Attachment A1

Peer Review of Organic Gas Emission Profiles



















8

APPENDIX A: FURTHER DESCRIPTION OF METHODOLOGY USED TO PREDICT

HEADSPACE VAPOR COMPOSITION

For each of the pure compounds present in gasoline, the saturation pressure at 100F (T=311 K)

was calculated using the Wagner equation:

ln Pr =

at + bt

1. 5

+ ct

3

+ dt

6

1 − t

where a, b, c, and d are constants specific to each species and τ=1- Tr. Pr and Tr are the reduced

pressure and temperature: Pr = Pi,sat/Pc and Tr = T/Tc where Pi,sat is the saturation vapor pressure

(atm), T is the temperature (K), and Pc and Tc are the critical pressure and temperature of pure

species i. Values of all parameters needed in the Wagner equation are tabulated in Appendix 1 of

Reid et al. (1987). For some compounds, the vapor pressure was estimated using alternate

equations such as Antoine or Frost-Kalkwarf-Thodos, again using data from Appendix 1 of Reid

et al. (1987).

The liquid fuel profiles that were provided specify composition in terms of weight fractions (wi)

instead of mole fractions (xi). The following formula was used to convert the liquid profiles

from mass to molar basis, using the molecular weights Mi for each species:

xi =

wi/ Mi

wi/ Mi

i

∑

Likewise the final headspace vapor composition profiles were converted from mole fraction (yi)

to weight fraction (wi) using the following formula:

wi =

yiMi

yiMi

i

∑

.
Appendix B: Full Headspace Vapor Speciation Profiles

MTBE 2% ETOH 2% ETOH 3.5% NO OXY

SAROAD wt % wt % wt % wt %

Number Species Name headspace headspace headspace headspace

45201 benzene 0.64 0.80 0.80 0.69

45202 toluene 1.36 1.31 1.24 0.86

45203 ethylbenzene 0.16 0.15 0.14 0.10

45209 n-propylbenzene 0.01 0.01 0.01 0.01

98043 isopropylbenzene (cumene) 0.00 0.00 0.00 0.00

91098 n-butylbenzene 0.00 0.00 0.00 0.00

98047 isobutylbenzene 0.00 0.00 0.00 0.00

45216 sec-butylbenzene 0.00 0.00 0.00 0.00

91111 s-pentylbenzene 0.00 0.00 0.00 0.00

91121 n-hexylbenzene 0.00 0.00 0.00 0.00

45205 m-xylene 0.23 0.22 0.21 0.14

45204 o-xylene 0.11 0.11 0.10 0.07

45206 p-xylene 0.12 0.12 0.11 0.08

99912 1-methyl-3-ethylbenzene 0.04 0.03 0.03 0.02

99914 1-methyl-4-ethylbenzene 0.01 0.01 0.01 0.01

99915 1-methyl-2-ethylbenzene 0.01 0.01 0.01 0.01

98152 1-methyl-3n-propylbenzene 0.00 0.00 0.00 0.00

98182 1-methyl-4n-propylbenzene 0.00 0.00 0.00 0.00

45113 1,3-diethylbenzene (meta) 0.00 0.00 0.00 0.00

98153 1-methyl-3-isopropylbenzene 0.00 0.00 0.00 0.00

91096 1-methyl-2-isopropylbenzene 0.00 0.00 0.00 0.00

98154 1,2-diethylbenzene (ortho) 0.00 0.00 0.00 0.00

91094 1-methyl-4-isopropylbenzene 0.00 0.00 0.00 0.00

98179 1-ethyl-2n-propylbenzene 0.00 0.00 0.00 0.00

45245 c11 dialkyl benzenes 0.00 0.00 0.00 0.00

91100 1-methyl-4-t-butylbenzene 0.00 0.00 0.00 0.00

45237 1,3-dipropylbenzene 0.00 0.00 0.00 0.00

91113 1,2-isodipropylbenzene 0.00 0.00 0.00 0.00

91120 1-methyl-4-n-pentylbenzene 0.00 0.00 0.00 0.00

91116 1,3-n-dipropylbenzene 0.00 0.00 0.00 0.00

45247 c12 dialkyl benzenes 0.00 0.00 0.00 0.00

45208 1,2,4-trimethylbenzene 0.03 0.03 0.03 0.02

45207 1,3,5-trimethylbenzene 0.02 0.02 0.01 0.01

45225 1,2,3-trimethylbenzene 0.00 0.00 0.00 0.00

45252 1,2-dimethyl-4-ethylbenzene 0.00 0.00 0.00 0.00

45257 1,3-dimethyl-5-ethylbenzene 0.00 0.00 0.00 0.00

45250 1,4-dimethyl-2-ethylbenzene 0.00 0.00 0.00 0.00

45251 1,3-dimethyl-4-ethylbenzene 0.00 0.00 0.00 0.00

45254 1,2-dimethyl-3-ethylbenzene 0.00 0.00 0.00 0.00

45253 1,3-dimethyl-2-ethylbenzene 0.00 0.00 0.00 0.00

91117 1,3,5-triethylbenzene 0.00 0.00 0.00 0.00

91119 1,2,4-triethylbenzene 0.00 0.00 0.00 0.00

98044 indan 0.00 0.00 0.00 0.00

98046 naphthalene 0.00 0.00 0.00 0.00

91104 1,2,3,5-tetramethylbenzene 0.00 0.00 0.00 0.00

91108 2-methylindan 0.00 0.00 0.00 0.00

91106 5-methylindan 0.00 0.00 0.00 0.00

91103 1,2,4,5-tetramethylbenzene 0.00 0.00 0.00 0.00

91107 4-methylindan 0.00 0.00 0.00 0.00

46751 dihydronaphthalene 0.00 0.00 0.00 0.00

91123 2-methylnaphthalene 0.00 0.00 0.00 0.00

91124 1-methylnaphthalene 0.00 0.00 0.00 0.00

91122 pentamethylbenzene 0.00 0.00 0.00 0.00

43242 cyclopentane 0.25 0.22 0.21 0.32

11
Appendix B: Full Headspace Vapor Speciation Profiles

43262 methylcyclopentane 1.26 1.10 1.05 1.61

43248 cyclohexane 0.13 0.11 0.11 0.17

43261 methylcyclohexane 0.22 0.53 0.50 0.34

91018 1-c-3-dimethylcyclopentane 0.19 0.46 0.43 0.29

91019 1-t-3-dimethylcyclopentane 0.17 0.42 0.40 0.27

91021 1-t-2-dimethylcyclopentane 0.14 0.35 0.33 0.22

98057 ethylcyclopentane 0.05 0.13 0.12 0.08

91029 1-c-2-dimethylcyclopentane 0.05 0.12 0.12 0.08

90064 dimethylcyclopentane 0.03 0.07 0.06 0.04

91038 1c,2t,3-trimethylcyclopentane 0.03 0.07 0.07 0.05

43116 c8 cycloparaffins 0.02 0.05 0.05 0.03

91031 1c,2t,4-trimethylcyclopentane 0.04 0.09 0.08 0.06

91032 1t,2c,3-trimethylcyclopentane 0.01 0.02 0.02 0.01

91047 t-1,2-dimethylcyclohexane 0.01 0.02 0.02 0.01

91050 1c,2c,3-trimethylcyclopentane 0.01 0.02 0.02 0.01

98180 cis-1,3-dimethylcyclohexane 0.01 0.02 0.02 0.02

98181 trans-1,4-dimethylcyclohexane 0.01 0.03 0.02 0.02

91045 t-2-ethylmethylcyclopentane 0.01 0.01 0.01 0.01

90116 propylcyclopentane 0.00 0.01 0.01 0.01

91055 c-1,2-dimethylcyclohexane 0.00 0.01 0.01 0.00

91033 1,1,2-trimethylcyclopentane 0.00 0.01 0.01 0.01

98059 trans-1,3-dimethylcyclohexane 0.00 0.01 0.01 0.00

91041 1,1-dimethylcyclohexane 0.00 0.00 0.00 0.00

91046 1,1-methylethylcyclopentane 0.00 0.00 0.00 0.00

91077 i-butylcyclopentane 0.00 0.01 0.01 0.01

91057 1,1,4-trimethylcyclohexane 0.00 0.01 0.01 0.00

91061 c-1,c-3,5-trimethylcyclohexane 0.00 0.00 0.00 0.00

91081 1,1-methylethylcyclohexane 0.00 0.00 0.00 0.00

91066 c1,t2,t4-trimethylcyclohexane 0.00 0.00 0.00 0.00

91085 n-butylcyclopentane 0.00 0.00 0.00 0.00

90120 propylcyclohexane 0.00 0.00 0.00 0.00

91064 1,1,3-trimethylcyclohexane 0.00 0.00 0.00 0.00

91074 1,1,2-trimethylcyclohexane 0.00 0.00 0.00 0.00

98060 trimethylcyclohexane 0.00 0.00 0.00 0.00

90101 butylcyclohexane 0.00 0.00 0.00 0.00

43213 1-butene 0.11 0.09 0.09 0.09

43225 2-methyl-1-butene 0.77 0.59 0.57 0.60

43224 1-pentene 0.42 0.32 0.31 0.33

43223 3-methyl-1-butene 0.10 0.07 0.07 0.07

98040 2-methyl-1-pentene 0.12 0.09 0.09 0.09

43245 1-hexene 0.07 0.05 0.05 0.05

98135 4-methyl-1-pentene 0.03 0.03 0.02 0.03

43211 3-methyl-1-pentene 0.02 0.02 0.02 0.02

43234 2,3-dimethyl-1-butene 0.01 0.01 0.01 0.01

91000 3,3-dimethyl-1-pentene 0.06 0.05 0.05 0.05

91008 4-methyl-1-hexene 0.01 0.01 0.01 0.01

90063 2,4-dimethyl-1-pentene 0.00 0.00 0.00 0.00

91005 5-methyl-1-hexene 0.00 0.00 0.00 0.00

43267 1-nonene 0.00 0.00 0.00 0.00

91067 2-methyl-1-octene 0.00 0.00 0.00 0.00

43216 trans-2-butene 0.09 0.07 0.07 0.07

43217 cis-2-butene 0.08 0.06 0.06 0.07

43228 2-methyl-2-butene 1.59 1.23 1.17 1.24

43226 trans-2-pentene 1.12 0.87 0.83 0.88

43227 cis-2-pentene 0.60 0.47 0.45 0.47

43292 cyclopentene 0.15 0.12 0.11 0.12

98004 2-methyl-2-pentene 0.18 0.14 0.13 0.14

11
Appendix B: Full Headspace Vapor Speciation Profiles

92000 1-methylcyclopentene 0.16 0.12 0.12 0.12

98034 trans-2-hexene 0.16 0.12 0.12 0.12

43272 3-methylcyclopentene 0.10 0.08 0.08 0.08

98035 cis-2-hexene 0.08 0.06 0.06 0.06

98136 trans-3-hexene 0.08 0.06 0.06 0.07

43293 4-methyl-trans-2-pentene 0.10 0.08 0.07 0.08

98163 3-methyl-cis-2-pentene 0.04 0.03 0.03 0.03

43273 cyclohexene 0.03 0.02 0.02 0.02

98003 cis-3-hexene 0.03 0.02 0.02 0.02

90029 3-methyl-cis-2-hexene 0.06 0.04 0.04 0.04

91027 3-methyl-trans-2-hexene 0.05 0.04 0.04 0.04

98006 trans-3-heptene 0.05 0.04 0.03 0.04

91001 4,4-dimethyl-2-pentene 0.02 0.02 0.02 0.02

91026 trans-2-heptene 0.02 0.02 0.02 0.02

91028 cis-2-heptene 0.02 0.02 0.02 0.02

90031 4-methyl-trans-2-hexene 0.02 0.01 0.01 0.01

90032 3-methyl-trans-3-hexene 0.02 0.01 0.01 0.01

91024 3-methyl-cis-3-hexene 0.01 0.01 0.01 0.01

91006 2-methyl-trans-3-hexene 0.01 0.01 0.01 0.01

98007 3-ethyl-2-pentene 0.01 0.01 0.01 0.01

91011 3,4-dimethyl-2-pentene 0.01 0.01 0.01 0.01

91017 5-methyl-cis-2-hexene 0.00 0.00 0.00 0.00

43263 trans-2-octene 0.00 0.00 0.00 0.00

43250 trans-4-octene 0.00 0.00 0.00 0.00

43266 cis-2-octene 0.00 0.00 0.00 0.00

91084 cis-3-nonene 0.00 0.00 0.00 0.00

91080 trans-3-nonene 0.00 0.00 0.00 0.00

91092 2,3-dimethyl-2-octene 0.00 0.00 0.00 0.00

90100 trans-1,3-pentadiene 0.07 0.05 0.05 0.05

43243 isoprene 0.03 0.02 0.02 0.02

90026 1,3-cyclopentadiene 0.02 0.02 0.02 0.02

99999 unidentified 0.00 0.00 0.00 0.00

43301 methyl alcohol 0.09 0.04 0.02 0.08

43302 ethyl alcohol 0.00 9.35 9.56 0.00

43303 n-propyl alcohol 0.03 0.01 0.01 0.03

43378 methyl t-butyl ether (MTBE) 15.20 0.00 0.00 0.00

43212 n-butane 9.49 10.31 10.36 7.42

43220 n-pentane 5.11 4.48 4.50 6.54

43231 n-hexane 1.08 0.94 0.95 1.38

43232 n-heptane 0.48 0.63 0.63 0.38

43233 n-octane 0.06 0.08 0.08 0.05

43235 n-nonane 0.01 0.01 0.01 0.00

43238 n-decane 0.00 0.00 0.00 0.00

43241 n-undecane 0.00 0.00 0.00 0.00

43255 n-dodecane 0.00 0.00 0.00 0.00

43214 isobutane 2.23 2.92 2.92 1.74

98132 isopentane 36.51 32.03 32.17 46.78

43229 2-methylpentane 5.10 4.48 4.50 6.54

43230 3-methylpentane 2.54 2.23 2.24 3.26

43295 3-methylhexane 1.10 2.67 2.68 1.72

43275 2-methylhexane 1.08 2.61 2.62 1.67

43300 3-ethylpentane 0.10 0.25 0.25 0.16

43298 3-methylheptane 0.10 0.24 0.24 0.15

98140 2-methylheptane 0.10 0.23 0.23 0.15

43297 4-methylheptane 0.04 0.10 0.10 0.06

91039 3-ethylhexane 0.01 0.02 0.02 0.01

98172 3-methyloctane 0.01 0.03 0.03 0.02

11
Appendix B: Full Headspace Vapor Speciation Profiles

98146 2-methyloctane 0.01 0.02 0.02 0.02

98173 4-methyloctane 0.01 0.02 0.02 0.01

91071 3-ethylheptane 0.00 0.01 0.01 0.00

90047 2-methylnonane 0.00 0.00 0.00 0.00

91090 3-methylnonane 0.00 0.00 0.00 0.00

91088 5-methylnonane 0.00 0.00 0.00 0.00

91089 3-ethyloctane 0.00 0.00 0.00 0.00

91097 3-ethylnonane 0.00 0.00 0.00 0.00

98130 2,2-dimethylpropane 0.07 0.06 0.06 0.09

98001 2,3-dimethylbutane 1.76 1.55 1.55 2.26

43291 2,2-dimethylbutane 0.43 0.38 0.38 0.55

43274 2,3-dimethylpentane 1.19 2.89 2.90 1.85

43271 2,4-dimethylpentane 1.03 2.49 2.51 1.60

90040 3,3-dimethylpentane 0.10 0.25 0.25 0.16

90042 2,2-dimethylpentane 0.01 0.01 0.01 0.01

43277 2,4-dimethylhexane 0.17 0.41 0.41 0.26

43278 2,5-dimethylhexane 0.12 0.30 0.30 0.19

98139 2,3-dimethylhexane 0.09 0.23 0.23 0.15

98138 2,2-dimethylhexane 0.03 0.08 0.08 0.05

91036 3-methyl-3-ethylpentane 0.01 0.04 0.04 0.02

98150 3,4-dimethylhexane 0.01 0.03 0.03 0.02

91034 2-methyl-3-ethylpentane 0.01 0.02 0.02 0.01

98171 3,3-dimethylhexane 0.01 0.02 0.02 0.01

98143 2,5-dimethylheptane 0.01 0.03 0.03 0.02

98145 2,3-dimethylheptane 0.01 0.01 0.01 0.01

91063 3,3-dimethylheptane 0.00 0.01 0.01 0.01

91069 3,4-dimethylheptane 0.00 0.01 0.01 0.01

91060 4,4-dimethylheptane 0.00 0.01 0.01 0.00

98144 3,5-dimethylheptane 0.00 0.00 0.00 0.00

98142 2,4-dimethylheptane 0.00 0.00 0.00 0.00

98176 2,5-dimethyloctane 0.00 0.00 0.00 0.00

98184 3,3-dimethyloctane 0.00 0.00 0.00 0.00

98149 2,4-dimethyloctane 0.00 0.00 0.00 0.00

98177 2,6-dimethyloctane 0.00 0.00 0.00 0.00

91086 3,6-dimethyloctane 0.00 0.00 0.00 0.00

98175 2,2-dimethyloctane 0.00 0.00 0.00 0.00

43160 2,2,3-trimethylbutane 0.02 0.06 0.06 0.04

43276 2,2,4-trimethylpentane 1.70 4.11 4.13 2.64

43279 2,3,4-trimethylpentane 0.25 0.61 0.62 0.39

43280 2,3,3-trimethylpentane 0.18 0.45 0.45 0.29

43296 2,2,3-trimethylpentane 0.03 0.07 0.07 0.04

98033 2,2,5-trimethylhexane 0.08 0.19 0.19 0.12

91053 2,3,4-trimethylhexane 0.01 0.02 0.02 0.02

98141 2,3,5-trimethylhexane 0.01 0.02 0.02 0.01

91059 2,2,3,trimethylhexane 0.01 0.01 0.01 0.01

45222 2,2,4-trimethylhexane 0.00 0.00 0.01 0.00

45223 2,4,4-trimethylhexane 0.00 0.00 0.00 0.00

11