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Determination of the Solubility Parameters of Biodiesel from


Vegetable Oils
Matheus M. Batista, Reginaldo Guirardello, and Maria A. Krah enbuhl*
School of Chemical EngineeringUNICAMP, 13083-970 Campinas, SP, Brazil
ABSTRACT: The fatty acid methyl esters of vegetable oils and animal fats, more commonly known as biodiesel, represent a
renewable, biodegradable, noninammable, and low toxicity alternative to diesel. In this study, the Hansen solubility parameters
(HSPs) and the interaction radius of the solute sphere (R0) were determined for the biodiesel derived from soybean oil, coconut
oil, palm oil, and castor oil, using 45 solvents and solvent mixtures. The values for the HSPs and R0 obtained for the dierent
biodiesels were soybean (15.03, 3.69, 8.92, and 11.33; MPa(1/2)); coconut (15.12, 3.99, 9.25, and 10.92; MPa(1/2)); palm (15.43,
5.28, 6.61, and 10.54; MPa(1/2)); and castor (16.10, 6.72, 9.11, and 11.78; MPa(1/2)). The HSPs of four biofuels were also
determined using the average values of the fatty esters of each oil, calculated using group contribution. Subsequently, the
solubilities of the biofuels were predicted using the van KrevelenHoftyzer, Greenhalgh, and Bagley approaches.

1. INTRODUCTION
Biodiesel is a renewable fuel for diesel engines produced from
biological oils and fats and considered as a potential source of
fuel. The use of biodiesel as a fuel is growing rapidly worldwide
since its production chain has promising potential in various
sectors, such as the social, environmental, and technological
sectors. From the environmental aspect, the emission of
pollutants such as SOx, CO, CO2, and hydrocarbons in exhaust
gas can be reduced.1,2
Many types of vegetable oil have been investigated for the
production of biodiesel, among which soybean, sunower, castor,
coconut, palm, canola, cottonseed, and others stand out, with
diversied fatty acid compositions. Methanol and ethanol are the
alcohols most frequently used in the transesterication reactions.
Therefore, biodiesel can be obtained by the transesterication of
triacylglycerol with an excess of alcohol. These triacylglycerols
are converted to the corresponding alkyl esters of straight chain
fatty acids, with glycerol and water as the byproducts.35 The
biodiesel production reaction can be carried out in the presence
of homogeneous (alkaline and acid), heterogeneous (zeolites,
sulfonic resins), or enzymatic (lipases) catalysts or with no
catalyst using supercritical conditions. The dierences between
the chemical structures of biodiesel (mixture of monoalkyl esters
of saturated and unsaturated long-chain fatty acids) and diesel
fuel (mixture of paranic, naphthenic, aromatics, and olens
from approximately C9 to C20) generate dierent results in their
basic properties, such as the cetane number, heat of combustion,
cold ow, oxidative stability, viscosity, and lubricity.68 Biodiesel
is also considered a biosolvent due to its properties (such as being
renewable, biodegradable, noninammable, nontoxic, ecofriendly, and having good solubility) and could be an integral
part of green chemistry, not only as an environmentally friendly
fuel alternative but also as an eective diluent for liquidliquid
extraction.9,10
The term solubility parameters (T) was rst used by
Hildebrand and Scott,11,12 who postulated that interactions such
as solvation should be stronger when the Ts of the solvent and
solute are equal. The Hildebrand solubility parameters are
determined in the absence of any specic interactions, especially
XXXX American Chemical Society

hydrogen-bonding. Hansen has extended the theory developed


by Hildebrand to polar and associated compounds by dividing
the T parameters into three-dimensional solubility parameters,
consisting of dispersive interactions, polar interactions, and
hydrogen-bonding interactions.13 These three components are
not arithmetically additive, but they appear as a vector, thus
representing Hildebrands solubility parameters (T) in the
three-dimensional space.14
Material with similar Hansen solubility parameters (HSPs)
will show physical anities. The theorical classical and group
contribution methods are also commom. The classical
method13,15 consists of testing the solute solubility in dierent
solvents and plotting these solvents in three-dimensional space.
The location of the center of the sphere determines the value of
the HSPs for the solute. The greatest distance between any two
solvents is taken as the diameter of the sphere and three HSP
values as the midpoint. Group contribution or additive methods
have a long tradition of successful use in predicting properties
that only require knowledge of the compounds chemical
structures to calculate the HSPs.16 The cohesive energy or
HSPs of solvents and solutes can be determined using the
methods of Barton,17 van Krevelen,18 Hoy,19 Breitkreutz,20
Askadskii,21 and Stefanis and Panayiotou.22,23
HSPs have been widely used to estimate the solubility or
miscibility of polymer blends; determine chemical resistance;
and analyze pharmaceuticals, mineral oils,13 carbon nanotubes,24
bitumens, 25 and asphaltenes.26 Medina Ganzales et al.
determined HSPs to fatty acid methyl esters (C8C18:2) for
use with biosolvent epoxy resins.27 Srinivas et al. characterized
the physicochemical properties (including HSPs) of methyl
soyate (soybean biodiesel methyl esters) as a renewable solvent
in liquidliquid separation.28 The present work estimated the
HSPs and radius of interaction sphere R0 of biodiesel derived
from four dierent vegetable oils, soybean, coconut, palm, and
Received: August 23, 2013
Revised: October 21, 2013

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importance of cohesive energy density, rather than the strength


of a single type of physical bond.
Skaarup and Hansen have developed an equation for the
solubility parameter distance, Ra, between two materials, based
on their respective partial solubility parameter components:13

castor, using an optimization technique. In the optimization


technique, mixtures of good and bad solvents were used to
improve the accuracy of R0 and hence of the HSPs. The
optimization method minimizes the radius of the sphere subject
to the constraints that good solvents are found within the sphere
while bad solvents are found outside the sphere. In the second
part of this work, the group contribution method was used to
predict the HSPs in order to investigate the theoretical solubility
of these biofuels. The group contribution method can be used as
a tool for the selection of possible solvents to be used by the
Hansen method, thus avoiding possible anomalies in the data t.
The extended use of biodiesel from dierent vegetable oils for
various applications is important, not only as an alternative fuel
but also as a sustainable and renewable solvent.
1.1. Solubility Parameter (Cohesive Energy Density).
The solubility parameters are sometimes also called the cohesion
energy parameter. Cohesive energy is a measure of all the
intermolecular forces responsible for the material cohesion and
can be dened as the square root of the cohesive energy density.
The relationship between the solubility parameter and cohesive
energy density is shown in the following expression:
= c1/2 =

1/2
E 1/2 HV RT

=
V

(Ra)2 = x( D1 D2)2 + y( P1 P2)2 + z( H1 H2)2


(5)

The subscripts are 1 for the solute and 2 for the solvent.
Hansen has suggested, on the basis of empirical test settings of x
= 4 and y = z = 1 that a doubling of the dispersive force converts
the otherwise elliptical shaped volume of the solubility body to an
almost spherical volume.13 However, the use of xed variables for
complex mixtures has been questioned.31 Other experiments
have shown that, in general, solubility regions are unsymmetrical.32 However, the overpowering practical evidence is that
the value of the constant 4 is the most usable value and has been
used in this paper.13,33 The HSPs of the solute at issue are at the
center of the spheroid body, and the solubility radius (R0) denes
a sphere that contains the good solvents, the bad ones being
outside.
The Relative Energy Dierence (RED) term in eq 6 is useful
for a quick evaluation of whether a solvent is likely to appear
inside the solubility sphere.

(1)

where is the solubility parameter, c the cohesive parameter, E


the latent heat of evaporation, V the molar volume, HV the
enthalpy of evaporation, R the gas constant, and T the
temperature. is measured in units of MPa1/2 or cal1/2 cm3/2
where one MPa1/2 is 2.0455 times larger than those in the
cal1/2cm3/2. This theory was developed for nonpolar, nonassociating systems, but the concept has been extended to polar
systems. Gharagheizi et al. divided the solubility parameter into
two portions, one nonpolar contribution and one polar
contribution.29,30 Hansen expanded this concept in an eort to
account for both polar and hydrogen bonding interactions in
solventpolymer systems via the use of a three-dimensional
solubility parameter (HSPs) such that the total solubility
parameter is separated into three independent parameters and
takes into account the (atomic) dispersion forces, (molecular)
polarity, and (molecular) hydrogen bonding (electron exchange). The basic equation that governs Hansens theory is
that which relates the total cohesion energy (E) of a system with
the three parameters discussed above.
E = ED + EP + EH

RED =

f ( Dbio , Pbio , Hbio , R 0) = 1 data fit

T2

(4)

D2

P2

H2

(7)

where

where ED, EP, and EH are dispersion, permanent-dipole/


permanent-dipole, and hydrogen bonding forces, respectively.
Dividing this by the molar volume gives the square of the total
(or Hildebrand) solubility parameter as the sum of the squares of
the Hansen D, P, and H components:
(3)

(6)

Either Ra or the RED number can be used to rank solvents and


solvent blends. A solvent with identical solubility parameters as
the solute will have a RED equal to 0. The bad solvents will have
RED values greater than 1, and good solvents will have RED
values less than or equal to 1. Solvents with RED 1 are very
important for nding the correct R0. Numbers less than 0.5
indicate that good anity is expected.14,34
1.2. Data Fitting Procedure. The HSPs and values for the
radius of interaction of the biodiesel from soybean oil, coconut
oil, palm oil, and castor oil were calculated using a program
created in GAMS (The General Algebraic Modeling System),
version 23.2.1. The procedure for data tting is based on the
algorithm described by Ma and Zhou35 and by Gharagheizi,36
which seeks to minimize the objective function given by eq 7:

(2)

E
E
E
E
= D + P + H
V
V
V
V

Ra
R0

data fit = (A1A 2...A n)1/ n

(8)

Ai = e(error_distance)

(9)

where Ai is the data t for the ith solvent, given in eqs 10 and 11.
For good solvents (sol(i) = 1):
Rai Ro if Rai > Ro
error distance =
0
if Rai Ro

(10)

For bad solvents (sol(i) = 0):

0
if Rai > Ro
error distance =
Ro Rai if Rai Ro

where D, P, and H are the dispersion, polar, and hydrogenbond parts of HSPs, respectively, which can be represented in a
three-dimensional coordinate system. The HSP coordinates of
the solute are determined by analyzing the solubility of this solute
in a series of solvents with known HSPs. The total solubility
parameter, T, is customarily related to room temperature (25
C). The solubility parameter concept demonstrates the

(11)

where
Rai2 = 4( Di Dbio)2 + ( Pi Pbio)2 + ( Hi Hbio)2
(12)
B

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A good t is given by a data t value close to 1. However, errors


may occur in the tting called outliers. Outliers are solvents
that do not dissolve the solute but are inside the sphere (wrong
in) or solvents that do dissolve the solute but are outside the
sphere (wrong out). When the number of such an outlier
decreases to zero, the t accuracy increases to 1. The quantities
that are tted are the values for the biodiesel (Dbio, Pbio, and
Hbio) and R0. The data that must be given for the tting are the
solvent values (Di, Pi, Hi) and the list of good and bad solvents
(sol(i)).
1.3. Nonlinear Programming Model. In this work, the
previously described procedure was transformed into an
equivalent nonlinear programming model to minimize the
multivariable objective function given by

H =

(13)

i=1

such that

ei Rai Ro

i {i = 1, ..., n: sol(i) = 1}

(14)

ei Ro Rai

i {i = 1, ..., n: sol(i) = 0}

(15)

Rai

ei 0

4( Di Dbio)2 + ( Pi Pbio)2 + ( Hi Hbio)2

Rai 0

Dbio 0

(16)

In this optimization model, the decision variables are ei, Rai,


Di, Pi, Hi, sol(i) and the parameters are Dbio, Pbio, Hbio, and R0.
The average value of D, P, and H of the good solvent and the
radius of 0 were chosen as the starting point.
The value of the data t can be calculated by

FDi
V

(20)

NA
i i + W MjBj
(21)

0.4126
D = ( NA
i i + W MjBj + 959.11)
i

(22)

P = ( NA
i i + W MjBj + 7.6134)
i

(23)

H = ( NA
i i + W MjBj + 7.7003)

(17)

The problem has been dened as nding a sphere with the


minimum radius containing the maximum number of good
solvents and the minimum number of bad solvents and outliers.
The advantage of this method is that it could be used to
determine more accurate HSPs, a smaller R0, and a better data t
as compared to Hansens.
1.4. Group Contribution Methods for the Estimation of
Solubility Parameters. This kind of method has been used to
estimate the solubility parameter: van Krevelen18 and Stefanis
and Panayiotou22,23 have reviewed these techniques and given
tables of group values. The sets of group constants given by van
Krevelen and Stefanis and Panayiotou seem to be most
comprehensive. The group contribution values of van Krevelen
are based on the cohesive energy data of polymers. The Stefanis
values are based on two kinds of characteristic group: rst-order
groups that describe the basic molecular structure of the
compounds and second-order groups, which are based on the
conjugation theory and improve the accuracy of the predictions.
These theoretical methods are useful in the case of compounds
for which experimental HSPs are not available.
1.4.1. The van Krevelen18 Method. The solubility parameter
components, D, P, and H may be calculated from the group
contributions using the following equations:
D =

E Hi
V

where Ci is the contribution of the type i rst-order group that


appears Ni times in the compound and Dj is the contribution of
the type j second-order group that appears Mj times in the
compound. The constant W is equal to 0 for compounds without
second-order groups and equal to 1 for compounds with secondorder groups.22
The HSPs components may be predicted using the following
equations:23

Hbio 0

1 n
data fit = exp ei
n i = 1

(19)

Ro 0

Pbio 0

where FDi is the type i group contribution of to the dispersion


forces, FPi is the group contribution to the polar forces, EHi is the
group contribution to the hydrogen-bonding energy, and V is the
molar volume of the substance.
1.4.2. The StefanisPanayiotou22 Method. The Stefanis
Panayiotou method can be described using two kinds of
functional group: rst-order groups (UNIFAC groups), which
describe the basic molecular structure of the compounds, and
second-order groups, which use the rst-order groups as building
blocks.22,23 The basic equation that gives the value of the
solubility parameters from the molecular structure is

min ei

FP2i

P =

(24)

However, eqs 23 and 24 are only valid for HSPs values greater
than 3 MPa(1/2). In the case of low P or low H values (less than 3
MPa(1/2)), the equations for the estimation and for P and H are
the following:22
P = ( NA
i i + W MjBj + 2.6560)
i

(25)

H = ( NA
i i + W MjBj + 1.3720)
i

(26)

The advantage of this method for estimating HSPs is that it can


be used for a broad series of organic compounds, including those
having complex multiring, heterocyclic, and aromatic molecular
structures. This predictive method is not only important for the
selection of solvents for a particular material but also for the
synthesis of new solvents with desired properties.22,23

2. EXPERIMENTAL SECTION
2.1. Materials. Commercial coconut and castor oils were purchased
from Campestre (Sao Paulo, Brazil). Rened soybean oil was purchased
from Cargill (Mairinque/SP, Brazil), and palm oil was obtained from
Agropalma (Para, Brazil). Potassium hydroxide (Synth-Brazil) was used
as the catalyst. All the other solvents used in this study were common,
high purity laboratory solvents obtained from commercial chemical
suppliers.

(18)
C

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Table 1. HSPs, Radius of Interaction, R0, and Correlation Coecients for Biofuels
biodiesel

D MPa(1/2)

P MPa(1/2)

H MPa(1/2)

T MPa(1/2

R0 MPa(1/2)

G/Ba

wrong inb

wrong outc

data td

soybean
coconut
palm
castor

15.03
15.12
15.43
16.10

3.69
3.99
5.28
6.72

8.92
9.25
6.61
9.11

17.86
18.17
17.60
19.68

11.33
10.92
10.54
11.78

35/25
35/25
35/25
40/20

0
0
0
0

1
1
1
1

0.993
0.993
0.955
0.956

Good and bad solvents. bSolvents that do not dissolve the biodiesel but are inside the sphere. cSolvents that do dissolve the biodiesel but are
outside the sphere. dFit accuracy.
2.2. Biodiesel Production. Biodiesel was produced from soybean,
coconut, and palm oils according to the following procedure: The
methyl esters were synthesized using 300 g of oil, 60 g of methanol, and
about 3 g of KOH. The mixture was stirred at a temperature of 60 C for
a period of 2 h. After 30 min, two dierent phases were observed: one
containing the methyl esters (less dense and clearer) and the other
containing glycerin (denser and darker). After resting for 24 h, the
glycerin was removed. The lighter phase (methyl esters) was puried by
washing with a solution containing 0.5% v/v of HCl, which neutralized
the remaining catalyst (KOH), conrmed by analyzing the wash water
with a 1% v/v phenolphthalein indicator. The washing was followed by
an evaporation step at 110 C. After purication, the biodiesel was
characterized.
The castor oil transesterication process was based on an earlier
work,7 using hexane as the cosolvent. The use of hexane increases the
reaction rate and facilitates phase separation (methyl esters and
glycerin). The separation and washing processes were carried out as
detailed above.
The conversion of the esters (Y; eq 27) was determined by highperformace size-exclusion chromatography (HPSEC; Waters, USA).
The Schoenfelder methodology is specic for the analyses of
triacylglycerols (TG), diacylglycerols (DG), monoacylglycerols (MG),
and glycerol (GL) and was adapted for the analysis of esters (EE)
because the ester peak appeared between the monacyglycerol and
glycerol peaks. The mobile phase was tetrahydrofuran (THF). C0 was
the raw material concentration (wt %) at t = 0 min and was Ci at the end
of the reaction. TG, DG, MG, EE, and GL were identied on the basis of
standard references (Sigma-Aldrich). The free fatty acids were
determined according to the American Oil Chemists Society (AOCS
ocial method Ca 5a-40).

Y=

C0 Ci
C0

3. RESULTS AND DISCUSSION


3.1. Calculation of the Hansen Solubility Parameters
for Biodiesel. The conversions of the biodiesels (fatty acid
methyl esters) were greater than 90.84% with acid numbers of
0.080 to 0.094 mg KOH/g and densities (20 C) between 0.857
and 0.915 g/cm3. Table 1 presents the HSPs for the four dierent
biodiesels calculated from the experimental data given in Table 2.
The values of the data ts were below 1 due to the presence of
outliers. In this case, ethanol was the solvent that dissolved the
soybean biodiesel (RED =1.038), coconut biodiesel (RED
=1.036), and palm biodiesel (RED = 1.260) but was outside the
sphere of solubility (wrong out), and methanol was wrong out for
the castor biodiesel. According to Redelius,25 the existence of
outliers located away from the interface of the spherical region
indicates that there are some solubility aspects of the solute that
are not completely covered by the Hansen approach. A
comparison of the RED biofuels is shown in Figure 1 for the
45 pure solvents listed in Table 2. The solvents (ethylene glycol
monobutyl ether acetate, ethyl acetate, n-butyl acetate,
tetrahydrofuran, and diethyl malonate) lower the RED values.
Consequently, these solvents are ideal for biofuels.
The values obtained for the HSPs of soybean biodiesel (D, P,
H = 15.03, 3.69, 8.92) and coconut biodiesel (D, P, H = 15.12,
3.99, 9.25) were very similar, due to the small dierences in
solubility between the experimental mixtures of the solvents. For
example, soybean biodiesel was insoluble in 70/30% dimethyl
sulfoxide/1-methyl-2-pyrrolidone, 70/30% diethylene glycol/mcresol, and 60/40% ethanolamine/ethanol, while for coconut
biodiesel, these values for insolubility were 80/20%, 80/20%, and
70/30%, values sucient to generate the small dierence
between the values of the HSPs. According to Table 1, the
HSPs of soybean biodiesel showed slightly dierent values from
those reported by Thiebaud-Roux and de Caro (D, P, H = 16.6,
5.2, 8.2) in 60 solvents38 and by Srinivas et al. (D, P, H = 15.40,
5.81, 4.99) in 41 solvents.28 Although both have created a
program using the MATLAB environment with a similar
algorithm to that one proposed by that work, these values
diered (HSPs) due to the use of dierent solvents in each study.
For the palm biodiesel (D, P, H = 15.43, 5.28, 6.61), the
value of D was also very similar to that of coconut biodiesel and
soybean biodiesel, although that for P was higher and that for H
lower. The smallest values for H were found for the solubility in
mixtures of 40/60% ethanolamine/aniline, 40/60% ethanolamine/dimetilformamide, 80/20% dimethyl sulfoxide/ethanol,
40/60% ethanolamine/ethanol, and 50/50% diethylene glycol/
1-methyl-2-pyrrolidone, proportions in which soybean biodiesel
and coconut biodiesel are soluble. Castor biodiesel showed
higher values for the solubility parameters (D, P, H = 16.1, 6.72,
9.11), since methyl ricinoleate contains a hydroxyl group, which
increases its solubility in solvents which exhibit strong hydrogen
bonds, such as the alcohols methanol and ethanol. Furthermore,
the presence of a hydroxyl group in the castor biodiesel increases
its lubricating power, and it is therefore an excellent candidate for

(27)

2.3. Solubility Test. The solubility tests were initially carried out in
45 organic solvents in order classify them as good (one-phase systems)
or bad (two-phase systems) solvents. According to the results obtained
for solubility in the 45 solvents, several solvent mixtures (bad/good
solvents) were prepared to improve the data and construct the solubility
sphere in three-dimensional space. The series consisted of volume ratios
(bad solvent/good solvent) of 90/10, 80/20, 70/30, 60/40, 50/50, 40/
60, 30/70, 20/80, and 10/90. The solubility parameters of the mixtures
were calculated using eq 28.
Dmix
,P ,H =

i Di , P , H
i

i = 1, 2, ..., N components
(28)

where i is the volume fraction i of the components in the solvent


mixture, and D, P, and H are the solubility parameters of dispersion,
polar, and hydrogen bonding, respectively. The procedure used to
determine solubility was as follows: 0.5 mL of biodiesel was placed in a
test tube with 4.5 mL of the test solvent or solvent mixture. The tube was
sealed with a suitable stopper to prevent solvent evaporation and stirred
vigorously for 24 h at room temperature. After shaking, the tube was
allowed to stand at room temperature for 6 days. The behavior of the
biodiesel was observed by a visual inspection. The solubility parameters
of the 45 solvents and 15 solvent mixtures were used to determine the
solubility prole of the biodiesel produced from the vegetable oils
studied here. The solubility behavior of the test substance was judged as
soluble (1) or insoluble (0).
D

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Table 2. Good and Bad Solvents for the Biofuels to Determine the Hansen Solubility Parameters
units of MPa(1/2)
solvents
1. n-hexane
2. n-heptane
3. cyclohexane
4. benzene
5. o-xylene
6. toluene
7. ethylbenzene
8. cumene
9. - methylstyrene
10. methanol
11. ethanol
12. propan-2-ol
13. octan-1-ol
14. hexan-1-ol
15. 2-methyl propan-1-ol
16. n-butanol
17. EGa
18. diethylene glycol
19. triethylene glycol
20. glycerol
21. EGMEAb
22. acetone
23. cyclohexanone
24. butanone
25. 4-methylpentan-2-one
26. ethyl acetate
27. n-butyl acetate
28. m-cresol
29. pyridine
30. DMFc
31. 1MPd
32. acetonitrile
33. nitrobenzene
34. diethyl ether
35. anisole
36. tetrahydrofuran
37. 1,4- dioxane
38. DMSOe
39. aniline
40. ethanolamine
41. diethyl malonate
42. carbon tetrachloride
43. 1,2-dichloroethane
44. formic acid
45. water
solvents mixture (vol %)
46. diethylene glycol/ethanol 90/10
47. diethylene glycol/ethanol 70/30
48. diethylene glycol/ethanol 60/40
49. diethylene glycol/ethanol 50/50
50. DMSO/1MP 80/20
51. DMSO/1MP 70/30
52. glycerol/ethanol 60/40
53. glycerol/ethanol 40/60
54. glycerol/ethanol 30/70
55. ethanolamine/aniline 90/10
56. ethanolamine/aniline 50/50
57. ethanolamine/aniline 40/60
58. EG/acetone 80/20

soybean

coconut

palm

castor

RED

RED

RED

RED

14.9
15.3
16.8
18.4
17.6
18.0
17.8
18.1
18.6
15.1
15.8
15.8
17.0
15.9
15.1
16.0
17.0
16.6
16.0
17.4
16.0
15.5
17.8
16.0
15.3
15.8
15.8
18.0
19.0
17.4
18.0
15.3
15.8
14.5
17.8
16.8
19.0
18.4
19.4
17.0
16.1
17.8
16.5
14.3
15.5

0.0
0.0
0.0
0.0
1.0
1.4
0.6
1.2
1.0
12.3
8.8
6.1
3.3
5.8
5.7
5.7
11.0
12.0
12.5
12.1
4.1
10.4
6.3
9.0
6.1
5.3
3.7
5.1
8.8
13.7
12.3
18.0
8.6
2.9
4.1
5.7
1.8
16.4
5.1
15.5
7.7
0.0
7.8
11.9
16.0

0.0
0.0
0.2
2.0
3.1
2.0
1.4
1.2
4.1
22.3
19.4
16.4
11.9
12.5
15.9
15.8
26.0
20.7
18.6
29.3
8.2
7.0
5.1
5.1
4.1
7.2
6.3
12.9
5.9
11.3
7.2
6.1
5.1
5.1
6.7
8.0
7.4
10.2
10.2
21.2
8.3
0.6
3.0
16.6
42.3

0.853
0.854
0.893
0.913
0.726
0.830
0.869
0.898
0.797
1.404
1.038*
0.707
0.438
0.398
0.641
0.655
1.676
1.302
1.168
1.990
0.187
0.622
0.637
0.602
0.478
0.249
0.269
0.643
0.875
1.000
0.936
1.288
0.623
0.357
0.528
0.369
0.733
1.275
0.790
1.543
0.450
0.941
0.687
1.000
3.141

0.923
0.922
0.956
0.966
0.773
0.880
0.923
0.951
0.838
1.416
1.036*
0.694
0.426
0.369
0.629
0.640
1.698
1.308
1.169
2.023
0.187
0.626
0.655
0.617
0510
0.255
0.298
0.632
0.890
1.000
0.944
1.315
0.644
0.409
0.543
0.363
0.757
1.288
0.794
1.256
0.394
1.000
0.716
1.000
3.220

0.809
0.803
0.830
0.872
0.667
0.751
0.802
0.819
0.764
1.632
1.260*
0.935
0.613
0.568
0.884
0.879
1.941
1.497
1.332
2.279
0.216
0.487
0.482
0.396
0.252
0.089
0.168
0.771
0.758
0.988
0.827
1.208
0.401
0.321
0.463
0.294
0.757
1.244
0.827
1.716
0.307
0.882
0.465
1.157
3.536

0.982
0.971
0.955
0.918
0.749
0.820
0.884
0.887
0.773
1.277*
0.892
0.623
0.405
0.300
0.607
0.575
1.487
1.084
0.943
1.787
0.236
0.374
0.448
0.392
0.450
0.208
0.354
0.476
0.590
0.659
0.595
1.000
0.457
0.543
0.418
0.175
0.662
0.914
0.584
1.277
0.108
0.965
0.531
0.831
2.927

16.5
16.4
16.3
16.2
18.3
18.3
16.8
16.4
16.3
17.2
18.2
18.4
16.7

11.7
11.0
10.7
10.4
15.6
15.2
10.8
10.1
9.8
14.5
10.3
9.3
10.9

20.6
20.3
20.2
20.1
9.6
9.3
25.3
23.4
22.4
20.1
15.7
14.6
22.2

1.065
1.193
1.169

1.221
1.195

1.398
1.377

1.212
1.169

1.117
1.422
1.430

1.325

1.567
1.158

1.006

1.000
1.018
1.170
dx.doi.org/10.1021/ef401690f | Energy Fuels XXXX, XXX, XXXXXX

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Table 2. continued
units of MPa(1/2)

solvents

59. EG/acetone 70/30


60. EG/acetone 60/40
61. EG/acetone 50/50
62. diethylene glycol/m-cresol 90/10
63. diethylene glycol/m-cresol 80/20
64. diethylene glycol/m-cresol 70/30
65. EG/propan-2-ol 80/20
66. EG/propan-2-ol 70/30
67. EG/propan-2-ol 60/40
68. EG/propan-2-ol 50/50
69. ethanolamine/DMF 60/40
70. ethanolamine/DMF 40/60
71. DMSO/ethanol 90/10
72. DMSO/ethanol 80/20
73. ethanolamine/ethanol 70/30
74. ethanolamine/ethanol 60/40
75. ethanolamine/ethanol 40/60
76. diethylene glycol/1MP 90/10
77. diethylene glycol/1MP 60/40
78. diethylene glycol/1MP 50/50
79 EG/aniline 70/30
80. EG/aniline 50/50
81. EG/aniline 40/60
82. EG/methanol/octan-1-ol 50/40/10
83. EG/methanol/octan-1-ol 50/20/30
84. EG/methanol/DMF 50/30/20
85. EG/methanol/DMF 50/10/40

16.6
16.4
16.3
16.7
16.9
17.0
16.8
16.6
16.5
16.4
17.2
17.2
18.1
17.9
16.6
16.5
16.3
16.7
17.2
17.3
17.7
18.2
18.4
16.2
16.6
16.5
17.0

10.8
10.8
10.7
11.3
10.6
9.9
10.0
9.5
9.0
8.6
14.8
14.4
15.6
14.9
13.5
12.8
11.5
12.1
12.1
12.2
9.2
8.1
7.5
10.8
9.0
11.9
12.2

20.3
18.4
16.5
19.9
19.1
18.4
24.1
23.1
22.2
21.2
17.2
15.3
11.1
12.0
20.7
20.5
20.1
19.6
15.3
14.0
21.3
18.1
16.5
23.1
21.0
22.0
19.8

soybean

coconut

palm

RED

RED

RED

castor
RED
1.014

1.071

1.070
1.082
1.000
1.135

1.059

1.238
1.308
1.214

1.287

1.296

1.282

1.286

1.198

1.206

1.431
1.241
1.146
1.389
1.326
1.419
1.002
1.007

1.001
1.024
1.090

1.197

1.056
1.114
1.237

1.197

1.200

1.427

1.268

1.271

1.444

1.181

Ethylene glycol. bEthylene glycol monobutyl ether acetate. cDimethylformamide. d1-Methyl-2-pyrrolidone. eDimethyl sulfoxide.

biofuels in the 45 pure solvents shown in Table 2. Figure 4d


represents a dimensional graph of a = P + H versus D, which
accentuates the combined eect of the polar and hydrogenbonding interactions on the four biofuels. It can be seen in Figure
4ad that using only the 45 pure solvents would not be sucient
to generate dierent HSPs for soybean biodiesel, coconut
biodiesel, and palm biodiesel, and therefore the use of solvent
mixtures (bad/good solvents) is a good technique for dierentiating the solubility of materials with similar chemical
structures.
3.2. Solubility Parameter Calculated for Biodiesel by
the Van Krevelen and StefanisPanayiotou Methods.
The general equation for the calculation of the three solubility
components of the biodiesel is as follows:

Figure 1. Comparison of RED values for biofuels.

use as an additive in products based on a mineral oil lubricant.39


Figure 2ad show the Hansen spheres plotted using threedimensional axes for the biofuels in 45 solvents + 15 solvent
mixtures. The blue symbols represent the solvents that dissolved
the biodiesels (good solvents) while the symbols in red represent
the solvents and solvent mixtures in which the biodiesels were
insoluble (bad solvents). It is evident that there were three bad
solvents with RED 1, due to high values for polar and
hydrogen-bonding interactions for ethylene glycol, glycerol, and
water, in the range from 11.0 to 16.0 and 26.042.3 MPa1/2.
Figure 3ad show the importance of using solvent mixtures such
as ethanolamine/aniline, ethylene glycol/acetone, and diethylene glycol/1-methyl-2-pyrrolidone, which have RED values
close to 1. This is an important factor in dening the region of
solubility.
Figure 4 shows the three-dimensional (Figure 4a) and twodimensional (Figures 4bd) contour plots of the HSPs for the

X = ( xixm)
i

(29)

where xi is the weight of the fatty acid methyl ester fractions


present in the soybean biodiesel, coconut biodiesel, palm
biodiesel, and castor biodiesel, the fractions being provided by
Gustone et al.40 For example, the approximate composition of
soybean biodiesel is 11.9% methyl palmitate, 4.3% methyl
stearate, 22.5% methyl oleate, 54.4% methyl linoleate, and 6.9%
methyl linolenate; the factor mx is the average of the solubility
parameters of the methyl esters obtained by the van Krevelen and
StefanisPanayiotou methods (see Table 3). The results of such
calculations are reported in Table 4.
As in the optimization method, the values for the HSPs
predicted by group contribution methods for soybean biodiesel
(D, P, H = 16.1, 1.6, 3.8), coconut biodiesel (D, P, H = 16.0,
F

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Figure 2. HSPs of biofuels in solvents + mixtures of solvents (a) soybean biodiesel, (b) coconut biodiesel, (c) palm biodisel, (d) castor biodiesel.

Figure 3. Solvent mixtures with RED values close to 1.000 for solvents (a) soybean biodiesel, (b) coconut biodiesel, (c) palm biodisel, (d) castor
biodiesel.

1.8, 4.2), and palm biodiesel (D, P, H = 16.1, 1.6, 3.6) were
similar, whereas those for castor biodiesel (D, P, H = 16.4, 3.3,
8.7) were higher. The fatty acid methyl esters present in these
biofuels represent a range of hydrocarbon chain lengths from C8
to C18, with 0 to 3 double bonds per ester and one C18OH
(hydroxyl). The CCOO group is a small portion of the molecule

that has a small dipole moment and poor ability to participate in


forming hydrogen bonds. For this reason, there was little
variation in the values for P and H of the methyl caprylate and
methyl linoleate. The only exception was the ricinoleate, which
has a functional hydroxyl group at C-12, which explains the
higher values obtained for the P and H of this ester as compared
G

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Figure 4. (a) Spherical region characterizing four biofuels in 45 pure solvents, (b) two-dimensional plot of P versus D, (c) two-dimensional plot of H
versus D, (d) two-dimensional plot of a versus D.

did not obey the approach of 5 MPa1/2. The variation in


of 13.514.3 MPa1/2 for soluble and 14.016.0 MPa1/2 for
insoluble, as in the optimization method, ethanol and methanol
(wrong out) did not t as soluble solvents, exhibiting the same
solubility error.
Comparative solubility methodologies can be used, such as
those of Greenhalgh et al.41 (eq 31) and Bagley et al.42 (eq 32)

to the others. Other studies27,28 have shown similar results for the
fatty acid methyl esters, where the results for the P and H
parameters were characterized by the presence of two oxygen
atoms from the functional group (CCOO) and the absence of
the electropositive hydrogen atom. As can be seen in Table 3, by
increasing the number of CH2 groups in one molecule of the
ester, the dispersion solubility parameter (D) increases, due to
the intermolecular forces (van der Waals forces). The structural
characteristics of the various fatty acid esters making up the
biodiesel, such as chain length, degree of unsaturation, and chain
branching, determine the overall properties of the biodiesel.
3.2.1. Theoretical Solubility of the Biofuels. The values of the
solubility parameters calculated by the group contribution
methods were then used to study the theorical solubility of the
four biofuels and the pure solvents listed in Table 2, using the
methodology developed by van Krevelen,18 Greenhalgh et al.,41
and Bagley et al.42 The dierence between the solubility
parameter of the solvent (s) and the biodiesel (bio) could then
be determined using the factor.
=

t = |ts tbio|
Rv =

4(vs vbio)2 + ( Hs Hbio)2

(31)

(32)

Greenhalgh et al. demonstrated that, in general, materials with


t < 7 MPa1/2 are soluble and t > 7 MPa1/2 are insoluble.16,41
The parameter v = (D + P)1/2 is the volume-dependent
solubility parameter. Bagley et al. concluded that the eects of D
and P were thermodynamically similar, while the eect of H was
quite dierent in nature.42
For the Greenhalgh solubility model (see Table 6), the
solvents cyclohexane, 4-methylpentan-2-one, and n-butyl acetate
were the best solvents for soybean biodiesel, coconut biodiesel,
and palm biodiesel. For castor biodiesel (with t > 7 MPa1/2),
-methylstyrene, butanone, and nitrobenzene were the best
solvents. This approach also introduced errors in the
classication solubility of the solvents (ethanol, methanol,
dimethyl sulfoxide) with the variation of t of 6.98.7
MPa1/2 being soluble and 7.810.3 MPa1/2 being insoluble.
According to the predictions for solubility by the Bagley
approach (Table 7), 4-methylpentan-2-one, n-butyl acetate, and
o-xylene were the best solvents for soybean biodiesel and palm
biodiesel, and 4-methylpentan-2-one, n-butyl acetate, and diethyl
ether were the best solvents for the coconut biodiesel. For castor
biodiesel, ethylene glycol monobutyl ether acetate, n-butyl
acetate, and tetrahydrofuran were the best solvents. The variation

( Ds Dbio)2 + ( Ps Pbio)2 + ( Hs Hbio)2


(30)

For good solubility between the solvent and biodiesel, the


dierence between the solubility parameters should be 5
MPa1/2.14,18 However, some studies16,43 showed variable
experimental systems that were miscible and were therefore
not provided for by this condition.
According to eq 30, the sequence of solubility of the biofuels in
the solvents can be calculated and is shown in Table 5. The
solvents o-xylene, diethyl ether, and toluene are the best solvents
for the soybean and palm biodiesels, whereas o-xylene, diethyl
ether and -methylstyrene were best for the coconut biodiesel
and ethylene glycol monobutyl ether acetate n-butyl acetate and
tetrahydrofuran for the castor biodiesel. However, these biofuels
H

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Article

5.9
5.7
5.2
4.2
3.6
3.2
3.5
3.9
4.2
9.3

16.7
17.0
16.9
16.7
16.4
16.3
16.6
16.7
16.8
19.2

Table 4. HSPs Calculated for the Biofuels According to eq 29

2.7
2.4
2.1
1.9
1.6
1.4
1.5
1.6
1.7
3.5
15.4
15.9
16.0
16.0
16.0
15.9
16.1
16.2
16.2
16.4
17.1
17.0
16.8
16.5
16.3
16.2
16.4
16.8
17.1
19.9
5.7
5.6
5.1
3.3
2.6
1.8
2.4
3.1
3.7
9.7
2.8
2.5
2.2
2.0
1.7
1.4
1.5
1.7
1.8
4.9

D MPa(1/2)

P MPa(1/2)

H MPa(1/2)

T MPa(1/2)

soybean
coconut
palm
castor

16.1
16.0
16.1
16.4

1.6
1.8
1.6
3.3

3.8
4.7
3.6
8.7

16.6
16.8
16.6
18.8

4. CONCLUSION
The HSPs and solubility spheres for four dierent biofuels were
determined by a solubility test in 45 solvents (with known
solubility parameters) and mixtures of solvents (with calculated
solubility parameters). The results of the solubility test were then
used to determine more accurate values for the HSPs and a
smaller R0 by the optimization method.
The solubilities of the soybean and coconut biodiesels were
very similar, leading to small dierences in the solubility
parameters. The D value of the palm biodiesel was also very
similar to those of the coconut and soybean biodiesels, but the
value for P was higher and that for H lower. The castor biodiesel
was soluble in strongly polar solvents such as methanol,
acetonitrile, and dimethyl sulfoxide, resulting in higher P and
H values.
The HSP values of the biofuels, derived using group
contribution methods, were empirically investigated for their
solubility in 45 solvents, using the van Krevelen, Grenhalgh, and
Bagley approaches. o-Xylene and ethylene glycol monobutyl
ether acetate were the best solvents according to the van
Krevelen approach, cyclohexane and -methylstyrene by the
Greenhalgh approach, and diethyl ether and 4-methylpentan-2one by the Bagley approach.
Group contribution methods to calculate the HSPs of the
biofuels are based on the knowledge of structural fragments of
fatty acid methyl esters. There is still a dierence between the
estimated and experimental methods, as errors exist for the
carboxyl functional group. The polar solubility parameter
(coming from the carboxyl functional group (CCOO)) provided
by the group contribution methods (Table 4) was substantially
lower than expected, especially if compared with the
experimental values shown in Table 1. The optimization method
is superior to other methods because it considers the bad
solvents data also as a part of the procedure for obtaining the
HSPs. These methods are based on the like dissolves like
principle and are useful approaches for the solubility problem.

6.0
5.7
5.3
5.0
4.5
4.5
4.6
4.6
4.6
8.9

Units are MPa1/2 for the D, P and H parameters.

2.6
2.3
2.0
1.8
1.5
1.4
1.5
1.5
1.5
2.1

AUTHOR INFORMATION

Corresponding Author

*Tel.: 55 19 3521 3964. Fax: 55 19 3521 3965. E-mail: mak@feq.


unicamp.br.
Notes

The authors declare no competing nancial interest.

14.9
15.9
16.0
16.0
15.9
15.8
16.0
15.9
15.7
16.1
CH3(CH2)5COOCH3
CH3(CH2)7COOCH3
CH3(CH2)9COOCH3
CH3(CH2)11COOCH3
CH3(CH2)13COOCH3
CH3(CH2)15COOCH3
CH3(CH2)7CHCH(CH2)7COOCH3
CH3(CH2)4CHCHCH2CHCH(CH2)7COOCH3
CH3CH2CHCHCH2CHCHCH2CHCH(CH2)7COOCH3
CH3(CH2)5CH(OH)CH2CHCH(CH2)7COOCH3
methyl caprylate
methyl caprate
methyl laurate
methyl myristate
methyl palmitate
methyl stearate
methyl oleate
methyl linoleate
methyl linolenate
methyl ricinoleate

biodiesel

in Rv was from 12.3 to 13.9 MPa1/2 for soluble and from 13.4
14.2 MPa1/2 for insoluble.
The acetonitrile, dimethylformamide, and dimethyl sulfoxide
solvents were not classied as soluble because the polar
parameter (P) predicted by eq 29 was substantially lower than
expected, especially if compared with the experimental values
shown in Table 2. A simple explanation was not found for the
behavior of the ethanol and methanol solvents. One explanation
may be that there are some aspects of solubility of such solvents
that are not fully covered by these theoretical methods.

16.3
17.0
17.0
16.9
16.6
16.5
16.7
16.6
16.4
18.5

15.9
15.9
15.9
16.0
16.0
16.0
16.2
16.4
16.6
16.7

H
P
D
H
P
D
chemical formula
fatty acid methyl esters

Table 3. Calculated values for the HSPs of the Fatty Acid Methyl Estersa

van KrevelenHoftyzer

StefanisPanayiotou

mean

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>14.0

<13.5

>16.0

<14.4

>16.0

<13.9

EGMEA < n-butyl acetate tetrahydrofuran < ethyl acetate anisole < octan-1-ol 1,4-dioxane < aniline < diethyl ether <. diethyl malonate < hexan-1-ol < m-cresol < cyclohexanone <4-methylpentan2-one < -methylstyrene < o-xylene < nitrobenzene < pyridine < butanone < toluene <1,2-dichloroethane < acetone < n-butanol < benzene 2-methyl propan-1-ol < ethylbenzene < cumene < propan2-ol < carbon tetrachloride < cyclohexane <11MP < n-hexane n-heptane < DMF < formic acid < ethanol < DMSO < triethylene glycol
diethylene glycol < acetonitrile < methanol < ethanolamine < EG < glycerol < water

o-xylene < toluene diethyl ether < -methylstyrene < ethylbenzene < cumene < benzene < n-butyl acetate < cyclohexane < carbon tetrachloride < n-heptane < anisole < n-hexane <4-methylpentan-2-one
1,4-dioxane < ethyl acetate < EGMEA cyclohexanone < tetrahydrofuran <1,2-dichloroethane < nitrobenzene < butanone < diethyl malonate < pyridine < aniline < octan-1-ol < acetone < hexanol <
m-cresol <1MP < n-butanol <2-methyl propan-1-ol < propan-2-ol < DMF
DMSO < acetonitrile < formic acid < ethanol < triethylene glycol < diethylene glycol < methanol < ethanolamine < EG < glycerol < water

o-xylene diethyl ether < -methylstyrene < n-butyl acetate < toluene < ethylbenzene < benzene cumene < anisole <4-methylpentan-2-one 1,4-dioxane carbon tetrachloride < cyclohexane < nheptane EGMEA ethyl acetate < n-hexane < cyclohexanone < tetrahydrofuran <1,2-dichloroethane < nitrobenzene < diethyl malonate < butanone < aniline < pyridine < octan-1-ol < acetone <
hexan-1-ol < m-cresol <1MP < n-butanol <2-methyl propan-1-ol < propan-2-ol < DMF
DMSO < formic acid < acetonitrile < ethanol < triethylene glycol < diethylene glycol < methanol < ethanolamine < EG < glycerol < water

o-xylene < diethyl ether < toluene -methylstyrene < ethylbenzene < benzene cumene n-butyl acetate < cyclohexane carbon tetrachloride < n-heptane anisole < n-hexane <4-methylpentan-2one 1,4-dioxane < ethyl acetate < EGMEAc < cyclohexanone < tetrahydrofuran <1,2-dichloroethane < nitrobenzene < butanone < diethyl malonate < pyridine aniline < octan-1-ol < acetone <
hexan-1-ol < m-cresol <1MPd < n-butanol <2-methyl propan-1-ol < propan-2-ol < DMFe
DMSOf < formic acid < acetonitrile < ethanol < triethylene glycol < diethylene glycol < methanol < ethanolamine < EGg < glycerol < water

solvent sequencea

all insoluble except acetonitrile and methanol

all insoluble except ethanol


all soluble

all insoluble except ethanol


all soluble

all insoluble except ethanol


all soluble

all soluble

solubilityb

The sequence of solvent power obtained using eq 30. bDetermined experimentally (see Table 2). cEthylene glycol monobutyl ether acetate. d1-Methyl-2-pyrrolidone. eDimethylformamide. fDimethyl
sulfoxide. gEthylene glycol.

castor

palm

coconut

<14.3

soybean

>16.0

(MPa1/2)

biodiesel

Table 5. The Solvent Sequences for the Biofuels According to the Values and the Experimental Results

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>10.3

<8.7

>7.8

<7.0

>7.8

<6.9

-methylstyrene butanone nitrobenzene < benzene < EGMEA 1,2-dichloroethane < anisole tetrahydrofuran < toluene cumene cyclohexanone ethyl acetate < diethyl malonate < o-xylene
ethylbenzene carbon tetrachloride < acetone < n-butyl acetate <1,4-dioxane <4-methylpentan-2-one < cyclohexane < octan-1-ol hexan-1-ol < pyridine < diethyl ether < n-heptane aniline <2-methyl
propan-1-ol < m-cresol < n-hexane <1MP < n-butanol < propan-2-ol < acetonitrile < DMF < formic acid < ethanol < DMSO < triethylene glycol
diethylene glycol < methanol < ethanolamine < EG < glycerol < water

cyclohexane <4-methylpentan-2-one < n-butyl acetate < diethyl ether < carbon tetrachloride < n-heptane o-xylene ethylbenzene < toluene cumene ethyl acetate < n-hexane < benzene EGMEA
1,2-dichloroethane < nitrobenzene < -methylstyrene butanone < anisole tetrahydrofuran < cyclohexanone < diethyl malonate < acetone <1,4-dioxane < octan-1-ol < hexan-1-ol < pyridine < aniline
<2-methyl propan-1-ol m-cresol <1MP < n-butanol < propan-2-ol
acetonitrile < DMF < formic acid < ethanol < DMSO < triethylene glycol < diethylene glycol < methanol < ethanolamine < EG < glycerol < water

cyclohexane <4-methylpentan-2-one < n-butyl acetate < diethyl ether < ethylbenzene carbon tetrachloride < n-heptane o-xylene ethyl acetate < cumene < n-hexane < EGMEA < benzene <1,2dichloroethane < nitrobenzene < -methylstyrene butanone < anisole tetrahydrofuran < cyclohexanone < diethyl malonate < acetone <1,4-dioxane < octan-1-ol < hexan-1-ol < pyridine < aniline <2methyl propan-1-ol < m-cresol <1MP < n-butanol < propan-2-ol
acetonitrile < DMF < formic acid < ethanol < DMSO < triethylene glycol < diethylene glycol < methanol < ethanolamine < EG < glycerol < water

cyclohexane <4-methylpentan-2-one < n-butyl acetate < diethyl ether < ethylbenzene carbon tetrachloride < n-heptane o-xylene < toluene ethyl acetate < cumene < n-hexane < EGMEAc < benzene
1,2-dichloroethane < nitrobenzene < butanone < -methylstyrene < anisole tetrahydrofuran < cyclohexanone < diethyl malonate < acetone <1,4-dioxane < octan-1-ol hexan-1-ol < pyridine < aniline
<2-methyl propan-1-ol < m-cresol <1MPd < n-butanol < propan-2-ol
acetonitrile < DMFe < formic acid < ethanol < DMSOf < triethylene glycol < diethylene glycol < methanol < ethanolamine < EGg < glycerol < water

solvent sequencea

all insoluble
except
methanol

all insoluble
except
DMF and
ethanol
all soluble

all insoluble
except
DMF and
ethanol
all soluble

all insoluble
except
DMF and
ethanol
all soluble

all soluble

solubilityb

The solvent power sequence obtained using eq 31. bDetermined experimentally (see Table 2). cEthylene glycol monobutyl ether acetate. d1-Methyl-2-pyrrolidone. eDimethylformamide. fDimethyl
sulfoxide. gEthylene glycol.

castor

palm

coconut

<7.0

soybean

>7.8

T
(MPa1/2)

biodiesel

Table 6. The Solvent Sequences for the Biofuels According to the T Values and the Experimental Results

Energy & Fuels


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dx.doi.org/10.1021/ef401690f | Energy Fuels XXXX, XXX, XXXXXX

>14.2

<13.9

>13.9

<12.9

>13.4

<12.3

EGMEA < ethyl acetate < tetrahydrofuran < diethyl malonate < n-butyl acetate < octan-1-ol < anisole < hexan-1-ol < acetone < nitrobenzene <4-methylpentan-2-one < butanone <1,4-dioxane < diethyl
ether < cyclohexanone < m-cresol < o-xylene < -methylstyrene <1,2-dichloroethane < aniline < n-butanol < toluene <2-methyl propan-1-ol < benzene < ethylbenzene < propan-2-ol < cumene < carbon
tetrachloride < cyclohexane < formic acid < pyridine < n-heptane < n-hexane <1MP < ethanol < DMF < triethylene glycol < acetonitrile
diethylene glycol < methanol < DMSO < ethanolamine < e < glycerol < water

4-methylpentan-2-one < n-butyl acetate < o-xylene < diethyl ether < cyclohexane < ethyl acetate < ethylbenzene nitrobenzene < n-heptane < toluene <1,2-dichloroethane < n-hexane carbon
tetrachloride < cumene egmea butanone < benzene < -methylstyrene < anisole < tetrahydrofuran < cyclohexanone < diethyl malonate < acetone <1,4- dioxane < octan-1-ol < hexan-1-ol < pyridine
< aniline < m-cresol <1MP < 2-methyl propan-1-ol n-butanol < propan-2-ol
formic acid < DMF < acetonitrile < ethanol < triethylene glycol < DMSO < diethylene glycol < methanol < ethanolamine < EG < glycerol < water

4-methylpentan-2-one < n-butyl acetate < diethyl ether < ethyl acetate < o-xylene < nitrobenzene < EGMEA < cyclohexane < ethylbenzene < n-heptane toluene 1,2-dichloroethane < butanone < nhexane < anisole tetrahydrofuran carbon tetrachloride < benzene cumene -methylstyrene < diethyl malonate < cyclohexanone < acetone <1,4-dioxane < octan-1-ol < hexan-1-ol < pyridine <
aniline < m-cresol <2-methyl propan-1-ol n-butanol <1MP < propan-2-ol
formic acid < DMF < acetonitrile < ethanol < triethylene glycol < DMSO < diethylene glycol < methanol < ethanolamine < EG < glycerol < water

4-methylpentan-2-one < n-butyl acetate < o-xylene < diethyl ether < ethyl acetate < cyclohexane nitrobenzene < ethylbenzene < n-heptane toluene 1,2-dichloroethane < EGMEAc butanone < nhexane carbon tetrachloride < cumene < benzene < -methylstyrene < anisole < tetrahydrofuran < cyclohexanone diethyl malonate < acetone <1,4-dioxane < octan-1-ol < hexan-1-ol < pyridine <
aniline < m-cresol <1MPd < 2-methyl propan-1-ol n-butanol < propan-2-ol
formic acid < DMFe < acetonitrile < ethanol < triethylene glycol < DMSOf < diethylene glycol < methanol < ethanolamine < EGg < glycerol < water

solvent sequencesa

all insoluble except methanol and


DMSO

all insoluble except DMF


and ethanol
all soluble

all insoluble except DMF


and ethanol
all soluble

all insoluble except DMF


and ethanol
all soluble

all soluble

solubilityb

The solvent sequence power obtained using eq 32. bDetermined experimentally (see Table 2). cEthylene glycol monobutyl ether acetate. d1-Methyl-2-pyrrolidone. eDimethylformamide. fDimethyl
sulfoxide. gEthylene glycol.

castor

palm

coconut

<12.7

soybean

>13.7

Rv
(MPa1/2)

biodiesel

Table 7. The Solvent Sequences for the Biofuels According to the Rv Values And The Experimental Results

Energy & Fuels


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dx.doi.org/10.1021/ef401690f | Energy Fuels XXXX, XXX, XXXXXX

Energy & Fuels

Article

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ACKNOWLEDGMENTS
The authors are grateful to CAPES for its nancial support.
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