Thermochemistry of Methyl

and Ethyl Esters from

Vegetable Oils

ANTOINE OSMONT, LAURENT CATOIRE, ISKENDER GOKALP
ICARE-CNRS and University of Orleans, 1C, avenue de la Recherche Scientifique, 45071 Orleans cedex 2, France
Received 2 January 2007; revised 6 March 2007; accepted 6 March 2007
DOI 10.1002/kin.20264
Published online in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: This paper deals with the gas-phase thermodynamic properties of methyl ester and
ethyl ester of vegetable oils (fatty acid methyl esters and fatty acid ethyl esters respectively)
present in biodiesel. The standard enthalpies of formation at 298.15 K, heat capacities, and
entropies in the temperature range 3005000 K are determined by means of quantum chemistry
calculations along with a protocol developed for these compounds. The resultant data, currently
not available in the literature for most of them, are critical to the modeling of combustion
chemistry of the subject compounds.
C 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 481

491, 2007

INTRODUCTION composition of biodiesel obtained from rapeseed oil is

Nowadays, about 97% of the fuels consumed by the
cars, trucks, and airplanes is petroleum based. There-
fore, the need for new fuels will be more and more
important in the forthcoming years. Several alterna-
tives are possible. Among them, fuels from biomass
are a credible alternative. However, because of their
high viscosity, pure vegetable oils are not interesting.
The way to get reliable fuels is then to proceed to the
transesterification of triglycerides contained in pure
vegetable oils with methanol, ethanol, or other low
molecular weight alcohols. Transesterification pro-
cesses are described in [1]. Vegetable oils are made of
many triglycerides; therefore, quite complex mixtures
of methyl or ethyl esters are obtained. It depends on
the oil, but generally these methyl or ethyl esters are
high molecular weight molecules, with saturated, or
monounsaturated, or polyunsaturated alkyl chains. The
Correspondence to: Laurent catoire; e-mail: catoire@
cnrs-orleans.fr.

c 2007 Wiley Periodicals, Inc.
(weight%) palmitic acid methyl ester 5, stearic acid
methyl ester 2.5, oleic acid methyl ester 59, linoleic
acid methyl ester 21, linolenic acid methyl ester 9,
eicosanoic acid methyl ester 1, and others 2.5. About
the same molecules are in soybean oil methyl esters
but with different amounts (weight%): palmitic acid
methyl ester 10, stearic acid methyl ester 4, oleic acid
methyl ester 23, linoleic acid methyl ester 53, linolenic
acid methyl ester 8, eicosanoic acid methyl ester <0.5,
and others 1.5. Compounds of interest are myristic
acid, palmitic acid, palmitoleic acid, stearic acid, oleic
acid, linoleic acid, linolenic acid, arachidic acid, and
their methyl and ethyl esters [1]. Molecular structures
of the compounds studied are given in Table I. Only
unsaturated compounds occurring naturally are consid-
ered here, i.e., all their double bonds are cis. Although
thermochemical data are available for low molecular
weight methyl and ethyl esters, thermochemical data
(enthalpy of formation, Cp and S) are rather scarce,
if any, for these large methyl or ethyl esters. The aim
of this paper is to propose gas-phase thermochemi-
cal properties for these methyl or ethyl esters to allow
482
OSMONT, CATOIRE, AND GOKALP

Table I Names and Structures of the Five Most Important Components in Rapeseed Oil Methyl Esters (RME) and
Soybean Oil Methyl Esters (SME)
Name Molecular Structure
Methyl palmitate O

O CH3

Methyl stearate O

O CH3

Methyl oleate O

CH3

Methyl linoleate

Methyl linolenate

some thermochemical calculations such as flame tem- COMPUTATIONAL METHOD

perature, ChapmanJouguet detonation velocity, flash
point, lower flammability limits and the building of
a detailed chemical kinetic model to be implemented
in codes devoted to the simulation of the combustion
of these fuels either pure or mixed with fossil fuels
(blends) to predict ignition delays, pollutants profiles,
flame speeds, etc.
Ab initio methods have been shown to be reliable tools
to estimate the thermochemistry of many compounds
[2]. However, the most accurate of these methods,
namely the G3 or G2 methods, are computationally
too expensive for large molecules [3]. Moreover, these
methods are validated with relatively small molecules

International Journal of Chemical Kinetics DOI 10.1002/kin

 THERMOCHEMISTRY OF METHYL AND ETHYL ESTERS FROM VEGETABLE OILS
and the validity of these methods for large molecules
remains to be demonstrated. Density functional meth-
ods, (B3LYP/6-311G(d,p) for instance) using conven-
tional atomization approach, have been shown to pro-
vide a reasonable way to treat naphthalene (C10 H8 ), a
quite large molecule [4], but the molecules under con-
sideration in this study are larger, up to 22 C-atoms.
For this reason, a protocol with a smaller basis set is
required. Consequently, a B3LYP/6-31G(d,p) method
using an atomization approach is derived in this study.
Wilcox and Russo [5] proposed a B3LYP/6-31G(d,p)
method for C, H, and N compounds with parametric
corrections for these atoms. It is of limited use for
the fuels considered here because calculations with O
atoms were not considered. A comparative study of
several existing approaches, including the semiempiri-
cal PM3 method, indicates that the B3LYP/6-31G(d,p)
protocol appears to be the best compromise between
numerical accuracy and expense. The model employed
in this paper includes zero-point energies and several
atomic corrections. Three atomic corrections are de-
rived for the molecules here: one for H-atoms, one
for C-atoms, and one for O-atoms. In this method, we
do not distinguish between O-atoms. The correction
to be applied to an O-atom in a carbonyl group is the
same than the one to be applied to an O-atom in a hy-
droxyl group or in an ether bond. The same holds for
C-atoms: the correction to be applied to a C involved
in a single bond is the same as the correction to be
applied to a C involved in double bonds. The method
employed in the present study is derived based on 311
compounds having well-calibrated enthalpies of for-
mation with uncertainty less than 1 kcal mol1 for most
of them. The 311 compounds are general organic com-
pounds from all the chemical families, including poly-
functional compounds. Only six low molecular weight
esters or carboxylic acids are considered in the deriva-
tion set. These six compounds are reported in Table IV.
The atomic corrections ci are determined by least-
square fitting of the 311 selected experimental gas-
phase standard enthalpies of formation at 298.15 K.
The gas-phase standard enthalpy of formation of
molecule j at 298.15 K can be determined from the
following equation:

phase enthalpies of formation for the species given in

f H298.15 K (g) = 627.51 Ej + ZPE j
o Table IV are not direct experimental measurements but
 
+ thermal corrections +
i
where i is the number of atom i in molecule j and ci
the atomic correction for atom i. Ej and ZPEj denote,
respectively, the electronic energy and zero-point en-
International Journal of Chemical Kinetics DOI 10.1002/kin
483
Table II Atomic Corrections c i Used in the Present
Model
Atom ci (hartree atom1 )
Ha 0.581896
Ca 38.115345
O 75.150410
a
These atomic corrections are not recommended for polycyclic
alkanes.
ergy, calculated using the Gaussian 98W and Gaussian
03 softwares. The units are hartree molecule1 for Ej ,
ZPEj and thermal corrections, and hartree atom1 for
ci , whereas
f H298.15
o 1
K (g) is in kcal mol . Table II
gives the three atomic corrections used in this study.
MODEL VALIDATION
The ab initio method developed and implemented in
the present study is validated for 342 compounds, in-
cluding almost all the chemical families and also poly-
functional compounds. The corresponding statistical
analysis is given in Table III. Based on these results,
we would expect the calculated enthalpies of forma-
tion obtained from these calculations to be accurate
to within 3 kcal mol1 . This indicates that the pre-
dicted results are sufficiently accurate enough to be
useful for combustion modeling. Maximum negative
and positive deviations are reported in Table III both
for those two sets of data. For the present study, the
agreement between experimental data and calculated
data is even better (mean absolute deviation is 1.8 kcal
mol1 ) and is reported in Table IV for carboxylic acids,
fatty acid methyl esters (FAME), and fatty acid ethyl
esters (FAEE). This shows that the derived method per-
forms better on average for carboxylic acids, methyl
esters, and ethyl esters than for other chemical classes.
Only six compounds of Table IV were included in the
derivation set.
RESULTS AND DISCUSSION
It is worthy to note that most of the experimental gas-
indirect ones according to
i ci
K (g) =
f H298.15 K (l) +
vap H298.15 K
o o o

f H298.15
for liquids
o

f H298.15 K (g) =
f H298.15
o
K (s) + o

sub H298.15 K
for solids
484
OSMONT, CATOIRE, AND GOKALP

Table III Statistical Analysis of the Ab Initio Method Used in This Study
Maximum Maximum
Number of Negative Positive 
Compounds Deviation Deviation
|
| (

)2
Derivation set 311 7.9 9.8 0.27 2.02 2.64
Validation set 342 7.0 10.7 0.15 2.46 3.09

|
|: Mean absolute deviation,
: mean deviation, and (

)2 : standard deviation.
All values are in kcal mol1 .

Absolute uncertainty for these species is larger than
direct measurements, since it is the sum of the ex-
perimental absolute uncertainties on the enthalpy of
sublimation or vaporization and on the condensed-
phase enthalpy of formation. Moreover, most of the
standard enthalpy of combustion from which stan-
dard enthalpy of formation are deduced and most
of the standard enthalpy of sublimation or vapor-
ization have been measured only one time [69].
Therefore, these experimental results need probably

Table IV Measured and Calculated Gas-Phase Standard Enthalpies of Formation at 298 K of Selected Compounds for
Validation for Esters and Carboxylic Acids of the Ab Initio Method Used in This Study

(g)
exp
Compound Name o

f Hexp o

f Hcalc

(g)

CH2 O2 a,b Formic acid 90.5 [14] 90.5 0

C2 H4 O2 a,b Methyl formate 86.6 [15] 88.8 2.2
C3 H6 O2 Ethyl formate 95.2 [15] 96.8 1.6
C2 H4 O2 a,b Acetic acid 103.4 [16] 103.5 0.1
103.7 0.1 [10] 0.2
C3 H6 O2 a,b Methyl acetate 98.0 [15] 101.3 3.3
C4 H8 O2 a,b Ethyl acetate 106.46 0.20 [17] 109.5 3.0
C3 H6 O2 b Propanoic acid 108.9 [16] 108.8 0.1
109.0 0.1 [10] 0.2
C5 H10 O2 a,b Ethyl propanoate 111.5 0.1 [13] 113.6 2.1
C4 H8 O2 b n-Butanoic acid 113.6 [16] 113.6 0.0
113.7 0.1 [10] 0.1
C6 H12 O2 b Ethyl butanoate 115.9 0.3 [13] 119.5 3.6
C5 H10 O2 b n-Pentanoic acid 118.6 [16] 118.3 0.3
118.6 0.2 [10] 0.3
C6 H12 O2 b Methyl pentanoate 112.5 0.4 [from 8] 116.1 3.6
C7 H14 O2 b Ethyl pentanoate 121.2 0.4 [13] 124.2 3.0
C6 H12 O2 n-Hexanoic acid 122.5 0.4 [8, 18] 123.0 0.5
123.0 0.4 [10] 0
123.4 0.6 [19] 0.4
122.5 0.6 [20] 0.5
C7 H14 O2 Methyl hexanoate 118.0 0.4 [8, 18] 120.8 2.8
125.2 0.4 [9] c
C8 H16 O2 Ethyl hexanoate 126.1 0.4 [13] 128.9 2.8
C7 H14 O2 n-Heptanoic acid 128.9 [16] 127.7 1.2
128.0 0.7 [8] 0.3
128.4 0.4 [10] 0.7
C8 H16 O2 Methyl heptanoate 123.5 0.4 [8, 18] 125.5 2.0
C9 H18 O2 Ethyl heptanoate 131.0 0.5 [13] 133.6 2.6
C8 H16 O2 Octanoic acid 132.4 [16] 132.4 0
132.6 0.3 [10] 0.2
C9 H18 O2 Methyl octanoate 127.7 0.7 [8] 130.2 2.5
134.8 0.6 [9] c
Continued

International Journal of Chemical Kinetics DOI 10.1002/kin

 THERMOCHEMISTRY OF METHYL AND ETHYL ESTERS FROM VEGETABLE OILS 485

Table IV Continued

(g)
exp
Compound Name o

f Hexp o

f Hcalc

(g)

C10 H20 O2 Ethyl octanoate 136.2 0.4 [13] 138.3 2.1

144.4 0.9 [9] c
C9 H18 O2 n-Nonanoic acid 138.5 [16] 137.1 1.4
138.0 0.5 [10] 0.9
C10 H20 O2 Methyl nonanoate 132.5 0.9 [8] 134.9 2.4
C11 H22 O2 Ethyl nonanoate 141.1 0.6 [15] 143.0 1.9
C10 H20 O2 n-Decanoic acid 142.2 [16] 141.9 0.3
142.2 0.5 [10] 0.3
C11 H22 O2 Methyl decanoate 137.2 1.0 [8] 139.6 2.5
145.1 0.7 [9] b
C11 H22 O2 n-Undecanoic acid 146.9 [16] 146.5 0.4
C13 H26 O2 Ethyl undecanoate 151.5 0.4 [13] 152.5 1.0
C12 H24 O2 n-Dodecanoic acid 153.5 1.1 [8] 151.3 2.2
C13 H26 O2 Methyl dodecanoate 147.7 1.5 [8] 149.0 1.3
152.7 1.2 [9] c
C14 H28 O2 n-Tetradecanoic acid 165.8 [16] 160.7 5.1
163.5 0.9 [8] 2.8
163.7 2.9 [21] 3
C15 H30 O2 Methyl tetradecanoate 161.0 1.3 [9] 158.4 c
157.4 1.7 [8] 1
C16 H32 O2 n-Hexadecanoic acid (palmitic acid) 176.3 2.0 [8] 170.1 6.2
C17 H34 O2 Methyl hexadecanoate 174.0 1.1 [9] 167.8 c
C18 H36 O2 n-Octadecanoic acid (stearic acid) 187.0 2.2 [8] 179.5 7.5
C19 H38 O2 Methyl octadecanoate 185.9 1.8 [9] 177.3 c
C20 H40 O2 Eicosanoic acid (arachidic acid) 194.3 3.0 [8] 188.9 5.4
C21 H42 O2 Methyl eicosanoate 194.8 1.7 [9] 186.7 c

=
f Hcalc(g)
o

f Hexp(g)
o
. All values are in kcal mol1 .
a
Compound included in the derivation set.
b
Measured and calculated gas-phase standard enthalpies of formation at 298.15 K.
c
Data from [9] have not been taken in account for the calculation of the mean average deviation between experimental data and calculations.

confirmation. Recent measurements of the enthalpy of
vaporization and of the enthalpy of sublimation are
reported in [1012], but no recent experimental deter-
mination of enthalpy of combustion (and therefore of
enthalpy of formation) is reported. Moreover, exper-
imental data are sometimes not consistent. The gas-
phase enthalpies of formation derived from the en-
thalpy of combustion reported by Freedman and Bagdy
[9] are from 4 to 8 kcal mol1 above (absolute value)
the enthalpies of formation derived from the enthalpies
of combustion reported by Adriaanse et al. [8].
Experimental data obtained by using other tech-
niques than combustion calorimetry by Verevkin [10]
and Wiberg and Waldron [13] are generally consistent
with the data derived from Adriaanse et al. [8]. There-
fore, although the reasons for these discrepancies re-
main unknown, enthalpy of formation data extracted
from Freedman and Bagdy [9] data probably have to
be considered as overestimated in absolute value by
48 kcal mol1 . Nevertheless, the paper of Freedman
and Bagby [9] is the unique source of experimental data
for quite a number of heavy esters. Table IV shows that
the agreement between experimentally derived and cal-
culated enthalpies of formation is generally good. The
mean average deviation between experiments (data ex-
tracted from [9] excluded for the reasons stated above)
and computations is 1.8 kcal mol1 , including palmitic,
stearic, and arachidic acids. The mean average de-
viation is apparently worse (about 6 kcal mol1 ) if
one considers palmitic, stearic, and arachidic acids
only. However, experimental difficulties of completely
burning these high molecular weight compounds are
well known and therefore the uncertainty ranges we
estimated here for experimental enthalpies of forma-
tion, i.e. about 23 kcal mol1 for palmitic, stearic,
and arachidic acids, are probably lower than the ac-
tual ones. For instance, the differences between the
values obtained from [8] and [9] are seen to differ
from one another by more than the sum of the uncer-
tainty ranges. Furthermore, computed data are seen to
be comprised between the data extracted from [8] and
[9] each time the comparisons are possible. It is the

International Journal of Chemical Kinetics DOI 10.1002/kin

486
OSMONT, CATOIRE, AND GOKALP

Table V Calculated Gas-Phase Standard Enthalpies of Formation at 298.15 K for Selected Esters and Carboxylic Acids
Position(s) of Chain
C i Unsaturation(s) Carboxylic Acids Methyl Esters Ethyl Esters
12 0 151.3 149.0 157.2
(see Table IV) (see Table IV)
14 0 160.7 158.4 166.6
(see Table IV) (see Table IV)
16 0 170.1 167.8 176.0
(see Table IV) (see Table IV)
16 1 9 139.9 133.7 145.8
17 0 174.8 172.6 180.7
17 1 9 144.7 142.5 150.6
18 0 179.5 177.3 185.4
(see Table IV) (see Table IV)
18 1 9 149.3 147.2 155.3
18 2 9,12 118.3 116.1 124.9
18 3 9,12,15 88.3 85.6 93.7
20 0 188.9 186.7 194.8
(See Table IV) (see Table IV)
C indicates the number of C-atoms in the corresponding fatty acid.
Boldface indicate that no experimental data are available in the literature for the enthalpy of formation of these compounds.

case for methyl hexanoate, methyl octanoate, methyl
decanoate, methyl dodecanoate, and methyl tetrade-
canoate, i.e. for high molecular weight molecules con-
taining up to 15 C-atoms. Compounds with 16 C-atoms
and more have been measured either by [8] or by [9],
and therefore experimental confirmations are needed.
It is also possible to compare these results to those
obtained from group additivity estimates. Domalski
and Hearing [16] report estimated standard enthalpy
of formation at 298.15 K for dodecanoic acid, tetrade-
canoic acid, palmitic acid, margaric acid, stearic acid,
eicosanoic acid, methyl dodecanoate, methyl tetrade-
canoate, and methyl palmitate with the group additivity
method they established, which is based on the same
concepts than Bensons method. For these compounds,
our results are consistent within 3 kcal mol1 with
Domalski and Hearings method [16] and the two meth-
ods are consistent. Therefore, the conventional group
additivity does as well as the method reported here
but the reported method is still more general, since
it incorporates only three atomic corrections, rather
than a large number of group values and can therefore
be applied to any C,H, and O containing molecule.
Moreover, Sumathi and Green [22] underlined that the
O-(CO)(C) and CO-(C)(O) groups are not well estab-
lished for esters due to the lack of experimental ther-
mochemical data and it can therefore be questionable
to consider such an estimation as a reference value.
Three fundamental thermochemical properties are
o 0 0
used in combustion:
f H298.15 K , CpT and ST . Table V
gives the standard gas-phase enthalpy of formation at
298.15 K derived with the method proposed here for
some heavy carboxylic acids and their methyl and ethyl
esters. For most of the compounds, no direct experi-
mental measurement is reported and indirect exper-
imental data are not feasible because of the lack of
some experimental data (enthalpy of combustion but
also enthalpy of sublimation or enthalpy of vaporiza-
tion). Scott and Radom [23] report that one of the
most successful procedures for obtaining fundamen-
tal vibrational frequencies is to use scaled frequen-
cies computed at the B3LYP/6-31G(d) level of theory.
B3LYP/6-31G(d,p) vibrational frequencies, scaled by
0.9613 as recommended by Scott and Radom [23],
from which heat capacities and entropies can be de-
rived, have been calculated. No experimental data are
available. The thermochemical data are summarized in
Tables VI and VII in a wide range of temperature from
ambient to 5000 K. For practical combustion applica-
tions, only data up to about 2000 K are needed. For
the simulation of the combustion of blends of FAMEs
or FAEEs with high-energy density fuels such as mis-
sile fuels or propellants, data at higher temperature are
needed. The thermochemical calculations (to get the
heat capacity and entropy) were carried out using the
Gaussian 98 [24] and Gaussian 03 [25] computational
chemistry programs. In Tables VI and VII, the entropy
and heat capacity are calculated following the har-
monic oscillator approximation. This approximation
is usually the one used in the combustion chem-
istry field, but, at high temperature, errors can result
if the harmonic oscillator approximation is used for

International Journal of Chemical Kinetics DOI 10.1002/kin

 THERMOCHEMISTRY OF METHYL AND ETHYL ESTERS FROM VEGETABLE OILS 487

Table VI Calculated C p (cal mol1 K1 ) in the Temperature Range of 3005000 K

Temperature (K)
Compounda 300 400 500 600 800 1000 1500 2000 2500 3000 3500 4000 4500 5000
Dodecanoic acid 67.3 87.2 105.2 120.6 144.5 161.8 187.8 200.8 207.8 212.0 214.7 216.4 217.7 218.6
70.8 89.0 105.0 118.7 140.2 155.9 179.7 191.5 197.8 201.5 203.9 205.4 206.5 207.2
Methyl dodecanoate 72.6 93.7 113.2 129.8 155.7 174.6 202.9 217.0 224.6 229.1 232.0 233.9 235.2 236.2
75.6 94.7 112.1 126.8 149.8 166.7 192.6 205.6 212.7 216.9 219.6 221.4 222.6 223.5
Ethyl dodecanoate 77.8 100.6 121.5 139.4 167.3 187.5 218.0 233.1 241.3 246.1 249.2 251.3 252.7 253.7
80.2 101.4 120.1 135.9 160.7 178.9 206.8 220.8 228.5 233.0 235.9 237.8 239.1 240.1
Tetradecanoic acid 77.4 100.5 121.6 139.5 167.4 187.5 217.9 233.0 241.2 246.1 249.2 251.2 252.7 253.7
81.7 103.0 121.6 137.6 162.6 180.9 208.5 222.2 229.5 233.8 236.5 238.3 239.6 240.5
Methyl tetradecanoate 82.7 107.1 129.5 148.7 178.6 200.4 233.0 249.2 258.0 263.2 266.4 268.6 270.2 271.3
86.5 108.7 128.8 145.9 172.4 191.8 221.4 236.2 244.4 249.2 252.2 254.2 255.7 256.7
Ethyl tetradecanoate 87.9 113.9 137.9 158.3 190.2 213.3 248.0 265.3 274.7 280.2 283.7 286.0 287.7 288.9
91.1 115.3 136.8 155.0 183.3 204.0 235.6 251.5 260.1 265.3 268.5 270.7 272.2 273.3
Palmitic acid 87.5 113.9 138.0 158.4 190.3 213.3 248.0 265.2 274.6 280.1 283.6 286.0 287.6 288.8
92.6 117.0 138.4 156.5 184.9 205.8 237.3 252.8 261.2 266.1 269.2 271.2 272.6 273.7
Methyl palmitate 92.8 120.4 145.9 167.6 201.5 226.1 263.1 281.4 291.3 297.2 300.9 303.4 305.2 306.4
97.3 122.4 145.2 164.5 194.4 216.3 249.8 266.7 275.9 281.3 284.8 287.1 288.7 289.9
Ethyl palmitate 98.0 127.3 154.2 177.2 213.1 239.1 278.1 297.5 308.0 314.2 318.2 320.8 322.6 324.0
101.8 129.1 153.3 173.7 205.3 228.5 264.0 281.9 291.6 297.4 301.1 303.5 305.2 306.5
Palmitoleic acid 85.8 111.3 134.4 153.9 184.0 205.8 238.6 254.9 263.7 269.0 272.3 274.5 276.1 277.2
88.9 112.1 132.6 149.9 176.9 196.9 227.3 242.4 250.6 255.4 258.4 260.4 261.8 262.8
Methyl palmitoleate 91.2 117.9 142.3 163.1 195.3 218.6 253.7 271.0 280.5 286.0 289.6 291.9 293.6 294.8
93.2 117.4 139.1 157.6 186.6 207.9 240.4 256.7 265.6 270.9 274.2 276.4 278.0 279.1
Ethyl palmitoleate 96.3 124.8 150.7 172.7 206.8 231.6 268.7 287.2 297.2 303.1 306.8 309.3 311.1 312.3
98.7 125.0 148.0 167.5 197.9 220.3 254.7 271.9 281.4 287.0 290.5 292.9 294.5 295.7
Margaric acid 92.5 120.5 146.1 167.9 201.7 226.2 263.0 281.3 291.3 297.2 300.9 303.4 305.1 306.4
97.9 123.9 146.6 165.9 195.9 217.9 251.3 267.9 276.8 282.1 285.4 287.6 289.1 290.2
Methyl margarate 97.9 127.1 154.0 177.1 213.0 239.0 278.1 297.5 308.0 314.2 318.2 320.8 322.6 324.0
102.3 129.6 153.7 173.9 205.4 228.6 264.0 281.9 291.6 297.4 301.1 303.5 305.2 306.5
Ethyl margarate 103.0 133.9 162.4 186.7 224.5 251.9 293.2 313.6 324.7 331.3 335.4 338.2 340.1 341.6
107.3 136.1 161.5 182.9 216.2 240.7 278.2 297.1 307.4 313.5 317.3 319.9 321.7 323.1
Margaroleic acid 91.0 118.1 142.6 163.4 195.5 218.7 253.6 271.0 280.4 286.0 289.5 291.9 293.6 294.8
94.0 118.7 140.5 158.9 187.8 209.0 241.5 257.7 266.4 271.5 274.7 276.8 278.3 279.4
Methyl margaroleate 96.3 124.7 150.6 172.6 206.8 231.6 268.7 287.2 297.2 303.1 306.8 309.3 311.1 312.3
98.3 124.2 147.3 166.9 197.5 220.0 254.5 271.9 281.3 286.9 290.5 292.8 294.5 295.7
Ethyl margaroleate 101.4 131.5 158.9 182.2 218.3 244.5 283.8 303.3 313.8 320.1 324.0 326.7 328.6 329.9
104.0 131.5 155.8 176.4 208.6 232.4 268.8 287.1 297.1 303.0 306.8 309.3 311.0 312.3
Stearic acid 97.6 127.2 154.3 177.3 213.1 239.1 278.1 297.4 308.0 314.2 318.1 320.8 322.6 324.0
103.1 131.1 155.3 175.4 207.0 230.4 265.8 283.3 292.7 298.3 301.7 304.1 305.7 306.9
Methyl stearate 102.9 133.8 162.2 186.5 224.4 251.9 293.2 313.6 324.7 331.3 335.4 338.2 340.1 341.6
108.3 136.6 162.0 183.4 216.8 241.2 278.5 297.3 307.5 313.6 317.4 320.0 321.8 323.1
Ethyl stearate 108.1 140.6 170.6 196.1 235.9 264.8 308.2 329.7 341.4 348.3 352.7 355.6 357.6 359.1
112.5 143.2 170.0 192.5 227.5 253.2 292.5 312.4 323.2 329.6 333.6 336.4 338.3 339.7
Oleic acid 95.9 124.7 150.7 172.8 206.9 231.6 268.6 287.1 297.1 303.0 306.8 309.3 311.0 312.3
99.5 126.0 149.5 169.1 199.7 222.1 256.2 273.1 282.3 287.7 291.1 293.3 294.9 296.0
Methyl oleate 101.4 131.3 158.7 182.0 218.2 244.4 283.8 303.3 313.8 320.1 324.1 326.7 328.6 329.9
103.7 131.0 155.2 175.8 208.1 232.0 268.6 287.0 297.0 303.0 306.7 309.2 311.0 312.3
Ethyl oleate 106.5 138.2 167.1 191.7 229.8 257.4 298.8 319.4 330.5 337.1 341.3 344.1 346.1 347.5
109.0 138.4 164.5 186.4 220.4 245.3 283.4 302.6 313.0 319.2 323.1 325.8 327.6 328.9
Linoleic acid 94.2 122.1 147.1 168.2 200.6 224.1 259.2 276.7 286.2 291.8 295.4 297.8 299.5 300.7
96.0 121.0 143.2 162.0 191.6 213.4 246.6 263.1 272.0 277.2 280.5 282.7 284.2 285.3
Methyl linoleate 99.6 128.7 155.0 177.4 211.9 236.9 274.3 292.9 303.0 308.9 312.7 315.2 317.0 318.3
100.9 127.3 150.9 170.8 202.1 225.0 259.9 277.5 287.0 292.7 296.3 298.7 300.4 301.6
Ethyl linoleate 104.7 135.5 163.4 187.0 223.5 249.8 289.4 309.0 319.6 325.9 329.9 332.6 334.5 335.8
107.4 135.7 160.8 181.7 214.3 238.1 274.6 293.0 303.0 308.9 312.7 315.2 316.9 318.2
Continued
International Journal of Chemical Kinetics DOI 10.1002/kin
488
OSMONT, CATOIRE, AND GOKALP

Table VI Continued
Temperature (K)
Compounda 300 400 500 600 800 1000 1500 2000 2500 3000 3500 4000 4500 5000
-Linolenic acid 92.4 119.4 143.4 163.5 194.3 216.5 249.8 266.3 275.3 280.6 284.0 286.3 287.9 289.0
94.0 118.5 139.9 158.0 186.1 206.7 238.1 253.6 262.0 267.0 270.1 272.1 273.6 274.6
Methyl linolenate 97.8 126.0 151.3 172.7 205.6 229.3 264.9 282.5 292.1 297.7 301.3 303.7 305.4 306.6
98.0 123.6 146.3 165.5 195.5 217.5 251.0 267.8 276.9 282.4 285.8 288.1 289.7 290.9
Ethyl linolenate 103.0 132.9 159.7 182.3 217.2 242.3 279.9 298.6 308.8 314.8 318.6 321.1 322.9 324.2
103.4 130.7 154.8 175.0 206.7 229.9 265.3 283.0 292.7 298.5 302.1 304.5 306.3 307.5
Arachidic acid 107.7 140.6 170.7 196.3 236.0 264.8 308.1 329.6 341.3 348.2 352.6 355.5 357.6 359.1
114.1 144.8 172.0 194.5 229.6 255.4 294.7 314.0 324.4 330.6 334.4 337.0 338.8 340.1
Methyl arachidate 113.0 147.1 178.6 205.4 247.3 277.6 323.2 345.8 358.1 365.3 369.9 373.0 375.1 376.7
119.3 150.4 178.3 202.2 239.2 266.1 307.2 327.9 339.2 345.8 350.0 352.9 354.8 356.3
Ethyl arachidate 118.2 154.0 186.9 215.0 258.8 290.6 338.3 361.9 374.8 382.3 387.1 390.4 392.6 394.2
123.4 156.8 186.2 211.1 249.8 278.1 321.3 343.0 354.8 361.8 366.3 369.3 371.3 372.9
a
For each compound, the first line represents the harmonic thermochemistry and the second line represents the anharmonic thermochemistry.

low-frequency modes that represent hindered internal
rotations or free internal rotations [26,27]. As the parti-
tion functions for a harmonic oscillator and for a free or
hindered rotor are quite different, some corrections to
the heat capacity and entropy are needed. For this study,
the normal vibrational modes corresponding to internal
rotations are identified at the B3LYP/6-31G(d,p) level
of theory by using the procedure of Ayala and Schlegel
[26] as implemented in Gaussian 03. The heat capacity
and entropy are then corrected using the tables of Pitzer
and Gwinn as given in [28]. The resulting anharmonic
thermochemistry is given in Tables VI and VII for Cp
and entropy, respectively. Corrections due to hindered
or free rotations are generally important because of

Table VII Calculated S (cal mol1 K1 ) in the Temperature Range of 3005000 K

Temperature (K)
Compounda 300 400 500 600 800 1000 1500 2000 2500 3000 3500 4000 4500 5000
Dodecanoic acid 145.0 167.1 188.6 209.2 247.3 281.5 352.7 408.7 454.3 492.6 525.5 554.3 579.9 602.9
150.9 173.8 195.4 215.8 253.0 286.1 354.4 407.9 451.4 487.8 519.1 546.4 570.7 592.5
Methyl dodecanoate 154.0 177.8 200.9 223.0 264.1 301.0 377.9 438.4 487.7 529.1 564.6 595.7 623.4 648.2
159.8 184.1 207.2 229.0 268.8 304.1 377.2 434.6 481.3 520.5 554.2 583.6 609.7 633.3
Ethyl dodecanoate 162.2 187.7 212.4 236.2 280.4 320.0 402.5 467.5 520.5 565.0 603.2 636.6 666.3 692.9
168.7 194.7 219.4 242.7 285.4 323.3 401.8 463.5 513.6 555.7 591.9 623.5 651.6 676.8
Tetradecanoic acid 160.1 185.5 210.3 234.1 278.3 317.9 400.4 465.4 518.4 562.8 601.0 634.4 664.1 690.8
165.6 192.1 217.1 240.8 284.0 322.3 401.6 463.7 514.1 556.4 592.6 624.3 652.5 677.8
Methyl tetradecanoate 169.2 196.3 222.7 248.0 295.2 337.5 425.7 495.2 551.8 599.4 640.2 675.9 707.7 736.2
175.3 203.3 229.8 254.8 300.6 341.3 425.3 491.3 544.9 590.0 628.6 662.4 692.5 719.5
Ethyl tetradecanoate 177.3 206.2 234.2 261.2 311.4 356.5 450.4 524.4 584.7 635.3 678.7 716.8 750.6 780.9
184.3 213.8 241.9 268.5 317.2 360.5 449.9 520.1 577.2 625.2 666.3 702.3 734.3 763.0
Palmitic acid 175.1 203.9 231.9 259.0 309.1 354.2 448.1 522.1 582.4 633.0 676.4 714.5 748.2 778.6
183.4 213.4 241.9 268.7 317.9 361.5 451.7 522.3 579.7 627.8 669.0 705.1 737.2 766.0
Methyl palmitate 184.1 214.6 244.3 272.9 326.0 373.8 473.3 551.8 615.8 669.5 715.6 755.9 791.8 824.0
191.1 222.6 252.4 280.6 332.3 378.1 473.0 547.4 608.0 658.8 702.5 740.7 774.6 805.1
Ethyl palmitate 192.4 224.6 256.0 286.2 342.4 392.9 498.2 581.1 648.8 705.5 754.3 796.9 834.8 868.9
200.1 233.1 264.6 294.4 349.0 397.4 497.6 576.3 640.4 694.1 740.2 780.6 816.5 848.7
Palmitoleic acid 175.1 203.3 230.7 257.0 305.6 349.2 439.6 510.7 568.7 617.2 659.0 695.5 727.9 757.1
191.0 219.8 247.1 272.8 319.8 361.6 447.9 515.6 570.7 616.8 656.4 691.1 721.9 749.5
Methyl palmitoleate 185.3 215.2 244.2 272.0 323.6 369.9 466.0 541.6 603.2 654.9 699.3 738.1 772.6 803.6
200.7 230.9 259.4 286.5 336.0 380.1 471.3 543.0 601.3 650.2 692.2 729.0 761.7 791.0
Continued

International Journal of Chemical Kinetics DOI 10.1002/kin

 THERMOCHEMISTRY OF METHYL AND ETHYL ESTERS FROM VEGETABLE OILS 489

Table VII Continued

Temperature (K)
Compounda 300 400 500 600 800 1000 1500 2000 2500 3000 3500 4000 4500 5000
Ethyl palmitoleate 193.6 225.2 255.9 285.4 340.0 389.0 490.8 570.9 636.2 690.9 738.0 779.1 815.6 848.5
207.3 239.3 269.7 298.5 351.1 397.8 494.4 570.3 632.1 684.0 728.5 767.4 802.0 833.1
Margaric acid 182.5 213.0 242.7 271.3 324.5 372.3 471.7 550.3 614.3 667.9 714.0 754.4 790.2 822.5
189.0 220.8 251.0 279.5 331.5 377.7 473.2 548.0 608.9 659.8 703.6 741.8 775.8 806.3
Methyl margarate 191.6 223.8 255.1 285.3 341.4 391.9 497.2 580.1 647.8 704.5 753.3 795.9 833.8 867.9
201.0 234.2 265.8 295.7 350.3 398.7 498.9 577.6 641.7 695.4 741.5 781.9 817.7 850.0
Ethyl margarate 199.9 233.8 266.8 298.6 357.8 411.0 522.0 609.5 680.7 740.6 792.0 837.0 876.9 912.8
207.2 242.0 275.2 306.6 364.1 415.1 520.7 603.6 671.1 727.7 776.4 818.9 856.7 890.7
Margaroleic acid 184.0 213.9 242.9 270.8 322.5 368.8 464.9 540.5 602.1 653.8 698.1 737.0 771.4 802.4
202.4 232.8 261.7 289.0 338.9 383.2 474.9 546.8 605.4 654.4 696.5 733.4 766.1 795.4
Methyl margaroleate 194.2 225.8 256.5 285.9 340.5 389.5 491.3 571.4 636.7 691.4 738.5 779.6 816.1 849.0
212.4 244.3 274.6 303.2 355.6 402.2 498.8 574.7 636.4 688.3 732.8 771.7 806.3 837.4
Ethyl margaroleate 201.6 234.9 267.3 298.4 356.0 407.7 515.2 599.8 668.8 726.6 776.2 819.7 858.3 893.0
219.7 253.5 285.5 315.8 371.2 420.4 522.4 602.5 667.8 722.5 769.5 810.7 847.2 880.0
Stearic acid 190.0 222.2 253.6 283.8 340.0 390.5 495.8 578.7 646.3 703.1 751.8 794.5 832.4 866.4
195.4 229.0 260.9 291.1 346.1 394.9 495.9 575.0 639.3 693.2 739.5 780.0 815.9 848.1
Methyl stearate 199.1 233.0 265.9 297.7 356.9 410.1 521.0 608.5 679.8 739.6 791.0 836.0 875.9 911.8
206.6 241.6 274.9 306.4 364.0 415.1 520.9 603.9 671.4 728.0 776.7 819.2 857.0 891.0
Ethyl stearate 207.5 243.1 277.7 311.2 373.4 429.3 545.9 637.9 712.8 775.7 829.8 877.1 919.1 956.8
217.1 253.7 288.7 321.7 382.1 435.8 546.8 634.0 705.0 764.5 815.7 860.4 900.1 935.9
Oleic acid 189.9 221.4 252.1 281.6 336.3 385.2 487.1 567.1 632.4 687.1 734.1 775.3 811.8 844.6
210.8 243.1 273.8 302.8 355.9 403.0 500.3 576.6 638.6 690.6 735.2 774.3 808.9 840.0
Methyl oleate 201.9 235.2 267.5 298.6 356.2 407.9 515.4 600.0 668.9 726.7 776.4 819.8 858.4 893.1
223.8 257.4 289.3 319.4 374.7 423.8 526.5 606.6 671.8 726.5 773.5 814.7 851.2 884.0
Ethyl oleate 209.6 244.6 278.6 311.3 372.0 426.4 539.6 628.7 701.3 762.2 814.5 860.3 900.9 937.4
228.3 263.7 297.5 329.5 388.1 440.1 547.6 632.1 700.8 758.5 808.0 851.4 890.6 925.2
Linoleic acid 190.6 221.5 251.5 280.2 333.3 380.8 479.1 556.4 619.2 671.9 717.2 756.8 792.0 823.6
200.3 231.4 260.8 288.6 339.5 384.7 478.3 551.8 611.6 661.6 704.6 742.2 775.6 805.6
Methyl linoleate 199.5 232.2 263.8 294.1 350.1 400.2 504.3 586.0 652.6 708.4 756.3 798.2 835.5 868.9
212.9 245.6 276.6 306.0 359.6 407.3 506.0 583.4 646.5 699.3 744.7 784.5 819.8 851.5
Ethyl linoleate 205.3 239.7 273.0 305.0 364.0 416.9 526.6 612.9 683.1 742.0 792.5 836.8 876.1 911.4
220.7 255.6 288.6 319.8 376.8 427.3 531.7 613.5 680.0 735.8 783.7 825.7 862.9 896.4
-Linolenic acid 187.2 217.5 246.8 274.8 326.3 372.2 467.1 541.4 601.9 652.6 696.2 734.3 768.1 798.5
202.2 232.6 261.5 288.6 338.1 382.0 472.5 543.3 600.9 649.2 690.6 726.8 758.9 787.8
Methyl linolenate 197.7 229.9 260.8 290.3 344.8 393.4 494.0 572.8 637.0 690.8 737.0 777.4 813.3 845.5
208.3 240.0 270.1 298.6 350.5 396.6 492.0 566.7 627.6 678.6 722.4 760.7 794.7 825.3
Ethyl linolenate 206.4 240.1 272.7 303.9 361.4 412.7 519.0 602.4 670.2 727.1 775.9 818.6 856.6 890.7
213.5 247.0 278.9 308.9 363.9 412.6 513.4 592.4 656.7 710.6 756.9 797.4 833.4 865.7
Arachidic acid 205.0 240.5 275.1 308.6 370.8 426.7 543.4 635.3 710.2 773.1 827.2 874.5 916.5 954.2
214.4 251.5 286.8 320.2 381.3 435.4 547.4 635.1 706.4 766.1 817.4 862.2 902.0 937.8
Methyl arachidate 214.1 251.3 287.6 322.6 387.7 446.3 568.7 665.1 743.7 809.7 866.4 916.0 960.0 999.7
222.1 260.8 297.4 332.1 395.6 452.0 568.7 660.2 734.7 797.2 850.8 897.8 939.5 976.9
Ethyl arachidate 222.4 261.3 299.3 335.9 404.1 465.5 593.5 694.4 776.7 845.8 905.1 957.0 1003.1 1044.6
231.3 271.5 309.7 345.9 412.2 471.2 593.1 688.8 766.8 832.1 888.3 937.4 981.0 1020.2
a
For each compound, the first line represents the harmonic thermochemistry and the second line represents the anharmonic thermochemistry.

the relatively high number of vibrations concerned for
the molecules considered here. For Cp , the neglect of
these corrections leads to an underestimation of the Cp
from 300 to 500 K and then to an overestimation of
the Cp . This overestimation increases with the size of
the molecule and increases with temperature. It ranges
from 6 to 12 cal mol1 K1 , depending on the size of
the molecule, at 1000 K and from about 9 to 19 cal
mol1 K1 , depending on the size of the molecule, at
2000 K. For entropy, the neglect of these corrections

International Journal of Chemical Kinetics DOI 10.1002/kin

490
OSMONT, CATOIRE, AND GOKALP
leads to an underestimation up to about 1500 K. In
the 15002000 K temperature range, corrected and un-
corrected entropies are about equal. The impact of the
corrections on the simulations cannot be demonstrated
at this time because there is no existing chemical ki-
netic model able to simulate the combustion behavior
of these compounds.
CONCLUSIONS
A protocol has been derived and validated for the pre-
dictions of the thermodynamic data needed for thermo-
chemical calculations and for the building of detailed
chemical kinetic models to simulate the combustion of
biodiesel. The level of theory, hybrid density functional
theory with a modest basis set, plus empirical correc-
tions, is found appropriate for the size of the molecules
and the current state of knowledge (quite minimal)
of their thermochemistry. Calculated and experimental
results compare well for high molecular weight com-
pounds up to methyl tetradecanoate. However for C9
up to C15 compounds, experimental data available in
the literature are seen to be somehow contradictory.
For C16 compounds and above, experimental data are
unique. Experimental reappraisal is probably needed
for high molecular weight methyl or ethyl esters. This
paper provides thermochemical data for 33 molecules
likely to be present in biodiesels. No experimental data
were available for 23 of them. Further works will con-
cern the computations of thermochemical data of radi-
cals and molecules likely to be formed during the ther-
mal decomposition and oxidation of methyl and ethyl
esters present in biodiesel.
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 THERMOCHEMISTRY OF METHYL AND ETHYL ESTERS FROM VEGETABLE OILS
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