# 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:

lnP

r

## =a t+b t1

.5

## +c t3

## +d t6



## 1

−t where a, b, c, and d are constants specific to each species andτ=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 orFrost-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:

x i

## =w

i

## /M i



## w i

## /M i i 

# ∑

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

## ) to weight fraction (wi

## )using the following formula:

w i

## =y

i

## M i 

## y i

## M i i 

# ∑ .Appendix B: Full Headspace Vapor Speciation Profiles

MTBE 2% ETOH 2% ETOH 3.5% NO OXY SAROAD wt % wt % wt % wt % NumberSpecies Name headspaceheadspaceheadspaceheadspace 45201 benzene 0.64 0.80 0.80 0.69 45202toluene 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 911082-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 911074-methylindan 0.00 0.00 0.00 0.00 46751 dihydronaphthalene 0.00 0.00 0.00 0.00 911232-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

11Appendix 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 91047t-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 91045t-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 98059trans-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 98060trimethylcyclohexane 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 980402-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 432342,3-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 910084-methyl-1-hexene 0.01 0.01 0.01 0.01 900632,4-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 910672-methyl-1-octene 0.00 0.00 0.00 0.00 43216trans-2-butene 0.09 0.07 0.07 0.07 43217 cis-2-butene 0.08 0.06 0.06 0.07 432282-methyl-2-butene 1.59 1.23 1.17 1.24 43226trans-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 980042-methyl-2-pentene 0.18 0.14 0.13 0.14

11Appendix B: Full Headspace Vapor Speciation Profiles

92000 1-methylcyclopentene 0.16 0.12 0.12 0.12 98034trans-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 98136trans-3-hexene 0.08 0.06 0.06 0.07 432934-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 98006trans-3-heptene 0.05 0.04 0.03 0.04 91001 4,4-dimethyl-2-pentene 0.02 0.02 0.02 0.02 91026trans-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 910062-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 910175-methyl-cis-2-hexene 0.00 0.00 0.00 0.00 43263trans-2-octene 0.00 0.00 0.00 0.00 43250trans-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 91080trans-3-nonene 0.00 0.00 0.00 0.00 91092 2,3-dimethyl-2-octene 0.00 0.00 0.00 0.00 90100trans-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 981402-methylheptane 0.10 0.23 0.23 0.15 432974-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

11Appendix B: Full Headspace Vapor Speciation Profiles

981462-methyloctane 0.01 0.02 0.02 0.02 981734-methyloctane 0.01 0.02 0.02 0.01 91071 3-ethylheptane 0.00 0.01 0.01 0.00 900472-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 981302,2-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 432742,3-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 432772,4-dimethylhexane 0.17 0.41 0.41 0.26 432782,5-dimethylhexane 0.12 0.30 0.30 0.19 98139 2,3-dimethylhexane 0.09 0.23 0.23 0.15 981382,2-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 910342-methyl-3-ethylpentane 0.01 0.02 0.02 0.01 98171 3,3-dimethylhexane 0.01 0.02 0.02 0.01 981432,5-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 910604,4-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 981762,5-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 981772,6-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 431602,2,3-trimethylbutane 0.02 0.06 0.06 0.04 432762,2,4-trimethylpentane 1.70 4.11 4.13 2.64 43279 2,3,4-trimethylpentane 0.25 0.61 0.62 0.39 432802,3,3-trimethylpentane 0.18 0.45 0.45 0.29 432962,2,3-trimethylpentane 0.03 0.07 0.07 0.04 980332,2,5-trimethylhexane 0.08 0.19 0.19 0.12 910532,3,4-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 452232,4,4-trimethylhexane 0.00 0.00 0.00 0.00

11