Fluid Phase Equilibria 171 Ž2000.

77–90
www.elsevier.nlrlocaterfluid

An excess Gibbs energy model to study the phase behavior of

aqueous two-phase systems of polyethylene glycolq dextran
Ali Haghtalab ) , Mohammad Ali Asadollahi
Chemical Engineering Department, Tarbiat Modarres UniÕersity (TMU), P.O. Box 14115-111, Tehran, Iran
Received 29 November 1999; accepted 13 April 2000

Abstract

A new model for the excess Gibbs energy named UNIQUAC-NRF is presented to study the phase behavior
of aqueous two-phase polymer–polymer systems. The assumptions of the NRTL-NRF model and the local
composition expression of the UNIQUAC model have been used in the development of the new model. Using
the random state as a reference state, a model for g E as function of the nonrandom factor has been developed
for binary and multicomponent mixtures.
The new model was applied for the prediction of the phase behavior of aqueous two-phase polymer–polymer
systems of polyethylene glycolq dextran. The interaction parameters were obtained for 25 systems. Comparing
the results of the UINQUAC and UNIQUAC-NRF models, it was shown that the present model is more
accurate. q 2000 Elsevier Science B.V. All rights reserved.

Keywords: Activity coefficient; Excess Gibbs energy; Aqueous two-phase systems; Polyethylene glycol; Dextran; Liquid–
liquid equilibria; UNIQUAC-NRF

1. Introduction

Aqueous solutions of two incompatible polymers such as polyethylene glycol Ž PEG. and dextran
ŽDEX. form liquid–liquid two-phase systems, in which each phase is rich with respect to one of the
phase-forming polymers. Proteins or enzymes added to such a system are partitioned unevenly
between the phases and increasing molecular weight of the protein causes a more uneven partitioning
w1,2x.
Beijerinck studied aqueous two-phase systems ŽATPS. as early as 1896 w3x. He discovered that
when appropriate concentrations of water, agar, and gelatin were mixed, a turbid solution resulted that

)
Corresponding author. Tel.: q98-21-8770436; fax: q98-21-8776058.
E-mail address: haghtalab@istn.irost.com ŽA. Haghtalab..

0378-3812r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 8 - 3 8 1 2 Ž 0 0 . 0 0 3 5 4 - X
78 A. Haghtalab, M.A. Asadollahir Fluid Phase Equilibria 171 (2000) 77–90

subsequently splits into two aqueous phases. Albertsson first applied such systems for separation of
plant cell particles w1x. He applied ATPS for the purification of a wide range of biomolecules such as
proteins, lipids, nucleic acids and whole cells w1,4x.
In the last decade ATPS have gained increasing attention in phase equilibrium thermodynamics.
There are two kinds of thermodynamic models which deal with the phase behavior of ATPS: lattice
models and osmotic virial expansion equations. Brooks w2x has developed a lattice model for particle
partitioning by extending the Flory-Huggins theory of polymer–solvent solutions to multicomponent
systems. Utilizing this model, Diamond and Hsu w5,6x presented two simple correlations to predict
protein partitioning in PEG-DEX ATPS. Since the Flory-Huggins model is not suitable for systems
with specific interactions Že.g., hydrogen bonding. , a modified Flory-Huggins model has been
proposed w7x which accounts for the deviation from random mixing due to specific interactions.
Furuya et al. w8x used this model to predict the phase behavior of PEG-DEX ATPS.
The use of osmotic virial expansions to represent the properties of ATPS gained popularity starting
with the work of Edmond and Ogston w9,10x. King et al. w11x applied the simple virial expansion
truncated after the second virial coefficient term to calculate the phase diagrams and protein-partition-
ing behavior of polymer–polymer ATPS. However, the application of the virial expansion truncated
at the second-order term is most appropriate for dilute polymer solutions w12x. On the other hand,
aqueous two-phase polymer systems, which generally contain 5–20% polymer, are in the semidilute
region, so that the elimination of higher order terms in the expansion may not be appropriate. Li et al.
w13x used the virial expansion truncated at the third-order term to predict the phase behavior of ATPS.
Cabezas et al. w14x, Grossmann et al. w15x and Gaube et al. w16x suggested other versions of the virial
models.
Grossmann et al. w17x used their model to describe the liquid–liquid equilibria in ATPS, predicting
the partitioning of some amino acids and low molecular peptides in the polymer–polymer w18,19x and
polymer–salt w20x ATPS. Haynes et al. w21x extended the virial model to include dilute electrolyte
solutions by adding Guggenheim’s extension of the Debye-Huckel ¨ limiting law to account for the
electrostatic forces.
The models based on local composition have been used to describe the behavior of aqueous
two-phase polymer–polymer systems. Kang and Sandler w22,23x, Hartounian et al. w24x used the
UNIQUAC model and more recently Wu et al. w25x used a modified NRTL model to deal with the
phase behavior of two-polymer ATPS.

Fig.1. Ža. Central cell 1; Žb. Central cell 2.

 A. Haghtalab, M.A. Asadollahir Fluid Phase Equilibria 171 (2000) 77–90 79

A new excess Gibbs energy model named UNIQUAC-NRF is presented in this work to study the
liquid–liquid equilibria in ATPS. In this new model, we used the same assumptions of NRTL-NRF
model, were proposed by Haghtalab and Vera w26,27x. In the NRTL-NRF model, the random state of
species is considered as reference state and the nonrandom factor, G , is used to show the deviation of
local composition from bulk composition. The NRTL-NRF model has been used for aqueous binary
and multi-electrolyte solutions w26,28x, weak electrolyte systems w29x and aqueous-organic systems
w30x. The present model was used for predicting the phase behavior of polymer–polymer ATPS,
particularly PEG-DEX ATPS, which are increasingly interesting for the separation of biomolecules.

2. The UNIQUAC-NRF model for binary non-electrolyte mixtures

For a binary mixture of components 1 and 2, one considers two central cells as shown in Fig.1.
For each central cell one can write, based on the concept of local area fractions,
ui j ui
s ti j Ž1.
uj j uj
Dui j
t i j s exp y ž RT / Ž2.

ui j q uj j s 1 Ž3.
Where u i and u j are the area fractions, and u i j and u j j are local area fractions of species i and j
surrounding central species j, respectively. D u i j and t i j are the energy of interaction and interaction
parameter of i–j pairs, respectively.
As mentioned in the NRTL-NRF model, the nonrandom factor G , is used to show the deviation of
local composition from bulk composition. Using this parameter, the local area fraction is related to the
bulk area fraction as:
u i j s u i Gi j Ž4.
In the case when Gi j approaches unity, the local area fraction of component i, u i j , approaches bulk
area fraction of component i.
The excess internal energy for each central cell can be written as,
U1E s U1 y U10 Ž5.
U2E s U2 y U20 Ž6.
Where U1, U2 are internal energies of cells of 1 and 2, and,U10 , U20 are internal energies of the same
cells in the reference states, i.e., the random state.
Using only pair interactions, the internal energies of the cells may be written as,
U1 s u 21U21 q u 11U11 Ž7.
U2 s u 12 U12 q u 22 U22 Ž8.
80 A. Haghtalab, M.A. Asadollahir Fluid Phase Equilibria 171 (2000) 77–90

The internal energies of cells in the reference state which are in the random state is given by:
U10 s u 2 U21 q u 1U11 Ž9.
U20 s u 1U12 q u 2 U22 Ž 10.
Substituting Eqs. Ž7. – Ž 10. in relations Ž 5. and Ž 6. , one finds:
U1E s U21Ž u 21 y u 2 . q U11Ž u 11 y u 1 . Ž 11.
U2E s U12 Ž u 12 y u 1 . q U22 Ž u 22 y u 2 . Ž 12.
If we consider a mixture consisting of N1 molecules of component 1 and N2 molecules of component
2, the total excess internal energy, will be,
1 1
U Es zq1 N1U1E q
zq N U E Ž 13.
2 2 2 2 2
Where q is a surface area parameter and z is the coordination number which is usually set equal to
10. Since the local and bulk area fractions must obey the area conservation equation, we have,
u 11 y u 1 s u 2 y u 21 Ž 14.
u 22 y u 2 s u 1 y u 12 Ž 15.
Substituting the ŽEqs. Ž 11. , Ž12., Ž14. and Ž 15. into Eq. Ž13., one finds,
1 1
U Es zq1 N1Ž u 21 y u 2 .Ž U21 y U11 . q zq2 N2 Ž u 12 y u 1 .Ž U12 y U22 . Ž 16.
2 2
Or:
U E s q1 n1 D u 21Ž u 21 y u 2 . q q2 n 2 D u12 Ž u 12 y u 1 . Ž 17.
Where n1, n 2 are the number of moles of components 1 and 2, respectively? D u12 and D u12 are:
1
D u 21 s z Ž U21 y U11 . NA Ž 18.
2
1
D u12 s z Ž U12 y U22 . NA Ž 19.
2
Where NA is Avogadro’s number. Then, the molar excess internal energy u E , is given by:
u E s q1 x 1 D u 21Ž u 21 y u 2 . q q2 x 2 D u12 Ž u 12 y u 1 . Ž 20.
Using relation Ž 4., Eq. Ž20. may be written as function of the nonrandom factor as:
u E s q1 x 1u 2 Ž G 21 y 1 . D u 21 q q2 x 2 u 1Ž G 12 y 1 . D u12 Ž 21.
Where:
t 21
G 21 s Ž 22.
u 1 q u 2t 21
t 12
G 12 s Ž 23.
u 2 q u 1t 12
 A. Haghtalab, M.A. Asadollahir Fluid Phase Equilibria 171 (2000) 77–90 81

To obtain an expression for the molar excess Helmholts energy a E , we use the Gibbs-Helmholtz
relation at constant volume and composition as,
d Ž a ErT .
s uE Ž 24.
d Ž 1rT .
Integration of Eq. Ž24. from to 1rTo to 1rT yields:
1
aE 1
T E
T
s H 1 u d
T(
ž / T
q Integration constant Ž 25.

Assuming that D u12 and D u12 are independent of temperature and that, as shown by Hildebrand and
Scott w32x, at low pressure Ž a E . T,V f Ž g E . T , P , Eq. Ž25. gives,
aE gE gE gE
ž / ž / ž / ž /
RT T ,V
f
RT T,P
s
RT C
q
RT R
Ž 26.

™
where C and R indicate the combinatorial and residual parts.
At 1rTo 0, we assume that components 1 and 2 form an athermal mixture and we use the
equation of Guggenheim w31x for athermal mixtures of molecules of arbitrary size and shape, as our
boundary condition:
gE aE SE f1 f2 z u1 u2
ž / ž /
RT C
f
RT athermal
sy
ž / R C
s x 1 ln
x1
q x 2 ln
x2
q
2
q1 x 1 ln
f1
q q2 x 2 ln
f2
Ž 27.

Where:
r1 x 1 r2 x 2
f1 s ; f2 s Ž 28.
r1 x 1 q r 2 x 2 r1 x 1 q r 2 x 2
q1 x 1 q2 x 2
u1 s ; u2s Ž 29.
q1 x 1 q q 2 x 2 q1 x 1 q q 2 x 2
r is volume parameter.
To derive an expression for the residual part, from Eq. Ž21. one can integrate Eq. Ž25.:
gE G 21 G 12
ž /
RT R
s q1 x 1 ln G 11 q u 2 ln
G 11
q q2 x 2 ln G 22 q u 1 ln
G 22
Ž 30.

The activity coefficient can be obtained from the above relations as,
fi z ui fi
lng iC s ln q qi ln q li y Ž xi li q x j l j . Ž 31.
xi 2 fi x1

Gi j Gji
lng iR s qi 1 q ln Gii y u i Gii y u j Gi j q u j Ž 1 y u i . ln
ž /
Gii Gj j
Ž 32 .
82 A. Haghtalab, M.A. Asadollahir Fluid Phase Equilibria 171 (2000) 77–90

Where:
Gii s Gjirt ji ; Gj j s Gi jrt i j Ž 33.
z
l i s Ž ri y qi . y Ž ri y 1 . Ž 34.
2

3. The UNIQUAC-NRF model for multicomponent non-electrolyte systems

Generalizing the relations obtained in Section 2, we can derive the molar excess Gibbs energy and
the activity coefficients for multicomponent mixtures:

gE n n Gji
ž /RT R
s Ý qi x i
is1
ln Gii q Ý u j ln G
js1
j/i
ii
Ž 35.

n Gi j Gji 1 n n G k l G lk
lng iR s qi 1 q ln Gii Ý u j Gi j q Ž1 y u i . Ý u j ln
js1 js1
j/i
ž /
Gii Gj j
y
2
Ý Ý
ks1 ls1
k/i l/k ,i
u k u l ln
ž G k k G ll /
Ž 36.
Finally the activity of component i is expressed as:

z ui fi n n
ln Ž a i . UNIQUACyNRF s ln f i q qi ln q li y Ý x j l j q qi 1 q ln Gii y Ý u j Gi j
2 fi xi js1 js1

n Gi j Gji 1 n n G k l G lk
q Ž1 y u i . Ý u j ln
js1
j/i
ž /
Gii Gj j
y
2
Ý Ý
ks1 ls1
k/i l/k ,2
u k u l ln
ž G k k G ll / Ž 37.

4. Application of UNIQUAC-NRF model for aqueous two-phase polymer systems

The liquid–liquid phase equilibrium is determined by the equality of the fugacity in the top Ž I. and
bottom ŽII. phases for all components in the solution:
f iI s f iII for all i Ž 38.
This equation can be written in terms of the difference of chemical potential with respect to reference
state,
DmIi s DmIIi Ž 39.
or in terms of the activity of component i,
a Ii s a IIi Ž 40.
 A. Haghtalab, M.A. Asadollahir Fluid Phase Equilibria 171 (2000) 77–90 83

Fig 2. The flow chart of experimental data reduction in ternary liquid–liquid equilibria.

Eq. Ž39. is widely used for polymer solutions instead of Eq. Ž40., because the activities of polymers in
the mixture are very small.
To optimize the interaction parameters, one should minimize the following objective function,
showing the equality of chemical potentials of each species between two phases:
M 3
2
Fm s Ý Ý Ž DmIi k y DmIIi k . Ž 41.
k i

where i and k are the number of species and tie lines, respectively.
Saddle and maximum points may be obtained during the minimization of the objective function.
Thus, one should minimize another objective function,
M 3 2
2
Fx s Ý Min Ý Ý Ž x iejk y x icjk . Ž 42.
k i j

Where x e and x c are the experimental and calculated mole fractions, respectively and j, i and k are
the numbers of phases, species and tie lines, respectively.
Since the mole fraction of polymer species is so small due to their high molecular weights, it is
better to use weight fraction Ž w . instead of mole fraction in Eq. Ž42. . In this case we can rewrite this
objective function as,
M 3 2
2
Fw s Ý Min Ý Ý Ž wiejk y wicjk . Ž 43.
k i j
84 A. Haghtalab, M.A. Asadollahir Fluid Phase Equilibria 171 (2000) 77–90

The flow chart for the computer program is shown in Fig. 2. Using the weight fraction instead of
mole fraction, Eq. Ž37. is transformed into,

z u iX Mi f iX n n
ln Ž a i . UNIQUACyNRF s ln f iX q Mi qXi ln X
X q Mi l i y Ý wj lXj q Mi qXi 1 q ln Gi Xi y Ý u jX Gi Xj
2 fi wi js1 js1

X
n
X
GiXj GjiX 1 n n
X X
G kXl G lkX
q Ž1 y u . i Ýu
js1
j/i
j ln
ž /
GiiX GjXj
y
2
Ý Ý
ks1 ls1
k/i l/k ,i
u uk l ln ž G kXk G llX / Ž 44.

Where,
riX wi
f iX s Ž 45.
Ý j r Xj wj

X
qXi wi
u is Ž 46.
Ý j qXj wj
ti j
Gi Xj s Ž 47.
Ý k u kX t k j

z 1
lXi s Ž riX y qXi . y riX y
2 ž Mi / Ž 48.

Here Mi denotes molecular weight of i component, riX and qXi are the volume and surface area
parameters of the i component per unit mass, f iX and u iX are volume and surface area fractions.

5. Results and discussion

Using the UNIQUAC-NRF model for calculation of the interaction parameters, one needs the
quantities r X and qX for all species. We used values of r X and qX reported by Kang and Sandler w22x,
which are shown in Table 1.
Using the UNIQUAC and UNIQUAC-NRF models and application of an optimization program
based on Powell w33x method, we determined the interaction parameters for many ternary mixtures of
PEG, DEX and Water.

Table 1
r X and qX parameters for components estimated by Kang and Sandler w22x
Component r X =10 2 qX =10 2
PEG 3.87 2.57
DEX 2.717 1.96
Water 5.11 7.78
 A. Haghtalab, M.A. Asadollahir Fluid Phase Equilibria 171 (2000) 77–90 85

The characteristics of these systems are shown in Table 2. The interaction parameters and RMSD
for each system are obtained by two models, which are shown in Table 3. It must be noted that the
definition of RMSD used here is similar to that of Kang and Sandler w22x,
2

RMSDs
1
N ) N
Ý Ý Ý
2

ks1 js1 is1

3

ž wicjk y wiejk
wicjk q wiejk / Ž 49.

Where N is the number of tie lines, w is the weight fraction of the species and i, j and k are the
number of species, phases and tie lines, respectively.
It is clear form Table 3 that the results of UNIQUAC-NRF model are more accurate than those of
UNIQUAC model. As one may observe from Table 3, for a few cases the accuracy of original
UNIQUAC model is almost the same as UNIQUAC-NRF. For two cases, B and Q, original
UNIQUAC model performs 2–4% better. It should be noted the nature of the new interaction
parameters for UNIQUAC-NRF model are different from the UNIQUAC parameters. These new
parameters correct for non-randomness. Using the non-randomness state for the reference state is
more physically meaningful, particularly for solid polymers dissolved in solvents.

Table 2
The specification of the used ternary systems in the present work
System Temperature Number of PEG DEX Mn=10y3 Mn=10y3 Reference
ŽK. of lines PEG DEX
A 293.15 7 PEG 6000 D17 6.0–7.5 23.0 w1x
B 273.15 4 PEG 6000 D17 6.0–7.5 23.0 w1x
C 293.15 4 PEG 6000 D37 6.0–7.5 83.0 w1x
D 293.15 5 PEG 4000 D48 3.0–3.7 180.0 w1x
E 273.15 6 PEG 3000 D 500 3.14 101.0 w34x
F 293.15 7 PEG 3000 D 500 3.14 101.0 w34x
G 313.15 7 PEG 3000 D 500 3.14 101.0 w34x
H 277.15 4 PEG 6000 D 500 6.23 179.347 w17x
I 283.15 4 PEG 6000 D 500 6.23 179.347 w17x
J 293.15 7 PEG 6000 D 500 6.23 179.347 w17x
K 313.15 4 PEG 6000 D 500 6.23 179.347 w17x
L 298.15 4 PEG 4000 D 10000 3.810 13.239 w35x
M 298.15 4 PEG 6000 D 10000 5.318 13.239 w35x
N 298.15 4 PEG 10000 D 10000 10.216 13.239 w35x
O 298.15 4 PEG 20000 D 10000 19.081 13.239 w35x
P 298.15 4 PEG 4000 D 60000 3.810 27.705 w35x
Q 298.15 4 PEG 6000 D 60000 5.318 27.705 w35x
R 298.15 4 PEG 10000 D 60000 10.216 27.705 w35x
S 298.15 4 PEG 20000 D 60000 19.081 27.705 w35x
T 298.15 4 PEG 4000 D 110000 3.810 52.066 w35x
U 298.15 4 PEG 6000 D 110000 5.318 52.066 w35x
V 298.15 4 PEG 10000 D 110000 10.216 52.066 w35x
W 298.15 4 PEG 20000 D 110000 19.081 52.066 w35x
X 298.15 8 PEG 8000 DT-500 8.920 167.0 w11x
Y 298.15 6 PEG 3350 DT-70 3.690 37.0 w11x
86 A. Haghtalab, M.A. Asadollahir Fluid Phase Equilibria 171 (2000) 77–90

Table 3
The interaction parameters and RMSD for the systems used in Table 2
System Modela Ab12 A 13 A 21 A 23 A 31 A 32 RMSD=10 2
A 1 y653.445 y208.261 288.516 y146.646 69.576 y804.814 3.60
2 y164.995 y269.794 y193.307 y294.712 y217.210 y83.472 3.90
B 1 y806.391 y240.649 705.233 y140.203 190.413 y720.313 5.40
2 y184.760 y261.007 y123.609 y276.988 y127.662 y1017.115 6.72
C 1 y1031.650 y305.347 427.831 y113.262 344.387 y971.523 12.47
2 55.699 y262.787 y212.537 y304.228 y161.530 y236.277 8.89
D 1 2226.100 y235.191 y141.585 y240.866 137.018 y37.867 11.86
2 148.287 y258.402 y98.731 y307.660 y19.517 226.908 6.56
E 1 y44.697 y252.069 88.062 y189.780 219.512 y64.643 14.27
2 q304.185 y241.798 q102.345 y291.830 y56.144 q256.493 7.86
F 1 y102.330 y255.482 113.303 y212.647 191.347 y81.925 9.85
2 y446.146 y276.147 y38.900 y315.648 y234.638 y335.965 9.60
G 1 y426.805 y260.719 891.406 y179.578 183.514 y256.183 8.41
2 y413.301 y292.044 y33.403 y328.455 y236.541 y288.034 8.61
H 1 y231.905 y310.138 737.987 y292.600 364.475 257.103 10.17
2 y407.014 y244.984 y57.745 y295.135 54.895 y310.135 3.01
I 1 y246.028 y311.388 y772.162 y287.673 358.001 229.627 6.54
2 y425.667 y250.880 y20.445 y300.946 y62.128 y295.125 4.21
J 1 y244.307 y320.440 594.218 y294.874 365.859 230.322 16.66
2 y258.360 y257.401 y138.960 y306.581 y28.206 y287.427 7.72
K 1 y260.939 y326.993 702.280 y300.264 355.057 212.579 17.81
2 y312.743 y276.620 y106.131 y330.171 y13.046 y295.566 6.64
L 1 y161.903 y156.832 169.090 y202.819 y149.965 y512.793 6.95
2 y243.780 y281.772 y322.109 y300.396 y281.117 y100.711 5.64
M 1 y34.397 y198.409 56.997 y152.453 33.095 y1044.43 3.83
2 y249.559 y276.683 y100.778 y305.545 y249.557 y153.424 4.55
N 1 y495.034 y197.826 57.277 y168.453 15.852 y1316.470 5.42
2 y110.128 y265.834 219.188 y311.164 151.688 y194.828 3.97
O 1 y107.371 y235.069 72.650 y234.074 176.443 y122.818 10.87
2 y247.239 y272.812 y325.302 y327.311 y159.403 y251.527 6.04
P 1 y3069.94 y255.537 3873.320 y130.470 108.951 y3063.950 6.35
2 y296.580 y286.013 y447.320 y303.544 y295.323 y185.097 5.70
Q 1 y3070.050 y224.575 1641.020 y131.077 109.154 y3056.990 5.92
2 y281.208 y321.245 y305.757 y298.632 y288.954 y146.134 9.54
R 1 y3072.620 y223.205 1219.140 y150.356 98.249 y3047.020 5.66
2 y98.410 y268.798 y147.996 y308.251 y149.944 y138.969 6.05
S 1 y270.306 y288.132 288.925 y242.558 275.307 y26.736 4.48
2 q88.194 y303.151 y516.004 y365.680 y409.085 y675.463 6.42
T 1 y261.905 y316.365 1140.030 y299.797 349.606 228.397 13.54
2 q169.024 510.662 598.316 1263.170 y22.022 500.208 4.17
U 1 y432.529 y287.381 7776.570 y206.315 274.686 y1286.740 10.73
2 q169.280 509.733 591.607 1263.120 y24.482 495.894 11.01
V 1 y260.445 y318.359 549.307 y291.492 352.403 182.350 8.80
2 y157.845 y273.152 349.165 y308.496 168.134 y199.842 4.59
W 1 856.395 y143.926 y79.178 y214.917 264.545 y462.055 6.32
2 y106.084 y271.827 362.260 y309.500 168.191 y199.172 5.74
 A. Haghtalab, M.A. Asadollahir Fluid Phase Equilibria 171 (2000) 77–90 87

Table 3 Ž continued .
System Modela Ab12 A 13 A 21 A 23 A 31 A 32 RMSD=10 2
X 1 y340.792 y264.754 688.646 y214.917 y264.543 y462.055 5.93
2 y312.123 y263.621 y159.738 y309.500 168.191 y199.172 4.65
Y 1 y286.645 y200.841 75.724 y147.764 31.575 y177.240 9.32
2 y352.018 y263.101 y33.702 y316.316 y46.229 y279.445 9.42
a
1sUNIQUAC, 2 sUNIQUAC-NRF.
b
A i j s Ž u i j y u j j .r R.

In the Fig. 3 the result of the UNIQUAC-NRF and UNIQUAC models have been shown for system
DEX500-PEG 6000 at 48C and compared with experimental results. It is apparent that there is a very
good agreement between calculated and experimental results. In Fig. 4 the results of the UNIQUAC-
NRF model for three systems ŽL, M, N. shown in Table 2, are compared. These systems are different
only in molecular weight of PEG. As it may be seen from Fig. 4, the higher the molecular weight of
the PEG, the lower the concentration required for phase separation. As the difference in molecular
size between the two polymers is increased, the constructed curves are more asymmetric.
The present results are in good agreement with results from other researchers w1,2x. In Fig. 5 the
results of the present model for four systems Ž H–K. shown in Table 2, are compared. These systems

Fig 3. The binodal curve for ATPS DEX 500–PEG 6000 at 408C using UNIQUAC-NRF and UNIQUAC models.
88 A. Haghtalab, M.A. Asadollahir Fluid Phase Equilibria 171 (2000) 77–90

Fig 4. The comparison of binodal curves for ATPS DEX and PEG with different molecular weight of PEG at 258C using
UNIQUAC-NRF model.

Fig 5. The comparison of binodal curves for ATPS DEX and PEG with different temperature using UNIQUAC-NRF model.

are different only in the temperature. As it may be seen from the figure, the temperature has little
effect on the location of binodal curve; however at lower temperatures, a lower concentration is
required for phase separation. The effect of temperature for a system near the critical composition is
relatively much larger than for a system removed from the critical composition.

List of symbols
L Size parameter in UNIQUAC equation
MW Molecular weight of solvent
Mi Molecular weight of component i
N Number of experimental points
R Gas constant
T Absolute temperature
Z Coordination number
 A. Haghtalab, M.A. Asadollahir Fluid Phase Equilibria 171 (2000) 77–90 89

ai j Interaction parameter between molecule i and j

gE Molar excess Gibbs free energy
m Molality
n Mole number
q Surface parameter
r Volume parameter
ui j Interaction parameter between molecule i and j
x Mole fraction

Greek letters
´ Error percent
g Activity coefficient
G Non-random factor
u Surface area fraction
k Boltzmann factor
f Volume fraction

Superscripts
cal Calculated value
exp Experimental value
I, II Two aqueous phases in equilibrium

Subscripts
i, j, k Component index
W Water
X Weight fraction index

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