Fluid Phase Equilibria 145 1998.

5368

Prediction and correlation of triglyceridesolvent solidliquid

equilibria with activity coefficient models
R.L. Smith Jr. ) , G.M. Acosta, K. Arai
Department of Chemical Engineering, Tohoku Uniersity, Aoba Aza Aramaki, Sendai 980-77, Japan
Accepted 10 October 1997

Abstract
Solidliquid equilibria SLE. for solventtriacylglyceride TAG. systems are studied with activity coefficient models. Systems consisted of 29 data sets of C10:0 to C18:0 saturated triglycerides in nine solvents,
benzene, acetone, carbon disulfide, carbon tetrachloride, chloroform, diethyl ether, ethanol, ethyl acetate, and
n-hexane making up 562 data points. Eighteen activity coefficient models containing 02 fitting parameters
were evaluated including a number of Flory Free Volume FFV. and Entropic Free Volume FEFV. models
evaluated by Coutinho et al. wJ.A.P. Coutinho, S.I. Andersen, E.H. Stenby, Evaluation of activity coefficient
models in prediction of alkane solidliquid equilibria, Fluid Phase Equilibria 103 1995. 2339x, the UNIFAC
model and its variations, the Wilson, UNIQUAC, and van Laar equations and some proposed modifications of
the FEFV and UNIFAC models. The modifications were as follows: i. a Flory type x parameter was added to
the FEFV model FEFV-X. and ii. the exponent in the UNIFAC combinatorial term was treated as a fitting
parameter UNIFAC-C .. Models were compared in terms of absolute average percent deviation AAPD. in
temperature. The best predictive model for TAGsolvent systems was found to be the Dortmund version of
UNIFAC. Addition of a fitting parameter to the UNIFAC models provided significant improvement. For the
UNIFAC-1977, UNIFAC Lyngby. and UNIFAC Dortmund., these exponents were found to be 0.897, 0.858,
and 0.749, respectively. The best single parameter correlative model was found to be the FEFV-X model, which
gave an AAPD of 0.305%. The Wilson equation was the best two parameter correlation equation and provided
an AAPD of 0.154%. q 1998 Elsevier Science B.V.
Keywords: Theory; Excess functions; Methods of calculation

1. Introduction
The solubility of triacylglycerides TAGs. in organic solvents is important for processing materials
such as collagen for production of sausage casing w1x. Recently, we have reported on the extraction of
)

Corresponding author.

0378-3812r98r19.00 q 1998 Elsevier Science B.V. All rights reserved.

PII S 0 3 7 8 - 3 8 1 2 9 7 . 0 0 3 0 3 - 8

R.L. Smith Jr. et al.r Fluid Phase Equilibria 145 (1998) 5368

54

fat from collagenfatwater mixtures with supercritical carbon dioxide and propane mixtures and
with liquid propane w2x. As a result of that study, it became important to compare models for
predicting and correlating TAG solubility in liquid solvents. In this work, we compare a number of
liquid models and show the importance of the entropic and enthalpic contributions.
Several works have evaluated models for predicting and correlating data related to this study.
Gmehling et al. w3x applied the UNIFAC model to the prediction of solidliquid equilibria SLE. and
eutectic systems with good results. Coutinho et al. w4x evaluated a number of predictive models for the
SLE of alkanealkane mixtures. They concluded that a FloryHuggins, Regular Solution, modified
UNIFAC, and original entropic free-volume models could not describe the liquid phase of alkane
systems accurately and that the Flory free volume and modified entropic free-volume models were the
simplest and most reliable. Fornari et al. w5x examined a number of UNIFAC models for the liquid
phase activity of vegetable oilhexane mixtures for vaporliquid equilibria calculations and concluded that the UNIFAC-3r4 model gave a better description of the infinite dilution hexane solvent
activity coefficients. Other researchers have evaluated activity coefficient models for specific experimental data sets that are related to this work from the point of view of model performance or system
similarity. Domanska w6x reported on the solubility of long-chain C 17 C 21 . ethylene glycol monoesters correlated with the Wilson model and found that the model provided partly satisfactory
results. Roberts et al. w7x reported on the solubility of long chain alkanes in heptane correlated with
regular solution, FloryHuggins, and HaulaitPirson models and concluded that the FloryHuggins
model tended to overestimate the solubility while the HaulaitPirson model gave the best agreement.
However, no studies have been performed on evaluation of models for TAGsolvent SLE. The
objective of this work is to correlate and predict TAGsolvent SLE with a number of liquid activity
coefficient models and to provide a set of recommendations.

2. Thermodynamics
The thermodynamics of SLE is derived in standard texts such as Ref. w8x. For the general
equilibrium between i components at constant T and P:
x isg is f ios s x ilg il f iol

1.

For a pure solid phase, the left-hand side of Eq. 1. becomes the fugacity of the pure solid. The
right-hand side contains the activity coefficient referenced to the standard state fugacity, f 1ol , that is
the hypothetical state of the solid component in the liquid state at the system temperature and under
its own saturation pressure. The solid fugacity and the standard state fugacity in the liquid are
normally written as a ratio. For a binary system with solid component 1:
f 1osrf 1ol s x 1l g 1l

2.

Consideration of a thermodynamic path to bring component 1 from the solid state to the hypothetical
liquid state in solution with the solvent at system temperature and assuming that the DCp is constant
and that the triple point can be approximated by the melting point, leads to evaluation of this ratio as:
ln x 1 s

D h fus
RT

1y

Tt
T

DCp
R

1y

Tt
T

DCp
R

ln

Tt
T

y lng 1

3.

R.L. Smith Jr. et al.r Fluid Phase Equilibria 145 (1998) 5368

55

Eq. 3. can be used to determine the solubility of a solid in a liquid. The DCp terms are normally
small and were set equal to zero in this work. Mishra and Yalkowsky w9x showed that this was a better
approximation than setting DCp equal to D St . Eq. 3. contains the assumption that only a single solid
phase is present. When the solid goes through a solidsolid transition, additional terms must be
included as discussed in Ref. w10x.
TAGs are known to exist in three main polymorphic states, denoted as the a-modification, the
b X-modification and the b-modification w11x. The a-modification is unstable and converts on the
order of seconds to the b X-modification. The b X-modification is the stable modification for odd-chain
TAGs and some even number TAGs. The b-modification is the most stable conformation. All three
modifications can be obtained by varying the degree of supercooling from the liquid phase. For
prediction and correlation in this work, only presence of the most stable b-modification was assumed,
which is appropriate since the mixtures in this work are even-monoacid TAG solvent systems.
Equilibrium between mixed TAG systems in the absence of solvents can be obtained from the work of
Wesdorp w12x.

3. Activity coefficient models

The activity coefficient can be written in terms of a combinatorial term, g icomb, a free volume term,
g and a residual term, g ires , as shown in Ref. w13x:
fv
i ,

lng i s lng icomb q lng ifv q lng ires

4.

The combinatorial term corresponds to the entropic contribution to the activity according to size and
shape and the free volume term corresponds to the entropic contribution according to size differences.
The residual term accounts for energetic interactions that are associated with the enthalpic contribution to the activity coefficient.
For this work, we evaluated a number of models that can be discussed in terms of Eq. 4. as shown
in Table 1. The FloryHuggins Flory. model w14,15x only contains a combinatorial term. The Flory
Free Volume FFV. model w16x and the Flory Entropic Free Volume FEFV. model w13x contain
combinatorial and free volume terms. The FloryHuggins model relates solution activity to volume
fraction whereas the models for the FFV and FEFV include a correction for the free volume by
subtracting off the Bondi 0 K close packed volume w17x from the molar volume of the liquid at a
given temperature. For these models, the solution is assumed to be a thermal and the residual term of
the activity that corresponds to the enthalpic contribution is set equal to zero. The Flory-x model
contains a residual term that has a single adjustable parameter. In this work, we also examine adding a
Flory-x residual term to the FEFV model and this is denoted FEFV-X.
UNIFAC w18,3x are predictive models that contain both combinatorial and residual terms but no
corrections for free volume. The Lyngby group w19x developed an improved UNIFAC that provided
superior heats of mixing and performance for larger molecules by eliminating the StavermanGuggenheim term in the combinatorial portion and introducing temperature dependent interaction
parameters. The Dortmund group w20x has developed the latest and most comprehensive versions of
UNIFAC which are continually are being updated with the Dortmund databank. The UNIQUAC-2r3

56

R.L. Smith Jr. et al.r Fluid Phase Equilibria 145 (1998) 5368

Table 1
Models evaluated
Model

Combinatorial and free volume terms

lng icomb qlng ifv s ln

FloryHuggins Flory.
Flory-x
Flory-Free Volume FFV.
Flory-Entropic Free Volume FEFV.
UNIFAC-77

UNIFAC-Lyngby 1987.
UNIFAC-Dortmund 1993.

UNIFAC-C
UNIQUAC r 2r3.

fi
xi

q1y

fi
xi

f i s x i Vi r x j Vj
f i s x i Vi r x j Vj
. 3 c r x j Vj 1r3 yVw1r3
. 3 c, cs1.1
f i s x i Vi1r3 yVw1r3
,i
,j
L
L
f i s x i Vi yVw ,i . r x j Vj yVw , j .
L s1yVw,small r Vw,large
lng icomb s ln f i r x i .q1y f i r x i
y z r2. qi ln u i rf i .
q1y f i ru i .
f s x i ri r x j r j
f i s x i rip r x j r jp, ps 2r3
lng icomb s1y f i qln f i .
y5qi 1yVi r Fi qln Vi r Fi ..
f s x i ri3r4 r x j r j3r4
f i s x i ricr x j r jc
lng icomb s ln f i r x i .
q z r2. qi ln u i rf i .
q l i y f i r x i . x j l j
f i s x i ri2r3 r x j r j2r3

Residual term
lng ires
y
s xf j2
y

s n k i.wln G k yln G k i. x

s n k i.wln G k yln G k i. x
s n k i.wln G k yln G k i. x
s n k i.wln G k yln G k i. x
y qi 1yln j u jt j,i .
j u jt i, j r k u kt k, j .

Flory, FFV, FEFV, UNIFAC are predictive models.

Flory-x , FEFV-X, UNIFAC-C each contain a single fitting parameter.
UNIQUAC-2r3, Wilson, van Laar each contain two fitting parameters.

model contains both combinatorial and residual terms with two fitting parameters in the residual term
for each binary pair. Wilson and van Laar models w8x contain two fitting parameters for each binary
pair and are known to provide accurate description of many solution activities. The Wilson model
essentially uses volume fractions in its formulation with a temperature dependence that is similar to
the UNIFAC and UNIQUAC residual terms.

4. Modification of UNIFAC configurational term

Various modifications to the combinatorial portions of the UNIFAC model have been made to
account for large size molecules such as polymers. Oishi and Prausnitz w21x developed the UNIFAC
method for polymer systems by introducing a free volume term based on Florys equation into the
activity coefficient framework in addition to the UNIFAC combinatorial term. In their theory, a
parameter c1 was used to modify the number of external degrees of freedom of the solvent along
with other functions that were based on a methylene subgroup reference. For their systems, c1 was
set equal to 1.1 although they noted that other values of c1 might be required. Kikic et al. w22x
developed the combinatorial 2r3 term that was used in the Lyngby version of UNIFAC. Fornari et al.

R.L. Smith Jr. et al.r Fluid Phase Equilibria 145 (1998) 5368

57

w5x found that for vegetable oilsolvent mixtures, an exponent of 3r4 in the UNIFAC combinatorial
term provided a better description of the boiling temperatures and solvent infinite dilution activity
coefficients. In this work, we have evaluated all versions of UNIFAC and in addition, we have treated
the exponent in the combinatorial terms as a fitting parameter. This is denoted as UNIFAC-C as
shown in the table. The functional form was first suggested by Donohue and Prausnitz w23x in their
interpolation method between the combinatorial entropy as given by an ideal solution and that given
by FloryHuggins.

5. TAGsolvent SLE data

Practically all TAGSLE data are dated to the 1950s and before. Data in Ref. w24x were abstracted
from Ref. w25x. The traceable data reference was found to be Ref. w26x. The original reference
contained a number of additional data over those abstracted in Ref. w24x or Ref. w25x. The data were
supplemented with the measurements in Refs. w27,28x to produce an initial data set in excess of 600
xT points. A small amount of TAGsolvent data for mixed TAGs w29x were not used because of
lack of melting point and heat of fusion data. After rejecting data points too close to the melting point
and data which showed extreme scatter in a log x vs. 1rT plot, the final data set consisted of 562
data points for five monoacid TAGs and in nine different solvents. Data in Ref. w27x were found to
differ greatly from the trends of group contribution equations such as UNIFAC and other data.
Although these data were included into data analyses, they are listed in the tables as separate data
sets.

6. TAGsolvent physical properties

Solvents and TAG properties extracted from the literature are shown in Tables 2 and 3. The stable
b form properties were used for the TAGs. Models that are based on volume fraction rather than
mole fraction require a molar volume at a given temperature. The temperature used is frequently taken
to be either the system temperature or a convenient reference such as 298.15 K. For these cases, the
Table 2
Solute physical properties and their literature sources
Substance

MW

Tc
wKx

Acentric
factor v

Vw
wcm3rmolx

V liq @T ref
wcm3rmolx

T ref
wKx

Tm
wKx

D H fus
wkcalrmolx

Tristearin SSS.
Tripalmitin PPP.
Trimyristin MMM.
Trilaurin LLL.
Tricaprin CCC.

891.49
807.33
723.17
639.01
554.49

914.3
903.1
892.1
859.7
825.9

1.708
1.630
1.542
1.441
1.392

604.89
543.51
482.13
420.75
359.37

1034.23
932.27
817.15
714.79
602.45

353.2
353.2
333.2
333.2
313.2

345.7
338.7
329.8
319.7
304.7

47.0
41.0
35.4
29.5
22.3

Sources: Tc , v : Ref. w30x; Bondi volume, Vw : Ref. w17x; Molar volume, V liq : Ref. w31x; Melting point temperature and heat of
fusion, Tm , D H fus : Ref. w32x.

R.L. Smith Jr. et al.r Fluid Phase Equilibria 145 (1998) 5368

58

Table 3
Solvent physical properties and their literature sources
Substance

MW

Tc
wKx

Acentric
factor v

Vw
wcm3rmolx

V liq @T ref
wcm3rmolx

T ref
wKx

Dipole
moment m wDx

Dielectric
constant

Benzene
Acetone
Carbon disulfide
Carbon tetrachloride
Chloroform
Diethylether
Ethanol
Ethyl acetate
n-Hexane

78.11
58.08
76.13
153.82
119.38
74.12
46.07
88.11
86.18

562.2
508.1
552.0
556.4
536.4
466.7
513.9
523.2
507.5

0.212
0.304
0.109
0.193
0.218
0.281
0.644
0.362
0.299

48.36
39.04
31.20
51.40
41.64
51.50
29.84
52.77
68.26

88.26
73.52
58.88
97.11
80.17
103.96
58.39
97.79
130.77

289
293
273
298
293
293
293
293
293

0
2.88
0.06
0
1.01
1.15
1.69
1.81
0.08

2.275
20.7
2.641
2.238
4.806
4.335
24.55
6.02
1.89

Sources: Tc , v , V liq : Ref. w31x; Bondi volume, Vw : Ref. w17x; m , : Ref. w33x.

Rackett equation w31x was used to extrapolate a reference density to obtain the hypothetical liquid
molar volume.

7. Solution method and objective function

Eq. 3. was solved with DZERO routine w34x that uses a combination of bracketing and step
searches depending on the value and sign of the function. Data were fit with an implementation of
NL2SOL w35,34x, which is a gradient search algorithm that takes Newton or GaussNewtonMarquardt
steps. The objective function O.F.. minimized was:
Error s

1
n

no . data points

is1

Texp y Tcalc
Texp

5.

Statistically, this form has the advantage over other O.F. such as those that compare mole fractions, in
that the calculated and experimental temperatures have the same order of magnitude. This means that
fitted values will not have a bias at higher and lower mole fractions.

8. TAGsolvent combinatorial and residual terms with UNIFAC

Fig. 1 shows TAGbenzene solvent combinatorial and residual terms plotted versus volume
fraction that were predicted from the UNIFAC 1977. model and calculated from the UNIFAC-C
model after fitting the experimental data. Only CCC and SSS are shown since other TAGs fall in
between these extremes. For this solvent, the combinatorial term is large compared with the residual
term and therefore entropic effects are much more important than enthalpic effects. At low volume
fractions, residual effects become important. As the dielectric constant or dipole moment of the

R.L. Smith Jr. et al.r Fluid Phase Equilibria 145 (1998) 5368

59

Fig. 1. Combinatorial and residual terms dashed lines. for tristearin SSS. and tricaprin CCC. in benzene as predicted by
the UNIFAC model dashdot line. and correlated by the UNIFAC-C model solid line. plotted against volume fraction of
the TAG. Volumes were calculated at the system temperature as described in the text.

solvent increases, as for acetone and ethanolTAG systems, the magnitude of the combinatorial and
residual terms become comparable. This behavior is important in understanding the performance of
activity models given in Table 1 and shown in detail below.

9. TAGsolvent SLE with UNIFAC and UNIFAC-C

The section discusses solubility calculations for a representative TAGnonpolar solvent system and
a representative TAGpolar solvent system. Fig. 2a shows solubility calculations for UNIFAC and
UNIFAC-C models, where the C was determined according to Eq. 5. for each binary system. For
CCC-benzene, the difference between the two models was small. However, as the size of the TAG
increased, entropic contributions increased and UNIFAC errors increased. The fitting parameter, C,
in the UNIFAC-C model greatly improved the accuracy. For polar solvents, the residual and
combinatorial terms become comparable as noted previously. Nevertheless, the C parameter also
improved the accuracy of UNIFAC for TAGacetone systems as shown in Fig. 2b. For the systems
studied, the system averaged parameter C was found to be close to 0.9 using the UNIFAC 1977.
parameters. For the Lyngby parameters w19x, the system averaged parameter C was found to be close
to 0.858 and for the Dortmund version w20x the system averaged parameter C was found to be close
to 0.749.

60

R.L. Smith Jr. et al.r Fluid Phase Equilibria 145 (1998) 5368

Fig. 2. Predicted and correlated solidliquid equilibria of TAGsolvent binary mixtures: a. benzene solvent; b. acetone
solvent. TAGs: tristearin SSS., triangles; tripalmitin PPP., filled circles; trimyristin MMM., squares; trilaurin LLL., filled
squares; tricaprin CCC. circles. Models: UNIFAC dashdot line.; UNIFAC-C solid line.. Data are those of Ref. w26x.

R.L. Smith Jr. et al.r Fluid Phase Equilibria 145 (1998) 5368

61

10. Evaluation of models

We evaluated all of the models in Table 1 and these results are summarized for all solvents in
Table 4. The systems were divided into nonpolar, slightly polar and polar groups. The Flory model
gave a qualitative description for most of the systems and greatly overpredicted the temperature as
shown by the mainly large positive bias values. The Flory model gave surprisingly good predictions
for the polar solvent systems. Adding a single parameter, x , to the Flory model that was determined
for each binary system greatly improved correlation as shown in the tables. There was only a small
improvement in the calculations when volume fractions were calculated at the system temperature as
opposed to 298 K as shown. The FFV and FEFV models gave good predictions for nonpolar systems
such as benzene but performed poorly as the solvent system became more polar. Addition of a Flory
type x parameter to the FFEV model to account for enthalpic effects, provided remarkable
correlation of the data as shown by the errors in the slightly polar and polar system tables. The
UNIFAC models provided fair ; 3% error. predictions for most systems. Adding the fitting
parameter C greatly improved the performance as shown in the table. By averaging all system data
as discussed below, a universal value of C s 0.897 was determined and this is shown as UNIFAC0.897 in the tables. The UNIFAC-0.897 model provided good prediction of the SLE data for most
systems. For the Lyngby and Dortmund versions of UNIFAC, the system averaged values of the

Table 4
Overall summary of temperature deviations for all systems
Model
Flory, 1 T.
Flory-X, 1 298K.
Flory-X, 1 T.
Flory-Free Volume FFV.
Flory-Entropic FEFV.
Flory-Entropic-X FEFV-X.
UNIFAC
UNIFAC-2r3
UNIFAC-3r4
UNIFAC-0.897
UNIFAC-C
UNIFAC L.
UNIFAC L.-C
UNIFAC D.
UNIFAC D.-C
UNIQUAC
van Laar
Wilson
Number of data points

All systems

Nonpolar

AAPD

BIAS

AAPD

7.828
2.148
2.123
2.234
2.185
0.305
2.719
3.040
2.606
1.976
0.553
1.769
0.279
1.066
0.385
0.274
0.179
0.154
562

22.612
3.617
3.567
0.790
y2.010
0.135
y7.655
5.203
2.633
y2.949
y0.034
3.910
0.047
y0.197
y0.026
0.351
0.063
0.000

8.078
2.096
2.070
2.123
1.854
0.350
1.598
2.572
1.949
0.999
0.349
2.243
0.331
0.781
0.325
0.374
0.207
0.207
227

Slightly polar

Polar

BIAS

AAPD

BIAS

AAPD

BIAS

23.771
3.725
3.668
1.840
0.218
0.051
y4.474
6.850
4.561
y0.364
0.117
5.417
y0.179
y0.520
y0.120
0.515
0.111
y0.089

7.416
1.927
1.898
2.485
2.075
0.275
4.234
2.667
2.826
3.340
0.927
1.884
0.333
1.433
0.446
0.229
0.144
0.123
31

20.993
3.133
3.078
2.444
y1.120
0.145
y11.947
y0.353
y2.631
y7.646
y0.191
3.507
0.291
0.800
0.173
0.248
0.057
0.049

8.198
2.754
2.742
1.918
3.154
0.271
1.802
4.887
3.550
1.082
0.166
0.477
0.043
0.870
0.380
0.156
0.194
0.106
104

23.679
4.455
4.432
y5.176
y8.850
0.297
y5.062
13.950
10.119
1.843
y0.017
1.513
y0.000
y1.710
y0.259
0.223
y0.030
0.089

Nonpolar solvents: benzene, carbon disulfide, carbon tetrachloride, n-hexane.

Slightly polar solvents: chloroform, diethyl ether, ethyl acetate.
Polar solvents: acetone, ethanol.

62

R.L. Smith Jr. et al.r Fluid Phase Equilibria 145 (1998) 5368

Fig. 3. Variation of UNIFAC exponent C in the combinatorial term versus absolute average percent deviation AAPD. in
temperature for all systems for original UNIFAC, UNIFAC-Lyngby, and UNIFAC-Dortmund.

parameter C were found to be 0.858 and 0.749, respectively. The UNIQUAC, Wilson, and van Laar
models, which contain two adjustable fitting parameters for each binary system, provided excellent
correlation of all data and all systems.

11. Overall evaluation

Using the UNIFAC-C model, we stepped C in 0.005 or so increments and recalculated all SLE
data and the resulting AAPD. Results are shown in Fig. 3 for each version of UNIFAC. The best
predictive model was found to be Dortmund version of UNIFAC. The Lyngby version of UNIFAC
and the FEFV, FFV models also provided good performance. The best single parameter model was
found to be FEFV-X followed by UNIFAC-C. The Wilson equation provided the best two parameter
fit of the data.

12. Model parameters

Parameters determined for one and two parameter models are shown in Tables 5 and 6. Within a
given solvent group, the parameters of all models showed some regularity as the TAG increased in
size from tricaprin to tristearin. Notable differences were observed in the data sets SSS q BZ 2. and
SSS q CF 2.. Only UNIFAC-C values seemed to be have less variation among solvent groups. Some
UNIFAC-C parameter values differed significantly from the proposed 0.897 value and so we explored

Table 5
Fitted constants for one-parameter models
Source

Flory-X 1
298 K.

Flory-X 1

Flory Entropic-X

UNIFAC-77 C

UNIFAC
-Lyngby C

UNIFACDortmund C

SSSqBZ
SSSqBZ
PPPqBZ
MMMqBZ
LLLqBZ
CCCqBZ
SSSqCS
MMMqCS
LLLqCS
CCCqCS
SSSqCT
SSSqHX
SSSqCF
SSSqCF
PPPqCF
MMMqCF
LLLqCF
SSSqDE
PPPqDE
MMMqDE
LLLqDE
CCCqDE
SSSqEA
SSSqAC
MMMqAC
LLLqAC
CCCqAC
SSSqET
CCCqET

1
2
1
1
1
1
1
1
1
1
2
2
1
2
1
1
2
1
1
1
1
1
2
3
3
3
3
1
1

y9.4439Eq00
y5.1166Eq00
y1.0532Eq01
y9.5303Eq00
y1.0322Eq01
y1.2691Eq01
y1.0558Eq01
y8.9327Eq00
y7.2738Eq00
y8.5216Eq00
y7.4906Eq00
y3.7629Eq00
y1.6066Eq01
y6.4001Eq00
y1.6451Eq01
y1.4832Eq01
y1.6200Eq01
y6.8952Eq00
y5.9607Eq00
y5.5181Eq00
y5.0148Eq00
y5.2020Eq00
y2.5403Eq00
3.2605Ey01
y5.4936Ey01
y1.0590Eq00
y1.8469Eq00
3.0580Eq00
1.3023Eq00

y9.4344Eq00
y5.0969Eq00
y1.0527Eq01
y9.5377Eq00
y1.0355Eq01
y1.2773Eq01
y1.0544Eq01
y8.9415Eq00
y7.2889Eq00
y8.5616Eq00
y7.4715Eq00
y3.7226Eq00
y1.6062Eq01
y6.3716Eq00
y1.6472Eq01
y1.4881Eq01
y1.6320Eq01
y6.8703Eq00
y5.9465Eq00
y5.5183Eq00
y5.0360Eq00
y5.2521Eq00
y2.5156Eq00
3.4705Ey01
y5.5254Ey01
y1.0666Eq00
y1.8671Eq00
3.0887Eq00
1.2984Eq00

2.4593Ey01
4.5768Eq00
y5.5123Ey01
y3.4416Ey01
y1.5648Ey01
y1.2493Eq00
1.0974Eq01
7.2222Eq00
5.7892Eq00
4.0607Eq00
4.0758Eq00
2.7398Eq00
2.6725Eq00
2.0275Eq00
1.6485Eq00
y4.1652Eq00
4.4479Eq00
y4.1584Eq00
y3.8829Eq00
y4.6403Eq00
3.5423Ey01
7.1976Ey01
7.3522Ey01
4.9535Ey01
y7.4000Ey04
1.4875Eq01
8.7655Eq00
5.7145Eq00
2.4693Eq00

8.8365Ey01
8.9149Eq02
0.0000Eq00
9.0550Ey01
7.2317Eq02
0.0000Eq00
8.6328Ey01
5.5850Eq02
0.0000Eq00
9.1271Ey01
7.2317Eq02
0.0000Eq00
9.4873Ey01
5.5850Eq02
0.0000Eq00
6.2854Ey01
8.9149Eq02
0.0000Eq00
9.8648Ey01
8.9149Eq02
0.0000Eq00
9.8310Ey01
7.2317Eq02
0.0000Eq00
1.0248Eq00
8.9149Eq02
0.0000Eq00
2.7815Ey01
7.2317Eq02

9.0975Ey01
5.6888Ey01
9.1225Ey01
9.3497Ey01
9.8145Ey01
9.1679Ey01
n.a.
n.a.
n.a.
n.a.
6.5225Ey01
8.3046Ey01
8.3001Ey01
8.8099Ey01
5.9736Ey01
9.2747Ey01
2.5824Ey01
9.1522Ey01
8.7115Ey01
9.0295Ey01
7.3267Ey01
6.7029Ey01
6.3232Ey01
6.1915Ey01
6.6180Ey01
8.5402Ey01
8.3182Ey01
6.9472Ey01
3.9692Ey01

8.0374Ey01
4.5603Ey01
7.6333Ey01
8.1991Ey01
7.8285Ey01
7.9000Ey01
5.4711Ey01
7.4220Ey01
7.3470Ey01
7.8758Ey01
6.7787Ey01
7.1131Ey01
7.0168Ey01
7.2048Ey01
6.4622Ey01
8.8211Ey01
4.5179Ey07
8.6797Ey01
8.1316Ey01
8.4004Ey01
8.0892Ey01
7.4585Ey01
6.9023Ey01
6.5807Ey01
6.5279Ey01
7.2491Ey01
6.4956Ey01
7.8945Ey01
6.8418Ey01

R.L. Smith Jr. et al.r Fluid Phase Equilibria 145 (1998) 5368

System

Key: BZ, benzene; CS, carbon disulfide; CT, carbon tetrachloride; HX, n-hexane; CF, chloroform; DE, diethyl ether; EA, ethyl acetate; AC, acetone; ET,
ethanol. n.a.: parameters not available.
Sources: 1, Ref. w26x; 2, Ref. w27x; 3, Ref. w28x.
63

64

Table 6
Fitted constants for two-parameter models
System

Source

UNIQUAC-2r3
u12

1
2
1
1
1
1
1
1
1
1
2
2
1
2
1
1
1
1
1
1
1
1
2
3
3
3
3
1
1

y1.4450Eq03
3.6037Eq03
8.1188Eq02
7.3295Eq02
7.7497Eq02
9.5312Eq02
y1.2526Eq03
y1.4180Eq03
y1.0008Eq03
y1.1388Eq03
2.6670Eq03
3.0574Eq03
1.7406Eq03
2.9250Eq03
1.3080Eq03
1.2409Eq03
1.3586Eq03
1.5962Eq02
y9.4607Eq02
y1.0284Eq03
y8.2179Eq02
y1.2230Eq03
2.7076Eq03
3.8340Eq03
y1.1581Eq02
y4.1997Eq02
1.7651Eq03
y2.2953Eq03
1.0528Eq03

Wilson
u 21 Jrmol.

Jrmol.

l12

1.7978Eq03
y1.8444Eq03
y8.9941Eq02
y8.0835Eq02
y8.4928Eq02
y1.0504Eq03
1.6768Eq03
2.0180Eq03
1.3669Eq03
1.7116Eq03
y1.7032Eq03
y1.7134Eq03
y1.7314Eq03
y1.6526Eq03
y1.5140Eq03
y1.4486Eq03
y1.5881Eq03
y1.8242Eq02
1.1821Eq03
1.3446Eq03
1.0365Eq03
1.6832Eq03
y1.4017Eq03
y1.4530Eq03
6.2773Eq02
9.3329Eq02
y8.6467Eq02
4.5526Eq03
3.6146Eq01

y1.0997Eq03
y5.6493Eq03
y5.9100Eq03
y4.8020Eq03
y3.6906Eq03
y3.7053Eq03
1.2145Eq03
2.3191Eq03
1.8666Eq03
3.7781Eq03
y2.0407Eq03
y7.8938Eq03
2.9675Eq02
y3.9327Eq03
y5.3536Eq03
y4.8914Eq03
y3.3710Eq03
y1.3946Eq03
1.0105Eq03
1.8665Eq03
7.2334Eq02
y5.8225Eq03
y3.2591Eq03
4.1993Eq03
8.2180Eq03
4.7990Eq03
y3.2266Eq03
1.2886Eq04
4.9936Eq03

van Laar
l 21

Jrmol.

9.8454Eq02
5.1643Eq03
1.6663Eq03
1.5761Eq03
1.3275Eq03
1.1767Eq03
1.7571Eq03
1.3118Eq03
1.3784Eq03
1.1560Eq03
1.9024Eq03
5.8695Eq04
y2.1758Eq02
3.7077Eq03
3.8909Eq02
3.4690Eq02
y2.3326Eq02
1.3400Eq03
1.1001Eq03
9.4203Eq02
9.5405Eq02
3.3979Eq03
6.4466Eq03
8.6443Eq03
2.4569Eq03
2.7136Eq03
6.2127Eq03
7.8290Eq03
7.0438Eq03

y4.6443Eq00
4.0000Ey05
y4.1545Eq00
y3.4298Eq00
y2.9315Eq00
y2.6914Eq00
y3.9363Eq00
y3.1467Eq00
y2.1987Eq00
y1.6759Eq00
y3.0446Eq00
1.6555Ey01
y9.8103Eq00
y1.4728Eq00
y8.1221Eq00
y7.2820Eq00
y7.7688Eq00
y2.8596Eq00
y1.9351Eq00
y1.4342Eq00
y1.2657Eq00
y1.1316Eq00
1.1067Eq00
3.9842Eq00
2.9262Eq00
2.0681Eq00
1.1410Eq00
7.3688Eq00
4.8512Eq00

y8.5196Ey01
y2.0000Ey05
y1.4606Eq00
y1.2254Eq00
y1.0451Eq00
y1.0789Eq00
y1.2461Eq00
y1.2405Eq00
y1.1138Eq00
y1.1860Eq00
y3.3741Ey01
6.6158Eq03
y1.3399Eq00
y1.6004Ey01
y1.7330Eq00
y1.6459Eq00
y1.5787Eq00
y7.6969Ey01
y8.9839Ey01
y1.0182Eq00
y6.8671Ey01
y1.1209Eq00
7.9054Ey01
8.3473Ey01
1.3390Ey02
y5.1734Eq03
y1.1976Eq05
5.0810Ey02
3.2852Ey01

Key: BZ, benzene; CS, carbon disulfide; CT, carbon tetrachloride; HX, n hexane; CF, chloroform; DE, diethyl ether; EA, ethyl acetate; AC, acetone; ET,
ethanol.
Sources: 1, Ref. w26x; 2, Ref. w27x; 3, Ref. w28x.

R.L. Smith Jr. et al.r Fluid Phase Equilibria 145 (1998) 5368

SSSqBZ
SSSqBZ
PPPqBZ
MMMqBZ
LLLqBZ
CCCqBZ
SSSqCS
MMMqCS
LLLqCS
CCCqCS
SSSqCT
SSSqHX
SSSqCF
SSSqCF
PPPqCF
MMMqCF
LLLqCF
SSSqDE
PPPqDE
MMMqDE
LLLqDE
CCCqDE
SSSqEA
SSSqAC
MMMqAC
LLLqAC
CCCqAC
SSSqET
CCCqET

Jrmol.

R.L. Smith Jr. et al.r Fluid Phase Equilibria 145 (1998) 5368

65

this further. For each TAGsolvent, we plotted the value of C from approximately 0 to 1.2 and
calculated the AAPD. Many of the AAPD curves versus C had a distinct minimum like that shown
in Fig. 3. For diethyl ether systems, AAPD versus C curves appeared differently and monotonically
increased as the value of C was increased from 0.1 to 1.2. For most TAG q DE systems, the AAPD
remained almost constant in for C values between 0.1 and 0.5. The SSS q DE system showed a
slight minimum at 0.485. Because of this, a more appropriate value of C for the diethyl ether
solvent group is probably 0.485. These analyses can be used to develop a set of recommendations for
calculating SLE of TAGsolvent mixtures.

13. Model recommendations

The recommended model depends greatly on the end use and the available data. For predictions of
TAGsolvent SLE, the Dortmund version of UNIFAC can provide SLE temperatures with average
deviations of around 1.07% or so. If C values are used, the error drops to 0.385%. If other UNIFAC
versions are being used, then the tabulated C values can greatly improve the prediction accuracy.
Further, if the original UNIFAC is used, then an average value of C s 0.897 works well. For the
Lyngby and Dortmund versions, average values of C that work well are 0.858 and 0.749,
respectively. The FEFV and FFV models also have merit due to their moderate accuracy and
simplicity. If only limited data are available, the FEFV-X model is suitable since a single adjustable
parameter provides greatly improved accuracy. The FEFV-X model is remarkably simple. For cases
where data are sufficient and where only correlation is required, the Wilson equation has been shown
to provide the most accurate correlations of TAGsolvent systems.

14. Conclusions
The Dortmund version of UNIFAC provides the best predictions of TAGsolvent systems. Various
UNIFAC models can be slightly modified to greatly improve performance by using an exponent in the
combinatorial term as a fitting parameter. For the UNIFAC-1977, UNIFAC Lyngby. and UNIFAC
Dortmund., these exponents were found to be 0.897, 0.858, and 0.749, respectively. The FFV and
FEFV also gave satisfactory predictions for TAGnonpolar and slightly polar solvent systems and
these models are considerably simpler than the UNIFAC models. Addition of a Flory-x type residual
term to a FEFV term gave the best overall one parameter correlation model FEFV-X. . The FEFV-X
model was also one of the simplest models. The Wilson equation was the best two parameter
correlation model.

15. Nomenclature
DCp
D H fus
c
C

Heat capacity
Enthalpy of fusion
Degrees of freedom
UNIFAC exponent in the combinatorial term

R.L. Smith Jr. et al.r Fluid Phase Equilibria 145 (1998) 5368

66

l
L
n
r
q
Tt
V
Vw
x
z
AAPD
BIAS
CCC
LLL
MMM
PPP
SSS
TAG

UNIQUAC parameter defined as zr2. ri y qi . y ri-1.

Wilson equation parameter
Number of data points
UNIFAC segment volume
UNIFAC segment area
Triple point temperature
Molar volume, usually at the given system temperature
Bondi 0 K molar volume
Mole fraction
Coordination number
Absolute average percent deviation, Eq. 5.
Bias of calculated values determined by: BIASs 1rn Tcalc y Texp . i
Tricaprin
Trilaurin
Trimyristin
Tripalmitin
Tristearin
Triacylglyceride

Subscripts
calc
exp
i, j

Calculated
Experimental
Indexes

Superscripts
comb
fv
l
o
res
s

Combinatorial
Free volume
Liquid
Standard state
Residual
Solid

Greek
b
g
x

Gk
G ki.

m
ui
t i, j
n ki.
v
F

Stable triacylglyceride form

Activity coefficient
Flory parameter, residual activity coefficient fitting parameter
Dielectric constant
Residual activity coefficient of functional group k in the mixture
Residual activity coefficient of functional group k in the mixture containing only
molecules of type i
Dipole moment
Area fraction of group i
Energy parameter between molecular segment i and j
Number of functional groups of type k in molecule i
Acentric factor
Volume fraction

R.L. Smith Jr. et al.r Fluid Phase Equilibria 145 (1998) 5368

f
L

67

Volume, free volume, or entropic fraction

Free volume ration as defined in Table 1

Acknowledgements
We would like to acknowledge the Research Center of Supercritical Fluid Technology Tohoku
Univ.. for support of this work.

References
w1x K.A. Boni, Process for recovering collagen, US Patent 5,229,497, 1993.
w2x G.M. Acosta, R.L. Smith Jr., J.E. Walsh, K.A. Boni, Beef shank fat solubility in supercritical carbon dioxidepropane
mixtures and in liquid propane, J. Food Sci. 60 5. 1995. 983987.
w3x J. Gmehling, G. Anderson, T.F. Prausnitz, J.M. Prausnitz, Solidliquid equilibria using UNIFAC, Ind. Eng. Chem.
Fundam. 17 4. 1978. 269273.
w4x J.A.P. Coutinho, S.I. Andersen, E.H. Stenby, Evaluation of activity coefficient models in prediction of alkane
solidliquid equilibria, Fluid Phase Equilibria 103 1995. 2339.
w5x T. Fornari, S. Bottini, E.A. Brignole, Application of UNIFAC to vegetable oilalkane mixtures, JAOCS 71 4. 1994.
391395.
w6x U. Domanska,
Solubility of long-chain fatty acid esters in selected organic one- and two-component solvents, J.

Solution Chem. 18 2. 1989. 173188.

w7x K.L. Roberts, R.W. Rousseau, A.S. Teja, Solubility of long-chain n-alkanes in heptane between 280 and 350 K, J.
Chem. Eng. Data 39 1994. 793795.
w8x J.M. Prausnitz, R.N. Lichtenthaler, E. Gomes de Azevedo, Molecular Thermodynamics of Fluid-Phase Equilibria, 2nd
edn., Prentice-Hall, NJ, 1986.
w9x D.S. Mishra, S.H. Yalkowsky, Solubility of organic compounds in nonaqueous systems: polycyclic aromatic hydrocarbons in benzene, Ind. Eng. Chem. Res. 29 1990. 22782283.
w10x P.B. Choi, E. McLaughlin, Effect of a phase transition on the solubility of a solid, AIChE J. 29 1. 1983. 150153.
w11x K. Larsson, in: F.B. Padley Ed.., The Lipids Handbook, Chapmann & Hall, London, 1986.
w12x L.H. Wesdorp, Liquid-multiple solid phase equilibria in fats, Ph.D. Thesis, Delft University, Netherlands, 1990.
w13x H.S. Elbro, Aa. Fredenslund, P. Rasmussen, A new simple equation for the prediction of solvent activities in polymer
solutions, Macromolecules 23 1990. 47074714.
w14x P.J. Flory, J. Chem. Phys. 9 1941. 660.
w15x M.L. Huggins, J. Chem. Phys. 9 1941. 440.
w16x P.J. Flory, Disc. Faraday Soc. 49 1970. 7.
w17x A. Bondi, Physical Properties of Molecular Crystals, Liquids and Glasses, Wiley, New York, 1968.
w18x Aa. Fredenslund, J. Gmehling, P. Rasmussen, VaporLiquid Equilibria Using UNIFAC, Elsevier, Amsterdam, 1977.
w19x B.L. Larsen, P. Rasmussen, A. Fredenslund, A modified UNIFAC group-contribution model for prediction of phase
equilibria and heats of mixing, IEC Res. 26 1987. 22742286.
w20x J. Gmehling, J. Li, M. Schiller, A modified UNIFAC model: 2. Present parameter matrix and results for different
thermodynamic models, Ind. Eng. Chem. Res. 32 1993. 178193.
w21x T. Oishi, J.M. Prausnitz, Estimation of solvent activities in polymer solutions using a group-contribution method, Ind.
Eng. Chem. Proc. Des. Dev. 17 3. 1978. 333339.
w22x I. Kikic, P. Alessi, P. Rasmussen, Aa. Fredenslund, On the combinatorial part of the UNIFAC and UNIQUAC models,
Can. J. Chem. Eng. 58 1980. 253258.
w23x M.D. Donohue, J.M. Prausnitz, Combinatorial entropy of mixing molecules that differ in size and shape. A simple
approximation for binary and multicomponent mixtures, Can. J. Chem. 53 1975. 15861592.

68

w24x
w25x
w26x
w27x
w28x
w29x
w30x
w31x
w32x
w33x
w34x
w35x

R.L. Smith Jr. et al.r Fluid Phase Equilibria 145 (1998) 5368

G.D. Fasman Ed.., Practical Handbook of Biochemistry and Molecular Biology, CRC Press, Boca Raton, FL, 1989.
K.S. Markley, Fatty Acids, 2nd edn., Part 1, Interscience Publishers, New York, 1960.
K.Z. Loskit, Zur kenntnis der triglyceride, Phys. Chem. Leipzig. 134 1928. 135155.
C.W. Hoerr, H.J. Harwood, The solubility of tristearin in organic solvents, J. Phys. Chem. 60 1956. 12651269.
O.S. Privett, E. Breault, J.B. Covell, L.N. Norcia, W.O. Lundberg, Solubilities of fatty acids and derivatives in acetone,
JAOCS 35 1958. 366370.
C. Chen, B.F. Daubert, Synthetic triacid triglycerides of saturated fatty acids, J. Am. Chem. Soc. 67 1945. 12561258.
Z.-R. Yu, S.S.H. Rizvi, J.A. Zollweg, Phase equilibria of oleic acid, methyl oleate, and anhydrous milk fat in
supercritical carbon dioxide, J. Supercrit. Fluids 5 1992. 114122.
R.C. Reid, J.M. Prausnitz, B.E. Poling, The Properties of Gases and Liquids, 4th edn., McGraw-Hill, New York, 1987.
M. Ollivon, R. Perron, Measurements of enthalpies and entropies of unstable crystalline forms of saturated even
monoacid triglycerides, Themochim. Acta 53 1982. 183194.
J.A. Dean Ed.., Langes Handbook of Chemistry, 13th edn., McGraw-Hill, New York, 1985.
Math 77, Language Systems, Sterling, VA, Release 4.1, April, 1994.
J.E. Dennis Jr., D.M. Gay, R.E. Welsch, An adaptive nonlinear least-squares algorithm, ACM Trans. Math. Software 7
3. 1981. 348383.