11 e8 HYCITRLL + OH = #.696 RCO3 + #.366 RO2C + #.103 RO2XC + 

#.103 zRNO3 + #.181 xHO2 + #.02 xRCO3 + #.012 xCO + #.02 

xHCHO + #.005 xCCHO + #.183 xRCHO + #.098 xACET + #.002 

xPROD2 + #.015 xMGLY + #.304 yR6OOH + #6.294 XC 

 Phot set= C2CHO e9 HYCITRLL + HV = HO2 + #1.43 RO2C + #.372 RO2XC + #.372 

zRNO3 + CO + #.628 xHO2 + #.006 xHCHO + #.622 xRCHO + 

#.006 xPROD2 + yR6OOH + #4.86 XC 

2-ethylhexyl benzoate 1.37e-11 e10 2EHXBOAT + OH = #.067 OH + #.039 HO2 + #1.286 RO2C + 

#.352 RO2XC + #.352 zRNO3 + #.039 CRES + #.067 AFG3 + 

#.539 xHO2 + #.045 xGLY + #.029 MGLY + #.382 xPROD2 + 

#.003 xRCO3 + #.101 xRCHO + #.037 xAFG1 + #.037 xAFG2 + 

#.801 yR6OOH + #.094 yRAOOH + #8.998 XC 

1-nitropropane 1.33e-12 e8 C3-NO2 + OH = #.955 RO2C + #.045 RO2XC + #.045 zRNO3 + 

#.955 xHO2 + #.129 xRCHO + yROOH + XN + #2.346 XC 

ethyl methyl ketone 

oxime 

1.25e-12 e11 EMKO + OH = #.04 {RO2XC + zRNO3} + #.96 {RO2C + xHO2 + 

xPROD2} + #-2 XC + XN 

 3.89e-12 e12 EMKO + OH = HO2 + EMKO-NO 

methyl nonafluoro 

butyl ether 

1.15e-12 e8 MEONC4F9 + OH = #.935 RO2C + #.065 RO2XC + #.065 zRNO3 

+ #.935 xHO2 + #.935 NROG + yROOH + #3.675 XC 

ethyl nonafluoro butyl 

ether 

7.97e-12 e8 ETONC4F9 + OH = #.902 RO2C + #.098 RO2XC + #.098 zRNO3 

+ #.902 xHO2 + #.019 xRCHO + #.883 NROG + yROOH + #4.473 

XC 

 [a] Rate constants are in units of cm3 molec-1 s-1. If a temperature dependence is used, it is given by k(T) 

= A exp(-Ea/RT), where T is the temperature in degrees k and R = 0.0019872. For photolysis 

reactions, the "Phot set" is the set of absorption cross sections and wavelength-dependent quantum 

yields (if any) given in Table A-3 of the SAPRC-07 documentation report (Carter, 2007a), and "qy" is 

the wavelength-independent quantum yield, if applicable. "Same k as Rxn xxx" indicates that the rate 

constant is the same as a reaction in the base mechanism as listed in Table A-2 of the SAPRC-07 

documentation report, where "xxx" is the reaction label. References for measured rate constants or 

photolysis data are as follows: 

1 Average of values tabulated by Carl and Crowley (1998). 

2 Rate constant from Tuazon et al (1994) 

3 Koch et al (1996) 

4 Average of values of Harris and Pitts (1983) and Anderson and Stephens (1988), as tabulated by 

Atkinson (1989). 

5 Harris and Pitts (1983) 

6 As recommended or tabulated by Atkinson and Arey (2003) 

7 As recommended or tabulated by Calvert et al (2002) 

Methods used to estimate rate constants or photolysis rates are as follows: 

e1 Estimated based on the NO3 + NMP rate constant and assuming ratios of rate constants for 

reactions of NO3 at various types of amine groups is the same as those estimated for the reactions 

of OH with those groups. Reaction assumed to occur only from NH or NH2 or from C-H bonds 

on carbons bonded to the amino group. 

e2 This represents the removal of amines available for gas-phase reaction by reacting with HNO3 to 

form the amine salt that is removed from the system. The rate constant shown is an estimated 

upper limit. The upper limit rate constant is arbitrarily estimated based on typical rate constants 

for radical + NOx reactions, which is sufficiently large that this would dominate over other gasphase reactions if gas-phase HNO3 were available. Because of the uncertainty and variability of 
Table A-1 (continued) 

66 

availability of HNO3 in atmospheric scenarios, the atmospheric reactivity calculations are carried 

out both with these amine + HNO3 reactions with the upper limit rate constant, and assuming that 

this reaction is negligible (or rapidly reversed). However, it is recommended that the reactivity 

values used for amines for regulatory applications be based on the assumption that net loss of the 

amine by this reaction is negligible. This will provide a reasonable upper limit on the magnitude 

of the amines' impacts on O3 under conditions where they will have their maximum impact. 

e3 Estimated from the estimated rate of reaction of OH at the alpha position, and correlations 

between this and the measured O3 rate constants of Tuazon et al (1994) for the methylamines and 

DMAE. 

e4 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. 

e5 This represents the reactions of N-centered radicals that lack alpha hydrogens with NO2 to form 

nitramines. Rate constant assumed to be the same as used for lumped higher acylperoxy (RCO3) 

+ NO2. The nitramines are very approximately represented by PROD2. The appropriateness of 

this representation is uncertain. 

e6 The formation of nitrosoamines is neglected because these products are rapidly decomposed by 

photolysis under conditions where ozone formation occurs. 

e7 This represents the reactions of N-centered radicals that lack alpha hydrogens with HO2 to form 

O2 and re-form the amine. The rate constant assumed to be the same as used for lumped higher 

acylperoxy (RCO3) + HO2. The amines that form these radicals are generally inhibitors, so 

representing them with reactive model species is inappropriate. Therefore, they are represented as 

being inert. 

e8 Estimated using the group-additivity estimation assignments implemented in the current 

mechanism generation system. See Carter (2000a) and the discussion of the mechanism 

generation system in this report. 

e9 Assumed to have the same photolysis rate as propionaldehyde (model species RCHO). 

e10 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 

compound. 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. 

e11 The rate constant for addition of OH to the C=N double 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). 

e12 The rate constants for addition to the methyl groups were estimated using the structure-reactivity 

methods incorporated in the mechanism generation system. 
67 

Table A-2. New lumped molecule representations used for atmospheric reactivity estimates of 

compounds added to the reactivity tabulations for this project. 

Compound Represented by (on molar basis) 

Hexyl cinnamal lumped c5+ unsaturated carbonyl species 

(isoprene product) 

Cinnamic aldehyde lumped c5+ unsaturated carbonyl species 

Amyl cinnamal lumped c5+ unsaturated carbonyl species 

4-vinylphenol styrene 

methylparaben (4-Hydroxybenzoic acid, methyl ester) o-cresol 

propylparaben o-cresol 

2,6-di-tert-butyl-p-cresol o-cresol 

beta-phenethyl alcohol benzyl alcohol 

Cinnamic alcohol β-methyl styrene 

anethol β-methyl styrene 

triethylene diamine triethyl amine 

lauryl pyrrolidone n-methyl-2-pyrrolidone 

o-dichlorobenzene p-dichlorobenzene 

2-chlorotoluene toluene 

methyl nonafluoroisobutyl ether methyl nonafluorobutyl ether 

ethyl nonafluoroisobutyl ether ethyl nonafluorobutyl ether 
68 

APPENDIX B. CHAMBER EXPERIMENT LISTING 

Table B-1. Summary chamber experiments relevant to this project. 

Run Date Type [b] Purpose and Conditions Results 

777 6/26 CO - NOx

Irradiation 

Characterize chamber radical 

source. ~25 ppb NOx and 50 ppm 

CO injected into both sides. 

Data indicated that chamber 

radical source in the normal 

range. Somewhat higher radical 

source in Side A. See Figure 4. 

778 6/27 Pure Air 

Irradiation 

Background characterization. No 

injections. 

4 ppb O3 formed after 5 hours on 

both sides. PM levels low on both 

sides but somewhat higher on 

Side A 

779 6/28 MIR surrogate + 

ethanolamine 

(both sides) 

Intended to be incremental 

reactivity experiment to evaluate 

ethanolamine mechanism, but 

~100 ppb ethanolamine injected 

into both sides, so no base case 

experiment was carried out. 

Results were similar to 

subsequent MIR surrogate 

experiments with similar levels of 

ethanolamine. Run not used for 

mechanism evaluation because of 

lack of base case data. 

780 6/29 MIR surrogate + 

ethanolamine 

Incremental reactivity experiment 

to evaluate ethanolamine 

mechanism. ~100 ppb 

ethanolamine injected into Side A.

Run ended early because of 

experimental problems. Results 

shown on Table 6 and Figure 7. 

781 7/3 MIR surrogate + 

AMP 

Incremental reactivity experiment 

to evaluate AMP mechanism. 0.5 

ppm AMP injected into Side A. 

Essentially no ozone formed on 

added AMP side. Measurement 

data are uncertain because of 

sampling problem, but data 

looked reasonable after an 

estimated correction was made. 

Results shown on Table 6, Table 

8, and Figure 6. 

782 7/5 MIR surrogate + 

AMP 

Repeat previous experiment 

because results were not as 

expected. 

Results similar to previous 

experiment. Measurement data are 

uncertain because of sampling 

problem, but data looked 

reasonable after an estimated 

correction was made Results 

shown on Table 6, Table 8 and 

Figure 6. 

783 7/6 MOIR/2 

surrogate + AMP

Incremental reactivity experiment 

to evaluate AMP mechanism. 

~100 ppb AMP injected into Side 

A. 

Results shown on Table 6, Table 8

and Figure 6. 

784 7/9 MOIR/2 

surrogate + AMP

Repeat previous experiment Results shown on Table 6, Table 8

and Figure 6. 
Table B-1 (continued) 

69 

Run Date Type [b] Purpose and Conditions Results 

785 7/10 MIR surrogate 

side equivalency 

test 

Test for side equivalency in 

reactivity experiments. Standard 

base case MIR surrogate - NOx

run on both sides. 

Reasonably good side equivalency

seen. Results summarized on 

Table 6 and Table 8. 

786 7/11 CO - air 

irradiation 

Characterize background NOx

offgasing. 50 ppm CO injected 

into both sides 

Data indicated that the NOx

offgasing rates were in the normal 

range Somewhat higher NOx

offgasing in Side A. See Figure 4.

787 7/12 Pure Air 

Irradiation 

Background characterization. No 

injections. 

3 ppb O3 formed after 5 hours on 

both sides. PM levels low on both 

sides but somewhat higher on 

Side A 

788 7/13 Pure Air 

Irradiation 

Background characterization. No 

injections. 

Results similar to previous run. 4 

ppb O3 formed after 5 hours on 

both sides. PM levels low on both 

sides but somewhat higher on 

Side A 

789 7/16 MOIR/2 

surrogate + AMP

Incremental reactivity experiment 

to evaluate AMP mechanism. ~50 

ppb AMP injected into Side B. 

Results shown on Table 6, Table 8

and Figure 6. 

790 7/17 MIR surrogate + 

ethanolamine 

Incremental reactivity experiment 

to evaluate ethanolamine 

mechanism. ~100 ppb 

ethanolamine injected into Side A.

Effect of ethanolamine on gasphase results was unexpectedly 

small, but effect on PM was large. 

Results shown on Table 6, Table 8

and Figure 7. 

791 7/18 MOIR/2 

surrogate + 

ethanolamine 

Incremental reactivity experiment 

to evaluate ethanolamine 

mechanism. ~50 ppb 

ethanolamine injected into Side A.

Effect of ethanolamine on gasphase results was unexpectedly 

small, but effect on PM was large. 

Results shown on Table 6, Table 8

and Figure 7. 

792 7/19 MOIR/2 

surrogate + AMP

Incremental reactivity experiment 

to evaluate AMP mechanism. ~50 

ppb AMP injected into Side A. 

Results shown on Table 6, Table 8

and Figure 6. 

793 7/24 MIR surrogate + 

d-Limonene 

Incremental reactivity experiment 

to evaluate d-limonene 

mechanism. 35 ppb d-limonene 

injected into Side A. 

Results shown on Table 6, Table 8

and Figure 11. 

794 7/25 d-Limonene - 

NOx Irradiation 

Evaluate d-limonene mechanism 

in the absence of other reactants. 

See Table 7. 

Data on Side A not useable 

because of instrument and 

sampling problem. Results for 

Side B shown on Table 7 and 

Figure 12 

795 7/26 d-Limonene - 

NOx Irradiation 

Evaluate d-limonene mechanism 

in the absence of other reactants. 

See Table 7. 

Results shown on Table 7 and 

Figure 12 
Table B-1 (continued) 

70 

Run Date Type [b] Purpose and Conditions Results 

796 7/27 Pure Air 

Irradiation 

Background characterization. No 

injections. 

Unusually high O3 and PM 

formation on both sides, with 

higher levels on Side A. Chamber 

apparently contaminated, though 

reason is unknown. 5-Hour O3

was 20 and 11 ppb on Sides A and

B, respectively. 

797 7/30 MIR surrogate + 

d-Limonene 

Incremental reactivity experiment 

to evaluate d-limonene 

mechanism. 26 ppb d-limonene 

injected into Side A. 

Results shown on Table 6, Table 8

and Figure 11. 

798 8/1 MOIR/2 

surrogate + 

ethanolamine 

Incremental reactivity experiment 

to evaluate ethanolamine 

mechanism. ~100 ppb 

ethanolamine injected into Side A.

Effect on O3 formation was 

relatively small. Results shown on 

Table 6, Table 8 and Figure 11. 

799 8/3 MIR surrogate + 

AMP 

Evaluate AMP mechanism with 

lower added AMP levels. ~60 ppb 

AMP injected into Side A. 

Results shown on Table 6, Table 8

and Figure 6. 

801 8/7 Pure Air 

Irradiation 

Background characterization. No 

injections. 

5-Hour O3 was 7 and 3 ppb on 

Sides A and B, respectively. PM 

levels low on both sides but 

somewhat higher on Side A. 

802 8/8 Pure Air 

Irradiation 

Background characterization. No 

injections. 

Results similar to previous run. 5-

Hour O3 was 5 and 2 ppb on 

Sides A and B, respectively. PM 

levels low on both sides but 

somewhat higher on Side A. 

804 8/13 MOIR/2 

surrogate + 

d-limonene 

Incremental reactivity experiment 

to evaluate d-limonene 

mechanism. 25 ppb d-limonene 

injected into Side A. 

Results shown on Table 6, Table 8

and Figure 11. 

805 8/14 MOIR/2 

surrogate + 

ethanolamine 

Incremental reactivity experiment 

to evaluate ethanolamine 

mechanism. ~250 ppb 

ethanolamine injected into Side A.

Results shown on Table 6, Table 8

and Figure 7. 

806 8/15 MOIR/2 

surrogate + tbutyl amine 

Incremental reactivity experiment 

to evaluate t-butyl amine 

mechanism. ~250 ppb t-butyl 

amine injected into Side A. 

t-Butyl amine caused significant 

inhibition of gas-phase reactivity. 

Results shown on Table 6, Table 8

and Figure 7. 

807 8/16 MOIR/2 

surrogate + 

isopropyl amine 

Incremental reactivity experiment 

to evaluate isopropyl amine 

mechanism. ~250 ppb isopropyl 

amine injected into Side A. 

Isopropyl amine enhanced rate of 

O3 formation. Results shown on 

Table 6, Table 8 and Figure 7. 
Table B-1 (continued) 

71 

Run Date Type [b] Purpose and Conditions Results 

808 8/17 CO - NOx

Irradiation 

Characterize chamber radical 

source. ~25 ppb NOx and 60 ppm 

CO injected into both sides. 

Data indicated that radical source 

rate was in normal range for Side 

A. No useable data for Side B 

because of sampling problems. 

See Figure 4. 

809 8/18 Pure Air 

Irradiation 

Background characterization. No 

injections. 

5-Hour O3 was 6 and 2 ppb on 

Sides A and B, respectively. PM 

levels low on both sides but 

somewhat higher on Side A. 

[a] “Surrogate” refers to the 8-component “Full Surrogate” as used in previous environmental chamber 

incremental reactivity studies in our laboratories, except that formaldehyde was removed and the 

other ROG components were increased by 10% to yield approximately the same reactivity as 

discussed by Carter and Malkina (2005). The designation “MIR Surrogate” refers to experiments with 

0.55 ppmC base case surrogate and 30 ppb NOx, The designation “MOIR/2 Surrogate” refers to 

experiments with 1.1 ppmC base case surrogate and 25 ppb NOx. 
72 

APPENDIX C. UPDATED VOC AND ATMOSPHERIC REACTIVITY LISTING 

Table C-1. Listing of VOCs for which atmospheric ozone impact estimates are available, their 

representation in the model, and their calculated atmospheric reactivity values in various 

reactivity scales. This tabulation is current as of December 20, 2007. 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

carbon monoxide 630-08-0 28.01 Exp 1 2 0 1 0.052 0.038 0.029 0.035±0.007

methane 74-82-8 16.04 Exp 1 0 6 0.014 0.008 0.006 0.008±0.002

ethane 74-84-0 30.07 Exp 1 3 0 1 0.26 0.183 0.132 0.163±0.043

propane 74-98-6 44.10 Exp 1 3 0 1 0.46 0.32 0.23 0.28±0.07 

n-butane 106-97-8 58.12 Exp 1 2 0 1 1.08 0.71 0.48 0.62±0.17 

n-pentane 109-66-0 72.15 Exp 1 0 6 1.22 0.80 0.51 0.69±0.21 

n-hexane 110-54-3 86.18 Exp 1 3 0 2 1.14 0.76 0.44 0.63±0.21 

n-heptane 142-82-5 100.20 Exp 1 0 6 0.97 0.64 0.33 0.51±0.20 

n-octane 111-65-9 114.23 Exp 1 1 0 2 0.80 0.53 0.23 0.40±0.19 

n-nonane 111-84-2 128.26 Exp 1 0,+ 6 b 0.68 0.45 0.171 0.32±0.18 

n-decane 124-18-5 142.28 Exp 1 0,+ 6 b 0.59 0.39 0.129 0.27±0.17 

n-undecane 1120-21-4 156.31 Exp 1 0,+ 6 b 0.52 0.35 0.104 0.23±0.15 

n-dodecane 112-40-3 170.33 Exp 1 2 0,+ 3 b 0.47 0.32 0.088 0.21±0.15 

n-tridecane 629-50-5 184.36 Exp 1 0,+ 6 b 0.45 0.30 0.083 0.198±0.140

n-tetradecane 629-59-4 198.39 Exp 1 2 0,+ 3 b 0.43 0.29 0.084 0.194±0.136

n-pentadecane 629-62-9 212.41 Exp 1 4 0,+ 3 b 0.42 0.28 0.085 0.189±0.130

n-c16 544-76-3 226.44 AdjP 1 3 0,+ 3 b 0.36 0.25 0.051 0.156±0.136

n-c17 629-78-7 240.47 LM 0,+ 7 b 0.34 0.24 0.048 0.147±0.128

n-c18 593-45-3 254.49 LM 0,+ 7 b 0.32 0.23 0.045 0.138±0.121

n-c19 629-92-5 268.52 LM 0,+ 7 b 0.31 0.21 0.043 0.131±0.115

n-c20 112-95-8 282.55 LM 0,+ 7 b 0.29 0.20 0.041 0.125±0.109

n-c21 629-94-7 296.57 LM 0,+ 7 b 0.28 0.194 0.039 0.119±0.104

n-c22 629-97-0 310.60 LM 0,+ 7 b 0.27 0.186 0.037 0.113±0.099

isobutane 75-28-5 58.12 Exp 1 3 0 2 1.18 0.70 0.48 0.63±0.16 

branched c5 alkanes 72.15 LM 0 8 1.36 0.88 0.61 0.78±0.20 

neopentane 463-82-1 72.15 Exp 1 0 6 0.65 0.38 0.26 0.34±0.09 

iso-pentane 78-78-4 72.15 Exp 1 0 6 1.36 0.88 0.61 0.78±0.20 

branched c6 alkanes 86.18 LM 0 8 1.22 0.77 0.51 0.67±0.19 

2,2-dimethyl butane 75-83-2 86.18 Exp 1 0 6 1.11 0.67 0.43 0.59±0.17 

2,3-dimethyl butane 79-29-8 86.18 Exp 1 0 6 0.90 0.61 0.41 0.53±0.13 

2-methyl pentane 107-83-5 86.18 Exp 1 0 6 1.40 0.84 0.52 0.72±0.23 

3-methylpentane 96-14-0 86.18 Exp 1 0 6 1.69 1.04 0.68 0.91±0.26 

branched c7 alkanes 100.20 LM 0 8 1.38 0.81 0.47 0.68±0.23 

2,2,3-trimethyl butane 464-06-2 100.20 Exp 1 0 6 1.05 0.62 0.39 0.54±0.15 

2,2-dimethyl pentane 590-35-2 100.20 Exp 1 0 6 1.04 0.63 0.38 0.53±0.17 

2,3-dimethyl pentane 565-59-3 100.20 Exp 0 7 1.25 0.77 0.48 0.66±0.20 

2,4-dimethyl pentane 108-08-7 100.20 Exp 1 0 6 1.46 0.84 0.51 0.72±0.23 

2-methyl hexane 591-76-4 100.20 AdjP 0 7 1.09 0.68 0.37 0.55±0.20 

3,3-dimethyl pentane 562-49-2 100.20 Exp 0 7 1.12 0.70 0.45 0.61±0.18 

3-methyl hexane 589-34-4 100.20 Exp 0 7 1.50 0.88 0.51 0.74±0.26 

3-ethylpentane 617-78-7 100.20 Exp 0 7 1.78 1.03 0.64 0.89±0.28 
Table C-1 (continued) 

73 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

branched c8 alkanes 114.23 LM 0 8 1.33 0.77 0.40 0.63±0.25 

2,2,3,3-tetramethyl butane 594-82-1 114.23 Exp 1 0 6 0.30 0.183 0.101 0.151±0.053

2,2,4-trimethyl pentane 540-84-1 114.23 Exp 1 3 0 2 1.20 0.67 0.41 0.58±0.18 

2,2-dimethyl hexane 590-73-8 114.23 Exp 1 0 6 0.94 0.55 0.29 0.45±0.17 

2,3,4-trimethyl pentane 565-75-3 114.23 Exp 1 0 6 0.95 0.60 0.35 0.50±0.16 

2,3-dimethyl hexane 584-94-1 114.23 Exp 0 7 1.09 0.67 0.37 0.55±0.20 

2,4-dimethyl hexane 589-43-5 114.23 Exp 0 7 1.61 0.90 0.48 0.74±0.28 

2,5-dimethyl hexane 592-13-2 114.23 Exp 0 7 1.35 0.78 0.42 0.64±0.24 

2-methyl heptane 592-27-8 114.23 Exp 0 7 0.97 0.61 0.29 0.48±0.20 

3-methyl heptane 589-81-1 114.23 Exp 0 7 1.12 0.70 0.35 0.55±0.22 

4-methyl heptane 589-53-7 114.23 Exp 0 7 1.14 0.68 0.34 0.54±0.22 

2,3,3-trimethylpentane 560-21-4 114.23 Exp 0 7 0.95 0.60 0.37 0.51±0.15 

3,3-dimethylhexane 563-16-6 114.23 Exp 0 7 1.15 0.68 0.38 0.57±0.20 

2,2,3-trimethyl-pentane 564-02-3 114.23 Exp 0 7 1.15 0.66 0.39 0.56±0.18 

3,4-dimethylhexane 583-48-2 114.23 Exp 0 7 1.40 0.83 0.48 0.70±0.24 

3-ethyl 2-methyl pentane 609-26-7 114.23 Exp 0 7 1.24 0.72 0.41 0.61±0.21 

branched c9 alkanes 128.26 LM 0 8 b 1.03 0.61 0.27 0.47±0.22 

2,2,5-trimethyl hexane 3522-94-9 128.26 Exp 0 7 b 1.05 0.59 0.31 0.49±0.19 

2,3,5-trimethyl hexane 1069-53-0 128.26 AdjP 1 0 6 b 1.12 0.66 0.34 0.54±0.21 

2,4-dimethyl heptane 2213-23-2 128.26 Exp 0 7 b 1.27 0.71 0.33 0.56±0.25 

2-methyl octane 3221-61-2 128.26 Exp 1 0,+ 6 b 0.73 0.47 0.183 0.34±0.18 

3,3-diethyl pentane 1067-20-5 128.26 Exp 1 0,+ 6 b 1.13 0.68 0.39 0.57±0.20 

3,5-dimethyl heptane 926-82-9 128.26 Exp 0 7 b 1.42 0.83 0.41 0.66±0.28 

4-ethyl heptane 2216-32-2 128.26 Exp 0 7 b 1.11 0.65 0.31 0.51±0.23 

4-methyl octane 2216-34-4 128.26 Exp 1 0,+ 6 b 0.85 0.53 0.23 0.40±0.20 

2,4,4-trimethylhexane 16747-30-1 128.26 Exp 0 7 b 1.25 0.70 0.37 0.58±0.22 

3,3-dimethylheptane 4032-86-4 128.26 Exp 0 7 b 1.04 0.62 0.32 0.50±0.20 

4,4-dimethylheptane 1068-19-5 128.26 Exp 0 7 b 1.18 0.65 0.33 0.53±0.22 

2,2-dimethylheptane 1071-26-7 128.26 Exp 0 7 b 0.92 0.53 0.26 0.42±0.18 

2,2,4-trimethylhexane 16747-26-5 128.26 Exp 0 7 b 1.17 0.64 0.31 0.52±0.21 

2,6-dimethylheptane 1072-05-5 128.26 Exp 0 7 b 0.94 0.55 0.25 0.43±0.20 

2,3-dimethylheptane 3074-71-3 128.26 Exp 0 7 b 0.98 0.61 0.30 0.48±0.20 

2,5-dimethylheptane 2216-30-0 128.26 Exp 0 7 b 1.23 0.73 0.36 0.58±0.24 

3-methyloctane 2216-33-3 128.26 Exp 0 7 b 0.88 0.55 0.24 0.42±0.20 

3,4-dimethylheptane 922-28-1 128.26 Exp 0 7 b 1.13 0.69 0.35 0.55±0.22 

3-ethylheptane 15869-80-4 128.26 Exp 0 7 b 0.99 0.60 0.27 0.46±0.21 

branched c10 alkanes 142.28 LM 0 8 b 0.83 0.50 0.20 0.37±0.19 

2,4,6-trimethyl heptane 2613-61-8 142.28 Exp 0 7 b 1.18 0.64 0.28 0.50±0.24 

2,4-dimethyl octane 4032-94-4 142.28 Exp 0 7 b 0.92 0.54 0.22 0.41±0.21 

2,6-dimethyl octane 2051-30-1 142.28 Exp 1 2 0,+ 2 b 0.98 0.56 0.25 0.43±0.21 

2-methyl nonane 871-83-0 142.28 Exp 1 2 0,+ 2 b 0.63 0.41 0.135 0.28±0.18 

3,4-diethyl hexane 19398-77-7 142.28 Exp 1 2 0,+ 2 b 0.81 0.49 0.24 0.38±0.16 

3-methyl nonane 5911-04-6 142.28 Exp 0 7 b 0.66 0.42 0.145 0.30±0.18 

4-methyl nonane 17301-94-9 142.28 Exp 0 7 b 0.76 0.47 0.181 0.34±0.19 

4-propyl heptane 3178-29-8 142.28 Exp 0 7 b 0.91 0.54 0.23 0.41±0.20 

2,4,4-trimethylheptane 142.28 Exp 0 7 b 1.22 0.65 0.31 0.53±0.23 

2,5,5-trimethylheptane 142.28 Exp 0 7 b 1.15 0.65 0.33 0.53±0.21 

3,3-dimethyloctane 4110-44-5 142.28 Exp 0 7 b 1.00 0.58 0.28 0.46±0.20 

4,4-dimethyloctane 15869-95-1 142.28 Exp 0 7 b 1.04 0.59 0.28 0.47±0.21 
Table C-1 (continued) 

74 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

2,2-dimethyloctane 15869-87-1 142.28 Exp 0 7 b 0.76 0.44 0.185 0.33±0.16 

2,2,4-trimethylheptane 14720-74-2 142.28 Exp 0 7 b 1.08 0.58 0.26 0.46±0.21 

2,2,5-trimethylheptane 142.28 Exp 0 7 b 1.17 0.65 0.34 0.54±0.21 

2,3,6-trimethylheptane 4032-93-3 142.28 AdjP 0 7 b 0.80 0.50 0.21 0.37±0.18 

2,3-dimethyloctane 7146-60-3 142.28 Exp 0 7 b 0.76 0.48 0.20 0.36±0.18 

2,5-dimethyloctane 142.28 Exp 0 7 b 0.92 0.55 0.22 0.41±0.21 

2-methyl-3-ethylheptane 14676-29-0 142.28 Exp 0 7 b 0.89 0.54 0.24 0.41±0.20 

4-ethyloctane 15869-86-0 142.28 AdjP 0 7 b 0.68 0.44 0.131 0.30±0.20 

branched c11 alkanes 156.31 LM 0 8 b 0.63 0.40 0.130 0.28±0.17 

2,3,4,6-tetramethyl heptane 61868-54-0 156.31 Exp 0 7 b 1.00 0.59 0.27 0.46±0.21 

2,6-dimethyl nonane 17302-28-2 156.31 Exp 0 7 b 0.69 0.42 0.149 0.30±0.17 

3,5-diethyl heptane 61869-02-1 156.31 Exp 0 7 b 0.99 0.58 0.23 0.43±0.23 

3-methyl decane 13151-34-3 156.31 Exp 0 7 b 0.55 0.36 0.106 0.24±0.16 

4-methyl decane 2847-72-5 156.31 Exp 0 7 b 0.59 0.38 0.118 0.26±0.17 

branched c12 alkanes 170.33 LM 0 8 b 0.54 0.35 0.077 0.22±0.17 

2,3,5,7-tetramethyl octane 62199-32-0 170.33 Exp 0 7 b 0.81 0.47 0.174 0.34±0.19 

2,6-diethyl octane 62183-94-2 170.33 Exp 0 7 b 0.86 0.51 0.22 0.39±0.19 

3,6-dimethyl decane 17312-53-7 170.33 AdjP 0 7 b 0.59 0.38 0.089 0.24±0.18 

3-methyl undecane 1002-43-3 170.33 Exp 0 7 b 0.50 0.33 0.091 0.22±0.15 

5-methyl undecane 1632-70-8 170.33 AdjP 0 7 b 0.46 0.31 0.040 0.179±0.169

branched c13 alkanes 184.36 LM 0 8 b 0.51 0.33 0.084 0.21±0.16 

2,3,6-trimethyl 4-isopropyl 

heptane 

 184.36 Exp 0 7 b 0.83 0.48 0.20 0.36±0.19 

2,4,6,8-tetramethyl nonane 14638-54-1 184.36 AdjP 0 7 b 0.66 0.38 0.105 0.26±0.18 

3,6-dimethyl undecane 17301-28-9 184.36 Exp 0 7 b 0.60 0.37 0.119 0.26±0.16 

3,7-diethyl nonane 184.36 Exp 0 7 b 0.79 0.45 0.176 0.34±0.18 

3-methyl dodecane 17312-57-1 184.36 Exp 0 7 b 0.46 0.31 0.082 0.20±0.14 

5-methyl dodecane 17453-93-9 184.36 AdjP 0 7 b 0.38 0.26 0.017 0.143±0.157

branched c14 alkanes 198.39 LM 0 8 b 0.47 0.30 0.077 0.197±0.146

2,4,5,6,8-pentamethyl 

nonane 

 198.39 Exp 0 7 b 0.84 0.51 0.20 0.37±0.20 

2-methyl 3,5-diisopropyl 

heptane 

 198.39 AdjP 0 7 b 0.47 0.30 0.066 0.189±0.150

3,7-dimethyl dodecane 82144-67-0 198.39 Exp 0 7 b 0.54 0.34 0.107 0.23±0.15 

3,8-diethyl decane 6224-52-8 198.39 AdjP 0 7 b 0.50 0.33 0.076 0.21±0.16 

3-methyl tridecane 6418-41-3 198.39 Exp 0 7 b 0.43 0.29 0.077 0.188±0.137

6-methyl tridecane 13287-21-3 198.39 AdjP 0 7 b 0.37 0.25 0.019 0.139±0.152

branched c15 alkanes 212.41 LM 0 8 b 0.42 0.28 0.067 0.179±0.138

2,6,8-trimethyl 4-isopropyl 

nonane 

 212.41 Exp 0 7 b 0.54 0.33 0.099 0.23±0.15 

3,7-dimethyl tridecane 212.41 Exp 0 7 b 0.47 0.30 0.091 0.20±0.14 

3,9-diethyl undecane 13286-72-1 212.41 Exp 0 7 b 0.43 0.29 0.078 0.188±0.138

3-methyl tetradecane 18435-22-8 212.41 Exp 0 7 b 0.40 0.27 0.074 0.178±0.130

6-methyl tetradecane 26730-16-5 212.41 AdjP 0 7 b 0.34 0.24 0.015 0.127±0.144

branched c16 alkanes 226.44 LM 0 8 b 0.40 0.26 0.074 0.174±0.127

2,7-dimethyl 3,5-

diisopropyl heptane 

 226.44 AdjP 0 7 b 0.44 0.28 0.057 0.176±0.148

3-methyl pentadecane 2882-96-4 226.44 Exp 0 7 b 0.38 0.26 0.072 0.170±0.124

4,8-dimethyl tetradecane 175032-36-7 226.44 Exp 0 7 b 0.41 0.27 0.076 0.180±0.130
Table C-1 (continued) 

75 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

7-methyl pentadecane 6165-40-8 226.44 Exp 0 7 b 0.38 0.26 0.071 0.168±0.124

branched c17 alkanes 240.47 LM 0 8 b 0.37 0.25 0.069 0.164±0.120

branched c18 alkanes 254.49 LM 0 8 b 0.35 0.24 0.066 0.155±0.113

branched c19 alkanes 268.52 LM 0 8 b 0.33 0.22 0.062 0.147±0.107

branched c20 alkanes 282.55 LM 0 8 b 0.32 0.21 0.059 0.140±0.102

branched c21 alkanes 296.57 LM 0 8 b 0.30 0.20 0.056 0.133±0.097

branched c22 alkanes 310.60 LM 0 8 b 0.29 0.193 0.054 0.127±0.093

cyclopropane 75-19-4 42.08 Exp 1 0 6 0.081 0.056 0.039 0.049±0.014

cyclobutane 287-23-0 56.11 Exp 1 0 6 1.11 0.72 0.48 0.63±0.21 

cyclopentane 287-92-3 70.13 AdjP 1 0 6 2.24 1.31 0.82 1.14±0.35 

c6 cycloalkanes 84.16 LM 0 8 1.14 0.73 0.41 0.60±0.21 

cyclohexane 110-82-7 84.16 AdjP 1 2 0 2 1.14 0.73 0.41 0.60±0.21 

isopropyl cyclopropane 3638-35-5 84.16 Exp 1 0 6 1.14 0.74 0.49 0.65±0.18 

methylcyclopentane 96-37-7 84.16 AdjP 0 7 2.05 1.14 0.66 0.97±0.34 

1,1-dimethylcyclopentane 1638-26-2 98.19 AdjP 0 7 0.99 0.58 0.29 0.47±0.19 

1,2-dimethylcyclopentane 2452-99-5 98.19 AdjP 0 7 1.86 1.00 0.54 0.84±0.32 

c7 cycloalkanes 98.19 LM 0 7 1.56 0.90 0.46 0.72±0.29 

1,3-dimethyl cyclopentane 2453-00-1 98.19 AdjP 0 7 1.81 0.97 0.51 0.80±0.31 

cycloheptane 291-64-5 98.19 AdjP 1 0 6 1.80 1.00 0.53 0.82±0.33 

ethyl cyclopentane 1640-89-7 98.19 AdjP 0 7 1.87 1.03 0.55 0.85±0.33 

methylcyclohexane 108-87-2 98.19 AdjP 1 0 6 1.56 0.90 0.46 0.72±0.29 

c8 bicycloalkanes 110.20 LM 0 8 1.39 0.80 0.41 0.65±0.26 

1,1,2-

trimethylcyclopentane 

4259-00-1 112.21 Exp 0 7 1.02 0.58 0.27 0.46±0.20 

1,1,3-

trimethylcyclopentane 

4516-69-2 112.21 Exp 0 7 0.92 0.53 0.23 0.41±0.19 

1,1-dimethyl cyclohexane 590-66-9 112.21 Exp 0 7 1.12 0.65 0.31 0.51±0.22 

1,2,3-

trimethylcyclopentane 

 112.21 Exp 0 7 1.50 0.83 0.42 0.67±0.28 

1,2,4-

trimethylcyclopentane 

 112.21 Exp 0 7 1.42 0.76 0.36 0.61±0.26 

1-methyl-3-

ethylcyclopentane 

 112.21 AdjP 0 7 1.51 0.82 0.39 0.66±0.29 

1,2-dimethylcyclohexane 583-57-3 112.21 AdjP 0 7 1.27 0.77 0.35 0.59±0.27 

1,4-dimethylcyclohexane 589-90-2 112.21 AdjP 0 7 1.48 0.81 0.37 0.64±0.29 

c8 cycloalkanes 112.21 LM 0 8 1.35 0.78 0.38 0.62±0.26 

1,3-dimethyl cyclohexane 591-21-9 112.21 AdjP 0 7 1.39 0.76 0.34 0.59±0.28 

cyclooctane 292-64-8 112.21 AdjP 1 0 6 1.31 0.74 0.32 0.57±0.28 

ethylcyclohexane 1678-91-7 112.21 Exp 0 7 1.35 0.78 0.38 0.62±0.26 

propyl cyclopentane 2040-96-2 112.21 AdjP 0 7 1.55 0.84 0.40 0.67±0.30 

cis-hydrindane; 

bicyclo[4.3.0]nonane 

496-10-6 124.22 AdjP 0 7 b 1.16 0.64 0.23 0.47±0.27 

c9 bicycloalkanes 124.22 LM 0 8 b 1.25 0.71 0.31 0.55±0.26 

1,2,3-trimethylcyclohexane 1678-97-3 126.24 AdjP 0 7 b 1.08 0.65 0.26 0.48±0.25 

1,3,5-trimethylcyclohexane 1839-63-0 126.24 Exp 0 7 b 1.03 0.57 0.21 0.42±0.23 

c9 cycloalkanes 126.24 LM 0 8 b 1.23 0.69 0.31 0.54±0.26 

1,1,3-trimethyl 

cyclohexane 

3073-66-3 126.24 Exp 1 0 6 b 1.08 0.60 0.25 0.46±0.23 
Table C-1 (continued) 

76 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

1-ethyl-4-methyl 

cyclohexane 

3728-56-1 126.24 AdjP 0 7 b 1.30 0.72 0.30 0.55±0.27 

propyl cyclohexane 1678-92-8 126.24 Exp 0 7 b 1.17 0.67 0.31 0.52±0.24 

c10 bicycloalkanes 138.25 LM 0 8 b 0.97 0.57 0.24 0.43±0.22 

isobutylclohexane; (2-

methylpropyl) cyclohexane 

1678-98-4 140.27 LM 0 8 b 0.88 0.53 0.22 0.40±0.20 

sec-butylcyclohexane 7058-01-7 140.27 LM 0 8 b 0.88 0.53 0.22 0.40±0.20 

c10 cycloalkanes 140.27 LM 0 8 b 0.96 0.56 0.23 0.42±0.21 

1,3-diethyl-cyclohexane 1678-99-5 140.27 AdjP 0 7 b 1.13 0.64 0.26 0.48±0.25 

1,4-diethyl-cyclohexane 1679-00-1 140.27 Exp 0 7 b 1.11 0.62 0.26 0.47±0.24 

1-methyl-3-isopropyl 

cyclohexane 

16580-24-8 140.27 Exp 0 7 b 0.90 0.54 0.22 0.40±0.20 

butyl cyclohexane 1678-93-9 140.27 Exp 1 0 6 b 0.88 0.53 0.22 0.40±0.20 

c11 bicycloalkanes 152.28 LM 0 8 b 0.80 0.48 0.172 0.34±0.20 

c11 cycloalkanes 154.29 LM 0 8 b 0.79 0.47 0.169 0.34±0.20 

1,3-diethyl-5-methyl 

cyclohexane 

164259-42-1 154.29 Exp 0 7 b 0.93 0.52 0.20 0.38±0.21 

1-ethyl-2-propyl 

cyclohexane 

62238-33-9 154.29 AdjP 0 7 b 0.70 0.44 0.140 0.30±0.20 

pentyl cyclohexane 4292-92-6 154.29 Exp 0 7 b 0.74 0.45 0.172 0.33±0.18 

c12 tricycloalkanes 164.29 LM 0 8 b 0.71 0.42 0.130 0.29±0.19 

c12 bicycloalkanes 166.30 LM 0 8 b 0.70 0.42 0.128 0.29±0.19 

c12 cycloalkanes 168.32 LM 0 8 b 0.69 0.41 0.127 0.29±0.19 

1,3,5-triethyl cyclohexane 164259-43-2 168.32 Exp 0 7 b 0.92 0.51 0.20 0.38±0.21 

1-methyl-4-pentyl 

cyclohexane 

75736-67-3 168.32 Exp 0 7 b 0.62 0.38 0.114 0.26±0.18 

hexyl cyclohexane 4292-75-5 168.32 AdjP 1 2 0 2 b 0.54 0.34 0.065 0.21±0.18 

c13 tricycloalkanes 178.31 LM 0 8 b 0.61 0.38 0.111 0.26±0.17 

c13 bicycloalkanes 180.33 LM 0 8 b 0.61 0.37 0.110 0.25±0.17 

c13 cycloalkanes 182.35 LM 0 8 b 0.60 0.37 0.109 0.25±0.17 

1,3-diethyl-5-propyl 

cyclohexane 

 182.35 Exp 0 7 b 0.86 0.48 0.193 0.36±0.19 

1-methyl-2-hexylcyclohexane 92031-93-1 182.35 Exp 0 7 b 0.49 0.32 0.086 0.21±0.16 

heptyl cyclohexane 5617-41-4 182.35 AdjP 0 7 b 0.45 0.30 0.049 0.181±0.166

c14 tricycloalkanes 192.34 LM 0 8 b 0.57 0.35 0.101 0.24±0.17 

c14 bicycloalkanes 194.36 LM 0 8 b 0.57 0.35 0.100 0.23±0.16 

c14 cycloalkanes 196.37 LM 0 8 b 0.56 0.34 0.099 0.23±0.16 

1,3-dipropyl-5-ethyl 

cyclohexane 

 196.37 Exp 0 7 b 0.82 0.46 0.186 0.34±0.18 

trans 1-methyl-4-heptyl 

cyclohexane 

205324-73-8 196.37 Exp 0 7 b 0.44 0.29 0.069 0.186±0.148

octyl cyclohexane 1795-15-9 196.37 AdjP 2 0 7 b 0.42 0.28 0.044 0.168±0.157

c15 tricycloalkanes 206.37 LM 0 8 b 0.54 0.33 0.097 0.22±0.16 

c15 bicycloalkanes 208.38 LM 0 8 b 0.53 0.33 0.096 0.22±0.15 

c15 cycloalkanes 210.40 LM 0 8 b 0.53 0.32 0.095 0.22±0.15 

1,3,5-tripropyl cyclohexane 210.40 Exp 0 7 b 0.78 0.43 0.179 0.33±0.17 

1-methyl-2-octyl 

cyclohexane 

 210.40 AdjP 0 7 b 0.42 0.28 0.075 0.182±0.139

nonyl cyclohexane 2883-02-5 210.40 AdjP 0 7 b 0.38 0.26 0.034 0.149±0.149
Table C-1 (continued) 

77 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

c16 tricycloalkanes 220.39 LM 0 8 b 0.50 0.31 0.091 0.21±0.15 

c16 bicycloalkanes 222.41 LM 0 8 b 0.50 0.31 0.090 0.21±0.14 

c16 cycloalkanes 224.43 LM 0 8 b 0.47 0.29 0.082 0.196±0.142

1,3-propyl-5-butyl 

cyclohexane 

 224.43 Exp 0 7 b 0.67 0.38 0.152 0.28±0.16 

1-methyl-4-nonyl 

cyclohexane 

39762-40-8 224.43 Exp 0 7 b 0.39 0.26 0.065 0.166±0.132

decyl cyclohexane 1795-16-0 224.43 AdjP 0 7 b 0.35 0.24 0.031 0.138±0.141

c17 tricycloalkanes 234.42 LM 0 8 b 0.47 0.29 0.086 0.197±0.137

c17 bicycloalkanes 236.44 LM 0 8 b 0.47 0.29 0.085 0.195±0.136

c17 cycloalkanes 238.45 LM 0 8 b 0.44 0.28 0.077 0.184±0.134

c18 tricycloalkanes 248.45 LM 0 8 b 0.45 0.27 0.081 0.186±0.129

c18 bicycloalkanes 250.46 LM 0 8 b 0.44 0.27 0.080 0.185±0.128

c18 cycloalkanes 252.48 LM 0 8 b 0.42 0.26 0.073 0.174±0.127

c19 tricycloalkanes 262.47 LM 0 8 b 0.42 0.26 0.076 0.176±0.122

c19 bicycloalkanes 264.49 LM 0 8 b 0.42 0.26 0.076 0.175±0.121

c19 cycloalkanes 266.51 LM 0 8 b 0.39 0.25 0.069 0.165±0.120

c20 tricycloalkanes 276.50 LM 0 8 b 0.40 0.25 0.073 0.167±0.116

c20 bicycloalkanes 278.52 LM 0 8 b 0.40 0.24 0.072 0.166±0.115

c20 cycloalkanes 280.53 LM 0 8 b 0.37 0.23 0.066 0.157±0.114

c21 tricycloalkanes 290.53 LM 0 8 b 0.38 0.23 0.069 0.159±0.110

c21 bicycloalkanes 292.54 LM 0 8 b 0.38 0.23 0.069 0.158±0.110

c21 cycloalkanes 294.56 LM 0 8 b 0.36 0.22 0.063 0.149±0.108

c22 tricycloalkanes 304.55 LM 0 8 b 0.36 0.22 0.066 0.152±0.105

c22 bicycloalkanes 306.57 LM 0 8 b 0.36 0.22 0.065 0.151±0.105

c22 cycloalkanes 308.58 LM 0 8 b 0.34 0.21 0.060 0.142±0.104

ethene 74-85-1 28.05 Exp 1 1 0 3 d 8.88 3.72 2.29 3.47±1.30 

propene 115-07-1 42.08 Exp 1 1 0 3 d 11.57 4.53 2.79 4.29±1.66 

1-butene 106-98-9 56.11 Exp 1 3 0 3 d 9.57 3.83 2.35 3.59±1.33 

c4 terminal alkenes 56.11 LM 0 7 9.57 3.83 2.35 3.59±1.33 

1-pentene 109-67-1 70.13 Exp 1 0 6 d 7.07 2.87 1.75 2.67±0.99 

3-methyl-1-butene 563-45-1 70.13 Exp 1 0 6 d 6.86 2.80 1.72 2.61±0.95 

c5 terminal alkenes 70.13 LM 0 7 7.07 2.87 1.75 2.67±0.99 

1-hexene 592-41-6 84.16 Exp 1 4 0 4 d 5.35 2.29 1.41 2.11±0.74 

3,3-dimethyl-1-butene 558-37-2 84.16 Exp 1 0 8 d 5.68 2.41 1.50 2.23±0.78 

3-methyl-1-pentene 760-20-3 84.16 Exp 0 8 6.00 2.50 1.52 2.31±0.83 

4-methyl-1-pentene 691-37-2 84.16 Exp 0 8 5.55 2.28 1.37 2.11±0.78 

c6 terminal alkenes 84.16 LM 0 8 5.35 2.29 1.41 2.11±0.74 

1-heptene 592-76-7 98.19 AdjP 1 0 8 d 4.29 1.86 1.09 1.68±0.61 

3,4-dimethyl-1-pentene 7385-78-6 98.19 Exp 0 8 4.72 1.98 1.18 1.81±0.66 

3-methyl-1-hexene 3404-61-3 98.19 Exp 0 8 4.27 1.86 1.10 1.69±0.61 

1-octene 111-66-0 112.21 Exp 0 8 3.14 1.37 0.77 1.22±0.47 

c8 terminal alkenes 112.21 LM 0 8 3.14 1.37 0.77 1.22±0.47 

2,4,4-trimethyl-1-pentene 107-39-1 112.21 Exp 0 8 3.31 1.23 0.66 1.13±0.52 

1-nonene 124-11-8 126.24 Exp 0 8 2.49 1.11 0.60 0.97±0.38 

c9 terminal alkenes 126.24 LM 0 8 2.49 1.11 0.60 0.97±0.38 

1-decene 872-05-9 140.27 Exp 0 8 2.07 0.93 0.49 0.80±0.33 

c10 terminal alkenes 140.27 LM 0 8 2.07 0.93 0.49 0.80±0.33 

1-undecene 821-95-4 154.29 Exp 0 8 1.77 0.80 0.41 0.68±0.29 
Table C-1 (continued) 

78 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

c11 terminal alkenes 154.29 LM 0 8 1.77 0.80 0.41 0.68±0.29 

c12 terminal alkenes 168.32 LM 0 8 1.56 0.71 0.36 0.60±0.26 

1-dodecene 112-41-4 168.32 Exp 0 8 1.56 0.71 0.36 0.60±0.26 

1-tridecene 2437-56-1 182.35 Exp 0 8 1.40 0.64 0.32 0.54±0.23 

c13 terminal alkenes 182.35 LM 0 8 1.40 0.64 0.32 0.54±0.23 

1-tetradecene 1120-36-1 196.37 Exp 0 8 1.27 0.58 0.29 0.49±0.21 

c14 terminal alkenes 196.37 LM 0 8 1.27 0.58 0.29 0.49±0.21 

1-pentadecene 13360-61-7 210.40 LM 0 8 1.18 0.54 0.27 0.46±0.20 

c15 terminal alkenes 210.40 LM 0 8 1.18 0.54 0.27 0.46±0.20 

isobutene 115-11-7 56.11 Exp 1 3 0 3 6.31 2.23 1.23 2.10±1.00 

2-methyl-1-butene 563-46-2 70.13 Exp 1 0 8 6.38 2.35 1.35 2.21±0.97 

2,3-dimethyl-1-butene 563-78-0 84.16 Exp 0 8 4.71 1.78 1.01 1.65±0.71 

2-ethyl-1-butene 760-21-4 84.16 Exp 0 8 5.04 1.89 1.06 1.76±0.77 

2-methyl-1-pentene 763-29-1 84.16 Exp 1 0 8 5.25 1.94 1.09 1.82±0.80 

2,4-dimethyl-1-pentene 2213-32-3 98.19 AdjP 0 8 5.91 2.40 1.42 2.21±0.86 

2,3-dimethyl-1-pentene 3404-72-6 98.19 Exp 0 8 5.04 2.10 1.21 1.91±0.74 

3,3-dimethyl-1-pentene 3404-73-7 98.19 Exp 0 8 4.75 2.13 1.35 1.96±0.64 

2-methyl-1-hexene 6094-02-6 98.19 Exp 0 8 4.99 2.08 1.19 1.89±0.74 

2,3,3-trimethyl-1-butene 594-56-9 98.19 Exp 0 8 4.42 1.79 1.06 1.65±0.64 

c7 terminal alkenes 98.19 LM 0 8 4.29 1.86 1.09 1.68±0.61 

3-methyl-2-isopropyl-1-

butene 

111823-35-9 112.21 AdjP 0 8 3.21 1.36 0.74 1.21±0.49 

4,4-dimethyl-1-pentene 762-62-9 126.24 Exp 0 8 3.02 1.29 0.72 1.15±0.45 

cis-2-butene 590-18-1 56.11 Exp 1 0 6 14.26 5.26 3.18 5.06±2.18 

trans-2-butene 624-64-6 56.11 Exp 1 1 0 3 15.20 5.51 3.29 5.30±2.37 

c4 internal alkenes 56.11 LM 0 7 14.73 5.39 3.23 5.17±2.27 

2-methyl-2-butene 513-35-9 70.13 Exp 1 0 6 14.20 4.83 2.73 4.68±2.41 

cis-2-pentene 627-20-3 70.13 Exp 1 0 6 10.28 3.99 2.46 3.79±1.47 

trans-2-pentene 646-04-8 70.13 Exp 1 0 6 10.47 4.02 2.46 3.82±1.51 

2-pentenes 70.13 LM 0 7 10.38 4.01 2.46 3.80±1.49 

c5 internal alkenes 70.13 LM 0 7 10.38 4.01 2.46 3.80±1.49 

3-methyl-trans-2-pentene 616-12-6 84.16 Exp 0 7 11.66 4.15 2.39 3.98±1.92 

2,3-dimethyl-2-butene 563-79-1 84.16 Exp 1 0 8 12.58 4.03 2.14 3.94±2.30 

2-methyl-2-pentene 625-27-4 84.16 Exp 1 0 8 11.03 3.88 2.22 3.73±1.79 

cis 4-methyl-2-pentene 84.16 LM 0 8 8.04 3.14 1.91 2.96±1.16 

cis-2-hexene 7688-21-3 84.16 Exp 0 8 8.22 3.22 1.98 3.04±1.17 

cis-3-hexene 7642-09-3 84.16 Exp 0 8 7.44 3.03 1.89 2.84±1.02 

cis-3-methyl-2-pentene 922-62-3 84.16 Exp 0 8 12.52 4.40 2.53 4.23±2.07 

trans 3-methyl-2-pentene 20710-38-7 84.16 Exp 0 8 13.20 4.61 2.64 4.44±2.18 

trans 4-methyl-2-pentene 674-76-0 84.16 Exp 1 0 8 8.04 3.14 1.91 2.96±1.16 

trans-2-hexene 4050-45-7 84.16 Exp 0 8 8.55 3.29 1.99 3.11±1.24 

trans-3-hexene 13269-52-8 84.16 Exp 0 8 7.42 3.01 1.87 2.82±1.02 

2-hexenes 592-43-8 84.16 LM 0 8 8.38 3.25 1.98 3.08±1.21 

c6 internal alkenes 84.16 LM 0 8 8.38 3.25 1.98 3.08±1.21 

4,4-dimethyl-cis-2-pentene 762-63-0 98.19 Exp 0 8 6.59 2.56 1.53 2.41±0.98 

2,4-dimethyl-2-pentene 625-65-0 98.19 Exp 0 8 9.31 3.27 1.84 3.13±1.53 

2-methyl-2-hexene 2738-19-4 98.19 Exp 0 8 9.50 3.33 1.86 3.18±1.57 

3-ethyl-2-pentene 816-79-5 98.19 Exp 0 8 9.76 3.54 2.05 3.38±1.60 

3-methyl-trans-3-hexene 3899-36-3 98.19 Exp 0 8 9.70 3.54 2.05 3.37±1.54 
Table C-1 (continued) 

79 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

cis-2-heptene 6443-92-1 98.19 Exp 0 8 7.08 2.79 1.69 2.62±1.03 

2-methyl-trans-3-hexene 692-24-0 98.19 Exp 0 8 6.11 2.51 1.55 2.34±0.85 

3-methyl-cis-3-hexene 4914-89-0 98.19 Exp 0 8 9.69 3.53 2.05 3.36±1.54 

3,4-dimethyl-cis-2-pentene 4914-91-4 98.19 Exp 0 8 9.19 3.23 1.79 3.08±1.56 

2,3-dimethyl-2-pentene 10574-37-5 98.19 Exp 1 0 8 9.79 3.27 1.75 3.15±1.74 

cis-3-heptene 7642-10-6 98.19 Exp 0 8 6.18 2.54 1.56 2.36±0.86 

trans 4,4-dimethyl-2-

pentene 

690-08-4 98.19 Exp 1 0 8 6.58 2.56 1.53 2.41±0.98 

trans-2-heptene 14686-13-6 98.19 Exp 1 0 8 7.06 2.79 1.69 2.62±1.02 

trans-3-heptene 14686-14-7 98.19 Exp 0 8 6.17 2.53 1.56 2.36±0.86 

2-heptenes 98.19 LM 0 8 6.17 2.54 1.56 2.36±0.86 

c7 internal alkenes 98.19 LM 0 8 6.17 2.53 1.56 2.36±0.86 

trans-2-octene 13389-42-9 112.21 Exp 0 8 5.92 2.34 1.40 2.19±0.87 

2-methyl-2-heptene 627-97-4 112.21 Exp 0 8 8.35 2.95 1.64 2.81±1.38 

cis-4-octene 7642-15-1 112.21 AdjP 0 8 4.60 1.93 1.13 1.75±0.67 

trans 2,2-dimethyl 3-

hexene 

690-93-7 112.21 Exp 0 8 4.86 2.05 1.26 1.89±0.68 

trans 2,5-dimethyl 3-

hexene 

692-70-6 112.21 AdjP 0 8 4.68 1.99 1.24 1.84±0.65 

trans-3-octene 14919-01-8 112.21 AdjP 0 8 5.20 2.18 1.31 2.00±0.74 

trans-4-octene 14850-23-8 112.21 AdjP 1 0 8 4.69 1.94 1.13 1.77±0.69 

3-octenes 112.21 LM 0 8 5.20 2.18 1.31 2.00±0.74 

c8 internal alkenes 112.21 LM 0 8 4.69 1.94 1.13 1.77±0.69 

2,4,4-trimethyl-2-pentene 107-40-4 112.21 Exp 0 8 6.30 2.28 1.26 2.14±1.02 

4-nonene 2198-23-4 126.24 LM 0 8 4.42 1.86 1.10 1.69±0.64 

3-nonenes 126.24 LM 0 8 4.42 1.86 1.10 1.69±0.64 

c9 internal alkenes 126.24 LM 0 8 4.42 1.86 1.10 1.69±0.64 

trans-4-nonene 10405-85-3 126.24 AdjP 0 8 4.42 1.86 1.10 1.69±0.64 

3,4-diethyl-2-hexene 59643-70-8 140.27 Exp 0 8 3.26 1.44 0.79 1.28±0.51 

cis-5-decene 7433-78-5 140.27 AdjP 0 8 3.56 1.52 0.85 1.36±0.55 

trans-4-decene 19398-89-1 140.27 AdjP 0 8 3.76 1.59 0.92 1.44±0.56 

c10 3-alkenes 140.27 LM 0 8 3.76 1.59 0.92 1.44±0.56 

c10 internal alkenes 140.27 LM 0 8 3.76 1.59 0.92 1.44±0.56 

trans-5-undecene 764-97-6 154.29 AdjP 0 8 3.49 1.49 0.87 1.35±0.52 

c11 3-alkenes 154.29 LM 0 8 3.49 1.49 0.87 1.35±0.52 

c11 internal alkenes 154.29 LM 0 8 3.49 1.49 0.87 1.35±0.52 

c12 2-alkenes 168.32 LM 0 8 3.05 1.31 0.74 1.17±0.46 

c12 3-alkenes 168.32 LM 0 8 3.05 1.31 0.74 1.17±0.46 

c12 internal alkenes 168.32 LM 0 8 3.05 1.31 0.74 1.17±0.46 

trans-5-dodecene 7206-16-8 168.32 AdjP 0 8 3.05 1.31 0.74 1.17±0.46 

trans-5-tridecene 23051-84-5 182.35 Exp 0 8 2.51 1.09 0.62 0.97±0.39 

c13 3-alkenes 182.35 LM 0 8 2.51 1.09 0.62 0.97±0.39 

c13 internal alkenes 182.35 LM 0 8 2.51 1.09 0.62 0.97±0.39 

trans-5-tetradecene 41446-66-6 196.37 Exp 0 8 2.28 0.99 0.57 0.88±0.36 

c14 3-alkenes 196.37 LM 0 8 2.28 0.99 0.57 0.88±0.36 

c14 internal alkenes 196.37 LM 0 8 2.28 0.99 0.57 0.88±0.36 

trans-5-pentadecene 74392-33-9 210.40 Exp 0 8 2.10 0.91 0.52 0.81±0.33 

c15 3-alkenes 210.40 LM 0 8 2.10 0.91 0.52 0.81±0.33 

c15 internal alkenes 210.40 LM 0 8 2.10 0.91 0.52 0.81±0.33 
Table C-1 (continued) 

80 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

c4 alkenes 56.11 LM 0 8 12.15 4.61 2.79 4.38±1.79 

c5 alkenes 70.13 LM 0 8 8.72 3.44 2.10 3.24±1.24 

c6 alkenes 84.16 LM 0 8 6.69 2.71 1.63 2.52±0.96 

c7 alkenes 98.19 LM 0 8 5.23 2.20 1.33 2.02±0.73 

c8 alkenes 112.21 LM 0 8 3.91 1.65 0.95 1.50±0.58 

c9 alkenes 126.24 LM 0 8 3.46 1.48 0.85 1.33±0.51 

c10 alkenes 140.27 LM 0 8 2.92 1.26 0.71 1.12±0.44 

c11 alkenes 154.29 LM 0 8 2.63 1.15 0.64 1.02±0.40 

c12 alkenes 168.32 LM 0 8 2.30 1.01 0.55 0.89±0.36 

c13 alkenes 182.35 LM 0 8 1.95 0.86 0.47 0.75±0.31 

c14 alkenes 196.37 LM 0 8 1.78 0.79 0.43 0.69±0.29 

c15 alkenes 210.40 LM 0 8 1.64 0.73 0.39 0.63±0.26 

cyclopentene 142-29-0 68.12 Exp 1 0 8 6.69 2.55 1.53 2.41±0.96 

3-methylcyclopentene 1120-62-3 82.14 Exp 0 8 5.00 2.03 1.25 1.90±0.70 

1-methyl cyclopentene 693-89-0 82.14 AdjP 0 8 12.45 4.46 2.57 4.27±1.99 

cyclohexene 110-83-8 82.14 Exp 1 4 0 4 4.89 2.02 1.25 1.88±0.68 

1-methyl cyclohexene 591-49-1 96.17 Exp 1 0 8 6.58 2.48 1.42 2.33±1.04 

4-methyl cyclohexene 591-47-9 96.17 Exp 0 8 4.08 1.68 1.03 1.56±0.58 

1,2-dimethyl cyclohexene 1674-10-8 110.20 Exp 0 8 5.57 2.10 1.11 1.93±0.94 

1,2-propadiene (allene) 463-49-0 40.06 Exp 1 0 11 8.15 3.90 2.48 3.55±1.14 

1-buten-3-yne (vinyl 

acetylene) 

689-97-4 52.07 LM 0 11 10.32 4.13 2.54 3.87±1.43 

1,2-butadiene 590-19-2 54.09 Exp 1 0 11 9.09 3.98 2.50 3.67±1.25 

1,3-butadiene 106-99-0 54.09 Exp 1 0 6 12.45 4.77 2.91 4.51±1.73 

trans 1,3-pentadiene 2004-70-8 68.12 Exp 0 8 12.33 4.82 2.97 4.54±1.70 

cis 1,3-pentadiene 1574-41-0 68.12 LM 0 8 12.33 4.82 2.97 4.54±1.70 

1,4-pentadiene 591-93-5 68.12 Exp 1 0 8 9.05 3.73 2.39 3.51±1.20 

1,2-pentadiene 591-95-7 68.12 Exp 1 0 11 7.68 3.21 1.99 2.98±1.05 

3-methyl-1,2-butadiene 598-25-4 68.12 Exp 1 0 11 10.11 4.01 2.46 3.76±1.40 

isoprene 78-79-5 68.12 Exp 1 2 0 1 10.48 3.97 2.36 3.74±1.49 

trans,trans-2,4-hexadiene 5194-51-4 82.14 LM 0 8 8.76 3.37 2.04 3.19±1.27 

trans 1,3-hexadiene 20237-34-7 82.14 LM 0 8 10.23 3.99 2.47 3.77±1.41 

trans 1,4-hexadiene 7319-00-8 82.14 Exp 1 0 8 8.52 3.35 2.04 3.15±1.21 

c6 cyclic or di-olefins 82.14 LM 0 8 8.59 3.33 2.03 3.16±1.24 

c7 cyclic or di-olefins 96.17 LM 0 8 7.21 2.85 1.72 2.67±1.05 

c8 cyclic or di-olefins 110.20 LM 0 8 4.78 1.98 1.16 1.80±0.70 

c9 cyclic or di-olefins 124.22 LM 0 8 4.49 1.89 1.12 1.72±0.65 

c10 cyclic or di-olefins 138.25 LM 0 8 3.82 1.61 0.94 1.46±0.57 

c11 cyclic or di-olefins 152.28 LM 0 8 3.54 1.51 0.88 1.37±0.53 

c12 cyclic or di-olefins 166.30 LM 0 8 3.08 1.32 0.75 1.18±0.47 

c13 cyclic or di-olefins 180.33 LM 0 8 2.54 1.10 0.63 0.98±0.40 

c14 cyclic or di-olefins 194.36 LM 0 8 2.31 1.00 0.57 0.89±0.36 

c15 cyclic or di-olefins 208.38 LM 0 8 2.12 0.92 0.52 0.82±0.34 

cyclopentadiene 542-92-7 66.10 LM 0 8 6.89 2.63 1.58 2.48±0.98 

3-carene 13466-78-9 136.23 Exp 1 3 0 4 3.18 1.26 0.73 1.17±0.47 

a-pinene 80-56-8 136.23 Exp 1 2 0 4 4.49 1.66 0.88 1.53±0.72 

b-pinene 127-91-3 136.23 Exp 1 2 0 4 3.43 1.41 0.76 1.26±0.53 

d-limonene 5989-27-5 136.23 Exp 1 2 0 4 4.50 1.71 0.96 1.60±0.72 

sabinene 3387-41-5 136.23 Exp 1 3 0 4 4.08 1.67 0.93 1.51±0.62 
Table C-1 (continued) 

81 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

terpene 136.23 LM 0 8 3.98 1.55 0.84 1.41±0.62 

Terpinolene 586-62-9 136.23 Exp 0 8 6.14 2.21 1.17 2.09±1.09 

styrene 100-42-5 104.15 Exp 1 2 0 2 1.66 0.186 -0.47 -.008±0.521

allylbenzene 300-57-2 118.18 LM 0 8 1.46 0.164 -0.41 -.007±0.460

a-methyl styrene 98-83-9 118.18 LM 0 8 1.46 0.164 -0.41 -.007±0.460

c9 styrenes 118.18 LM 0 8 1.46 0.164 -0.41 -.007±0.460

b-methyl styrene 637-50-3 118.18 Exp 1 0 8 0.94 0.113 -0.33 -.035±0.307

c10 styrenes 132.20 LM 0 8 1.31 0.147 -0.37 -.006±0.411

benzene 71-43-2 78.11 Exp 1 2 0? 4 0.69 0.104 -0.146 0.042±0.202

toluene 108-88-3 92.14 Exp 1 2 0 4 3.93 1.38 0.55 1.20±0.70 

ethyl benzene 100-41-4 106.17 Exp 1 3 0 4 2.96 1.15 0.50 0.99±0.51 

c9 monosubstituted 

benzenes 

 120.19 LM 0 8 1.96 0.80 0.35 0.68±0.34 

n-propyl benzene 103-65-1 120.19 Exp 1 0 8 1.96 0.80 0.35 0.68±0.34 

isopropyl benzene 

(cumene) 

98-82-8 120.19 Exp 1 0 8 2.45 0.94 0.39 0.81±0.43 

c10 monosubstituted 

benzenes 

 134.22 Exp 0 8 2.29 0.92 0.41 0.79±0.39 

n-butyl benzene 104-51-8 134.22 LM 0 8 2.29 0.92 0.41 0.79±0.39 

s-butyl benzene 135-98-8 134.22 LM 0 8 2.29 0.92 0.41 0.79±0.39 

t-butyl benzene 98-06-6 134.22 Exp 1 0 8 1.91 0.70 0.27 0.60±0.35 

n-pentylbenzene 538-68-1 148.24 LM 0 8 2.04 0.84 0.38 0.72±0.34 

c11 monosubstituted 

benzenes 

 148.24 Exp 0 8 2.04 0.84 0.38 0.72±0.34 

c12 monosubstituted 

benzenes 

 162.27 Exp 0 8 1.84 0.77 0.36 0.66±0.31 

c13 monosubstituted 

benzenes 

 176.30 Exp 0 8 1.68 0.71 0.34 0.61±0.28 

c14 monosubstituted 

benzenes 

 190.32 Exp 0 8 1.54 0.66 0.32 0.57±0.26 

c15 monosubstituted 

benzenes 

 204.35 Exp 0 8 1.43 0.62 0.30 0.53±0.24 

c16 monosubstituted 

benzenes 

 218.38 Exp 0 8 1.33 0.58 0.29 0.50±0.22 

c17 monosubstituted 

benzenes 

 232.40 LM 0 8 1.25 0.55 0.27 0.47±0.20 

c18 monosubstituted 

benzenes 

 246.43 LM 0 8 1.18 0.52 0.25 0.44±0.19 

c19 monosubstituted 

benzenes 

 260.46 LM 0 8 1.11 0.49 0.24 0.42±0.18 

c20 monosubstituted 

benzenes 

 274.48 LM 0 8 1.06 0.46 0.23 0.40±0.17 

c21 monosubstituted 

benzenes 

 288.51 LM 0 8 1.01 0.44 0.22 0.38±0.16 

c22 monosubstituted 

benzenes 

 302.54 LM 0 8 0.96 0.42 0.21 0.36±0.16 

c8 disubstituted benzenes 1330-20-7 106.17 LM 0 8 7.72 2.59 1.21 2.37±1.26 

m-xylene 108-38-3 106.17 Exp 1 1 0 4 9.73 3.20 1.55 2.97±1.57 

o-xylene 95-47-6 106.17 Exp 1 2 0 4 7.58 2.58 1.20 2.34±1.24 

p-xylene 106-42-3 106.17 Exp 1 3 0 4 5.78 1.98 0.86 1.77±0.97 
Table C-1 (continued) 

82 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

c9 disubstituted benzenes 120.19 LM 0 8 5.78 2.01 0.94 1.82±0.94 

m-ethyl toluene 620-14-4 120.19 Exp 1 0 8 7.39 2.49 1.20 2.29±1.19 

o-ethyl toluene 611-14-3 120.19 Exp 1 0 8 5.54 1.96 0.91 1.76±0.91 

p-ethyl toluene 622-96-8 120.19 Exp 1 0 8 4.39 1.59 0.72 1.41±0.73 

o-cymene; 1-methyl-2-(1-

methylethyl)benzene 

527-84-4 134.22 LM 0 8 5.43 1.91 0.91 1.73±0.88 

1-methyl-2-npropylbenzene 1074-17-5 134.22 LM 0 8 5.43 1.91 0.91 1.73±0.88 

m-cymene; 1-methyl-3-(1-

methylethyl)benzene 

535-77-3 134.22 LM 0 8 7.08 2.39 1.17 2.21±1.13 

1-methyl-3-npropylbenzene 1074-43-7 134.22 LM 0 8 7.08 2.39 1.17 2.21±1.13 

1-methyl-4-npropylbenzene 1074-55-1 134.22 LM 0 8 4.39 1.58 0.73 1.41±0.71 

c10 disubstituted benzenes 134.22 LM 0 8 5.64 1.96 0.94 1.78±0.91 

m-c10 disubstituted 

benzenes 

 134.22 Exp 0 8 7.08 2.39 1.17 2.21±1.13 

o-c10 disubstituted 

benzenes 

 134.22 Exp 0 8 5.43 1.91 0.91 1.73±0.88 

p-c10 disubstituted 

benzenes 

 134.22 Exp 0 8 4.39 1.58 0.73 1.41±0.71 

m-diethyl benzene 141-93-5 134.22 LM 0 8 7.08 2.39 1.17 2.21±1.13 

o-diethyl benzene 135-01-3 134.22 LM 0 8 5.43 1.91 0.91 1.73±0.88 

1-methyl-4-

isopropylbenzene (pcymene) 

99-87-6 134.22 Exp 1 0 8 4.41 1.57 0.71 1.40±0.72 

p-diethyl benzene 105-05-5 134.22 LM 0 8 4.39 1.58 0.73 1.41±0.71 

m-c11 disubstituted 

benzenes 

 148.24 Exp 0 8 6.12 2.08 1.03 1.92±0.98 

o-c11 disubstituted 

benzenes 

 148.24 Exp 0 8 4.68 1.67 0.80 1.51±0.75 

p-c11 disubstituted 

benzenes 

 148.24 Exp 0 8 3.82 1.40 0.66 1.25±0.62 

1-butyl-2-methylbenzene 148.24 LM 0 8 4.68 1.67 0.80 1.51±0.75 

1-ethyl-2-n-propylbenzene 148.24 LM 0 8 4.68 1.67 0.80 1.51±0.75 

o-t-butyl toluene; 1-(1,1-

dimethylethyl)-2-

methylbenzene 

1074-92-6 148.24 LM 0 8 4.68 1.67 0.80 1.51±0.75 

1-methyl-3-n-butylbenzene 1595-04-6 148.24 LM 0 8 6.12 2.08 1.03 1.92±0.98 

p-Isobutyl toluene; 1-

methyl-4(2-methylpropyl) 

benzene 

5161-04-6 148.24 LM 0 8 3.82 1.40 0.66 1.25±0.62 

c11 disubstituted benzenes 148.24 LM 0 8 4.88 1.72 0.83 1.56±0.78 

m-c12 disubstituted 

benzenes 

 162.27 Exp 0 8 5.48 1.87 0.92 1.73±0.87 

o-c12 disubstituted 

benzenes 

 162.27 Exp 0 8 4.18 1.50 0.72 1.35±0.67 

p-c12 disubstituted 

benzenes 

 162.27 Exp 0 8 3.43 1.26 0.60 1.13±0.55 
Table C-1 (continued) 

83 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

1,3-di-n-propylbenzene 162.27 LM 0 8 4.18 1.50 0.72 1.35±0.67 

1,4 diisopropyl benzene 162.27 LM 0 8 3.43 1.26 0.60 1.13±0.55 

3-isopropyl cumene; 1,3-

diisopropyl benzene 

99-62-7 162.27 LM 0 8 5.48 1.87 0.92 1.73±0.87 

c12 disubstituted benzenes 162.27 LM 0 8 4.36 1.54 0.75 1.40±0.70 

m-c13 disubstituted 

benzenes 

 176.30 Exp 0 8 4.90 1.68 0.83 1.55±0.78 

o-c13 disubstituted 

benzenes 

 176.30 Exp 0 8 3.73 1.35 0.66 1.22±0.60 

p-c13 disubstituted 

benzenes 

 176.30 Exp 0 8 3.08 1.15 0.55 1.02±0.49 

c13 disubstituted benzenes 176.30 LM 0 8 3.90 1.39 0.68 1.27±0.62 

m-c14 disubstituted 

benzenes 

 190.32 Exp 0 8 4.42 1.53 0.76 1.41±0.70 

o-c14 disubstituted 

benzenes 

 190.32 Exp 0 8 3.36 1.23 0.60 1.11±0.54 

p-c14 disubstituted 

benzenes 

 190.32 Exp 0 8 2.79 1.05 0.51 0.93±0.44 

c14 disubstituted benzenes 190.32 LM 0 8 3.52 1.27 0.62 1.15±0.56 

c15 disubstituted benzenes 204.35 LM 0 8 3.20 1.16 0.58 1.06±0.51 

m-c15 disubstituted 

benzenes 

 204.35 Exp 0 8 4.02 1.40 0.70 1.29±0.64 

o-c15 disubstituted 

benzenes 

 204.35 Exp 0 8 3.05 1.12 0.55 1.01±0.49 

p-c15 disubstituted 

benzenes 

 204.35 Exp 0 8 2.54 0.96 0.47 0.86±0.40 

m-c16 disubstituted 

benzenes 

 218.38 Exp 0 8 3.68 1.29 0.65 1.19±0.58 

o-c16 disubstituted 

benzenes 

 218.38 Exp 0 8 2.79 1.04 0.51 0.93±0.44 

p-c16 disubstituted 

benzenes 

 218.38 Exp 0 8 2.33 0.89 0.44 0.80±0.37 

c16 disubstituted benzenes 218.38 LM 0 8 2.93 1.07 0.53 0.97±0.46 

c17 disubstituted benzenes 232.40 LM 0 8 2.76 1.01 0.50 0.91±0.44 

c18 disubstituted benzenes 246.43 LM 0 8 2.60 0.95 0.47 0.86±0.41 

c19 disubstituted benzenes 260.46 LM 0 8 2.46 0.90 0.45 0.82±0.39 

c20 disubstituted benzenes 274.48 LM 0 8 2.33 0.85 0.42 0.77±0.37 

c21 disubstituted benzenes 288.51 LM 0 8 2.22 0.81 0.40 0.74±0.35 

c22 disubstituted benzenes 302.54 LM 0 8 2.12 0.77 0.39 0.70±0.33 

isomers of ethylbenzene 106.17 LM 0 8 5.38 1.88 0.86 1.69±0.89 

isomers of propylbenzene 120.19 LM 0 8 6.19 2.18 1.10 2.00±0.97 

c9 trisubstituted benzenes 25551-13-7 120.19 LM 0 8 10.84 3.72 2.02 3.50±1.66 

1,2,3-trimethyl benzene 526-73-8 120.19 Exp 1 2 0 4 11.94 4.07 2.19 3.83±1.83 

1,2,4-trimethyl benzene 95-63-6 120.19 Exp 1 2 0 4 8.83 3.14 1.71 2.93±1.34 

1,3,5-trimethyl benzene 108-67-8 120.19 Exp 1 2 0 4 11.75 3.96 2.15 3.76±1.81 

1,2,3-c10 trisubstituted 

benzenes 

 134.22 Exp 0 8 10.16 3.50 1.90 3.29±1.55 

1,2,4-c10 trisubstituted 

benzenes 

 134.22 Exp 0 8 7.54 2.71 1.48 2.53±1.14 
Table C-1 (continued) 

84 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

1,3,5-c10 trisubstituted 

benzenes 

 134.22 Exp 0 8 10.10 3.43 1.87 3.25±1.55 

1,2,3,4-tetramethylbenzene 488-23-3 134.22 LM 0 8 9.26 3.21 1.75 3.02±1.41 

1,2,4,5-tetramethylbenzene 95-93-2 134.22 LM 0 8 9.26 3.21 1.75 3.02±1.41 

1,2-dimethyl-3-

ethylbenzene 

933-98-2 134.22 LM 0 8 10.16 3.50 1.90 3.29±1.55 

1,2-dimethyl-4-

ethylbenzene 

934-80-5 134.22 LM 0 8 7.54 2.71 1.48 2.53±1.14 

1,3-dimethyl-2-

ethylbenzene 

2870-04-4 134.22 LM 0 8 10.16 3.50 1.90 3.29±1.55 

1,3-dimethyl-4-

ethylbenzene 

874-41-9 134.22 LM 0 8 7.54 2.71 1.48 2.53±1.14 

1,3-dimethyl-5-

ethylbenzene 

934-74-7 134.22 LM 0 8 10.10 3.43 1.87 3.25±1.55 

1,4-dimethyl-2-

ethylbenzene 

1758-88-9 134.22 LM 0 8 7.54 2.71 1.48 2.53±1.14 

1,2,3,5 tetramethyl benzene 527-53-7 134.22 LM 0 8 9.26 3.21 1.75 3.02±1.41 

isomers of butylbenzene 134.22 LM 0 8 5.55 1.98 1.01 1.81±0.87 

c10 trisubstituted benzenes 134.22 LM 0 8 9.26 3.21 1.75 3.02±1.41 

c10 tetrasubstituted 

benzenes 

 134.22 LM 0 8 9.26 3.21 1.75 3.02±1.41 

1,2,3-c11 trisubstituted 

benzenes 

 148.24 Exp 0 8 8.88 3.07 1.67 2.89±1.36 

1,2,4-c11 trisubstituted 

benzenes 

 148.24 Exp 0 8 6.61 2.39 1.31 2.23±1.00 

1,3,5-c11 trisubstituted 

benzenes 

 148.24 Exp 0 8 8.91 3.03 1.65 2.87±1.37 

pentamethylbenzene 700-12-9 148.24 LM 0 8 8.13 2.83 1.54 2.66±1.24 

1-methyl-3,5-

diethylbenzene 

2050-24-0 148.24 LM 0 8 8.91 3.03 1.65 2.87±1.37 

isomers of pentylbenzene 148.24 LM 0 8 4.86 1.75 0.89 1.60±0.76 

c11 trisubstituted benzenes 148.24 LM 0 8 8.13 2.83 1.54 2.66±1.24 

c11 tetrasubstituted 

benzenes 

 148.24 LM 0 8 8.13 2.83 1.54 2.66±1.24 

c11 pentasubstituted 

benzenes 

 148.24 LM 0 8 8.13 2.83 1.54 2.66±1.24 

1,2,3-c12 trisubstituted 

benzenes 

 162.27 Exp 0 8 7.95 2.76 1.49 2.59±1.22 

1,2,4-c12 trisubstituted 

benzenes 

 162.27 Exp 0 8 5.93 2.15 1.18 2.00±0.90 

1,3,5-c12 trisubstituted 

benzenes 

 162.27 Exp 0 8 8.02 2.73 1.49 2.58±1.23 

1-(1,1-dimethylethyl)-3,5-

dimethylbenzene 

98-19-1 162.27 LM 0 8 8.02 2.73 1.49 2.58±1.23 

isomers of hexylbenzene 162.27 LM 0 8 4.37 1.57 0.80 1.44±0.68 

c12 trisubstituted benzenes 162.27 LM 0 8 7.30 2.55 1.39 2.39±1.11 

c12 tetrasubstituted 

benzenes 

 162.27 LM 0 8 7.30 2.55 1.39 2.39±1.11 

c12 pentasubstituted 

benzenes 

 162.27 LM 0 8 7.30 2.55 1.39 2.39±1.11 
Table C-1 (continued) 

85 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

c12 hexasubstituted 

benzenes 

 162.27 LM 0 8 7.30 2.55 1.39 2.39±1.11 

1,2,3-c13 trisubstituted 

benzenes 

 176.30 Exp 0 8 7.11 2.48 1.34 2.33±1.09 

1,2,4-c13 trisubstituted 

benzenes 

 176.30 Exp 0 8 5.33 1.94 1.06 1.80±0.80 

1,3,5-c13 trisubstituted 

benzenes 

 176.30 Exp 0 8 7.23 2.47 1.35 2.34±1.11 

c13 trisubstituted benzenes 176.30 LM 0 8 6.56 2.30 1.25 2.15±1.00 

1,2,3-c14 trisubstituted 

benzenes 

 190.32 Exp 0 8 6.48 2.26 1.23 2.12±0.99 

1,2,4-c14 trisubstituted 

benzenes 

 190.32 Exp 0 8 4.86 1.77 0.97 1.65±0.73 

1,3,5-c14 trisubstituted 

benzenes 

 190.32 Exp 0 8 6.63 2.27 1.23 2.14±1.02 

c14 trisubstituted benzenes 190.32 LM 0 8 5.98 2.10 1.15 1.97±0.91 

c15 trisubstituted benzenes 204.35 LM 0 8 5.49 1.93 1.05 1.81±0.83 

1,2,3-c15 trisubstituted 

benzenes 

 204.35 Exp 0 8 5.92 2.07 1.13 1.94±0.90 

1,2,4-c15 trisubstituted 

benzenes 

 204.35 Exp 0 8 4.45 1.63 0.89 1.51±0.67 

1,3,5-c15 trisubstituted 

benzenes 

 204.35 Exp 0 8 6.09 2.09 1.14 1.97±0.93 

1,2,3-c16 trisubstituted 

benzenes 

 218.38 Exp 0 8 5.43 1.91 1.04 1.79±0.83 

1,2,4-c16 trisubstituted 

benzenes 

 218.38 Exp 0 8 4.09 1.50 0.82 1.39±0.62 

1,3,5-c16 trisubstituted 

benzenes 

 218.38 Exp 0 8 5.62 1.93 1.05 1.82±0.86 

c16 trisubstituted benzenes 218.38 LM 0 8 5.04 1.78 0.97 1.67±0.77 

c17 trisubstituted benzenes 232.40 LM 0 8 4.74 1.67 0.91 1.57±0.72 

c18 trisubstituted benzenes 246.43 LM 0 8 4.47 1.58 0.86 1.48±0.68 

c19 trisubstituted benzenes 260.46 LM 0 8 4.23 1.49 0.81 1.40±0.64 

c20 trisubstituted benzenes 274.48 LM 0 8 4.01 1.42 0.77 1.33±0.61 

c21 trisubstituted benzenes 288.51 LM 0 8 3.82 1.35 0.74 1.26±0.58 

c22 trisubstituted benzenes 302.54 LM 0 8 3.64 1.29 0.70 1.20±0.55 

indene 95-13-6 116.16 LM 0 10 1.49 0.167 -0.42 -.007±0.468

indan 496-11-7 118.18 LM 0 10 3.24 1.15 0.44 0.99±0.56 

naphthalene 91-20-3 128.17 Exp 1 4 + 5 3.28 1.14 0.48 1.01±0.54 

methyl indans 132.20 LM 0 10 2.89 1.03 0.39 0.89±0.50 

tetralin 119-64-2 132.20 Exp 1 4 + 5 2.89 1.03 0.39 0.89±0.50 

methyl naphthalenes 1321-94-4 142.20 Exp + 10 3.00 1.02 0.41 0.90±0.51 

1-methyl naphthalene 90-12-0 142.20 LM + 10 3.00 1.02 0.41 0.90±0.51 

2-methyl naphthalene 91-57-6 142.20 LM + 10 3.00 1.02 0.41 0.90±0.51 

c11 tetralin or indan 146.23 LM + 10 2.61 0.93 0.35 0.80±0.45 

1-ethylnaphthalene 1127-76-0 156.22 LM + 10 2.73 0.93 0.37 0.82±0.46 

c12 naphthalenes 156.22 LM + 10 3.85 1.30 0.60 1.19±0.62 

c12 monosubstituted 

naphthalene 

 156.22 LM + 10 2.73 0.93 0.37 0.82±0.46 
Table C-1 (continued) 

86 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

c12 disubstituted 

naphthalenes 

 156.22 LM + 10 4.96 1.67 0.82 1.55±0.78 

2,3-dimethyl naphthalene 581-40-8 156.22 Exp 1 4 + 5 4.96 1.67 0.82 1.55±0.78 

dimethyl naphthalenes 156.22 LM + 10 4.96 1.67 0.82 1.55±0.78 

c12 tetralin or indan 160.26 LM 0 10 2.39 0.85 0.32 0.73±0.41 

c13 naphthalenes 170.25 LM 0 10 3.53 1.19 0.55 1.09±0.57 

c13 monosubstituted 

naphthalene 

 170.25 LM 0 10 2.51 0.85 0.34 0.76±0.42 

c13 disubstituted 

naphthalenes 

 170.25 LM 0 10 4.55 1.53 0.75 1.42±0.72 

c13 trisubstituted 

naphthalenes 

 170.25 LM 0 10 4.55 1.53 0.75 1.42±0.72 

c13 tetralin or indan 174.28 LM 0 10 2.19 0.78 0.30 0.67±0.38 

c14 naphthalenes 184.28 LM 0 10 3.26 1.10 0.51 1.01±0.53 

c14 tetralin or indan 188.31 LM 0 10 2.03 0.72 0.28 0.62±0.35 

c15 naphthalenes 198.30 LM 0 10 3.03 1.02 0.47 0.93±0.49 

c15 tetralin or indan 202.34 LM 0 10 1.89 0.67 0.26 0.58±0.33 

c16 naphthalenes 212.33 LM 0 10 2.83 0.96 0.44 0.87±0.46 

c16 tetralin or indan 216.36 LM 0 10 1.77 0.63 0.24 0.54±0.30 

c17 naphthalenes 226.36 LM 0 10 2.65 0.90 0.41 0.82±0.43 

c17 tetralin or indan 230.39 LM 0 10 1.66 0.59 0.22 0.51±0.29 

c18 naphthalenes 240.38 LM 0 10 2.50 0.84 0.39 0.77±0.40 

c18 tetralin or indan 244.41 LM 0 10 1.56 0.56 0.21 0.48±0.27 

c19 naphthalenes 254.41 LM 0 10 2.36 0.80 0.37 0.73±0.38 

c19 tetralin or indan 258.44 LM 0 10 1.48 0.53 0.20 0.45±0.25 

c20 naphthalenes 268.44 LM 0 10 2.24 0.76 0.35 0.69±0.36 

c20 tetralin or indan 272.47 LM 0 10 1.40 0.50 0.190 0.43±0.24 

c21 naphthalenes 282.46 LM 0 10 2.13 0.72 0.33 0.66±0.34 

c21 tetralin or indan 286.49 LM 0 10 1.33 0.47 0.181 0.41±0.23 

c22 naphthalenes 296.49 LM 0 10 2.03 0.68 0.31 0.63±0.33 

c22 tetralin or indan 300.52 LM 0 10 1.27 0.45 0.172 0.39±0.22 

acetylene 74-86-2 26.04 Exp 1 2 - 3 0.95 0.38 0.20 0.35±0.16 

methyl acetylene 74-99-7 40.06 Exp 1 - 7 6.67 2.51 1.39 2.33±1.05 

1,3-butadiyne 460-12-8 50.06 Exp 0 11 5.56 2.56 1.65 2.36±0.80 

2-butyne 503-17-3 54.09 Exp 1 0 10 16.34 5.63 3.19 5.38±2.50 

ethyl acetylene 107-00-6 54.09 Exp 1 - 7 6.05 2.27 1.26 2.10±0.94 

methanol 67-56-1 32.04 Exp 1 3 0 2 0.66 0.32 0.20 0.29±0.10 

ethanol 64-17-5 46.07 Exp 1 3 0 2 1.45 0.84 0.57 0.75±0.23 

isopropyl alcohol 67-63-0 60.10 Exp 1 2 0 2 0.59 0.35 0.26 0.32±0.07 

n-propyl alcohol 71-23-8 60.10 Exp 1 0 6 2.39 1.23 0.79 1.10±0.37 

isobutyl alcohol 78-83-1 74.12 Exp 1 0 6 2.42 1.16 0.72 1.04±0.35 

n-butyl alcohol 71-36-3 74.12 Exp 1 0 6 2.77 1.38 0.88 1.24±0.41 

s-butyl alcohol 78-92-2 74.12 Exp 1 0 6 1.29 0.73 0.50 0.66±0.18 

t-butyl alcohol 75-65-0 74.12 Exp 1 2 + 2 0.39 0.22 0.141 0.195±0.056

cyclopentanol 96-41-3 86.13 Exp 1 0 6 1.65 0.87 0.57 0.78±0.23 

2-pentanol 6032-29-7 88.15 Exp 1 0 6 1.53 0.83 0.55 0.74±0.22 

3-pentanol 584-02-1 88.15 Exp 1 0 6 1.56 0.82 0.55 0.75±0.22 

pentyl alcohol 71-41-0 88.15 Exp 1 0 6 2.72 1.33 0.84 1.20±0.40 
Table C-1 (continued) 

87 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

isoamyl alcohol (3-methyl1-butanol) 123-51-3 88.15 Exp 1 0 6 3.06 1.42 0.90 1.30±0.43 

2-methyl-1-butanol 137-32-6 88.15 Exp 0 7 2.31 1.14 0.72 1.03±0.33 

cyclohexanol 108-93-0 100.16 AdjP 1 0 6 1.83 1.01 0.63 0.88±0.28 

1-hexanol 111-27-3 102.17 AdjP 1 0 6 2.56 1.29 0.81 1.15±0.38 

2-hexanol 626-93-7 102.17 AdjP 1 0 6 1.96 1.14 0.73 1.00±0.31 

4-methyl-2-pentanol 

(methyl isobutyl carbinol) 

108-11-2 102.17 AdjP 0 7 2.52 1.34 0.87 1.20±0.36 

1-heptanol 111-70-6 116.20 Exp 1 0 6 1.74 0.91 0.55 0.80±0.27 

dimethylpentanol (2,3-

dimethyl-1-pentanol) 

10143-23-4 116.20 Exp 0 7 2.13 1.05 0.64 0.94±0.31 

1-octanol 111-87-5 130.23 Exp 1 2 + 2 1.33 0.73 0.40 0.61±0.23 

2-ethyl-1-hexanol 104-76-7 130.23 Exp 0 7 1.90 0.94 0.54 0.82±0.29 

2-octanol 4128-31-8 130.23 Exp 1 2 + 2 1.84 0.98 0.59 0.85±0.29 

3-octanol 20296-29-1 130.23 Exp 1 2 + 2 2.15 1.10 0.67 0.96±0.33 

4-octanol 589-62-8 130.23 AdjP 1 0 6 2.09 1.10 0.65 0.95±0.33 

5-methyl-1-heptanol 7212-53-5 130.23 AdjP 0 7 1.69 0.85 0.47 0.73±0.27 

trimethylcyclohexanol 1321-60-4 142.24 AdjP 0 7 1.73 0.92 0.50 0.77±0.30 

dimethylheptanol (2,6-

dimethyl-2-heptanol) 

13254-34-7 144.25 Exp 0 7 0.87 0.48 0.24 0.39±0.16 

2,6-dimethyl-4-heptanol 108-82-7 144.25 AdjP 0 7 1.96 0.99 0.56 0.85±0.32 

menthol 89-78-1 156.27 Exp 0 7 1.34 0.70 0.40 0.60±0.22 

8-methyl-1-nonanol 

(isodecyl alcohol) 

25339-17-7 158.28 Exp 0 7 0.97 0.53 0.26 0.43±0.18 

1-decanol 112-30-1 158.28 Exp 0 7 0.98 0.53 0.27 0.43±0.18 

3,7-dimethyl-1-octanol 106-21-8 158.28 Exp 0 7 1.11 0.58 0.30 0.48±0.20 

Trimethylnonanol, 

threo/erythro; 2,6,8-

trimethyl-4-nonanol 

123-17-1 186.33 AdjP 0 7 1.23 0.64 0.31 0.52±0.23 

ethylene glycol 107-21-1 62.07 Exp 1 2 0 2 3.03 1.49 1.00 1.37±0.41 

propylene glycol 57-55-6 76.09 AdjP 1 2 0 2 2.50 1.16 0.75 1.07±0.34 

glycerol 56-81-5 92.09 AdjP 0 7 3.07 1.36 0.84 1.25±0.45 

1,3-butanediol 107-88-0 90.12 Exp 1 0 6 3.22 1.58 1.02 1.43±0.45 

1,2-butandiol 584-03-2 90.12 AdjP 1 0 6 2.45 1.11 0.72 1.03±0.33 

1,4-butanediol 110-63-4 90.12 Exp 0 7 2.62 1.24 0.78 1.13±0.39 

2,3-butanediol 90.12 AdjP 1 0 6 4.25 1.86 1.08 1.68±0.70 

pentaerythritol 115-77-5 136.15 AdjP 0 7 2.10 0.98 0.62 0.89±0.30 

1,2-dihydroxy hexane 6920-22-5 118.17 AdjP 0 7 2.45 1.18 0.73 1.06±0.36 

2-methyl-2,4-pentanediol 107-41-5 118.17 Exp 1 0 6 1.40 0.68 0.44 0.62±0.19 

2-ethyl-1,3-hexanediol 94-96-2 146.23 AdjP 0 7 1.94 0.98 0.60 0.87±0.30 

dimethyl ether 115-10-6 46.07 Exp 1 3 0 2 0.76 0.54 0.43 0.50±0.09 

trimethylene oxide 503-30-0 58.08 Exp 1 0 6 4.31 2.41 1.74 2.22±0.61 

1,3-dioxolane 646-06-0 74.08 Exp 0 7 4.77 2.21 1.59 2.10±0.58 

dimethoxy methane 109-87-5 76.09 AdjP 1 0 6 0.89 0.64 0.50 0.59±0.11 

tetrahydrofuran 109-99-9 72.11 Exp 1 0 6 4.11 2.11 1.41 1.92±0.56 

diethyl ether 60-29-7 74.12 Exp 1 2 0 2 3.65 1.73 1.12 1.59±0.49 

1,4-dioxane 123-91-1 88.11 Exp 0 7 2.49 1.29 0.90 1.19±0.32 

alphamethyltetrahydrofuran 96-47-9 86.13 Exp 1 0 6 3.78 1.87 1.22 1.69±0.52 
Table C-1 (continued) 

88 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

tetrahydropyran 142-68-7 86.13 Exp 1 0 6 3.04 1.65 1.07 1.47±0.43 

ethyl isopropyl ether 625-54-7 88.15 Exp 0 7 3.65 1.62 1.04 1.50±0.49 

methyl n-butyl ether 628-28-4 88.15 Exp 1 0 6 3.00 1.57 1.04 1.42±0.42 

methyl t-butyl ether 1634-04-4 88.15 Exp 1 3 0 2 0.70 0.43 0.29 0.38±0.10 

2,2-dimethoxy propane 77-76-9 104.15 Exp 0 7 0.46 0.29 0.20 0.26±0.06 

di n-propyl ether 111-43-3 102.17 Exp 1 0 6 2.93 1.55 1.04 1.40±0.40 

ethyl n-butyl ether 628-81-9 102.17 Exp 1 0 6 3.34 1.61 1.03 1.46±0.46 

ethyl t-butyl ether 637-92-3 102.17 Exp 1 0 6 1.94 0.97 0.62 0.88±0.27 

methyl t-amyl ether 994-05-8 102.17 Exp 1 0 6 1.61 0.90 0.59 0.80±0.23 

diisopropyl ether 108-20-3 102.17 Exp 0 7 3.44 1.45 0.89 1.34±0.48 

ethylene glycol diethyl 

ether; 1,2-diethoxyethane 

629-14-1 118.17 Exp 0 7 2.82 1.40 0.90 1.26±0.38 

acetal (1,1-diethoxyethane) 105-57-7 118.17 Exp 0 7 3.47 1.51 0.97 1.40±0.46 

4,4-dimethyl-3-oxahexane 919-94-8 116.20 Exp 0 7 1.87 0.94 0.58 0.84±0.27 

2-butyl tetrahydrofuran 1004-29-1 128.21 Exp 0 7 1.99 0.99 0.55 0.85±0.32 

di-isobutyl ether 628-55-7 130.23 Exp 1 0 6 1.11 0.63 0.38 0.54±0.17 

di-n-butyl ether 142-96-1 130.23 Exp 1 0 6 2.70 1.33 0.82 1.18±0.39 

2-methoxy-1-(2-methoxy1-methylethoxy)-propane; 

dipropylene glycol 

dimethyl ether 

89399-28-0 162.23 AdjP 0 7 1.92 0.95 0.62 0.86±0.26 

di-n-pentyl ether 693-65-2 158.28 AdjP 1 0 6 2.00 1.07 0.64 0.92±0.32 

2-methoxyethanol 109-86-4 76.09 Exp 1 0 6 2.86 1.29 0.84 1.20±0.39 

1-methoxy-2-propanol 107-98-2 90.12 AdjP 1 2 0 2 2.34 1.22 0.85 1.12±0.31 

2-ethoxyethanol 110-80-5 90.12 Exp 1 3 0 2 3.61 1.62 1.03 1.49±0.49 

2-methoxy-1-propanol 1589-47-5 90.12 Exp 0 7 2.96 1.21 0.75 1.13±0.41 

3-methoxy-1-propanol 1320-67-8 90.12 Exp 0 7 3.76 1.63 1.03 1.52±0.52 

diethylene glycol 111-46-6 106.12 AdjP 0 7 3.27 1.43 0.90 1.32±0.45 

tetrahydro-2-furanmethanol 97-99-4 102.13 Exp 0 7 3.22 1.40 0.87 1.29±0.44 

1-ethoxy-2-propanol 1569-02-4 104.15 Exp 0 7 2.96 1.47 0.94 1.33±0.41 

2-propoxyethanol 2807-30-9 104.15 AdjP 0 7 3.19 1.50 0.98 1.38±0.43 

3-ethoxy-1-propanol 111-35-3 104.15 Exp 1 0 6 3.98 1.75 1.09 1.61±0.55 

3-methoxy-1-butanol 2517-43-3 104.15 Exp 1 0 6 3.81 1.56 0.97 1.46±0.53 

2-(2-methoxyethoxy) 

ethanol 

111-77-3 120.15 AdjP 0 7 2.55 1.26 0.85 1.16±0.33 

1-propoxy-2-propanol 

(propylene glycol n-propyl 

ether) 

1569-01-3 118.17 AdjP 0 7 2.56 1.32 0.89 1.20±0.34 

2-butoxyethanol 111-76-2 118.17 Exp 1 2 0 2 2.80 1.26 0.76 1.14±0.39 

3 methoxy -3 methylbutanol 56539-66-3 118.17 Exp 0 7 1.46 0.77 0.49 0.69±0.22 

n-propoxypropanol 30136-13-1 118.17 Exp 0 7 3.65 1.66 1.05 1.52±0.50 

2-(2-ethoxyethoxy) ethanol 111-90-0 134.17 Exp 1 3 0 2 3.13 1.46 0.91 1.32±0.44 

dipropylene glycol isomer 

(1-[2-hydroxypropyl]-2-

propanol) 

110-98-5 134.17 AdjP 0 7 2.20 1.14 0.76 1.04±0.30 

triethylene glycol 112-27-6 150.17 Exp 0 7 3.13 1.46 0.91 1.32±0.44 

1-tert-butoxy-2-propanol 57018-52-7 132.20 AdjP 0 7 1.53 0.81 0.51 0.72±0.22 

2-tert-butoxy-1-propanol 94023-15-1 132.20 Exp 0 7 1.78 0.72 0.41 0.66±0.26 
Table C-1 (continued) 

89 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

n-butoxy-2-propanol 

(propylene glycol n-butyl 

ether) 

5131-66-8 132.20 Exp 0 7 2.59 1.28 0.81 1.15±0.37 

2-(2-propoxyethoxy) 

ethanol 

6881-94-3 148.20 Exp 0 7 2.72 1.32 0.83 1.18±0.38 

dipropylene glycol methyl 

ether isomer (1-methoxy-2-

[2-hydroxypropoxy]-

propane) 

 148.20 AdjP 0 7 1.88 0.96 0.64 0.87±0.25 

dipropylene glycol methyl 

ether isomer (2-[2-

methoxypropoxy]-1-

propanol) 

13588-28-8 148.20 AdjP 0 7 2.48 1.13 0.72 1.04±0.34 

2-[2-(2-methoxyethoxy) 

ethoxy] ethanol 

112-35-6 164.20 Exp 0 7 2.44 1.22 0.77 1.09±0.35 

2-hexyloxyethanol 112-25-4 146.23 AdjP 0 7 1.98 0.99 0.58 0.86±0.30 

2,2,4-trimethyl-1,3-

pentanediol 

144-19-4 146.23 Exp 0 7 1.46 0.77 0.48 0.68±0.22 

2-(2-butoxyethoxy)-ethanol 112-34-5 162.23 Exp 2 0 7 2.27 1.09 0.65 0.96±0.34 

dipropylene glycol ethyl 

ether 

15764-24-6 162.23 Exp 0 7 2.61 1.20 0.72 1.07±0.37 

2-[2-(2-ethoxyethoxy) 

ethoxy] ethanol 

112-50-5 178.23 Exp 0 7 2.33 1.15 0.71 1.02±0.34 

tetraethylene glycol 112-60-7 194.23 Exp 0 7 2.39 1.15 0.71 1.03±0.35 

1-(butoxyethoxy)-2-

propanol 

124-16-3 176.25 AdjP 0 7 1.81 0.95 0.59 0.83±0.26 

2-[2-(2-propoxyethoxy) 

ethoxy] ethanol 

23305-64-8 192.25 Exp 0 7 2.05 1.02 0.62 0.90±0.30 

tripropylene glycol 24800-44-0 192.25 Exp 0 7 2.07 1.04 0.64 0.92±0.31 

2,5,8,11-tetraoxatridecan13-ol 23783-42-8 208.25 Exp 0 7 1.85 0.94 0.57 0.83±0.28 

2-(2-ethylhexyloxy) 

ethanol 

1559-35-9 174.28 AdjP 0 7 1.44 0.76 0.38 0.62±0.26 

2-(2-hexyloxyethoxy) 

ethanol 

112-59-4 190.28 AdjP 0 7 1.72 0.90 0.52 0.77±0.27 

glycol ether dpnb {1-(2-

butoxy-1-methylethoxy)-2-

propanol} 

29911-28-2 190.28 AdjP 0 7 1.72 0.87 0.53 0.77±0.25 

2-[2-(2-butoxyethoxy) 

ethoxy] ethanol 

143-22-6 206.28 Exp 0 7 1.85 0.92 0.55 0.81±0.28 

tripropylene glycol 

monomethyl ether 

25498-49-1 206.28 Exp 0 7 1.81 0.91 0.55 0.80±0.27 

diethylene glycol mono(2-

ethylhexyl) ether 

1559-36-0 218.33 Exp 0 7 1.45 0.75 0.42 0.64±0.24 

3,6,9,12-tetraoxahexadecan-1-ol 1559-34-8 250.33 AdjP 0 7 1.61 0.82 0.49 0.71±0.25 

tripropylene glycol n-butyl 

ether 

55934-93-5 248.36 Exp 0 7 1.55 0.75 0.43 0.65±0.24 

methyl formate 107-31-3 60.05 Exp 1 0 6 0.053 0.043 0.035 0.040±0.007

ethyl formate 109-94-4 74.08 Exp 1 0 6 0.45 0.27 0.193 0.25±0.07 
Table C-1 (continued) 

90 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

methyl acetate 79-20-9 74.08 Exp 1 2 0 2 0.067 0.055 0.043 0.050±0.010

gamma-butyrolactone 96-48-0 86.09 Exp 0 7 0.90 0.56 0.38 0.50±0.14 

ethyl acetate 141-78-6 88.11 Exp 1 2 0 3 0.59 0.35 0.23 0.31±0.09 

methyl propionate 554-12-1 88.11 Exp 1 0 6 0.63 0.32 0.20 0.29±0.10 

n-propyl formate 110-74-7 88.11 Exp 1 0 6 0.72 0.44 0.29 0.39±0.13 

isopropyl formate 625-55-8 88.11 Exp 0 7 0.34 0.24 0.176 0.22±0.05 

ethyl propionate 105-37-3 102.13 Exp 1 0 6 0.73 0.42 0.27 0.37±0.11 

isopropyl acetate 108-21-4 102.13 Exp 1 2 0 2 1.03 0.57 0.39 0.52±0.14 

methyl butyrate 623-42-7 102.13 Exp 1 0 6 1.05 0.55 0.34 0.49±0.16 

methyl isobutyrate 547-63-7 102.13 Exp 1 2 0 2 0.58 0.33 0.21 0.29±0.10 

n-butyl formate 592-84-7 102.13 Exp 1 0 6 0.77 0.48 0.32 0.42±0.13 

propyl acetate 109-60-4 102.13 Exp 1 0 6 0.72 0.45 0.30 0.40±0.12 

ethyl butyrate 105-54-4 116.16 Exp 1 0 6 1.11 0.60 0.38 0.53±0.17 

isobutyl acetate 110-19-0 116.16 Exp 0 7 0.58 0.40 0.28 0.35±0.08 

methyl pivalate 598-98-1 116.16 Exp 1 2 0 2 0.33 0.20 0.120 0.169±0.055

n-butyl acetate 123-86-4 116.16 Exp 1 2 0,+ 2 0.77 0.49 0.31 0.42±0.13 

n-propyl propionate 106-36-5 116.16 Exp 1 0 6 0.78 0.47 0.30 0.41±0.14 

s-butyl acetate 105-46-4 116.16 Exp 1 0 6 1.24 0.75 0.51 0.67±0.18 

t-butyl acetate 540-88-5 116.16 Exp 1 3 0 2 0.172 0.097 0.059 0.084±0.027

butyl propionate 590-01-2 130.18 Exp 0 7 0.78 0.48 0.29 0.40±0.14 

amyl acetate 628-63-7 130.18 AdjP 0 7 0.77 0.49 0.28 0.41±0.14 

n-propyl butyrate 105-66-8 130.18 Exp 1 0 6 0.98 0.56 0.34 0.49±0.16 

isoamyl acetate (3-

methylbutyl acetate) 

123-92-2 130.18 Exp 0 7 1.01 0.60 0.36 0.51±0.17 

2-methyl-1-butyl acetate 624-41-9 130.18 Exp 0 7 1.01 0.62 0.40 0.54±0.15 

ethyl 3-ethoxy propionate 763-69-9 146.18 AdjP 0 7 3.50 1.44 0.84 1.32±0.51 

hexyl acetates 144.21 LM 0 7 0.72 0.46 0.24 0.37±0.14 

2,3-dimethylbutyl acetate 144.21 Exp 0 7 0.69 0.43 0.25 0.36±0.12 

2-methylpentyl acetate 144.21 Exp 0 7 0.90 0.53 0.29 0.44±0.17 

3-methylpentyl acetate 144.21 AdjP 0 7 0.99 0.59 0.33 0.49±0.17 

4-methylpentyl acetate 144.21 Exp 0 7 0.75 0.45 0.24 0.36±0.14 

isobutyl isobutyrate 97-85-8 144.21 Exp 0 7 0.55 0.35 0.20 0.29±0.09 

n-butyl butyrate 109-21-7 144.21 Exp 1 0 6 1.01 0.57 0.32 0.48±0.17 

n-hexyl acetate 142-92-7 144.21 AdjP 0 7 0.62 0.41 0.20 0.32±0.13 

methyl amyl acetate (4-

methyl-2-pentanol acetate) 

108-84-9 144.21 Exp 0 7 1.27 0.67 0.37 0.56±0.21 

n-pentyl propionate 624-54-4 144.21 AdjP 0 7 0.65 0.40 0.20 0.32±0.13 

2,4-dimethylpentyl acetate 158.24 Exp 0 7 0.84 0.47 0.22 0.37±0.16 

2-methylhexyl acetate 158.24 AdjP 0 7 0.62 0.39 0.162 0.29±0.14 

3-ethylpentyl acetate 158.24 Exp 0 7 1.01 0.59 0.31 0.48±0.19 

3-methylhexyl acetate 158.24 Exp 0 7 0.81 0.49 0.24 0.38±0.16 

4-methylhexyl acetate 158.24 Exp 0 7 0.74 0.44 0.21 0.35±0.15 

5-methylhexyl acetate 158.24 AdjP 0 7 0.52 0.33 0.123 0.24±0.13 

isoamyl isobutyrate 2050-01-3 158.24 Exp 0 7 0.75 0.43 0.22 0.35±0.14 

n-heptyl acetate 112-06-1 158.24 Exp 0 7 0.57 0.38 0.161 0.28±0.14 

2,4-dimethylhexyl acetate 172.26 AdjP 0 7 0.68 0.41 0.162 0.30±0.16 

2-ethyl-hexyl acetate 103-09-3 172.26 AdjP 0 7 0.58 0.36 0.125 0.26±0.15 

3,4-dimethylhexyl acetate 172.26 AdjP 0 7 0.79 0.48 0.23 0.38±0.16 

3,5-dimethylhexyl acetate 172.26 Exp 0 7 0.90 0.51 0.23 0.40±0.18 
Table C-1 (continued) 

91 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

3-ethylhexyl acetate 172.26 Exp 0 7 0.82 0.49 0.23 0.38±0.17 

3-methylheptyl acetate 172.26 Exp 0 7 0.59 0.38 0.149 0.28±0.15 

4,5-dimethylhexyl acetate 172.26 AdjP 0 7 0.61 0.37 0.156 0.28±0.14 

4-methylheptyl acetate 172.26 Exp 0 7 0.58 0.36 0.142 0.26±0.14 

5-methylheptyl acetate 172.26 AdjP 0 7 0.53 0.34 0.113 0.24±0.15 

n-octyl acetate 112-14-1 172.26 Exp 0 7 0.50 0.33 0.120 0.23±0.13 

2,3,5-teimethylhexyl 

acetate 

 186.29 AdjP 0 7 0.77 0.45 0.20 0.35±0.16 

2,3-dimethylheptyl acetate 186.29 Exp 0 7 0.63 0.40 0.168 0.30±0.15 

2,4-dimethylheptyl acetate 186.29 AdjP 0 7 0.60 0.36 0.111 0.25±0.16 

2,5-dimethylheptyl acetate 186.29 Exp 0 7 0.70 0.43 0.179 0.32±0.16 

2-methyloctyl acetate 186.29 AdjP 0 7 0.44 0.29 0.068 0.185±0.138

3,5-dimethylheptyl acetate 186.29 AdjP 0 7 0.72 0.42 0.158 0.31±0.17 

3,6-dimethylheptyl acetate 186.29 Exp 0 7 0.69 0.42 0.163 0.31±0.16 

3-ethylheptyl acetate 186.29 Exp 0 7 0.55 0.35 0.126 0.25±0.14 

4,5-dimethylheptyl acetate 186.29 AdjP 0 7 0.61 0.38 0.149 0.28±0.14 

4,6-dimethylheptyl acetate 186.29 Exp 0 7 0.70 0.40 0.160 0.30±0.16 

4-methyloctyl acetate 186.29 Exp 0 7 0.54 0.34 0.122 0.24±0.14 

5-methyloctyl acetate 186.29 AdjP 0 7 0.48 0.31 0.082 0.20±0.14 

n-nonyl acetate 143-13-5 186.29 Exp 0 7 0.45 0.30 0.096 0.20±0.13 

3,6-dimethyloctyl acetate 200.32 Exp 0 7 0.70 0.42 0.171 0.31±0.16 

3-isopropylheptyl acetate 200.32 AdjP 0 7 0.46 0.30 0.082 0.20±0.14 

4,6-dimethyloctyl acetate 200.32 Exp 0 7 0.68 0.40 0.153 0.29±0.16 

3,5,7-trimethyloctyl acetate 214.34 AdjP 0 7 0.57 0.34 0.104 0.24±0.15 

3-ethyl-6-methyloctyl 

acetate 

 214.34 AdjP 0 7 0.55 0.34 0.104 0.23±0.15 

4,7-dimethylnonyl acetate 214.34 AdjP 0 7 0.43 0.27 0.057 0.171±0.136

methyl dodecanoate 

{methyl laurate} 

111-82-0 214.34 Exp 0 7 0.40 0.26 0.074 0.175±0.118

2,3,5,7-tetramethyloctyl 

acetate 

 228.37 Exp 0 7 0.54 0.33 0.113 0.23±0.14 

3,5,7-trimethylnonyl 

acetate 

 228.37 AdjP 0 7 0.54 0.32 0.099 0.22±0.14 

3,6,8-trimethylnonyl 

acetate 

 228.37 AdjP 0 7 0.51 0.31 0.077 0.20±0.15 

2,4,6,8-tetramethylnonyl 

acetate 

 242.40 AdjP 0 7 0.43 0.26 0.057 0.168±0.134

3-ethyl-6,7-dimethylnonyl 

acetate 

 242.40 AdjP 0 7 0.53 0.33 0.104 0.23±0.15 

4,7,9-trimethyldecyl 

acetate 

 242.40 AdjP 0 7 0.35 0.22 0.022 0.126±0.128

methyl myristate {methyl 

tetradecanoate} 

124-10-7 242.40 Exp 0 7 0.37 0.24 0.067 0.159±0.110

2,3,5,6,8-

pentaamethylnonyl acetate 

 256.42 Exp 0 7 0.57 0.35 0.136 0.26±0.14 

3,5,7,9-tetramethyldecyl 

acetate 

 256.42 AdjP 0 7 0.40 0.25 0.046 0.155±0.136

5-ethyl-3,6,8-

trimethylnonyl acetate 

 256.42 AdjP 0 7 0.69 0.40 0.154 0.30±0.16 

dimethyl carbonate 616-38-6 90.08 Exp 1 2 0 2 0.055 0.045 0.035 0.041±0.008
Table C-1 (continued) 

92 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

propylene carbonate 108-32-7 102.09 Exp 1 2 + 2 0.26 0.184 0.137 0.166±0.037

methyl lactate 547-64-8 104.10 Exp 1 0 6 2.63 1.06 0.58 0.96±0.43 

2-methoxyethyl acetate 110-49-6 118.13 Exp 0 7 1.08 0.65 0.47 0.59±0.14 

ethyl lactate 97-64-3 118.13 Exp 1 0 6 2.42 1.04 0.60 0.94±0.38 

methyl isopropyl carbonate 51729-83-0 118.13 Exp 1 2 0 2 0.59 0.34 0.23 0.31±0.08 

1-methoxy-2-propyl acetate 108-65-6 132.16 Exp 1 2 0,+ 2 1.63 0.83 0.56 0.76±0.21 

2-ethoxyethyl acetate 111-15-9 132.16 Exp 0 7 1.76 0.89 0.58 0.80±0.24 

2-methyoxy-1-propyl 

acetate 

70657-70-4 132.16 Exp 0 7 1.06 0.59 0.41 0.54±0.13 

methoxypropanol acetate 84540-57-8 132.16 Exp 0 7 1.76 0.93 0.60 0.83±0.26 

dimethyl succinate 106-65-0 146.14 Exp 1 2 0 2 0.21 0.131 0.081 0.113±0.034

ethylene glycol diacetate 111-55-7 146.14 Exp 0 7 0.62 0.37 0.24 0.32±0.11 

diisopropyl carbonate 6482-34-4 146.18 Exp 0 7 0.94 0.49 0.30 0.43±0.14 

1,2-propylene glycol 

diacetate 

623-84-7 160.17 Exp 0 7 0.57 0.36 0.24 0.32±0.08 

dimethyl glutarate 1119-40-0 160.17 AdjP 1 2 0 2 0.39 0.22 0.108 0.179±0.075

2-butoxyethyl acetate 112-07-2 160.21 Exp 0 7 1.52 0.80 0.50 0.70±0.22 

dimethyl adipate 627-93-0 174.19 AdjP 1 0 6 1.72 0.80 0.44 0.70±0.27 

2-(2-ethoxyethoxy) ethyl 

acetate 

112-15-2 176.21 AdjP 0 7 1.39 0.74 0.47 0.65±0.20 

dipropylene glycol npropyl ether isomer #1  176.25 AdjP 0 7 1.89 0.96 0.60 0.85±0.27 

dipropylene glycol methyl 

ether acetate isomer #1 

 190.24 AdjP 0 7 1.30 0.68 0.42 0.59±0.19 

dipropylene glycol methyl 

ether acetate isomer #2 

 190.24 AdjP 0 7 1.43 0.72 0.44 0.64±0.21 

dipropylene glycol methyl 

ether acetate isomers 

88917-22-0 190.24 LM 0 7 1.37 0.70 0.43 0.62±0.20 

glyceryl triacetate 102-76-1 218.20 Exp 0 7 0.50 0.31 0.178 0.26±0.09 

2-(2-butoxyethoxy) ethyl 

acetate 

124-17-4 204.26 Exp 0 7 1.29 0.68 0.40 0.58±0.20 

substituted c7 ester (c12) 216.32 LM 0 7 0.75 0.39 0.20 0.32±0.13 

1-hydroxy-2,2,4-

trimethylpentyl-3-

isobutyrate 

18491-15-1 216.32 Exp 0 7 0.84 0.40 0.21 0.34±0.14 

3-hydroxy-2,2,4-

trimethylpentyl-1-

isobutyrate 

77-68-9 216.32 AdjP 0 7 0.71 0.39 0.191 0.31±0.13 

texanol isomers 25265-77-4 216.32 LM 1 2 0 2 0.75 0.39 0.20 0.32±0.13 

substituted c9 ester (c12) 216.32 LM 0 7 0.75 0.39 0.20 0.32±0.13 

dimethyl sebacate 106-79-6 230.30 Exp 0 7 0.38 0.23 0.070 0.161±0.102

diisopropyl adipate 6938-94-9 230.30 Exp 0 7 1.22 0.52 0.22 0.43±0.22 

triethyl citrate 77-93-0 276.28 Exp 0 8 0.66 0.31 0.155 0.26±0.11 

2,2,4-trimethyl-1,3-

pentanediol diisobutyrate 

6846-50-0 286.41 Exp 0 7 0.33 0.20 0.062 0.140±0.088

ethylene oxide 75-21-8 44.05 Exp 1 0 6 0.036 0.032 0.026 0.029±0.005

propylene oxide 75-56-9 58.08 Exp 1 0 6 0.28 0.21 0.159 0.188±0.037

1,2-epoxybutane 106-88-7 72.11 Exp 1 0 6 0.85 0.62 0.46 0.55±0.13 

formic acid 64-18-6 46.03 Exp 1 0 6 0.062 0.045 0.035 0.041±0.008

acetic acid 64-19-7 60.05 Exp 1 0 6 0.67 0.32 0.20 0.29±0.10 
Table C-1 (continued) 

93 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

glycolic acid 79-14-1 76.05 AdjP 0 8 2.35 0.92 0.49 0.84±0.39 

peroxyacetic acid 79-21-0 76.05 LM 0 8 0.53 0.26 0.162 0.23±0.08 

acrylic acid 79-10-7 72.06 AdjP 0 8 11.38 4.00 2.27 3.81±1.76 

propionic acid 79-09-4 74.08 Exp 0 7 1.18 0.57 0.34 0.51±0.19 

methacrylic acid 79-41-4 86.09 Exp 0 8 18.56 6.17 3.52 5.95±2.85 

isobutyric acid 79-31-2 88.11 Exp 0 7 1.16 0.59 0.38 0.53±0.17 

butanoic acid 107-92-6 88.11 AdjP 0 7 1.76 0.88 0.55 0.79±0.26 

malic acid 6915-15-7 134.09 AdjP 0 8 6.92 2.44 1.33 2.29±1.08 

3-methylbutanoic acid 503-74-2 102.13 AdjP 0 7 4.17 1.69 0.98 1.56±0.64 

adipic acid 124-04-9 146.14 AdjP 0 8 2.95 1.41 0.88 1.27±0.43 

2-ethyl hexanoic acid 149-57-5 144.21 Exp 0 7 3.21 1.39 0.75 1.23±0.50 

methyl acrylate 96-33-3 86.09 Exp 0 8 11.50 3.90 2.19 3.73±1.77 

vinyl acetate 108-05-4 86.09 Exp 0 8 3.16 1.21 0.72 1.14±0.46 

2-methyl-3-butene-2-ol 115-18-4 86.13 Exp 1 0 8 4.81 2.00 1.29 1.88±0.64 

ethyl acrylate 140-88-5 100.12 Exp 0 8 7.71 2.87 1.67 2.70±1.13 

methyl methacrylate 80-62-6 100.12 Exp 0 8 15.67 5.20 2.95 5.02±2.41 

ethyl methacrylate 97-63-2 114.14 Exp 0 8 12.50 4.21 2.38 4.04±1.92 

hydroxypropyl acrylate 2918-23-2 130.14 Exp 0 8 4.82 1.94 1.16 1.80±0.68 

n-butyl acrylate 141-32-2 128.17 Exp 0 8 4.95 1.91 1.08 1.76±0.73 

isobutyl acrylate 106-63-8 128.17 AdjP 0 8 4.64 1.81 1.01 1.66±0.69 

butyl methacrylate 97-88-1 142.20 Exp 0 8 8.71 2.96 1.64 2.82±1.34 

isobutyl methacrylate 97-86-9 142.20 Exp 0 8 8.63 2.93 1.62 2.79±1.34 

α-terpineol 98-55-5 154.25 Exp 0 8 4.62 1.67 0.90 1.57±0.78 

Citronellol (3,7-dimethyl6-octen-1-ol) 106-22-9 154.25 Exp 0 8 5.80 2.05 1.12 1.94±0.97 

Linalool 78-70-6 156.27 Exp 0 8 5.44 1.96 1.09 1.85±0.91 

Geraniol 106-24-1 172.26 Exp 0 8 5.10 1.88 1.06 1.78±0.86 

2-ethyl-hexyl acrylate 103-11-7 184.28 Exp 0 8 2.46 0.96 0.47 0.85±0.39 

Hexyl cinnamal 101-86-0 216.32 LM 0 10 2.93 1.08 0.64 1.03±0.42 

furan 110-00-9 68.07 Exp 1 3 - 4 9.03 3.57 2.10 3.33±1.34 

2-methyl furan 534-22-5 82.10 Exp 1 3 0 4 8.20 3.19 1.88 2.99±1.21 

3-methyl furan 930-27-8 82.10 Exp 1 3 0 4 6.77 2.77 1.68 2.58±0.97 

2-ethyl furan 3208-16-0 96.13 LM 0 8 7.01 2.72 1.61 2.55±1.03 

2,5-dimethyl furan 625-86-5 96.13 Exp 1 3 0 4 7.78 2.96 1.75 2.79±1.15 

formaldehyde 50-00-0 30.03 Exp 1 1 0 1 b 9.59 2.89 1.41 2.79±1.68 

acetaldehyde 75-07-0 44.05 Exp 1 2 0 1 6.46 2.53 1.62 2.42±0.86 

propionaldehyde 123-38-6 58.08 Exp 1 0 6 6.96 2.72 1.72 2.58±0.93 

2-methylpropanal 78-84-2 72.11 Exp 1 0 7 5.15 2.08 1.35 1.98±0.67 

butanal 123-72-8 72.11 Exp 1 0 7 5.85 2.30 1.45 2.18±0.78 

c4 aldehydes 72.11 LM 0 7 5.85 2.30 1.45 2.18±0.78 

2,2-dimethylpropanal 

(pivaldehyde) 

630-19-3 86.13 Exp 1 0 8 4.80 1.88 1.21 1.80±0.63 

3-methylbutanal 

(isovaleraldehyde) 

590-86-3 86.13 Exp 1 0 8 4.89 1.91 1.22 1.82±0.65 

pentanal (valeraldehyde) 110-62-3 86.13 Exp 1 0 8 4.98 1.98 1.26 1.88±0.66 

c5 aldehydes 86.13 LM 0 8 4.98 1.98 1.26 1.88±0.66 

glutaraldehyde 111-30-8 100.12 Exp 0 8 4.21 1.70 1.13 1.62±0.54 

hexanal 66-25-1 100.16 Exp 1 0 8 4.26 1.70 1.08 1.60±0.56 

c6 aldehydes 100.16 LM 0 8 4.26 1.70 1.08 1.60±0.56 
Table C-1 (continued) 

94 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

heptanal 111-71-7 114.19 Exp 1 0 8 3.60 1.43 0.90 1.35±0.48 

c7 aldehydes 114.19 LM 0 8 3.60 1.43 0.90 1.35±0.48 

2-methyl-hexanal 925-54-2 114.19 Exp 0 8 3.45 1.41 0.88 1.32±0.46 

octanal 124-13-0 128.21 Exp 0 8 3.08 1.22 0.74 1.14±0.42 

c8 aldehydes 128.21 LM 0 8 3.08 1.22 0.74 1.14±0.42 

Hydroxycitronellal 107-75-5 154.25 Exp 0 8 2.54 1.02 0.61 0.94±0.35 

glyoxal 107-22-2 58.04 Exp 1 0 6 12.59 3.95 2.02 3.81±2.18 

methyl glyoxal 78-98-8 72.06 Exp 1 0 6 16.60 5.25 2.85 5.10±2.70 

acrolein 107-02-8 56.06 Exp 1 3 0 2 7.37 2.69 1.62 2.56±1.02 

crotonaldehyde 4170-30-3 70.09 Exp 1 0 8 9.34 3.35 1.98 3.20±1.34 

methacrolein 78-85-3 70.09 Exp 1 2 0 2 5.96 2.19 1.34 2.09±0.81 

hydroxy methacrolein 40364-84-9 86.09 Exp 0 8 6.16 2.36 1.42 2.22±0.85 

lumped c5+ unsaturated 

carbonyl species 

 100.12 Exp 0 8 6.33 2.34 1.39 2.22±0.90 

Cinnamic aldehyde 104-55-2 132.16 LM 0 10 4.79 1.77 1.05 1.68±0.68 

Amyl cinnamal 122-40-7 202.29 LM 0 10 3.13 1.16 0.69 1.10±0.45 

benzaldehyde 100-52-7 106.12 Exp 1 3 0 2 -0.71 -0.73 -1.05 -0.89±0.26

tolualdehyde 120.15 LM 0 7 -0.63 -0.65 -0.93 -0.78±0.23

acetone 67-64-1 58.08 Exp 1 1 0 2 0.35 0.146 0.088 0.135±0.049

cyclobutanone 1191-95-3 70.09 Exp 1 0 8 0.58 0.34 0.23 0.30±0.09 

methyl ethyl ketone 78-93-3 72.11 Exp 1 2 0 2 1.45 0.62 0.37 0.56±0.20 

cyclopentanone 120-92-3 84.12 Exp 1 0 8 1.08 0.65 0.42 0.57±0.17 

c5 cyclic ketones 84.12 LM 0 8 1.08 0.65 0.42 0.57±0.17 

2-pentanone 107-87-9 86.13 Exp 1 2 0 2 2.72 1.33 0.85 1.21±0.38 

3-pentanone 96-22-0 86.13 Exp 1 0 6 1.18 0.59 0.37 0.52±0.18 

c5 ketones 86.13 LM 0 7 2.72 1.33 0.85 1.21±0.38 

methyl isopropyl ketone 563-80-4 86.13 Exp 1 0 6 1.60 0.79 0.50 0.71±0.22 

2,4-pentanedione 123-54-6 100.12 Exp 0 8 0.99 0.38 0.22 0.35±0.14 

cyclohexanone 108-94-1 98.14 Exp 1 2 0 2 1.25 0.72 0.42 0.61±0.22 

c6 cyclic ketones 98.14 LM 0 7 1.25 0.72 0.42 0.61±0.22 

4-methyl-2-pentanone 108-10-1 100.16 Exp 1 2 0 3 3.78 1.67 1.07 1.55±0.51 

methyl n-butyl ketone 591-78-6 100.16 Exp 1 0 8 3.02 1.49 0.94 1.34±0.43 

methyl t-butyl ketone 75-97-8 100.16 Exp 1 0 8 0.62 0.32 0.20 0.29±0.09 

c6 ketones 100.16 LM 0 8 3.02 1.49 0.94 1.34±0.43 

c7 cyclic ketones 112.17 LM 0 8 1.09 0.63 0.37 0.53±0.19 

2-heptanone 110-43-0 114.19 Exp 1 3 ? 4 2.23 1.16 0.69 1.01±0.34 

2-methyl-3-hexanone 7379-12-6 114.19 Exp 0 8 1.44 0.77 0.47 0.67±0.23 

di-isopropyl ketone 565-80-0 114.19 Exp 1 0 8 1.23 0.67 0.40 0.58±0.21 

c7 ketones 114.19 LM 0 8 2.23 1.16 0.69 1.01±0.34 

5-methyl-2-hexanone 110-12-3 114.19 AdjP 1 0 8 2.28 1.19 0.76 1.06±0.33 

3-methyl-2-hexanone 2550-21-2 114.19 Exp 0 8 2.43 1.25 0.77 1.10±0.37 

c8 cyclic ketones 126.20 LM 0 8 0.97 0.56 0.33 0.47±0.17 

2-octanone 111-13-7 128.21 Exp 1 0 8 1.29 0.73 0.39 0.60±0.23 

c8 ketones 128.21 LM 0 8 1.29 0.73 0.39 0.60±0.23 

c9 cyclic ketones 140.22 LM 0 8 0.87 0.50 0.30 0.43±0.15 

2-propyl cyclohexanone 94-65-5 140.22 AdjP 0 8 1.40 0.76 0.38 0.62±0.27 

4-propyl cyclohexanone 40649-36-3 140.22 Exp 0 8 1.72 0.89 0.49 0.75±0.29 

2-nonanone 821-55-6 142.24 Exp 1 0 8 0.98 0.57 0.27 0.44±0.19 
Table C-1 (continued) 

95 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

di-isobutyl ketone (2,6-

dimethyl-4-heptanone) 

108-83-8 142.24 Exp 1 0 8 2.57 1.15 0.68 1.03±0.37 

c9 ketones 142.24 LM 0 8 0.98 0.57 0.27 0.44±0.19 

camphor 76-22-2 152.23 Exp 0 8 0.43 0.26 0.089 0.184±0.112

c10 cyclic ketones 154.25 LM 0 8 0.79 0.46 0.27 0.39±0.14 

2-decanone 693-54-9 156.27 AdjP 1 0 8 0.80 0.48 0.187 0.35±0.19 

c10 ketones 156.27 LM 0 8 0.80 0.48 0.187 0.35±0.19 

2,6,8-trimethyl-4-

nonanone; isobutyl heptyl 

ketone 

123-18-2 184.32 Exp 0 8 1.56 0.75 0.39 0.63±0.26 

biacetyl 431-03-8 86.09 Exp 1 0 6 20.10 6.46 3.68 6.31±3.15 

methylvinyl ketone 78-94-4 70.09 Exp 1 3 0 2 9.56 3.68 2.24 3.47±1.35 

mesityl oxide (2-methyl-2-

penten-4-one) 

141-79-7 98.14 LM 0 8 6.46 2.39 1.41 2.26±0.92 

isophorone {3,5,5-

trimethyl-2-

cyclohexenone} 

78-59-1 138.21 LM 0 8 4.58 1.70 1.00 1.60±0.65 

1-nonene-4-one 61168-10-3 140.22 Exp 0 8 3.00 1.24 0.71 1.12±0.43 

hydroxy acetone 116-09-6 74.08 Exp 1 0 8 3.21 1.20 0.66 1.11±0.49 

dihydroxyacetone 96-26-4 90.08 Exp 0 8 3.72 1.43 0.80 1.32±0.57 

methoxy acetone 5878-19-3 88.11 Exp 1 0 8 1.96 0.95 0.63 0.88±0.25 

diacetone alcohol 123-42-2 116.16 Exp 0 8 0.56 0.30 0.184 0.26±0.09 

phenol 108-95-2 94.11 LM 0 8 2.75 0.163 -0.89 -.057±0.876

c7 alkyl phenols 1319-77-3 108.14 LM 0 5 2.40 0.142 -0.78 -.050±0.762

m-cresol 108-39-4 108.14 LM 4 -,0 5 2.40 0.142 -0.78 -.050±0.762

p-cresol 106-44-5 108.14 LM 4 0? 5 2.40 0.142 -0.78 -.050±0.762

o-cresol 95-48-7 108.14 Exp 1 4 ? 5 2.40 0.142 -0.78 -.050±0.762

4-vinylphenol 2628-17-3 120.15 LM 0 11 1.44 0.161 -0.41 -.007±0.452

2,4-dimethyl phenol 105-67-9 122.16 LM 0 8 2.12 0.125 -0.69 -.044±0.675

2,5-dimethyl phenol 122.16 LM 0 8 2.12 0.125 -0.69 -.044±0.675

3,4-dimethyl phenol 95-65-8 122.16 LM 0 8 2.12 0.125 -0.69 -.044±0.675

2,3-dimethyl phenol 526-75-0 122.16 LM 0 8 2.12 0.125 -0.69 -.044±0.675

2,6-dimethyl phenol 576-26-1 122.16 LM 0 8 2.12 0.125 -0.69 -.044±0.675

c8 alkyl phenols 122.16 LM 0 8 2.12 0.125 -0.69 -.044±0.675

methylparaben (4-

hydroxybenzoic acid, 

methyl ester) 

99-76-3 152.15 LM 0 11 1.70 0.101 -0.55 -.036±0.542

2,3,5-trimethyl phenol 697-82-5 136.19 LM 0 8 1.90 0.113 -0.62 -.039±0.606

2,3,6-trimethyl phenol 2416-94-6 136.19 LM 0 8 1.90 0.113 -0.62 -.039±0.606

c9 alkyl phenols 136.19 LM 0 8 1.90 0.113 -0.62 -.039±0.606

c10 alkyl phenols 150.22 LM 0 8 1.73 0.102 -0.56 -.036±0.549

propylparaben 94-13-3 180.20 LM 0 11 1.44 0.085 -0.47 -.030±0.458

c11 alkyl phenols 164.24 LM 0 8 1.58 0.094 -0.51 -.033±0.502

c12 alkyl phenols 178.27 LM 0 8 1.45 0.086 -0.47 -.030±0.463

2,6-di-tert-butyl-p-cresol 128-37-0 220.35 LM 0 10 1.18 0.070 -0.38 -.024±0.374

benzyl alcohol 100-51-6 108.14 Exp 1 2 0 4 5.08 1.77 0.85 1.62±0.82 

methoxybenzene; anisole 100-66-3 108.14 Exp 1 0 8 6.61 2.25 1.04 2.05±1.09 

beta-phenethyl alcohol 98-85-1 122.16 LM - 11 4.49 1.57 0.76 1.44±0.73 
Table C-1 (continued) 

96 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

2-phenoxyethanol; ethylene 

glycol phenyl ether 

122-99-6 138.16 Exp 0 8 4.43 1.64 0.85 1.50±0.69 

phthalic anhydride 85-44-9 148.12 Exp 0 8 2.53 0.92 0.41 0.81±0.44 

cinnamic alcohol 104-54-1 134.18 LM -1 10 0.83 0.099 -0.29 -.031±0.270

1-phenoxy-2-propanol 770-35-4 152.19 LM 0 8 1.55 0.63 0.28 0.54±0.27 

anethol 104-46-1 148.20 LM 0 11 0.75 0.090 -0.26 -.028±0.245

1,2-diacetyl benzene 704-00-7 162.19 Exp 1 0 8 2.20 0.80 0.34 0.70±0.39 

diethyl phthalate 84-66-2 222.24 Exp 0 8 1.58 0.59 0.26 0.52±0.27 

2-ethylhexyl benzoate 5444-75-7 234.33 Exp 0 10 0.92 0.42 0.176 0.34±0.17 

Di n-butyl phthalate 84-74-2 278.34 Exp 0 8 1.21 0.48 0.22 0.42±0.20 

nitrobenzene 98-95-3 123.11 Exp 1 0 8 0.054 0.007 -0.013 0.002±0.016

m-nitrotoluene 99-08-1 137.14 Exp 1 0 8 0.49 0.165 0.035 0.130±0.102

para toluene isocyanate 622-58-2 133.15 Exp 1 2 0 5 1.04 -0.077 -0.52 -.167±0.377

2,4-toluene diisocyanate 584-84-9 174.16 Exp 1 2 0 5 -0.084 -0.54 -0.82 -0.61±0.24

2,6-toluene diisocyanate 91-08-7 174.16 LM 4 0 5 -0.084 -0.54 -0.82 -0.61±0.24

toluene diisocyanate 

(mixed isomers) 

26471-62-5 174.16 LM 0 5 -0.084 -0.54 -0.82 -0.61±0.24

methylene diphenylene 

diisocyanate 

101-68-8 250.25 Exp 0 8 0.88 0.020 -0.31 -.044±0.273

methylamine 74-89-5 31.06 Exp 1 + 13 a,n 7.25 4.04 2.60 3.57±1.10 

dimethyl amine 124-40-3 45.08 Exp 1 + 13 a,n 2.65 1.84 1.33 1.61±0.57 

ethyl amine 75-04-7 45.08 Exp 1 + 13 a,n 5.45 2.97 1.91 2.63±0.81 

trimethyl amine 75-50-3 59.11 Exp 1 + 13 a,n 5.27 2.75 1.81 2.48±0.75 

isopropylamine 75-31-0 59.11 Exp 4a + 12 a,n 6.97 3.26 2.06 2.97±0.97 

t-butyl amine 75-64-9 73.14 Exp 1 4a - 12 a -3.26 -1.06 -0.44 -0.99±0.70

triethyl amine 121-44-8 101.19 Exp + 13 a,n 3.07 1.48 0.91 1.31±0.45 

triethylene diamine 280-57-9 112.17 LM + 13 a,n 2.77 1.33 0.82 1.18±0.40 

ethanolamine 141-43-5 61.08 Exp 3a + 12 a,n 6.59 2.99 1.85 2.72±0.93 

dimethylaminoethanol 108-01-0 89.14 Exp 1 + 13 a,n 5.15 2.21 1.40 2.05±0.70 

2-amino-1-butanol 96-20-8 89.14 Exp + 13 a,n 4.79 2.14 1.31 1.95±0.67 

2-amino-2-methyl-1-

propanol 

124-68-5 89.14 Exp 3a - 12 a -2.68 -0.80 -0.30 -0.76±0.62

diethanol amine 111-42-2 105.14 Exp + 13 a,n 2.22 1.08 0.70 0.98±0.32 

triethanolamine 102-71-6 149.19 Exp + 13 a,n 3.25 1.37 0.81 1.25±0.46 

triisopropanolamine 122-20-3 191.27 Exp + 13 a,n 1.99 0.96 0.60 0.86±0.29 

methyl nitrite 624-91-9 61.04 Exp 1 0 6 10.94 4.76 4.20 5.05±1.35 

acrylonitrile 107-13-1 53.06 Exp 1 0 10 2.18 1.09 0.73 1.01±0.29 

1-nitropropane 108-03-2 89.09 Exp 0 8 0.20 0.147 0.108 0.131±0.029

ethyl methyl ketone oxime 96-29-7 87.12 Exp 0 10 1.55 1.32 1.45 1.40±0.30 

n-methyl-2-pyrrolidone 872-50-4 99.13 Exp 1 2 0 2 2.28 1.16 0.68 1.01±0.35 

lauryl pyrrolidone 2687-96-9 253.42 LM 0 11 0.89 0.45 0.27 0.40±0.14 

methyl chloride 74-87-3 50.49 Exp 1 0 10 0.037 0.020 0.013 0.018±0.005

dichloromethane 75-09-2 84.93 Exp 1 0 10 0.038 0.026 0.018 0.023±0.006

methyl bromide 74-83-9 94.94 Exp 1 0 10 0.018 0.010 0.006 0.009±0.003

chloroform 67-66-3 119.38 Exp 1 0 10 0.020 0.014 0.010 0.012±0.003

carbon tetrachloride 56-23-5 153.82 LM 0 1 0 0 0 0 

methylene bromide 74-95-3 173.83 LM 0 1 0 0 0 0 

ethyl chloride 75-00-3 64.51 Exp 1 0 10 0.27 0.168 0.111 0.147±0.044

1,1-dichloroethane 75-34-3 98.96 Exp 1 0 10 0.065 0.043 0.030 0.038±0.009
Table C-1 (continued) 

97 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

1,2-dichloroethane 107-06-2 98.96 Exp 1 0 10 0.21 0.099 0.058 0.088±0.032

ethyl bromide 74-96-4 108.97 Exp 1 0 20 0.121 0.075 0.050 0.066±0.020

1,1,1-trichloroethane 71-55-6 133.40 Exp 1 0 10 0.005 0.003 0.002 0.003±0.001

1,1,2-trichloroethane 79-00-5 133.40 Exp 1 0 10 0.082 0.043 0.026 0.038±0.012

1,2-dibromoethane 106-93-4 187.86 Exp 1 0 20 0.098 0.047 0.028 0.042±0.015

1,2-dichloropropane 78-87-5 112.99 Exp 0 10 0.28 0.136 0.082 0.121±0.042

n-propyl bromide 106-94-5 122.99 Exp 1 2x -,+2 20 n 0.40 0.22 0.135 0.190±0.061

1-chlorobutane 109-69-3 92.57 Exp 0 10 1.04 0.59 0.37 0.52±0.16 

n-butyl bromide 109-65-9 137.02 Exp 1 2x -,+2 20 n 0.78 0.44 0.28 0.38±0.12 

3-(chloromethyl)-heptane 123-04-6 148.67 LM 0 10 0.86 0.53 0.27 0.42±0.17 

vinyl chloride 75-01-4 62.50 Exp 1 0 10 2.71 1.42 0.95 1.29±0.37 

1,1-dichloroethene 75-35-4 96.94 Exp 0 10 2.76 1.22 0.82 1.13±0.36 

trans-1,2-dichloroethene 156-60-5 96.94 Exp 1 0 10 1.66 0.75 0.44 0.67±0.25 

cis-1,2-dichloroethene 96.94 LM 0 10 1.66 0.75 0.44 0.67±0.25 

trichloroethylene 79-01-6 131.39 Exp 1 2x +2 20 0.61 0.33 0.21 0.29±0.09 

perchloroethylene 127-18-4 165.83 Exp 1 0 10 0.029 0.020 0.013 0.017±0.005

3-chloropropene 76.52 Exp 0 10 12.20 4.04 2.20 3.84±1.89 

trans-1,3-dichloropropene 10061-02-6 110.97 Exp 1 2m 0 3 5.00 1.83 1.03 1.71±0.76 

cis-1,3-dichloropropene 10061-01-5 110.97 Exp 1 2m 0 3 3.66 1.44 0.83 1.33±0.55 

1,3-dichloropropene 

mixture 

 110.97 LM 1 2 0 2 4.25 1.61 0.92 1.49±0.64 

2-(cl-methyl)-3-cl-propene 1871-57-4 125.00 Exp 1 4 - 20 6.75 2.30 1.30 2.18±1.01 

monochlorobenzene 108-90-7 112.56 Exp 1 0 8 0.31 0.045 -0.068 0.017±0.091

p-dichlorobenzene 106-46-7 147.00 Exp 0 10 0.171 0.025 -0.039 0.009±0.051

o-dichlorobenzene 95-50-1 147.00 LM 0 8 0.171 0.025 -0.039 0.009±0.051

hexafluorobenzene 392-56-3 186.05 Exp 1 0 8 0.045 0.006 -0.011 0.002±0.014

2-chlorotoluene 95-49-8 126.58 LM 1 8 2.86 1.00 0.40 0.88±0.51 

benzotrifluoride 98-08-8 146.11 Exp 1 0 8 0.29 0.109 0.042 0.092±0.053

p-trifluoromethyl-clbenzene 98-56-6 180.55 Exp 1 0 8 0.122 0.047 0.018 0.039±0.023

methyl nonafluorobutyl 

ether 

163702-07-6 234.06 Exp 0 8 0.051 0.041 0.030 0.036±0.008

methyl nonafluoroisobutyl 

ether 

163702-08-7 234.06 LM 0 8 0.051 0.041 0.030 0.036±0.008

ethyl nonafluorobutyl ether 163702-05-4 264.09 Exp + 8 0.190 0.124 0.084 0.108±0.026

ethyl nonafluoroisobutyl 

ether 

163702-06-5 264.09 LM + 8 0.190 0.124 0.084 0.108±0.026

chloroacetaldehyde 107-20-0 78.50 Exp 1 0 7 12.44 3.72 1.85 3.58±2.05 

chloropicrin 76-06-2 164.38 Exp 1 2 0 1 1.87 1.08 1.16 1.18±0.19 

hexamethyldisiloxane 107-46-0 162.38 Exp 1 3 0 5 -0.030 0.020 0.032 0.020±0.020

hydroxymethyldisiloxane 164.35 Exp 1 3 0 5 -0.137 -0.019 0.015 -.015±0.043

d4 cyclosiloxane 556-67-2 296.62 Exp 1 3 0 5 -0.059 -0.014 0.001 -.011±0.016

d5 cyclosiloxane 541-02-6 370.77 Exp 1 4 0 5 -0.070 -0.016 0.001 -.014±0.019

carbon disulfide 75-15-0 76.14 Exp 1 2 0 2 0.23 0.159 0.125 0.147±0.026

methyl isothiocyanate 556-61-6 73.12 Exp 1 2 0 2 0.31 0.21 0.186 0.20±0.03 

dimethyl sulfoxide 67-68-5 78.13 Exp 1 2 -2,0 4 6.63 2.47 1.54 2.37±0.97 

molinate 187.30 Exp 0 7 1.43 0.70 0.43 0.62±0.21 

eptc (s-ethyl 

dipropylthiocarbamate) 

759-94-4 189.32 Exp 1 2 0 2 1.57 0.82 0.50 0.72±0.24 
Table C-1 (continued) 

98 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

pebulate 203.34 Exp 0 7 1.58 0.79 0.46 0.69±0.25 

thiobencarb 257.78 Exp 0 8 0.64 0.27 0.100 0.21±0.12 

methyl iodide 74-88-4 141.94 Exp 0 3 -0.52 -2.02 -2.65 -2.11±0.68

 

Base ROG Mixture 14.44 Mix 0 7 3.56 1.46 0.81 1.32±0.53 

Final LEV -- RFA 14.03 Mix 0 7 3.48 1.43 0.77 1.28±0.54 

TLEV Exhaust -- RFA 14.04 Mix 0 7 3.95 1.58 0.86 1.43±0.61 

TLEV Exhaust -- Phase 2 14.12 Mix 0 7 3.91 1.58 0.87 1.43±0.60 

Final LEV -- Phase 2 14.22 Mix 0 7 3.39 1.40 0.77 1.26±0.52 

TLEV Exhaust -- LPG 14.86 Mix 0 7 2.02 0.89 0.55 0.82±0.28 

TLEV Exhaust -- CNG 15.22 Mix 0 7 0.71 0.34 0.22 0.31±0.10 

TLEV Exhaust -- E-85 20.74 Mix 0 7 2.48 1.18 0.75 1.08±0.35 

TLEV Exhaust -- M-85 27.45 Mix 0 7 1.56 0.62 0.35 0.57±0.24 

Composite mineral spirit 

(naphthas or lactol spirits) 

(CARB Profile ID 802) 

 14.06 Mix 0 7 1.75 0.80 0.36 0.66±0.31 

Safety-Kleen Mineral 

Spirits "A" (Type I-B, 91% 

Alkanes) 

 14.08 Mix 2 0,+ 7 1.09 0.57 0.23 0.44±0.22 

Safety-Kleen Mineral 

Spirits "B" (Type II-C) 

 14.10 Mix 2 0,+ 7 0.62 0.38 0.127 0.27±0.17 

Safety-Kleen Mineral 

Spirits "C" (Type II-C) 

 14.11 Mix 2 0,+ 7 0.62 0.39 0.126 0.27±0.17 

Exxon Exxol(r) D95 Fluid 14.11 Mix 2 0 7 0.53 0.33 0.104 0.23±0.15 

Safety-Kleen Mineral 

Spirits "D" (Type II-C) 

 14.12 Mix 2 0,+ 7 0.62 0.39 0.127 0.27±0.17 

Exxon Isopar(r) M Fluid 14.15 Mix 2 0 7 0.51 0.33 0.099 0.22±0.15 

Thinning Solvent/Mineral 

Spirits (Cal Poly Slo. 1996) 

 14.40 Mix 0 7 1.79 0.85 0.41 0.71±0.30 

Aromatic 100 13.36 Mix 2 0 7 7.55 2.62 1.34 2.43±1.19 

Kerosene 13.94 Mix 2 0 7 1.45 0.67 0.29 0.54±0.26 

Regular mineral spirits 13.97 Mix 2 0 7 1.73 0.78 0.34 0.64±0.30 

Reduced Aromatics 

Mineral Spirits 

 14.05 Mix 2 0 7 1.06 0.56 0.22 0.43±0.22 

Dearomatized Alkanes, 

mixed, predominately C10-

C12 

 14.09 Mix 2 0 7 0.77 0.46 0.172 0.34±0.19 

VMP Naphtha 14.16 Mix 2 0 7 1.10 0.64 0.29 0.50±0.23 

Synthetic isoparaffinic 

alkane mixture, 

predominately C10-C12 

 14.20 Mix 2 0 7 0.66 0.41 0.139 0.29±0.17 

ASTM-3C1 "Highly 

Branched" rep'n 

 14.20 Mix 0 7 1.00 0.59 0.26 0.45±0.21 

Oxo-Tridecyl Acetate 16.19 Mix 0 7 0.52 0.31 0.106 0.22±0.14 

Oxo-Dodecyl Acetate 16.30 Mix 0 7 0.56 0.33 0.114 0.24±0.14 

Oxo-Decyl Acetate 16.71 Mix 2 0 7 0.64 0.39 0.151 0.29±0.15 

Oxo-Nonyl Acetate 16.89 Mix 0 7 0.67 0.40 0.159 0.30±0.16 

Oxo-Octyl Acetate 17.23 Mix 0 7 0.76 0.46 0.20 0.35±0.16 

Oxo-Heptyl Acetate 17.58 Mix 0 7 0.79 0.47 0.23 0.37±0.16 

Oxo-Hexyl Acetate 18.02 Mix 0 7 0.83 0.51 0.27 0.41±0.16 
Table C-1 (continued) 

99 

Codes [b] Reactivity (gm O3 / gm VOC) Description CAS MWt 

[a] Rep k a Expt Bias Unc MIR MOIR EBIR Base 

 

Unspeciated C6 Alkanes 

(n-, br-, and cyc-) 

 14.25 Mix 0 8 1.25 0.80 0.49 0.68±0.22 

Unspeciated C7 Alkanes 

(n-, br-, and cyc-) 

 14.22 Mix 0 8 1.26 0.77 0.41 0.62±0.23 

Unspeciated C8 Aromatics 13.27 Mix 0 8 7.56 2.56 1.20 2.34±1.23 

Unspeciated C8 Alkanes 

(n-, br-, and cyc-) 

 14.19 Mix 0 8 1.16 0.70 0.34 0.55±0.23 

Unspeciated C9 Aromatics 13.34 Mix 0 8 8.11 2.82 1.47 2.62±1.27 

Unspeciated C9 Alkanes 

(n-, br-, and cyc-) 

 14.18 Mix 0 8 0.96 0.57 0.24 0.43±0.21 

Unspeciated C10 

Aromatics 

 13.39 Mix 0 8 7.21 2.52 1.31 2.34±1.12 

Unspeciated C10 Alkanes 

(n-, br-, and cyc-) 

 14.16 Mix 0 8 0.79 0.48 0.186 0.35±0.19 

Unspeciated C11 

Aromatics 

 13.43 Mix 0 8 7.02 2.46 1.31 2.29±1.08 

Unspeciated C11 Alkanes 

(n-, br-, and cyc-) 

 14.15 Mix 0 8 0.64 0.40 0.131 0.28±0.17 

Unspeciated C12 

Aromatics 

 13.32 Mix 0 8 5.70 1.98 1.03 1.84±0.88 

Unspeciated C12 Alkanes 

(n-, br-, and cyc-) 

 14.14 Mix 0 8 0.59 0.37 0.118 0.26±0.16 

Unspeciated C13 

Aromatics 

 13.53 Mix 0 8 5.72 2.01 1.08 1.88±0.88 

Unspeciated C13 Alkanes 

(n-, br-, and cyc-) 

 14.13 Mix 0 8 0.53 0.34 0.106 0.23±0.15 

Unspeciated C14 

Aromatics 

 13.56 Mix 0 8 5.22 1.84 0.98 1.72±0.80 

Unspeciated C14 Alkanes 

(n-, br-, and cyc-) 

 14.12 Mix 0 8 0.50 0.32 0.100 0.22±0.15 

Unspeciated C15 

Aromatics 

 13.59 Mix 0 8 4.77 1.69 0.90 1.58±0.73 

Unspeciated C15 Alkanes 

(n-, br-, and cyc-) 

 14.12 Mix 0 8 0.47 0.30 0.097 0.21±0.14 

Unspeciated C16 

Aromatics 

 13.62 Mix 0 8 4.39 1.56 0.83 1.45±0.67 

Unspeciated C16 Alkanes 

(n-, br-, and cyc-) 

 14.11 Mix 0 8 0.43 0.28 0.087 0.190±0.131

[a] Molecular weights for complex mixtures (base ROG mixture and mixtures listed below it) are given on a per 

carbon basis. 

[b] 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 Carter (2007a) or Table A-1 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 atmospheric 

reactivity values. The adjusted product mechanism is given in Carter et al (2007a). 
Table C-1 (continued) 

100 

LM This compound is represented using the "Lumped Molecule" method. See Carter et al 

(2007a) or Table A-2. 

Mix This is represented by a complex mixture of detailed model species. The compositions of 

these mixtures are given in Carter et al (2007a). 

"k a" ... Codes indicating of measurement data for the reaction rate constants 

1 The OH radical rate constant has been measured. See Carter (2007a) or Table A-1 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 

and given by Carter (2007a). 

blank The OH radical rate constant or (if primarily photoreactive) the photolysis rate 

parameters had to be estimated. See Carter (2007a) for documentation of the estimation 

method used. 

"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 and Warren (2007). 

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 and Warren 

(2007). 

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, the first indicates observed or probable bias for predictions of rates of 

NO oxidation and O3 formation, which is important in affecting MIR reactivity, and the 

second indicates observed or probable bias for low NOx conditions. E.g. "0,+" if chamber 

data available indicates that the model simulated rates of NO oxidation and O3 formation 

but overpredicted final O3 yields in NOx-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. 
Table C-1 (continued) 

101 

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 phase. 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 mechanism 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 

changed. 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. 

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 likely 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 

generally 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 lumped molecule or mixture representations that are considered 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 lumped molecule representations whose appropriateness has some 

uncertainty. 
Table C-1 (continued) 

102 

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 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 The estimated mechanism is extremely uncertain that it needs to be evaluated. This code 

is also used for 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. 

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 HNO3, 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 HNO3 is 

negligible (as may be applicable if the HNO3 formed in gas-phase reactions is removed 

from the gas phase by other means) and one also assuming that all the emitted VOC is 

available for gas-phase reaction except that the reaction with gas-phase HNO3 is fast and 

there is no other sink for HNO3 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 used 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 O3 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 

uncertainties 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 NOx is limited. This should affect MIR values but will 

lead to too high reactivities in lower NOx scenarios. 
Table C-1 (continued) 

103 

a This compound may react with HNO3 to form a non-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 gasphase species and the equilibrium constant is unknown, (b) the sources and other sinks 

for HNO3 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 HNO3 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 HNO3 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. 

+ 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.