Fuel 126 (2014) 162168

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Fuel
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Estimation of surface tension of fatty acid methyl ester and biodiesel

at different temperatures
Suriya Phankosol a, Kaokanya Sudaprasert a, Supathra Lilitchan b, Kornkanok Aryusuk c,
Kanit Krisnangkura c,
a
Division of Energy Technology, School of Energy, Environment and Materials, King Mongkuts University of Technology Thonburi, Bangkok 10140, Thailand
b
Department of Nutrition, Faculty of Public Health, Mahidol University, Rachathewi, Bangkok 10400, Thailand
c
Division of Biochemical Technology, School of Bioresources and Technology, King Mongkuts University of Technology Thonburi (Bangkhuntien), Bangkok 10150, Thailand

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Two equations are derived for 34.0

estimation of the surface tension (c) 32.0
of fatty acid methyl ester (FAME) and 32.0
biodiesel. 30.0
30.0
(mN/m2)

 The c of pure FAME is estimated from

(mN/m2)
its chain lengths (z) and number of 28.0 28.0
double bonds (m). y = 0.8035x + 5.2636
26.0 y = 0.9144x + 2.6099
cal

 c = 60.211  0.4307z  0.1125T + R = 0.9276

(cal)
R = 0.9709 26.0
0.00207zT + 3.676m  0.00893mT. 24.0
 The c of biodiesel is estimated from
its fatty acid composition and c of 22.0 24.0
FAMEs. 22.0 24.0 26.0 28.0 30.0 32.0 34.0 36.0 24.0 26.0 28.0 30.0 32.0 34.0
2)
lit (mN/m2) (lit) (mN/m

Estimated versus literature surface tensions of FAMEs at 20- Estimated versus literature surface tensions of biodiesels at
100 oC. 30-80 oC.

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

Article history: Surface tension (c) is an important physical property of biodiesel for atomization and complete combus-
Received 8 January 2014 tion in the diesel engine. In this study, the Martins rule of free energy additivity is extended to cover the
Received in revised form 20 February 2014 free energy of interfacial interaction of a liquid. Finally, an equation (c = 60.211  0.4307z  0.1125T +
Accepted 21 February 2014
0.00207zT + 3.676m  0.00893mT) is derived for estimation of the surface tension of an individual fatty
Available online 6 March 2014
acid methyl ester (FAME), where T, z and m are absolute temperature, number of carbon atoms and num-
ber of double bond(s) of fatty acid, respectively. When the proposed equation was used for estimation of
Keywords:
the surface tension of FAMEs, the deviation range was 0.035.54% and the average absolute deviation
Biodiesel
Fatty acid methyl ester
(AAD) was 1.32% at temperature between 20 and 100 C.
Free energy Also, the proposed equation can be used for estimation of the surface tension of a biodiesel. In this case,
Surface tension the average carbon numbers (zavg) and average number of double bonds (mavg) must be used in place of z
and m, respectively. Thus, the prior knowledge of surface tension of individual FAME is not necessary. The
estimated surface tensions of biodiesels at temperatures between 30 and 80 C were in good agreement
with the literature values. The deviation range was 0.105.70% and the AAD was 2.09%.
2014 Elsevier Ltd. All rights reserved.

1. Introduction

Corresponding author. Tel.: +66 2 470 7759; fax: +66 2 452 3479. Although surface tension (c) is not included in the commercial
E-mail address: kanit.kri@kmutt.ac.th (K. Krisnangkura). biodiesel specication, it is one of the most important fundamental

http://dx.doi.org/10.1016/j.fuel.2014.02.054
0016-2361/ 2014 Elsevier Ltd. All rights reserved.
 S. Phankosol et al. / Fuel 126 (2014) 162168
properties of liquid fuel that affects atomization [13]. Atomization
is the rst stage of combustion in the diesel engine. Oxygen in the
air will react rapidly with fuel on the outer surface of the oil drop-
let and releases tremendous amount of heat to the surrounding.
This will initiate other competitive reactions, such as charring or
coking and polymerization. Thus, enhanced atomization and prop-
er airfuel mixing are important for proper combustion of the fuel,
which increase engine efciency and reduce toxic pollutants [4].
Experimental determination of surface tension of biodiesels
from different sources and processes is time consuming, but they
are necessary for mathematical models. A good mathematical
model should provide not only the accurate surface tension value
but it should also correlate the chemical structure of the estimated
substance for further development or renement of the model.
There are many mathematical models for estimation of the c of
general liquids [517], but model for estimation of the c of biodie-
sel are few [18].
The c of a pure liquid can be estimated by the classical equation
of Macleod [5] from their liquid (qL) and vapor (qv) densities at
equilibrium.
c KqL  qv 4 1 Thus, the overall equation is quite complicated but the model
where K is the temperature-independent but compound-dependent
constant.
This equation was slightly modied by Sugden [7] to,
c Pch qL  qv 4 2 are correlated to the Gibbs free energies of interfacial interaction
1/4
where Pch (is the parachor) = K .
The parachor was assumed to be additive with respect to chem-
ical structures. Only 11 chemical groups were assigned for the
parachor values. The molecular descriptor values were rened
and expanded by Quayle [8] to over 50 chemical groups. The sur-
face tension value in Eq. (2) is very sensitive to the values of the
parachor and density because it is correlated to the fourth power
of the parachor and densities. Therefore, any error in the parachor
or density, the error on surface tension will be amplied. Eq. (2)
has been shown to be good for prediction of surface tension for
many organic compounds [18,19].
Nevertheless, Escobedo and Mansoorithere [20] pointed out that
there were many shortcomings in Eq. (2): (1) the parachor was actu-
ally a temperature-dependent parameter whose relationship with
temperature was not known, (2) the empirical nature of the para-
chor made it difcult in deriving a more accurate expression to sur-
face tension, and (3) the absolute average percent deviation (AAD%)
in surface tension prediction increased with increasing complexity
of the molecular structure of the uid under consideration.
Guggenheim [21] calculated several physical properties (includ-
ing surface tension) of gases and liquids to the principle of corre-
sponding states. He pointed out that the power of Eq. (1) was 11/
3 not 4. The surface tension of a pure liquid has also been corre-
lated to its viscosity [14,22,23]. Also, neural networks have been
proposed to probe the functional group contribution to the surface
tension of pure liquids [16,17].
1.1. Surface tension of biodiesel
Models for estimation of surface tension of a liquid mixture,
such as biodiesel, are few [18]. Allen et al. [18] used the Dalton-
type mass-average equation (Eq. (3)) for calculation of surface ten-
sion of biodiesels.
X
n
cBDF xi ci 3 where A is the surface area.
i1
where cBDF and ci are surface tension of biodiesel and component i,
respectively; xi is mass fraction of the component i.
163
The surface tension of individual FAME was derived from its
parachor. However, Allen et al. [18] found that Eq. (3) consistently
over-predicted the surface tension values. Hence, a weight factor
for each fatty acid methyl ester was added to correct the difference
between the calculated and the experimental values. Therefore, the
added weight factors would undoubtedly complicate the method
of calculation.
Shu et al. [24] also used the Dalton-type mass-average equation
(Eq. (3)) for estimation of the surface tension of biodiesels, but the
surface tensions of individual fatty acid methyl esters were derived
from topological structure indices. However, weight factors were
required for the calculation for the surface tension of biodiesel. Fre-
itas et al. [25] compared the surface tensions of 10 biodiesels esti-
mated by Eq. (2), with the density gradient theory based on the
cubic-plus-association equation of state. The AAD was 7.7% for
Eq. (2) with the Allens parachors and 1.3% with the Knotts0 para-
chors, while the AAD was 9.7% for the gradient theory based on
the cubic-plus-association equation of state.
A different approach for estimation of biodiesel was proposed
by Li et al. [26]. The excess Gibbs free energy was correlated to
the Wilson equation and the surface tension to Gibbs free energy.
could be used to predict surface tension of 124 binary mixture
and 16 multi-component systems at ambient temperature with
overall AAD of 0.54% and 1.36%, respectively.
In this study, the surface tensions of pure FAME and its mixture
DsFAME G [26]. The DsFAME G of a pure FAME is obtained from
the sum of individual DGs contributed from the molecular struc-
tural groups, while the DGs of a biodiesel is obtained from the
sum of individual DGs contributed from its FAMEs.
2. Theory
2.1. Surface tension of saturated FAME
For a compound having the molecular structure of CH3(CH2)z-
1X, Martin [27] divided the molecule into different groups; X,
CH2, CH3. The free energy of transfer from solution to gas of the
molecule was derived from the sum of the free energies of all the
contribution groups.
DG DGf DG1 DG2    DGz 4
DG1 . . . DGz are the free energies of the methylene and methyl
groups, which are not very different. Thus, they are average to dG
and Eq. (4) is shortened to Eq. (5).
DG DGf zdG 5
where DGf is the free energy from the functional group, X; dG is the
change in free energy/carbon atom; z is the number of carbon atoms.
The Martins rule of free energy additivity has been successfully
extended to other physical phenomena, gas chromatographic peak
width, vapor pressure of a liquid, viscosity of a FAME and viscosity
of biodiesel [2831]. In this study, the Martins rule of free energy
additivity is extended to cover the surface tension of a liquid. The
relationship between the surface tension and free energy of inter-
facial interaction of a liquid at constant temperature, pressure and
composition is shown in Eq. (6) [26].
 s
@G
c 6
@A T;P;ni
From basic thermodynamics,
DG DH  T DS 7
164 S. Phankosol et al. / Fuel 126 (2014) 162168

Eq. (8) is obtained by combining Eqs. (5)(7). At constant T, Eq. (9) is reduced to Eq. (16).
DHsf T DSsf zdH s
zdTS s
c a0 b0 z 16
c   8
DA DA DA DA where
Grouping
a0 a cT 17
c a bz cT dzT 9
and
DHs s dSs s
where a DAf , b DDHA , c  DAf and d dS
DA
. 0
b b dT 18
Therefore, Eq. (9) will be the equation for calculation of surface
tension of saturated fatty acid methyl ester. 0
Thus, a and c are the intercept and the slope of the a T plot. Simi-
larly, b and d are the intercept and the slope of the b0 T plot.
2.2. Surface tension of unsaturated FAME
3.2. Determination of numeric constants of Eq. (13)
For unsaturated FAME, DGsdb is assigned for the free energy of
interfacial interaction of the double bond and it is the difference The four numeric values (a, b, c and d) of Eq. (13) are the same as
between the interfacial interaction of unsaturated FAME (DGsunsat ) Eq. (9). Two additional constants, e and f, are solved by two simul-
and saturated FAME (DGssat ). taneous equations.
mDGsdb DGsunsat  DGssat 10
3.3. Determination of average carbon numbers and number of double
bond(s)
DGsunsat DGssat mDGsdb 11
where db and m stand for double bond and number of double bond, As it was pointed out earlier that biodiesel was a mixture of
respectively.Combining Eqs. (5) and (11), FAMEs of different compositions, it could be arbitrarily treated as
a single FAME with the average carbon numbers (zavg) and the
DGs DGsf zdGssat mDGsdb 12 average number of double bond(s) (mavg). They are calculated as
Combining Eqs. (6), (7), and (12), shown in Eqs. (19) and (20), respectively.
X
n
c a bz cT dzT em fmT 13 zavg xi z i 19
DHsdb DSsdb i1
where e DA
, and f DA
.
X
n
2.3. Surface tension of biodiesel mavg xi mi 20
i1
For biodiesel, the free energy of interfacial interaction
(DGsbiodiesel ) is the sum of free energies of interfacial interaction of
3.4. Statistical analysis
individual FAME contributed to the mixture.
X
n Statistical analysis was performed on Microsoft Excel 2010. The
DGsbiodiesel yi DGsi 14 average absolute deviation (AAD) was calculated from Eq. (21).
i1
k 
X 
where yi is the mole fraction of component (FAME) i, DGsi is the free jclit  ccal j
AAD  100 N 21
energy of interfacial interaction of component (FAME) i. i1
clit
Substitution Eq. (6) into Eqs. (14) and (15), a similar equation to
where c(lit) and c(cal) are the experimental and predicted surface ten-
Eq. (3) (the Dalton-type mass-average equation), is obtained.
sions, respectively. N is the number of data points.
X
n
cbiodiesel yi c i 15
i1
4. Results and discussion

Alternatively, the c of biodiesel can be estimated by Eq. (13), if
the number of carbon atoms and number of double bond(s) of fatty
acids are averaged and the mixture is arbitrarily treated as a single
FAME.
3. Methodology
The surface tensions of pure saturated FAMEs were experimen-
tal values measured by the rise of a liquid in a capillary tube re-
ported by Jasper [32]. The surface tension values of unsaturated
FAMEs were calculated by using Eq. (2) with Knotts parachors
[19]. For biodiesel, the experimental values were those reported
by Freitas et al. [25]. The surface tensions were measured by using
a Nima dynamic surface tensiometer, model DST9005.
3.1. Determination of the numeric constants of Eq. (9)
All the four numeric constants of Eq. (9) were solved according
to Krisnangkura et al. [33] and they are briey described below.
4.1. Surface tension of short chain saturated FAMEs
Generally, the linear free energy relationship in Eq. (5) is limited
to a narrow range of carbon numbers for many physical properties
of FAMEs and the lowest number is ve or higher [30]. Although
there has not been reported on the relationship between DGs and
z, it is speculated that this phenomenon should be observed in
the surface tension of liquid as well. Knotts et al. [19] also used
two parachor values for methylene groups. One was for methylene
of short chain length (C1C11) and another for long chain length
(C12 and longer). Thus, in this study, FAMEs were divided into
two groups, C5:0C12:0 and C12:0C22:0 or higher.
Using surface tension data of Jasper [32], the cz and cT plots
gave families of straight lines with coefcient of determination (R2)
greater than 0.929 and 0.999 as shown in Figs. 1 and 2, respec-
tively. Shu et al. [24] showed that the c of FAMEs increased linearly
with carbon numbers (C8C18) with the R2 = 0.986. Also, Li et al.
[13] and Roosta et al.[17] showed that the c of many organic com-
pounds varied linearly with temperature.
 S. Phankosol et al. / Fuel 126 (2014) 162168 165

The plot between the calculated (ccal) and literature (c(lit)) values
31.0
20 C is linear with the intercept, slope, R2 and standard error of
29.0 30 C 0.0473, 0.9981, 0.9972 and 0.171, respectively.
40 C
27.0 50 C
4.2. Surface tension of long chain saturated and unsaturated FAMEs
(mN/m2)

60 C
25.0 70 C
80 C
90 C Short chain fatty acids are minor components found in naturally
23.0
100 C occurring fats and oils and they are not suitable for production of
21.0 biodiesel. Long chain fatty acids are much more abundant in nature
and they are feed stock of biodiesel. However, long chain saturated
19.0 fatty acids occurred in nature are both saturated and unsaturated
17.0 with different number of double bonds. Thus, Eq. (13) was derived
5 7 9 11 13 for determination of c of unsaturated FAMEs.
Carbon numbers of the fatty acids (z) The numeric constants (a, b, c and d) of Eq. (9) for long chain
FAMEs were similarly solved by the a0 T and the b0 T plots. Substi-
Fig. 1. The cz plots of FAMEs at different temperatures (C). tution these four constants into Eq. (9) give Eq. (23), which was
good for estimation of long chain FAME. However, methyl dode-
canoate (C12:0) could be estimated either by Eq. (22) or Eq. (23).
33.0 C5 C6 C7 In the temperature range 20100 C, Eq. (22) gave a slightly lower
31.0 C8 C10 C12 AAD (0.44) than Eq. (23) (0.67).

29.0 c 60:21  0:4307z  0:1125T 0:0021zT 23

27.0 As it was pointed out that Eq. (13) was derived for unsaturated
(mN/m2)

25.0 FAMEs. There are two additional constants in Eq. (13), e and f. The
four constants for saturated FAMEs (a, b, c and d) have the same
23.0 numeric values for both saturated and unsaturated FAMEs. There-
21.0 fore, the two additional constants, e and f, in Eq. (13) are simply
solved by two simultaneous equations. Substitution all the six nu-
19.0
meric constants into Eq. (13) give Eq. (24), which is good for esti-
17.0 mation of both saturated and unsaturated FAMEs. For saturated
15.0 FAME, number of double bond is zero and Eq. (24) is reduced to
280 300 320 340 360 380 Eq. (23).
T (K)
c 60:211  0:4307z  0:1125T 0:00207zT 3:676m
Fig. 2. The cT plots of FAMEs of different z.  0:00893mT 24
The estimated c of eight types of saturated and unsaturated
The numeric values of a, b, c and d obtained from the a0 T and FAMEs at 20100 C by Eq. (24) are summarized in Table 2. Percent
the b0 T plots were 57.58, 0.1645, 0.1172 and 0.0024, respec- differences between the calculated and literature surface tension
tively. Substitution these numeric values into Eqs. (9) and (22) is values are listed in the parentheses. The calculated surface tension
obtained and it is the numeric form of Eq. (9) for estimation the values for both saturated and unsaturated FAMEs agree well with
surface tension of short chain FAMEs (see Fig. 3). the literature values. The AAD was 1.21% and the highest difference
was 5.07% (methyl palmitoleate at 90 C). The calculated surface
c 57:58  0:1645z  0:1172T 0:0024zT 22 tension values of methyl palmitoleate show higher differences
The c of short chain saturated FAMEs (C5C12) generated from from the literatures [19,32] values at all temperatures. In addition,
Eq. (22) at different temperatures are listed in Table 1 together plot of ccal against clit values of both saturated and unsaturated
with the percent differences (in parentheses) between the litera- FAMEs is linear with a slope, 0.9144; intercept, 2.61; R2, 0.971
ture [32] and the calculated values. The AAD is 0.59. The highest and the standard error, 0.397.
and lowest percent differences are 1.43 and 0.01, respectively. The sensitivity of surface tension of FAMEs (Eq. (25)) can be ob-
tained by differentiating Eq. (24) with respect to T. Eq. (25) shows
that the change in c per degree kelvin depends on the chain length
32.0 and degree of unsaturation of the FAMEs. Generally, the increment
30.0 in temperature tends to decrease the surface tension of the FAMEs.
28.0 FAMEs of longer chain length is less sensitive to temperature than
the shorter chain length, while the higher degree of unsaturation is
(lit) (mN/m2)

26.0
more sensitive to the change in temperature.
24.0  
y = 0.9981x + 0.0473 dc
22.0
R = 0.9972 0:1125 0:00207z  0:00893m 25
dT z;m
20.0
18.0
16.0 4.3. Surface tensions of biodiesels
16.0 18.0 20.0 22.0 24.0 26.0 28.0 30.0 32.0
(cal) (mN/m2) Commercial biodiesels are derived from vegetable oils or animal
fats via transmethylation. Therefore, biodiesels are mixture of
Fig. 3. Estimated versus literature surface tensions of short chain FAMEs at 20 FAMEs of different compositions and vary according to the sources.
100 C. As it was pointed out earlier that the surface tension of biodiesel, in
166 S. Phankosol et al. / Fuel 126 (2014) 162168

Table 1
Estimated surface tensions (mN/m2) of short chain saturated FAMEs at 20100C by Eq. (22). Numbers in parentheses are percent difference between the calculated and the
literature values [32].

z Temperature (C)
10 20 30 40 50 60 70 80 90 100
5 26.99 25.93 24.87 23.82 22.76 21.70 20.64 19.59 18.53 17.47
(0.66) (0.66) (0.62) (0.61) (0.56) (0.51) (0.50) (0.44) (0.42) (0.35)
6 27.49 26.46 25.43 24.40 23.37 22.33 21.30 20.27 19.24 18.20
(0.27) (0.31) (0.39) (0.44) (0.54) (0.60) (0.71) (0.79) (0.93) (1.02)
7 28.00 26.99 25.99 24.98 23.97 22.97 21.96 20.95 19.95 18.94
(0.14) (0.05) (0.01) (0.08) (0.15) (0.28) (0.37) (0.46) (0.62) (0.74)
8 28.51 27.52 26.54 25.56 24.58 23.60 22.62 21.64 20.65 19.67
(1.46) (1.45) (1.40) (1.38) (1.36) (1.34) (1.32) (1.25) (1.22) (1.19)
10 29.52 28.59 27.66 26.73 25.80 24.86 23.93 23.00 22.07 21.14
(0.34) (0.27) (0.24) (0.17) (0.10) (0.26) (0.07) (0.12) (0.22) (0.33)
12 30.53 29.65 28.77 27.89 27.01 26.13 25.25 24.37 23.49 22.61
(0.43) (0.24) (0.28) (0.33) (0.37) (0.46) (0.52) (0.58) (0.64) (0.75)

AAD = 0.57%.

Table 2
Estimated surface tensions (mN/m2) of long chain saturated and unsaturated FAMEs at 20100 C by Eq. (24). Numbers in parentheses are percent differences between the
calculated and the literature values [19,32].

z m T (C)
20 30 40 50 60 70 80 90 100
16 0 30.05 (0.33) 29.26 (0.29) 28.46 (0.22) 27.67 (0.17) 26.87 (0.09) 26.08 (0.34) 25.29 (0.05) 24.49 (0.11) 23.70 (0.21)
16 1 31.12 (1.93) 30.23 (2.58) 29.35 (3.18) 28.47 (3.67) 27.59 (4.14) 26.70 (4.55) 25.82 (4.88) 24.94 (5.07) 24.05
18 0 30.40 (0.81) 29.65 (0.74) 28.90 (0.70) 28.14 (0.62) 27.39 (0.57) 26.64 (0.49) 25.89 (0.43) 25.13 (0.34) 24.38 (0.28)
18 1 31.47 (1.28) 30.63 (0.64) 29.79 (0.05) 28.94 (0.45) 28.10 (0.90) 27.26 (1.28) 26.42 (1.61) 25.58 24.74
18 2 32.54 (0.66) 31.61 (0.21) 30.67 (0.14) 29.74 (0.37) 28.81 (0.59) 27.88 (0.68) 26.95 (0.74) 26.02 (0.76) 25.09
18 3 33.60 (0.59) 32.58 (0.38) 31.56 (0.19) 30.54 (0.12) 29.53 (0.18) 28.51 (0.29) 27.49 (0.54) 26.47 (0.90) 25.45 (1.28)
20 1 31.82 (1.66) 31.02 (0.91) 30.22 (0.23) 29.42 (0.45) 28.62 (1.04) 27.82 (1.54) 27.02 (2.03) 26.22 (2.42) 25.42 (2.64)
22 1 32.17 (1.04) 31.41 (0.16) 30.66 (0.70) 29.90 (1.53) 29.14 (2.29) 28.38 (2.96) 27.62 (3.58) 26.86 (4.17) 26.10

AAD 1.21%; maximum difference = 5.07%; minimum = 0.05%.

this study, was simply determined by the rule of free energy addi-
tivity as shown in Eq. (14). Combining Eqs. (6) and (14) gives Eq.
(15), where xi is the mole fraction of component i. Thus, only fatty
acid composition and c of individual FAME is required for the cal-
culation. The c of individual FAME was estimated in the previous
section. Fatty acid compositions of several biodiesels were re-
ported by Freitas et al. [25]. They are converted to mole fractions
and summarized in Table 3. Also, the zavg and mavg of each biodiesel
are included in the Table. Table 4 summarizes the surface tensions
of different biodiesels at temperature between 30 and 80 C, to-
gether with%AAD. It can be seen that the calculated surface tension
(ccal) are in good agreement with the literature values (clit) at all
temperatures.
Biodiesel from soybean A showed the lowest AAD of 0.85%,
while biodiesel from palm oil gives the highest AAD of 3.93%.
The overall AAD of 10 types of biodiesels were 1.84%. The overall
AAD of 10 biodiesels was better than those of the MacLeodSugden
equation with Allen0 s parachors (7.7%) and the density gradient

Table 3
Mole fractions of different biodiesels.

Fatty acid Mole fractions

Soybean A Rapeseed Palm Sunower Soybean B SR (GP)a SRa RPa SPa SPRa
C10:0 0 0.00016 0.00046 0 0 0 0 0.00031 0.00016 0.00016
C12:0 0 0.00055 0.00318 0.00027 0.00000 0.00027 0.00041 0.00270 0.00243 0.00190
C14:0 0.00085 0.00085 0.00669 0.00085 0.00000 0.00157 0.00109 0.00645 0.00012 0.00455
C16:0 0.11648 0.05695 0.44625 0.06950 0.17540 0.11448 0.09656 0.24715 0.27331 0.20481
C16:1 0.00076 0.00220 0.00138 0.00098 0.00000 0.00142 0.00164 0.00183 0.00119 0.00151
C18:0 0.03864 0.01601 0.03829 0.04152 0.03750 0.02610 0.02713 0.02929 0.03914 0.03211
C18:1 0.22672 0.61813 0.40198 0.23675 0.28480 0.40556 0.41388 0.51669 0.32315 0.41872
C18:2 0.53220 0.21113 0.09462 0.63990 0.50230 0.36477 0.37377 0.15208 0.31152 0.27698
C18:3 0.07027 0.07012 0.00087 0.00121 0 0.07111 0.07043 0.03049 0.03540 0.04648
C20:0 0.00341 0.00542 0.00313 0.00684 0 0.00395 0.00413 0.00434 0.00345 0.00409
C20:1 0.00207 0.01227 0.00131 0.00027 0 0.00605 0.00615 0.00598 0.00178 0.00474
C22:0 0.00660 0.00291 0.00072 0.00066 0 0.00372 0.00381 0.00196 0.00261 0.00270
C22:1 0.00199 0.00159 0.00000 0.00125 0 0.0010 0.00100 0.00074 0.00098 0.00124
C24:0 0 0.00170 0.00111 0 0 0 0 0 0.00476 0
zave 17.83 17.96 17.13 17.90 17.54 17.83 17.86 17.54 17.54 17.63
mave 1.52 1.27 0.62 1.53 1.30 1.37 1.39 0.94 1.08 1.14
a
SR, soybean + rapeseed; SR(GP), soybean + rapeseed biodiesel from Portuguese biodiesel producers (Prio and Galp); RP, rapeseed + palm; SP, soybean + palm; SPR,
soybean + palm + rapeseed.
 S. Phankosol et al. / Fuel 126 (2014) 162168 167

Table 4
Surface tensions of biodiesels at different temperatures calculated by Eq. (24) (ccal) and the literature values (clit) [25].

Feed stock Surface tension Temperature (C)

30 40 50 60 70 80 AAD (%)
Soybean A ccal 31.10 30.21 29.32 28.43 27.54 26.65 0.85
clit 31.71 30.56 29.45 28.16 27.40 26.68
%D 1.93 1.15 0.45 0.95 0.51 0.12
Rapeseed ccal 30.89 30.03 29.16 28.29 27.43 26.56 2.43
clit 32.18 31.17 30.14 28.60 27.39
%D 4.00 3.67 3.25 1.07 0.14
Palm ccal 30.13 29.30 28.48 27.65 26.83 26.00 3.93
clit 31.89 30.55 29.86 28.62 27.84 26.62
%D 5.53 4.08 4.63 3.38 3.64 2.33
Sunower ccal 31.13 30.24 29.35 28.47 27.58 26.69 1.29
clit 31.15 29.39 28.29 27.47 26.04
%D 2.93 0.14 0.59 0.36 2.45
Soybean B ccal 30.86 29.98 29.11 28.23 27.36 26.49 1.14
clit 30.89 29.74 28.66 27.98 26.97 25.97
%D 0.11 0.82 1.57 0.91 1.45 1.99
a
SR (GP) ccal 30.95 30.08 29.20 28.32 27.44 26.57 0.97
clit 31.57 30.55 29.54 28.50 27.59 26.57
%D 1.96 1.55 1.16 0.63 0.53 0.01
SRa ccal 30.98 30.10 29.23 28.35 27.47 26.59 1.41
clit 31.64 30.52 29.46 27.90 27.14 26.22
%D 2.08 1.36 0.79 1.61 1.22 1.42
RPa ccal 30.47 29.62 28.78 27.93 27.09 26.25 2.67
clit 30.74 29.70 28.50 27.71 26.89
%D 3.63 3.10 1.98 2.24 2.39
SPa ccal 30.60 29.74 28.89 28.03 27.17 26.32 2.17
clit 31.27 30.47 29.70 28.76 27.68 26.68
%D 2.15 2.39 2.74 2.54 1.83 1.36
SPRa ccal 30.68 29.82 28.96 28.10 27.24 26.38 1.56
clit 31.53 30.49 29.40 28.56 27.29 26.07
%D 2.69 2.20 1.50 1.61 0.18 1.19

Overall AAD = 1.84%.

a
SR, soybean + rapeseed; SR(GP), soybean + rapeseed biodiesel from Portuguese biodiesel producers (Prio and Galp); RP, rapeseed + palm; SP, soybean + palm; SPR,
soybean + palm + rapeseed.

theory based on the cubic-plus-association equation of state (9.7%),
but it is slightly higher than the MacLeod-Sugden equation with
Knotts0 parachors (1.3%) [25]. Shu et al. [24] reported that the c
of FAMEs estimated from their topological indices at 40 C had
the highest relative error of 2.21%. However, when the c of biodie-
sel was determined by Dalton-type mass-average equation, the
weight factor of individual FAME was required for the calculation.
The correlation between the estimated and literature surface
tension values of biodiesels is shown in Fig. 4. The slope and inter-
cept of the plot is 0.8035 and 5.2636 with the R2 of 0.9276 and the
standard error was 0.3977. Some statistical values are summarized
in Table 5.
The fatty acids of biodiesels in this work are mainly 16 and 18
carbon atoms with some minor components of shorter and longer
carbon chain length. The molecular weight of these fatty acids are
not very different from the average molecular weight, thus, it is
speculated that mass fraction can be used in place of mole fraction.
Using mass fraction of fatty acid in the calculation has certain
advantage that it can be easily obtained from gas chromatographic
analysis with the most widely used ame ionization detector. It
was found that the estimated c of different biodiesels from the
two methods were approximately the same. On the other hand,

Table 5
Regression statistics of calculated and literature surface tensions of biodiesels
32.0 between 30 and 80 C at 10 C interval.

Biodiesel type Intercept Slope RSQ Standard error %AAD

30.0
(cal) (mN/m2)

Soybean A 3.9962 0.8581 0.9895 0.1909 0.85

Rapeseed 7.9886 0.7082 0.9936 0.1263 2.43
28.0 Palm 4.555 0.8043 0.9946 0.1271 3.93
y = 0.8035x + 5.2636 Sunower 7.9824 0.7195 0.9848 0.1995 1.29
R = 0.9276 Soybean B 2.9411 0.907 0.9848 0.1162 1.14
26.0 SR (GP)a 3.225 0.8789 0.9997 0.0316 0.97
SRa 6.3599 0.7496 0.9921 0.1658 1.41
RPa 3.1346 0.8638 0.9931 0.1278 2.67
24.0 SPa 1.5504 0.9249 0.9956 0.1193 2.17
24.0 26.0 28.0 30.0 32.0 34.0 SPRa 5.5634 0.7951 0.9969 0.1005 1.56

(lit) (mN/m2) a
SR, soybean + rapeseed; SR(GP), soybean + rapeseed biodiesel from Portuguese
biodiesel producers (Prio and Galp); RP, rapeseed + palm; SP, soybean + palm; SPR,
Fig. 4. Estimated versus literature surface tensions of biodiesels at 3080 C. soybean + palm + rapeseed.
168 S. Phankosol et al. / Fuel 126 (2014) 162168

the overall AAD (1.70%) for the mass fraction method was slightly Acknowledgements
lower than that obtained from mole fraction (1.84%).
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with represented by average carbon numbers and average number
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