Fluid Phase Equilibria 317 (2012) 5964

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Fluid Phase Equilibria

journal homepage: www.elsevier.com/locate/fluid

Method of contribution of groups to estimate thermodynamic properties of

components of biodiesel formation in liquid phase
Amanda C. Oliveira, Luiz F. Moura, Dilson Cardoso
Catalysis Laboratory Chemical Engineering Department, Federal University of So Carlos, PO Box 676, 13565-905 So Carlos, SP, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: An additive group contribution method extended from the Joback and Reid method for the liquid phase
Received 26 April 2011 was developed in order to predict enthalpies of formation and absolute entropies in the standard state.
Received in revised form The method uses the alkanes as reference chemical substances. In the case of enthalpy of formation, the
20 September 2011
methodology was tested for 50 chemicals related to the formation reactions of biodiesel and for absolute
Accepted 23 September 2011
entropy it was tested for 15 compounds. The results were compared with data from the literature. The
Available online 1 October 2011
relative deviations found in the enthalpy estimates were lower than 6% and in the predicted entropy they
were lower than 3%. The method was accurate to estimate the properties for triacylglycerides, such as
Keywords:
Enthalpy of formation
glycerol triacetate and glycerol trioleate (triolein). Additionally, to develop the method, two equations
Liquid phase were derived and used to supplement gaps found in the literature regarding the absolute entropies of
Joback the gaseous and liquid phase, both in its standard state.
Group-contribution method The contribution of this work is the development of a method using the group contributions to estimate
Biodiesel the thermodynamic properties of reactions in the liquid phase, important to the formation of biodiesel.
Transesterication 2011 Elsevier B.V. All rights reserved.

1. Introduction
The growing demand for renewable fuels has resulted in
increased scientic research in the area of biofuels. Biodiesel, a
mixture of fatty acid esters, is an excellent alternative as a sup-
plementary fuel to fossil diesel fuel, representing a substantial
perspective for the future [3]. Therefore, many studies on the pro-
duction of biodiesel, both experimental and theoretical, have been
published in the literature [35].
The esterication and transesterication reactions are the main
routes for biodiesel production [6,7], but estimates of composi-
tion values in the balance of these reactions are hampered by the
lack of reliable thermochemical properties of fatty acids and esters,
especially triacylglycerides.
Estimates of thermochemical property values in the standard
state of 1 atm and 298.15 K are generally made through group con-
tribution methods, such as those proposed by Joback and Reid [1],
Benson [8], Thinh [9], Yoneda [10] and Cardozo [11,12]. Most of
these methods are based on the fact that, for organic substances,
the values of thermodynamic properties are the sum of the contri-
butions of individual groups consisting of one carbon atom and its
links with neighboring atoms.
Corresponding author. Fax: +55 16 3351 8266.
E-mail addresses: dilson@ufscar.br, dilsoncardoso@gmail.com (D. Cardoso).
The Joback and Reid method [1] is an extension of the Lydersen
method, one of the most traditional group contribution methods.
Lapuerta et al. [13] studied and compared four methods to esti-
mate the standard enthalpy of formation of methyl and ethyl esters
of fatty acids. Three of these methods (Joback, Benson-bonds and
Benson-groups) are based on contribution groups. The other one is
based on a computational method (software Gaussian3).
The aforementioned methods, with the exception of the work
of Cardozo [11,12], are limited to the gas phase.
To study the chemical equilibrium of reactions in the liquid
phase, the mole fraction of component i, xi can be estimated by
Eq. (1). In this equation, the equilibrium constant of a reaction can
be related to activities (ai ) of the components of a reaction system.
The activity of a component i, shows how active it is in a solution
with regards to a reference state adopted [14].
 
K= a i = (i xi )i (1)
In Eq. (1), ai is the activity of component i, K is the equilibrium
constant in the reaction temperature,  i is the activity coefcient
of compound iand i is the stoichiometric coefcient related to
component i of the reaction.
The activity coefcient estimates can be made using the excess
Gibbs energy models, which are widely used to estimate the com-
positions of the equilibrium phases [14].
The value of the equilibrium constant at a given tempera-
ture and pressure is related to its value in the standard state,

0378-3812/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.uid.2011.09.026
60
assuming that the enthalpy of reaction, Hr , does not vary much
with temperature, using Eq. (2).
K Hr
1 1

= (2)
K R T T
Values of equilibrium constant in the standard state, K , are
given by Eq. (3), in which Gr is the Gibbs energy of reaction,
T is the temperature in the standard state and R is the universal
gas constant.
 G 
K = exp
r
RT
The Gibbs energy of a reaction can be dened in terms of its
enthalpy, Hr , its entropy, Sr and T , as shown in Eq. (4).
Gr = Hr T Sr
In this equation, the enthalpy and entropy can be dened as
follows:
 N   N
 
Hr = Hf
Hf
i products i reactants
 N   N 
 
Sr = S S
i products i reactants
In Eqs. (5) and (6), Hf is the standard enthalpy of formation, S is
the standard absolute entropy and N is the total number of products
or reactants in the reaction. However, values for Hf and S are
rarely in the literature [2], mainly for chemical species related to
the formation of biodiesel.
Enthalpy is one of the thermodynamic properties related to the
internal energy, which is dened due to its usefulness in applying
thermodynamics to practical problems [14].
Entropy is useful because it is a function of state or property.
It owes its existence to the second law of thermodynamics, from
which it appears the same way as does the internal energy from
the rst law [14].
Therefore, by analyzing Eqs. (1)(6), one can see the need for
available data for enthalpy of formation and absolute entropy for
the study of chemical equilibrium reactions.
2. Development of the group contribution method
In order to ll the gaps related to the calculation of Gibbs energy
of reaction for the compounds of biodiesel production, a group
contribution method to estimate the thermodynamic properties of
two liquid phases was developed in this work, namely the absolute
entropy and enthalpy of formation, both in the standard state. These
estimates were applied to the following linear chain compounds:
carboxylic acids, esters and alcohols. The method develops a Basic
Equation to estimate the approximate value of the contribution of
chemical groups present in linear liquid alkanes, that is (CH3 ) and
(CH2 ).
From the contribution value of enthalpy and entropy of these
two groups, the values were estimated for other groups in the
chemical compounds involved in the esterication and transester-
ication reactions.
This method takes the liquid alkanes as a reference, due to
the fact that this group has methylene and methyl groups as con-
stituents, which are also part of most chemical groups. Moreover,
it is relatively easy to nd reliable thermodynamic properties of
alkanes in the literature [2].
A.C. Oliveira et al. / Fluid Phase Equilibria 317 (2012) 5964
2.1. Standard enthalpy of formation: estimation of the Base
Equation
A Base Equation was developed to estimate the enthalpy of for-
mation, in the standard state, for esters, alcohols and carboxylic
acids with linear chains, in the liquid phase. Thus, it began with
the principle that the standard enthalpy of formation of the liq-
uid phase is approximately equal to the difference between the
enthalpy of formation of the gas phase and the enthalpy of vapor-
ization, as shown by Smith and Van Ness [14], in Eq. (7).
(3) Hf,l
= Hf,g Hv (7)
In this equation, Hf,g and Hf,l are the standard enthalpies of
formation in the gas and liquid phase, respectively, and Hv is the
standard enthalpy of vaporization.
In Eq. (7), the standard enthalpy of formation from the gaseous
(4) phase, and the standard enthalpy of vaporization were substituted,
respectively, by Joback and Reids equation [7] (Eq. (8)) to estimate
this property for the alkanes and with the linear regression results,
seen in Eq. (9). This linear equation was obtained from the data
 analysis of enthalpies of vaporization of the liquid linear alkanes
(5) according to the number of carbons, nCr . The enthalpy data for the
regression were obtained from the literature [2].
Hf,g = 68.29 + (76.45 nCH3 ) + (20.64 nCH2 ) (8)
2
(6) Hv = 4.96 (nC ) + 1.74 (R = 0.999) (9)
Papers published in the literature [1517] show that the values
of enthalpy of vaporization increase with the increase of number
of carbons in the chain of an organic compound. Therefore, by
increasing the number of carbons in a linear alkane, the value of
its enthalpy of vaporization also increases linearly, in agreement
with Eq. (9).
As the linear alkanes consist of two terminal methyl groups
(CH3 ) and nC 2 methylene groups (CH2 ), Eq. (9) becomes:
Hv = 4.96 (nCH3 + nCH2 ) + 1.74 (R2 = 0.999) (10)
Finally, with the substitution of Eqs. (8) and (10) in Eq. (7), we
have the Base Equation (Eq. (11)), which can be used to estimate
the enthalpies of formation of liquid linear alkanes in the standard
state.
Hf,l = 66.6 + (81.4 nCH3 ) + (26.4 nCH2 ) (11)
In Eqs. (8), (10) and (11), nCH2 and nCH3 represent, respectively, the
number of methylenic and methyl groups in a particular molecule.
With Eq. (11) the value of the contribution of groups (CH3 ) and
(CH2 ) was found for the enthalpy of liquid organic compounds,
which are 81.4 and 26.4 kJ mol1 , respectively. From the value of
these two groups the other groups were estimated, whose results
are shown in Table 2.
2.2. Standard absolute entropy: estimation of the Base Equation
To estimate the average entropy contribution of the methylene
groups, the absolute entropies of twelve linear alkane liquids were
analyzed [2]. The estimates were carried out using Eq. (12):
N
[Sl (Cn H2n+2 ) Sl (Cn1 H2n )i
S(CH2 )m = i=1
(12)
N
In this equation, N is the number of contributions analyzed and
S(CH2 )m represents the mean entropy contributions of the
methylene group. Sl (Cn H2n+2 ) and Sl (Cn1 H2n ) refers to the abso-
lute entropy of an alkane with n carbons and another with carbons,
respectively (n 1).
A similar treatment was performed to determine the average
entropy contribution of the methyl group, as shown in Eq. (13). In
 A.C. Oliveira et al. / Fluid Phase Equilibria 317 (2012) 5964 61

this case the same alkanes were also used to estimate the average Substituting CPg,l , by Eq. (22) in Eq. (19) we arrive at Eq. (23),
contribution of the methylene group. which allows to estimate the absolute standard entropy of the liq-
N uid phase, in which Sv is the entropy of vaporization at normal
i=1
[(Sl n(CH2 ) S(CH2 ) )/2]i
S(CH3 )m = (13) boiling temperature, Tb .
N
In the previous equation, Sl represents the absolute entropy in the Sl = Sg Sv + k (Hv Hf,g + Hf,l ) (23)
literature [2], nCH2 is the number of groups (CH2 ) in the linear
In Eq. (23), the expressions Sv and k can be calculated by Eqs.
alkane chain and S(CH3 )m refers to the average contributions of
(24) and (25).
entropy of the methyl group.
The values found from Eqs. (12) and (13), for the contributions Hv
Sv = (24)
of entropy of groups (CH2 ) and (CH3 ) were, respectively, 84.3 Tb
and 31.9 kJ mol1 . From these values the Base Equation, which will
ln(Tb /T )
enable to calculate the entropy of any linear alkane liquid, can be k
= (25)
written as follows: (Tb T )

Sl = 31.8 nCH3 + 84.2 nCH2 (14) The values of absolute entropy of compounds in the liquid phase
to estimate the average contributions of chemical groups, in this
Further details of the Eqs. (12)(14) are given in Appendix A. study, were not found in the literature, they were estimated by Eq.
(23). This, in turn, is the function of the enthalpy of formation of the
2.3. Equation to estimate absolute standard entropy of the liquid gaseous and liquid phases, Hf,g and Hf,l , of the vaporization
and gaseous phase enthalpy, Hv (Tb ), of the absolute entropy of the gaseous phase,
Sg , and of the normal boiling temperature, Tb .
In the NIST databank [2] there are several gaps related to the Therefore, to estimate the absolute value of the entropy of the
absolute entropies of the gas and liquid phase of the long-chain liquid phase, the values of all these thermodynamic properties are
esters and carboxylic acids that participate in biodiesel. Therefore, needed. The values of such properties were searched in the NIST
it was necessary to deduce two equations in order to obtain such database [2] or estimated using the Joback and Reid method [1].
thermodynamic properties. Surprisingly, it was found that for all carboxylic acids, esters and
The equation to estimate the absolute entropy of the liquid alcohols, with linear chains, shown in Tables 3 and 4, Eq. (25), calcu-
phase was deduced from Eqs. (15) and (16), which were written lated at standard temperature (T = 288.15 K), provided a constant
considering that the variations of enthalpy and entropy are inde- value k = 0.003.
pendent of pressure. When the absolute entropy of the gas phase Sg was not found
Tb in NIST [2], Eq. (26) was used. The Joback and Reid method [1] was
H = CP dT (15) used in this equation to estimate the standard entropy of formation
T from the gas phase, Sf,g . As this method [1] estimates, in addi-
Tb
CP tion to other properties, the values of Gibbs energy of formation,
S = dT (16) Gf,g , and enthalpy of formation Hf,g , the value of Sf,g can
T
T
be predicted.
The deduction steps from Eq. (15) are represented by Eqs. n  n 
Sg =Sf,g +(nC ) 5.74+
(17)(19). H O
130.57+ 205.04 (26)
2 2

Hl = Hl + CP,l (Tb T ) (17)
In Eq. (26), Sg is estimated at J mol1 K1 and nC , nH and nO are,

Hg = Hg + CP,g (Tb T ) (18) respectively, the numbers of carbon, hydrogen and oxygen present
in a given chemical species. The constants cited in this equation
H v = Hf,g Hf,l + CPg,l (Tb T ) (19)
(5.74; 130.57 and 205.04 J mol1 K1 ), refer to the absolute entropy
In Eqs. (17) and (18), Hg and Hl are the absolute enthalpies of the gas in the standard state of carbon, hydrogen and oxygen, respec-
gaseous and liquid phase, respectively. Hg and Hl represent the tively, taken from NIST [2].
enthalpies related to the standard state; CP,g and CP,l refer to the
average specic heat of the gaseous and liquid phase, respectively. 2.4. Methodology to analyze the contributions of molecular
Eq. (19) is the difference between Eqs. (18) and (17). The term groups
CPg,l , refers to the difference between the average specic heat of
the liquid and gaseous phases. The chemical compounds and molecular radicals chosen to
Solving the integral of Eq. (16), for the gaseous and liquid phase, develop the group contribution method were those present in the
respectively, we have Eqs. (20) and (21). esterication and transesterication reactions.
T  The average values of contributions, H and S , of water and
Sg = Sg + CPg ln b
(20) formic acid were calculated from the NIST data [2]. The contribu-
T
T  tions of the radicals shown in Table 1 were estimated using Eqs.
Sl = Sl + CPl ln b
(21) (2729), with the exception of the methyl and methylene groups,
T as these are part of the Base Equations (Eqs. (11) and (14)).
T  N
Sv = Sg Sl + CPg,l ln b
(22) [Hf,l (literature) Base Equation (Eq. (11)]i
T H = i=1
(27)
N
In Eqs. (20) and (21), Sg and Sl represent the absolute gas and N
liquid entropies, respectively, related to the normal boiling temper- i=1
[Sl (literature) Base Equation (Eq. (14))]i
ature. Sg and Sl represent the absolute entropies for the standard S = (28)
N
state. N
As in the case of enthalpy, Eq. (22) shows the difference between i=1
[Sl (Eq. (23) Base Equation (Eq. (14)]i
S = (29)
Eqs. (21) and (20). N
62 A.C. Oliveira et al. / Fluid Phase Equilibria 317 (2012) 5964

Table 1 Table 4
Chemical compounds and the molecular radicals for the group-contribution method. Comparison between the estimated values of enthalpy of formation and those found
in the literature of linear chain chemical compounds.
Name Groups
1
Chemical substances Hf,l (kJ mol ) Standard deviation
Methyl CH3
(%)b
Methylenic CH2
Vinylidene HC CH Literaturea Eq. (30)
Methylidene CH
Formic acid 425.5 425.1 0.1
Vinyl H2 C CH
Acetic acid 483.5 478.9 1.0
Ester COO
Propanoic acid 510.8 505.3 1.1
Formyl HCOO
Butanoic acid 533.9 531.7 0.4
Carboxyl COOH
Pentanoic acid 558.9 558.1 0.1
Formic acid HCOOH
Hexanoic acid 581.8 584.5 0.5
Hydroxyl OH
Heptanoic acid 608.5 610.9 0.4
Primary alcohol CHOH Octanoic acid 634.8 637.3 0.4
Water HOH Nonanoic acid 658.0 663.7 0.9
Decanoic acid 714.1 690.1 3.4
Stearic acid 947.2 901.3 4.8
Table 2 Oleic acid 764.8 780.6 2.1
Estimation of the contribution of the entropy of the (OH) group. Linolenic acid 508.8 539.2 6.0
Linoleic acid 634.7 659.9 4.0
1
Alcohols Sl (J mol K1 ) si (J mol 1 K 1 ) Methanol 238.4 248.4 4.2
Ethanol 276.0 274.8 0.4
Literaturea Base Equation
1-Propanol 302.5 301.2 0.4
Ethanol 116.2 160.7 44.5 iso-Propanol 317.0 313.2 1.2
1-Propanol 148.1 192.8 44.7 1-Butanol 328.0 327.6 0.1
1-Butanol 180.0 228.0 48.0 2-Butanol 342.0 339.6 0.7
1-Pentanol 211.9 258.9 47.0 1-Pentanol 351.6 354.0 0.7
1-Hexanol 243.8 287.4 43.6 2-Pentanol 365.2 366.0 0.2
1-Hexanol 377.5 380.4 0.8
Arithmetic average (S ) 45.6 1.9 2-Hexanol 392.0 392.4 0.1
a
Ref. [2]. 1-Heptanol 403.4 406.8 0.8
1-Nonanol 453.6 459.6 1.3
1-Decanol 478.1 486.0 1.7
Table 3 1-Undecanol 504.9 512.4 1.5
Contributions of the entropy and enthalpy groups to the liquid phase. 2-Heptanol 416.9 418.8 0.5
1-Dodecanol 528.5 538.8 1.9
Groups S [J mol1 K1 )] H [kJ mol1 ] 1,2-Butanodiol 523.8 518.2 1.1
1,3-Butanodiol 501.0 518.2 3.4
CH3 84.2 81.4
Glycerol 669.6 670.4 0.1
CH2 31.8 26.4
Methyl acetate 445.9 447.6 0.4
HC CH 56.6 67.9
Ethyl acetate 480.6 474.0 1.4
CH 22.4 27.4 Butyl acetate 529.2 526.8 0.5
H2 C CH 116.6 22.1 Methyl propionate 471.1 474.0 0.6
COO 59.5 351.4 Propyl propionate 530.9 526.8 0.8
HCOO 116.5 374.2 Ethyl propionate 505.6 500.4 1.0
COOH 76.6 464.1 Butyl propionate 555.2 553.2 0.4
HCOOH 130.1 491.7 Methyl butyrate 497.1 500.4 0.7
OH 46.0 234.6 Ethyl butyrate 528.4 526.8 0.3
CHOH 15.7 215.5 Propyl butyrate 567.8 553.2 2.6
HOH 69.9 352.4 Butyl butyrate 590.4 579.6 1.8
Triolein 2193.7 2162.3 1.4
Glyceryl triacetate 1330.8 1257.2 5.5
Ethyl oleate 775.8 775.7 0.0
In Eqs. (27)(29), the variable N represents the number of chem- Methyl oleate 727.6 749.3 3.0
Methyl linoleate 604.9 628.6 3.9
ical species analyzed, and the literature cited in the rst two refers
Methyl linolenate 492.7 507.9 3.1
to the NIST database [2].
As for the absolute entropy Sl , of the chemical compounds, Standard deviation arithmetic average 0.2
studied in this work, it was not found in the literature [2], it was

Eq. 
a
Ref. [2].
estimated using Eq. (23), and the contribution of entropy S was b
S.D.(%) = (30)literature
100
literature
calculated using Eq. (29).
As an example to estimate the entropy contribution of the group,
using Eq. (28), Table 2 shows in the second column the values of
absolute entropy of the standard liquid phase, taken from the lit- were also used to nd the contributions for enthalpy, as well as for
erature [2], of some linear alcohols. In the third column the values entropy.
of this property are listed for the methyl and methylene groups,
and in the last column are the results of the contribution of the
2.5. General Equations
hydroxyl group in each of the alcohols, obtained from the differ-
ence between the two previous columns. The mean and standard
As it is an additive-group contribution, from Eq. (11) we can
deviation of these contributions are indicated in the last line of this
deduce the General Equation (30), which allows estimating the
table. As can be noticed, the standard deviation was small, indicat-
standard enthalpies of formation in the liquid phase.
ing that this method can be applied to estimate the absolute value
of entropy in the standard liquid phase of primary alcohols. 
Similar to the calculation made in Table 2, for the other groups Hf,l = 66.6 + ni H (30)
and compounds listed in Table 1, the mean and standard deviation i
 A.C. Oliveira et al. / Fluid Phase Equilibria 317 (2012) 5964 63

Table 5 The enthalpies of formation and absolute entropies estimated by

Comparison between the estimated values of absolute entropy and those found in
group contribution (Eqs. (30) and (31)) were compared with those
the literature of linear chain chemical compounds.
available in the literature [2] and are also included in Tables 4 and 5,
1
Chemical substances Sl (J mol K1 ) Standard respectively. As indicated in these tables, the arithmetic mean of
deviation (%)b deviations between the calculated values, and that of the literature,
Literaturea Eq. (31) was 0.2% and 0.5%, for the estimations of enthalpies and entropies,
Formic acid 131.8 130.1 1.3
respectively. This result indicates that the method proposed here
Acetic acid 158.0 160.8 1.8 is quite accurate when compared to the literature data.
Butanoic acid 226.4 224.4 0.9 The method used in this work was also used to estimate the
Pentanoic acid 259.8 256.2 1.4 values of entropies and enthalpies of more complex compounds,
Methanol 127.2 130.2 2.4
such as glycerol tri-esters used in biodiesel production.
Ethanol 159.9 162.0 1.3
1-Propanol 192.8 193.8 0.5 As shown in Table 4, the estimated enthalpy of formation was
iso-Propanol 180.6 184.1 1.9 performed and compared with the literature data [2] for triolein
1-Butanol 225.7 225.6 0.0 and glycerol triacetate, nding relative deviations of 1.4% and
2-Butanol 213.1 215.9 1.3 5.5%, respectively.
1-Pentanol 258.9 257.4 0.6
1-Hexanol 287.4 289.2 0.6
Table 5 shows the absolute entropy for glycerol triacetate also
1-Heptanol 325.9 321.0 1.5 estimated, nding a deviation of 3%.
Ethyl acetate 259.8 259.7 0.0 As the amount of information on the enthalpy of formation
Glyceryl triacetate 458.3 472.3 3.0 of chemical compounds in the liquid phase available in the NIST
Standard deviation arithmetic average 0.5 database [2] is greater than the absolute entropy, the number of
compounds used for comparison in Table 4 was lower than those

Eq. 
a
Ref. [2].
b
S.D.(%) = (31)literature
100
in Table 5.
literature

4. Conclusions
Table 6
Analysis of the entropy contributions of groups (CH3 ) and (CH2 ).
The estimation results of the thermodynamic properties
1
Alkanes Sl (J mol K1 ) Eq. (33) Eq. (32) through the group contribution methodology of compounds in the
Literaturea S (CH3 ) S (CH2 )
liquid phase in the standard state, involved in the biodiesel forma-
n-Pentane 265.3 84.9 30.8 tion, were compared with the information available in the literature
n-Hexane 296.2 84.4 [2]. The mean relative deviations for both information data was of
n-Heptane 327.3 84.0 33.2
n-Octane 360.5 84.7
0.2% for the enthalpy formation estimates and 0.5% for absolute
n-Nonane 391.4 84.2 32.4 entropy estimates. In addition, the method can be used to estimate
n-Decane 423.8 84.5 both thermodynamic properties for tri-glycerol esters, with relative
n-Undecane 454.7 84.0 31.9 deviations of less than 6%.
n-Dodecane 486.5 84.0
n-Tridecane 518.9 84.3 32.0
n-Tetradecane 550.9 84.3 List of symbols
n-Pentadecane 582.1 84.0 30.4 a activity
n-Hexadecane 612.4 83.3
Cp heat capacity (J mol1 K1 )
Arithmetic average 84.2 0.4 31.8 1.0 CP average heat capacity at constant pressure (J mol1 K1 )
a
Ref. [2]. C Pg,l difference between average heat capacity of liquid and
gaseous phase (J mol1 K1 )
Gf Gibbs energy of formation (kJ mol1 )
In turn, from Eq. (14), the General Equation to estimate the
Gr Gibbs energy of reaction (kJ mol1 )
absolute entropies in the liquid phase in the standard state can
H absolute enthalpy (kJ mol1 )
be represented by Eq. (31).
Hf enthalpy of formation (kJ mol1 )

Sl = ni S (31) Hr enthalpy of reaction (kJ mol1 )
Hv enthalpy of vaporization (kJ mol1 )
i
H enthalpy contribution (kJ mol1 )
In Eqs. (30) and (31), the index i refers to the type of group indi- K equilibrium constant at temperature T
cated in Table 1 and ni corresponds to the number of such groups, n number
which are present in the chemical compound, whose thermochem- R universal gas constant (J mol1 K1 )
ical property, Hf,l or Sl , is sought to be estimated. S absolute entropy (J mol1 K1 )
S entropy of reaction (J mol1 K1 )
3. Results and discussions S entropy contribution (J mol1 K1 )
T temperature (K)
Table 3 shows the values of entropy Sl and enthalpy Hf,l x mole fraction in liquid phase
of water and formic acid, obtained from the literature [2] and the k constant of Eq. (23) (
=0.003)
entropy and enthalpy contributions of the groups listed in it.
Using the entropy contribution values, S , and enthalpy values, Subscripts
H , listed in Table 3, in Eqs. (30) and (31), the enthalpies of for- b normal boiling point
mation and absolute entropies in the standard state of 50 and 15 C carbon
chemical substances were estimated, respectively. Tables 4 and 5 f formation
show the results and the substances which participate in the for- g gas phase
mation of biodiesel, such as linear chain carboxylic acids, esters and H referred to enthalpy or hydrogen
alcohols. i species i or group-parameter
64 A.C. Oliveira et al. / Fluid Phase Equilibria 317 (2012) 5964

l liquid phase Next, with the mean value of the entropy contributions of group
O oxygen (CH2 ) calculated by Eq. (12), the value of the group contribution
r reaction (CH3 ) of linear liquid alkanes can be estimated by Eq. (33):
S referred to entropy
Sl n(CH2 ) S(CH
v vaporization 2 )m
S(CH = (33)
3) 2
Superscript where, Sl is the absolute value of entropy in the literature [2]
standard state of a linear alkane, n(CH2 ) is the number of groups (CH2 ) in the
alkane chain being analyzed and S(CH2 )m is the mean contribution
Greek letters of group (CH2 ), shown in Table 6.
 activity coefcient The division by 2 in Eq. (33) is due to the presence of two groups
 stoichiometric coefcient of reaction (CH3 ) in the linear alkane chain being analyzed.
After estimating the contributions of CH3 of various alkanes
using Eq. (33), as seen in Table 6, Eq. (13) was used to obtain the
Acknowledgement arithmetic mean of the entropic contribution for this group.
Thus, Eq. (14) is the result of applying Eqs. (12) and (13).
The authors are grateful to CNPq for nancial support.
References
Appendix A.
[1] K.G. Joback, R.C. Reid, Chem. Eng. Commun. 57 (1987) 233243.
[2] P.J. Linstrom, W.G. Mallard (Eds.), NIST Chemistry Web Book, NIST Standard Ref-
This session discussed in detail the steps to nd Eq. (14), in this erence Database Number 69, National Institute of Standards and Technology,
Gaithersburg, 2010 http://webbook.nist.gov.
work called Base Equation. [3] J. Janaun, N. Ellis, Renew. Sustain. Energy Rev. 14 (2010) 13121320.
The Base Equation was used to nd the entropy contributions of [4] Y.C. Sharma, B. Singh, S.N. Upadhyay, Fuel 87 (2008) 23552373.
the molecular groups in Table 3. And in this case, the Base Equation [5] S.P. Singh, D. Singh, Renew. Sustain. Energy Rev. 14 (2010) 200216.
[6] R. Tesser, L. Casale, D. Verde, D.M. Serio, E. Santacesaria, Chem. Eng. J. 154 (2009)
also has the alkane group as a reference. 2533.
To nd the contributions of groups (CH3 ) and (CH2 ), absolute [7] J. He, B. Xu, A. Zhang, C. Zhou, Chem. Eng. Process. 49 (2010) 132137.
entropies of liquid alkanes extracted from the literature were used [8] S.W. Benson, Thermochemical Kinetics: Methods for the Estimation of Ther-
mochemical, Second ed., John Wiley, New York, 1976, p. 320.
[2], as shown in Table 6.
[9] T.P. Thinh, T.K. Trong, Can. J. Chem. Eng. 54 (1976) 344357.
First, the values of the entropy contributions of the group [10] Y. Yoneda, Bull. Chem. Soc. Jpn. 52 (1979) 12971314.
(CH2 ) were analyzed for the liquid alkanes using Eq. (32). [11] R.L. Cardozo, AIChE J. 32 (1986) 844848.
[12] R.L. Cardozo, AIChE J. 37 (1991) 290298.
S(CH2 ) = Si(Cn H2n+2 ) Si(Cn1 H2n ) (32) [13] M. Lapuerta, J. Fernndez, F. Oliva, Chem. Phys. Lipids 163 (1976) 172181.
[14] J.M. Smith, H.C. Van Ness, M.M. Abbott, Introduction to Chemical Engineering
where, Sl(Cn H2n+2 ) and Sl(Cn1 H2n ) are the absolute values of entropy, Thermodynamics, Fifth ed., New York, 1996.
[15] J.S. Chickos, H. Zhao, G. Nichols, Thermochim. Acta 424 (2004) 111121.
in the literature [2], of an alkane with n carbons and another with
[16] L. Shen, K.S. Alexander, Thermochim. Acta 340341 (1999) 271278.
n 1 carbons. The term S represents the value of the entropy [17] R.C. Reid, J.M. Prausnitz, T.K. Sherwood, The Properties of Gases and Liquids,
contribution. Fourth ed., McGraw-Hill, New York, N.Y., 1987.