/llllm

ELSEVIER Fluid Phase Equilibria 103 (1995) 119 141

Measurement and correlation of liquid-liquid equilibria for

dextran-poly(ethylene glycol)-water aqueous two-phase
systems at 20°C
Takeshi Furuya *, Yoshio Iwai, Yoshiaki Tanaka, Hirohisa Uchida,
Sunao Yamada, Yasuhiko Arai
Department of Chemical Engineering, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812, Japan
Received 8 March 1994; accepted in final form 7 July 1994

Abstract

The liquid-liquid equilibria (LLE) for the dextran-poly(ethylene glycol)-water aqueous two-phase systems with
various polymer molecular weights were measured at 20°C. The molecular weight distributions of dextran (DEX) and
poly(ethylene glycol) (PEG) in the PEG-rich phase (top phase) and DEX-rich phase (bottom phase) were also
measured. To take into account deviations from random mixing, the interaction term of the conventional F l o r y - H u g -
gins equation was empirically modified. The molecular weight distribution of DEX was expressed by a F distribution
function because the DEX sample used showed a wide molecular weight distribution though the PEG samples were
almost monodispersed. LLE and molecular weight distributions were correlated successfully using a continuous
thermodynamic approach.

Keywords: Experimental; Liquid-liquid; Polymers; Dextran; Poly(ethylene glycol); Water; Molecular weight distribu-
tion; Modified Flory-Huggins equation

1. Introduction

With the increasing importance of modern biotechnology, there is growing interest in efficient
methods for the large-scale recovery and purification of bioproducts. Aqueous two-phase
systems provide a successful method for separating mixtures of biomolecules (Albertsson, 1986;
Walter et al., 1985). For the design of such a separation system, a knowledge of the liquid-
liquid equilibria (LLE) of aqueous two-phase systems is needed. Usually, dextran and

* Corresponding author.

0378-3812/95/$09.50 © 1995 Elsevier Science B.V. All rights reserved

SSDI 0 3 7 8 - 3 8 1 2 ( 9 4 ) 02572-X
120 T. Furuya et al. / Fluid Phase Equilibria 103 (1995) 119-141

poly(ethylene glycol) are used as water-soluble polymers. As the polymers possess a molecular
weight distribution, the effect of the molecular weight distribution as well as the average
molecular weight on LLE becomes very important. In recent years, therefore, experimental LLE
data for aqueous two-phase systems containing a molecular weight distribution measurement
have been reported (Connemann, 1992; Connemann et al., 1991; Gaube et al., 1993a; Kang et
al., 1989). In this study, LLE of the dextran-poly(ethylene glycol)-water aqueous two-phase
system with various molecular weights were measured at 20°C, and the molecular weight
distributions of polymers in the top and bottom phases were measured. The present data may
add to our knowledge about the LLE of the dextran poly(ethylene glycol)-water aqueous
two-phase system.
A successful model for correlating the LLE of an aqueous two-phase system and the
molecular weight distributions of polymers in both phases is needed to optimize the separation
process. The U N I Q U A C equation was used by Kang et al. (1989) and Kang and Sandler
(1987), and the osmotic virial equation was adopted by Gaube et al. (1993b) and King
et al. (1988). The F l o r y - H u g g i n s equation has also been used often for the correlation of
phase equilibria of polymer solutions. However, it has been pointed out that the F l o r y -
Huggins equation is not necessarily suitable for systems which have specific interactions such
as hydrogen bonding (King et al., 1988; Yu et al., 1993). In this study, therefore, an attempt
is made to improve the F l o r y - H u g g i n s equation. To take into account the deviations
from random mixing, the interaction term of the conventional Flory-Huggins equation was
empirically modified. The molecular weight distribution was expressed by a F distribution
function and the liquid-liquid equilibria of the present aqueous two-phase systems were
correlated using a continuous thermodynamic approach (Cotterman et al., 1985; Kehlen and
R/itzsch, 1983).

2. Experimental

2. I. Materials

Poly(ethylene glycol) (PEG) samples with two different molecular weights were purchased
from Wako Pure Chemical Ind. as PEG4000 (number-average molecular weight Mn = 2900, lot
No. LKP0209) and PEGG000 ( M n = 8 5 0 0 , lot No. PTL1876). Dextran (DEX) T40
(Mn = 18 800, lot NO. NH04575), DEX T70 (Mn = 37 900, lot No. PC08625) and DEX T500
((a) Mn = 191 000, lot No. PA08143, (b) Mn = 170 300, lot No. QC11346) were purchased from
Pharmacia Inc. The DEX 140 (M, = 35 600, lot No. DSL2657) was purchased from Wako Pure
Chemical Ind. The PEG molecular weight standards used to make a molecular weight calibra-
tion curve were purchased from Polymer Laboratories. Pullulan, used as molecular weight
calibrant for dextran, was purchased from Showa Denko K.K. The number- and weight-average
molecular weights of DEX and PEG are shown in Table 1. The number- and weight-average
molecular weights of PEGs and DEX 140 were determined using size exclusion chromatography
(SEC).. Those of DEX T40, T70, T500(a) and T500(b) were as reported by the manufacturer.
Water was purified with a Millipore Milli-Q system. All reagents were used without further
purification.
 T. Furuya et al. / HuM Phase Equilibria 103 (1995) I19-141 121

Table 1
Molecular weights of polymers

Polymer Mn Mw Mw/ Mn

DEX T40 18800 38000 2.02

DEX T70 37900 66700 1.76
DEX 140 35600 139800 3.93
DEX T500(a) 191000 476000 2.49
DEX T500(b) 170300 503000 2.95
PEG4000 2900 3100 1.07
PEG6000 8500 8800 1.04

2.2. M e t h o d s

F o u r kinds of polymer solution with different concentrations were prepared by weighing from
the stock solutions of P E G and D E X for measurement of liquid-liquid equilibria (LLE). The
pH was adjusted as 7 by adding phosphate buffer (10 m M L 1). The solutions thus prepared
were shaken for 12 h and settled for 5 days. After phase separation had occurred, each phase
was withdrawn using a syringe. Polymer concentrations and polymer molecular weight distribu-
tions were measured by size-exclusion liquid c h r o m a t o g r a p h y (SEC). The chromatographic
equipment consisted of an H P L C pump (CCPE, Tosoh), a degasser (SD-8022, Tosoh) and a
refractive-index detector (RI-8000, Tosoh). The eluant was water and the flow rate was 0.7 ml
min 1. Two three-column systems (TSKgel G3000PWxL x 3, TSKgel G6000PWxL + TSKgel
G3000PWxL × 2) were used. The columns were placed in a column thermostat (Model-557,
GL-Science). The analytical conditions for the polymers are shown in Table 2. All L L E
measurements were performed at 20 _+ 0.1°C.

2.3. Results

The experimental liquid-liquid equilibrium data for the D E X T 4 0 - P E G 4 0 0 0 - w a t e r , DEX

T 7 0 - P E G 4 0 0 0 - w a t e r , D E X 140 P E G 4 0 0 0 - w a t e r , DEX T 5 0 0 ( a ) - P E G 4 0 0 0 water and D E X

Table 2
Analytical conditions of polymers

System Eluant Flow rate Column Column temperature

(ml min i) (°C)

DEX T40- PEG4000 Water 0.7 TSKgel G3000PWxL x 3 50

DEX T70-PEG4000 Water 0.7 TSKgel G3000PWxL x 3 50
DEX 140 PEG4000 Water 0.7 TSKgel G6000PWxL+
TSKgel G3000PWxL x 2 65
DEX T500(a) PEG4000 Water 0.7 TSKgel G6000PWxL+
TSKgel G3000PWxL x 2 50
DEX T500(b)-PEG6000 Water 0.7 TSKgel G6000PWxL+
TSKgel G3000PWxL x 2 65
122 T. Furuya et al. / Fluid Phase Equilibria 103 (1995) 119-141

T 5 0 0 ( b ) - P E G 6 0 0 0 - w a t e r aqueous two-phase systems are shown in Tables 3 - 7 respectively.

The volume ratios ( = volume of top phase/volume of total system) measured are also shown in
these tables.
The accuracy of the experimental LLE data is estimated to be within _+3% from the
reproducibility. The present results for the DEX T40 PEG4000-water and the DEX T500(a)-
PEG4000-water aqueous two-phase systems are compared with the literature values (A1-
bertsson, 1986; Connemann et al., 1991) in Fig. 1. The present results coincide with the LLE
data reported in the literature, though the molecular weights of the polymers are slightly

Table 3
Liquid-liquid equilibria for the DEX T40 PEG4000 water aqueous two-phase system at 20°C

Feed Top Bottom Volume

ratio
DEX PEG Water DEX PEG Water DEX PEG Water
(wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.'¼,) (wt.%)

6.01 8.98 85.01 4.16 10.03 85.81 16.03 3.96 80.01 0.80
6.51 9.50 83.99 2.75 11.42 85.83 18.82 2.98 78.20 0.76
7.00 10.02 82.98 1.95 12.45 85.60 21.51 2.41 76.08 0.74
7.50 10.50 82.00 1.53 13.49 84.98 23.66 2.20 74.14 0.73

Table 4
Liquid-liquid equilibria for the DEX T 7 0 - P E G 4 0 0 0 - w a t e r aqueous two-phase system at 20°C

Feed Top Bottom Volume

ratio
DEX PEG Water DEX PEG Water DEX PEG Water
(wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%)

5.49 8.53 85.98 2.19 10.16 87.65 15.55 3.40 81.05 0.75
6.00 9.00 85.00 1.42 11.40 87.18 18.22 2.78 79.00 0.73
6.51 9.50 83.99 0.96 12.24 86.80 20.89 2.28 76.83 0.73
7.00 10.02 82.98 0.68 13.15 86.17 23.31 1.94 74.75 0.72

Table 5
Liquid-liquid equilibria for the DEX 140-PEG4000 water aqueous two-phase system at 20°C

Feed Top Bottom Volume

. . . . . ratio
DEX PEG Water DEX PEG Water DEX PEG Water
(wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.°/,) (wt.%) (wt.%) (wt.%)

5.03 8.00 86.97 2.09 9.32 88.59 14.31 3.41 82.28 0.75
5.52 8.57 85.91 1.39 10.46 88.15 17.24 2.81 79.95 0.74
6.00 9.00 85.00 1.06 11.29 87.65 19.38 2.38 78.24 0.73
6.52 9.51 83.97 0.83 12.30 86.87 21.05 2.03 76.92 0.72
 T. Furuya et al. / Fluid Phase Equilibria 103 (1995) 119-141 123

Table 6
Liquid-liquid equilibria for the DEX T500(a)-PEG4000-water aqueous two-phase system at 20°C

Feed Top Bottom Volume

ratio
DEX PEG Water DEX PEG Water DEX PEG Water
(wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%)

4.28 7.31 88.41 1.00 8.98 90.02 11.76 3.81 84.43 0.75
4.50 7.50 88.00 0.75 9.29 89.96 12.75 3.49 83.76 0.73
5.01 8.00 86.99 0.37 10.42 89.21 15.57 2.81 81.62 0.73
6.00 9.01 84.99 0.12 11.89 87.99 19.76 2.01 78.23 0.72

Table 7
Liquid-liquid equilibria for the DEX T500(b)-PEG6000 water aqueous two-phase system at 20°C

Feed Top Bottom Volume

ratio
DEX PEG Water DEX PEG Water DEX PEG Water
(wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%)

2.50 5.50 92.00 0.45 6.41 93.14 11.49 1.28 87.23 0.80
3.00 6.00 91.00 0.28 7.23 92.49 13.41 0.96 85.63 0.77
3.50 6.50 90.00 0.17 8.02 91.81 15.17 0.73 84.10 0.76
4.00 7.00 89.00 0.10 8.83 91.07 17.12 0.54 82.34 0.75

different. In Fig. 2, the effect o f the molecular weight o f D E X on the phase behavior is shown
by c o m p a r i n g the s m o o t h e d binodal curves obtained for the various aqueous two-phase systems.
It can be seen that the two-liquid-phase region increases with increasing D E X molecular weight.
F r o m Tables 6 and 7, it can also be seen that the two-liquid-phase region increases with
increasing P E G molecular weight.
T h e experimental average molecular weights o f the polymers in the t op and b o t t o m phases are
shown in Tables 8 - 1 2 . T he accuracy o f the experimental average molecular weights o f the
polymers is estimated to be within _+ 10% from the reproducibility. P E G samples used in this
study have a n a r r o w molecular weight distribution, so that no significant molecular weight
distribution difference was observed between the top and b o t t o m phases. However, the average
molecular weights o f D E X are different in b o t h phases because the D E X samples used show a
wide molecular weight distribution (see Table A1 in Appendix). As an example, the molecular
weight distributions o f D E X T40 in the t op and b o t t o m phases for the D E X T 4 0 - P E G 4 0 0 0 -
water aqueous two-phase system are shown in Fig. 3. " F e e d " shows the molecular weight
distribution o f D E X T40 used in this measurement. " T o p " and " B o t t o m " show that o f D E X
T40 in the to p and b o t t o m phases respectively. T he detailed molecular weight distributions are
shown in Tables A 2 - A 6 in Appendix. It can be seen that the small a m o u n t s o f low molecular
 124 T. Furuya et al. / Fluid Phase Equilibria 103 (1995) 119 141

20 I 1 I

o~
15
l @ '
VlO • 0
L~
LU
Q_

q.'o
0 I I I I
0 5 10 15 20 25

DE)< (wt%)
Fig. 1. Liquid-liquid equilibria for the DEX T40 P E G 4 0 0 0 - w a t e r and DEX T500(a) PEG4000 water aqueous
two-phase systems at 20'~C: ©, DEX T40 (present work); [], DEX T500(a) (present work); 0 , DEX DI7 PEG4000
(Albertsson, 1986); II, DEX 500-PEG3000 ( C o n n e m a n n et al., 1991).

20 , L , ,

15
F
Q~ Two-liquid phases

Si " " " " ......

0 i i i t
0 5 10 15 20 25
DE× (wt%)
Fig. 2. Effect of molecular weight of DEX on phase diagrams for D E X - P E G 4 0 0 0 - w a t e r aqueous two-phase systems
at 20"C: - - , DEX T40; - . . , DEX T70; - , DEX 140; - - - , DEX T500(a).
 T. Furuya et al./ Fluid Phase Equilibria 103 (1995) 119-141 125

Table 8
Average molecular weight of polymers in the top and bottom phases for the DEX T40-PEG4000 water aqueous
two-phase system at 20c'C

DEX T40 PEG4000

Feed Top Bottom Top Bottom

DEX PEG M. Mw Mw/M~ M n M,~ MwlM . M, Mw MwlM, Mr, Mw MwlMn

(wt.%) (wt.%)

6.01 8.98 14000 24400 1.74 23700 47800 2.02 3000 3100 1.03 3000 3100 1.03
6.51 9.50 12800 22900 1.79 24400 45100 1.85 3000 3100 1.03 3100 3200 1.03
7.00 10.02 10300 16700 1.62 22700 43800 1.93 3000 3100 1.03 3000 3100 1.03
7.50 10.50 9300 14500 1.56 21700 42000 1.94 3000 3100 1.03 3000 3100 1.03

Table 9
Average molecular weight of polymers in the top and bottom phases for the DEX T 7 0 - P E G 4 0 0 0 - w a t e r aqueous
two-phase system at 20°C

DEX T70 PEG4000

Feed Top Bottom Top Bottom

DEX PEG Mn Mw Mw/M n M. Mw Mw/M,, Mn Mw Mw/M n M, Mw Mw/M,

(wt.%) (wt.%)

5.49 8.53 27500 44500 1.62 47800 78700 1.65 2900 3000 1.03 2900 3000 1.03
6.00 9.00 21600 34600 1.60 46600 75900 1.63 2900 3000 1.03 2900 3000 1.03
6.51 9.50 17700 28600 1.62 45400 73700 1.62 2900 3000 1.03 2900 3000 1.03
7.00 10.02 15400 24300 1.58 44400 72400 1.63 2900 3000 1.03 2900 3000 1.03

Table 10
Average molecular weight of polymers in the top and bottom phases for the DEX 140-PEG4000 water aqueous
two-phase system at 20°C

DEX 140 PEG4000

Feed Top Bottom Top Bottom

DEX PEG M, Mw M,,,/Mn M n Mw Mw/M, Mn Mw Mw/Mn Mn Mw Mw/Mn

(wt.%) (wt.%)

5.03 8.00 24400 61000 2.50 58500 176700 3.02 3000 3100 1.03 3000 3100 1.03
5.52 8.57 19200 42500 2.21 57500 171100 2.98 2900 3100 1.07 3000 3100 1.03
6.00 9.00 17000 35400 2.08 60300 158800 2.63 2900 3100 1.07 3000 3100 1.03
6.52 9.51 14400 26600 1.85 56100 150300 2.68 3000 3100 1.03 3000 3100 1.03
 126 T. Furuya et al. / Fluid Phase Equilibria 103 (1995) 119-141

Table 11
Average molecular weight of polymers in the top and bottom phases for the DEX T500(a)-PEG4000 water aqueous
two-phase system at 20°C

DEX T500(a) PEG4000

Feed Top Bottom Top Bottom

DEX PEG Mn Mw M,,/Mn Mn Mw Mw/Mn Mn Mw Mw/M n M, Mw Mw/Mn

(wt.%) (wt.%)

4.28 7.31 118800 184100 1.55 222300 548100 2.47 3000 3100 1.03 2800 3000 1.07
4.50 7.50 101700 156900 1.54 197800 516200 2.61 2900 3100 1.07 2900 3100 1.07
5.01 8.00 78500 122400 1.56 211100 494500 2.34 2900 3000 1.03 2800 3000 1.07
6.00 9.01 55200 82700 1.50 199500 476700 2.39 2900 3000 1.03 2800 3000 1.07

Table 12
Average molecular weight of polymers in the top and bottom phases for the DEX T500(b)-PEG6000 water aqueous
two-phase system at 20°C

DEX T500(b) PEG6000

Feed Top Bottom Top Bottom

DEX PEG Mn Mw M,,c/Mn Mn Mw Mw/Mn M n M,,, Mw/M, Mn Mw Mw/Mn

(wt.%) (wt.%)

2.50 5.50 76200 176800 2.32 202500 520000 2.57 8300 8700 1.05 8100 8500 1.05
3.00 6.00 68500 171400 2.50 188100 492900 2.62 8400 8800 1.05 8400 8700 1.04
3.50 6.50 59700 147900 2.48 182200 487400 2.68 8600 8900 1.03 8300 8600 1.04
4.00 7.00 47900 78300 1.63 177800 467400 2.63 8500 8900 1.05 8000 8400 1.05

w e i g h t f r a c t i o n s o f D E X T 4 0 are p a r t i t i o n e d to the t o p phase, while t h o s e o f high m o l e c u l a r

w e i g h t f r a c t i o n s are p a r t i t i o n e d to the b o t t o m phase.
I n Figs. 4 ( a ) a n d 4(b), the w e i g h t - a v e r a g e m o l e c u l a r weights o f D E X T 4 0 a n d D E X 140 in
b o t h p h a s e s f o r e a c h s y s t e m are p l o t t e d a g a i n s t the tie-line length, respectively. T h e tie-line
length is defined as follows:
Tie-line length =
ft. TOP
/~WDEX
. BOTh, 2
-- WDEX)
(. , T O P ,~,BOT~2]I/2
At- ~ 4 p E G - - vVpEGl ] (1)

w h e r e w d e n o t e s the w e i g h t fraction. It is s h o w n t h a t the w e i g h t - a v e r a g e m o l e c u l a r weights o f

D E X increase with d e c r e a s i n g tie-line length in b o t h p h a s e s as p o i n t e d o u t b y C o n n e m a n n et al.
(1991). W i t h d e c r e a s i n g tie-line length, the D E X c o n c e n t r a t i o n in the t o p p h a s e is increased.
T h u s , m o r e D E X f r a c t i o n s with a h i g h e r m o l e c u l a r w e i g h t h a v e to be p a r t i t i o n e d to the t o p
p h a s e , r e s u l t i n g in a h i g h e r a v e r a g e m o l e c u l a r weight o f D E X . C o r r e s p o n d i n g l y , the a v e r a g e
m o l e c u l a r w e i g h t o f D E X in the b o t t o m p h a s e is increased, since the D E X f r a c t i o n w h i c h
 T. Furuya et al. / Fluid Phase Equilibria 103 (1995) 119-141 127

1.2 I I

1.0 0 0

0 EHO
[] []
0
v
I O.8 0 H []

O
[] S
0.6 []
i
0 o
A
[]
0.4 O []
[]
O
[] el
0.2 o aaaa
OH ~A &A

0.0 ._~i=t~ I ,~a~j.~ o

3.0 4.0 5.0 6.0
IogM (-)
Fig, 3. Molecular weight distribution of DEX T40 in top and bottom phases for the DEX T40-PEG4000-water
aqueous two-phase system at 20°C: O, feed with DEX 7.5 wt.% and PEG 10.5 wt.%; A, top; [~, bottom.

partitioned to the top phase has a lower molecular weight than that in bottom phase (see also
Fig. 7 shown later).

3. Correlation

3. I. Distribution function

As shown in Fig. 3, the D E X sample has a wide molecular weight distribution. To describe
the molecular weight distribution o f D E X , the following F distribution function (Cotterman et
al., 1985; Cotterman and Prausnitz, 1985; Kehlen and Rfitzsch, 1983) was adopted:

- fl~F(~) exp- (2)

where F is a g a m m a function and the parameter 7 fixes the origin where F is zero; c~ and fl are
adjustable parameters. The mean 0 and the variance 0-2 are given by the following equations
(Cotterman et al., 1985):

0 = ~fl + 7 (3)
0 -2 = CXj~2 (4)
 128 T. Furuya et al./ Fluid Phase Equilibria 103 (1995) 119-141

5.0 I I I

4.0

'!-,
o 3.0
X

2.0

1.0 I I I

10 15 20 25 30
(a) Tie-Line Length wt%)

2.0

2~ .... - ~ - 2 > - -~_

1.5 _ ,4 ~'-~--z5 -

v
I
U9

1.0-
X

0-. -.

0.5-
-"---0-_._
~-0

0.0 I I

10 15 20 25
(b) Tie-Line Length (wt%)
Fig. 4. (a) Experimental w e i g h t - a v e r a g e molecular weight o f D E X T40 in t o p a n d b o t t o m phases for D E X
T 4 0 - P E G 4 0 0 0 - w a t e r aqueous two-phase systems at 2 0 C : - © - , D E X T40 in top; - A , D E X T40 in b o t t o m ; . . . . ,
feed D E X T40, Mw = 3.8 x 10 4. ( b ) Experimental w e i g h t - a v e r a g e molecular weight of D E X 140 in top and b o t t o m
phases for D E X 1 4 0 - P E G 4 0 0 0 - w a t e r aqueous two-phase systems at 20°C: © , D E X 140 in top; A - , D E X 140
in b o t t o m ; . . . . . feed D E X 140, Mw = 1.398 x 105.
 T. Furuya et al. / Fluid Phase Equilibria 103 (1995) 119-141 129

Table 13
Parameters of the F distribution functions

Polymer e /~ 7

DEX T40 9.5596 0.1267 3.17

DEX T70 13.8246 0.0861 3.50
DEX 140 11.7873 0.1358 3.23
DEX T500(a) 9.2103 0.1334 4.21
DEX T500(b) 10.3481 0.1369 4.00

The normalization condition is as follows:

fo~ F(I) d I = 1 (5)

The parameters c~, /~ and 7 for D E X T40, T70, 140, T500(a) and T500(b) are listed in Table
13. As an example, the correlated result of the molecular weight distribution for D E X T40 is
shown in Fig. 5.

1.2 I I

1.0 0

°°

0.8

0.6
0

~0.4
"0
O ~0 ,

0.2

3.0
oO~
0.0 _o~O
4.0
I

5.0
, o 6.0
IogM (-)
Fig. 5. Molecular weight distribution of DEX T40 and F distribution function: ©, feed; , calculated.
130 T. Furuya et al. / Fluid Phase Equilibria 103 (1995) 119 141

3.2. Laguerre-Gauss quadrature method

The Laguerre-Gauss quadrature method was used to choose the pseudocomponents to

describe DEX (Cotterman and Prausnitz, 1985). The Laguerre-Gauss quadrature method is
given by the following equation (Yamashita and Satake, 1965):

fo f ( x ) e x p ( - x ) dx =
i=l
~o(x~)f(xi) (6)

where f ( x ) is any function, e)(x~) is the weighing factor and f(x~) is the function to be integrated
at the quadrature point x~. Comparing Eqs. (2) and (6), we see that x = ( I - 7 ) / f l , and the
following equation can be derived:

F(I) d I = --x ~ ~ e x p ( - x ) dx (7)

From Eqs. (6) and (7)} the following equation can be derived:
1 1 1 1
exp( - x) dx =
3(
f0-~ X ~ ~ o)(x, ) x i (8)
i=l

When the number of quadrature points (the number of pseudocomponents) s is given, the
weighting factors {o(xg) at the quadrature points x~ are given in tabulated values. To match the
weighting factors ~o(x~) and quadrature points xi in the range of the distributed variable, the
following equations can be used:
I~ =/Jx~ + 7 (9)
{o(x,)p
{o(L) - (10)
exp(-xi)
The weight fraction wi of pseudocomponent i is given by the following equation:
w~ = co(Ii )F(Ii ) (11)
From Eqs. (9) -(11), the molecular weights Mi ( = Is) and weight fractions w~ of the pseudocom-
ponents can be obtained. In this study, eight quadrature points were used.

3.3. Modified Flory Huggins equation

When two aqueous phases are in equilibrium with each other, the chemical potential
differences (A/~i =/ti -/~pure) of component i in both phases are identical:
(Ap~) v°p = (A/~) B°T i = 1, 2 . . . . n (12)
Simultaneous solution of Eq. (12) for all components gives equilibrium compositions for the
aqueous two-phase system, when a suitable chemical potential equation can be obtained. The
U N I Q U A C equation (Kang et al., 1989; Kang and Sandler, 1987) and the osmotic virial
equation (Gaube et al., 1993b; King et al., 1988) have been adopted. Gaube et al. (1993c) and
Haynes et al. (1989) succeeded in evaluating the values of second and third virial coefficients
from the vapor pressure data for water (VLE). The Flory-Huggins equation has also been
 T. Furuya et al./ Fluid Phase Equilibria 103 (1995) 119-141 131

widely applied to predict the chemical potentials of polymer solutions (Kang and Sandler, 1987;
Diamond and Hsu, 1990). However, the Flory-Huggins equation is not necessarily suitable for
systems which have specific interactions such as hydrogen bonding (King et al., 1988; Yu et al.,
1993). Further, to correlate LLE of polymer solutions quantitatively, the Flory-Huggins
interaction parameter Z is not constant in many cases and it depends on the composition and
polymer molecular weight (Iwai et al., 1990). In this study, an attempt is made to improve the
Flory-Huggins equation empirically. To take into account deviations from random mixing
caused by specific interactions such as hydrogen bonding, the exponent ~,j is empirically
introduced into the interaction term of the conventional Flory-Huggins equation. A modified
Flory-Huggins model proposed here for the Gibbs energy of mixing is as follows:

RT i j>i
where ~i and m~ denote the volume fraction of component i and the ratio of the molar volume
of component i to a reference volume, respectively. Here, the reference volume was taken to be
that of component 3, water (thus m 3 1). Z0 is an interaction parameter between components
=

i and j, R is the gas constant and T is the temperature. The present form, Eq. (13), is suggested
by studies of H/da (1983) and Kumagae et al. (1992) on electrolyte solutions. When ~;2 = 1 and
o~ji = 1, Eq. (13) becomes the conventional Flory-Huggins equation. As ~/i and ~j (volume
fraction) are smaller than unity
@~ij • ~/i (O~ij < 1) (14a)
~ 0 < Oi (e,j > 1) (14b)
These expressions indicate that the contact probability of molecules i with molecules j can be
adjusted by introducing the exponent ~0. This means that the deviations from random mixing
in the aqueous polymer solutions can be evaluated empirically. For the same components, the
following expression is valid:

O~ii = (Xjj = 1 (15)

The chemical potential difference for component i can be obtained by differentiation of the
excess Gibbs energy of mixing with respect to the amount of the component, n~, and is given by
the following equation:

RTA]Ai- ln ~Ji -q- l - mi ~j mj

~tJ -b mi ~j )('ij O~O~ laij-1)

-- m~ ~ Z Zj~ ~ ? ~b~J (~jk + ~ j -- 1) (16)

j k>j

3.4. Results

3.4. I. L i q u i d - l i q u i d equilibria
To correlate the LLE for the D E X ( 1 ) - P E G ( 2 ) - w a t e r ( 3 ) aqueous two-phase system using
Eq. (16) based on Eq. (12), the specific volumes of components are required to calculate the
132 T. Furuya et al. I FluM Phase Equilibria 103 (1995) 119 141

volume fractions. In this study, 0.626 c m 3 g ~ and 0.832 c m 3 g-~ were used for the specific
volumes of DEX and PEG respectively (Kang and Sandier, 1987).
For a ternary system, the modified Flory-Huggins equation given by Eq. (16) contains three
interaction parameters g0, which characterize the mutual interaction between components i and
j, and six adjustable parameters c% which characterize the deviation from random mixing. Gaube
et al. (1993c) and Haynes et al. (1989) succeeded in evaluating the second and third virial
coefficients used in the osmotic virial equation from the vapor pressure data for water (VLE).
However, there are few VLE data in the literature (Gaube et al., 1993c; Haynes et al., 1989) and
the molecular weights of polymers used in the literature are different from those used in this
study. Therefore, it is difficult to determine the values of interaction parameters from VLE data.
In this study, they were determined by fitting the model to the experimental data by minimizing
the deviation defined by the following equation:

Deviation = 100 ,
± ]
~wt",piE×P_ W,p~ ) 2 X 4)
},,: (17)
=lp=li=|

where W,p~
- Exp.and w,pi
Calc. are the experimental and calculated weight fractions of component i in the

phase p at tie-line t respectively. In the present correlation for LLE, the flash-calculation
algorithm (Cotterman and Prausnitz, 1985) was adopted. The compositions of both phases and
the volume ratio were calculated from the composition of feed.
From the correlated results of LLE for the DEX T40-PEG4000-water, DEX T70-
PEG4000-water, DEX 140 PEG4000-water and DEX T500(a) PEG4000-water aqueous
two-phase systems, the parameters Zl2 and )~13showed different optimum values for each system.
Therefore Zu (J = 2 for PEG a n d j = 3 for water) was expressed empirically as a function of the
ratio of molecular weights M ~ / M j . From the data regression, we can obtain the following
expression:

+ a j log, , ÷ b,,r log, ,1 (18)

\ JVJjl \Mill
where M~ and Mj are the molecular weights of the pseudocomponents of DEX and of
component j respectively. The weight-average molecular weight of PEG was used for M2. Z °, a
and b are the empirical parameters. Six other cqj parameters are needed for correlation. Since ~13,
~3~ and ~21 were found to be more effective at improving the correlated results, these three
parameters were adjusted by fitting and the other ~j parameters were set to unity. These
parameters as determined are presented in Table 14.
Further, the LLE for the DEX T500(b)-PEG6000 water aqueous two-phase system were
correlated by adjusting 2:°2 and Z23 because )~0 was found to be dependent on the molecular
weight of PEG. It was found that the other constants a u and b u in Eq. (18) were not affected
by the molecular weight of PEG. The values of Z% and )~23for the PEG6000 system are also
presented in Table 14. Deviations between experimental and correlated LLE are shown in Table
15. As an example, the correlated results for the DEX 140 PEG4000-water aqueous two-phase
system are shown in Fig. 6. In this figure, dotted line shows a correlated result by using the
conventional Flory-Huggins equation. The correlated results by using the modified F l o r y - H u g -
gins equation are better than those by using the conventional Flory-Huggins equation.
 T. Furuya et al. / Fluid Phase Equilibria 103 (1995) 119 141 133

T a b l e 14
I n t e r a c t i o n p a r a m e t e r s for D E X ( 1 ) P E G ( 2 ) - w a t e r ( 3 ) aqueous two-phase systems

Xo % a,) b0

PEG4000 PEG6000

Z]~2 0.03246 0.01208 o~,3 = 1.0003 a,2 = --6.297 x 10 -3 b12 = 5.817 x 10 4

Z°3 0.5011 0.5011 c%, =0.8591 a , 3 = 1.201 x 10 3 b13 = --9.535 x 10 4
Z23 0.2953 0.2506 0121 = 0.7736

T a b l e 15
Deviations in correlation for aqueous two-phase systems

System Deviation " (wt.%)

DEX T40- PEG4000-water 0.86

DEX T70-PEG4000-water 0.68
DEX 140 P E G 4 0 0 0 water 0.49
DEX T500(a)- PEG4000-water 0.56
DEX T500(b) P E G 6 0 0 0 - w a t e r 0.32

a D e v i a t i o n = 100{[El4=, Ep2 =, E 3 , (w~,~v" -~,m'c"l~)2]/(6x 4)} '/2, where W,p

E,p.
i a n d wtp
c,,~.
i are the experimental a n d
calculated weight fractions o f c o m p o n e n t i in phase p at tie-line t, respectively.

20 l I I I I

15

v 10

Iii
12.

0 I I I I

0 5 10 15 20 25
DEX (wt%)
Fig. 6. Calculated a n d experimental L L E (tie-line) for the D E X 1 4 0 - P E G 4 0 0 0 - w a t e r aqueous two-phase system at
20°C: 0 , feed; © - - - © , experimental; - - , calculated with modified F l o r y - H u g g i n s equation; . . . , calculated with
c o n v e n t i o n a l F l o r y - H u g g i n s equation.
134 T. Furuya et al. / Fluid Phase Equilibria I03 (1995) 119-141

6.0 I I

A
A
5.0 ¸

V I 4.0
LO
I
o' I " - - 3 . 0
×

2.0 O

1.0 O

0.0 = n
10 15 20 25

Tie-Line Length (wt%)

Fig. 7. Calculated and experimental weight-average molecular weight of DEX T500(a) in top and bottom phases for
the DEX T500(a)-PEG4000 water aqueous two-phase system at 20"C: ©, experimental in top; A, experimental in
bottom; • - , calculated in top; - • - , calculated in bottom; . . . , feed DEX T500(a), Mw = 4.76 x 105.

3.4.2. Average molecular weight

The average molecular weights calculated from the correlated results of L L E in the top and
b o t t o m phases for the D E X T 5 0 0 ( a ) - P E G 4 0 0 0 - w a t e r aqueous two-phase system are shown in
Fig. 7. The calculated weight-average molecular weight decreases with increasing tie-line length
in both phases. It can be seen that the trend in the experimental results can be explained by the
present calculation.

4. Conclusions

The liquid-liquid equilibrium data for d e x t r a n - p o l y ( e t h y l e n e glycol) - water aqueous two-

phase systems with various molecular weights were reported at 20°C. The molecular weight
distributions of dextran and poly(ethylene glycol) in the top and b o t t o m phases were also
measured. Since the dextran sample used here was a polydisperse polymer, the molecular weight
distributions of dextran were different in the two phases. On the other hand, no significant
difference in molecular weight distribution in the two phases was observed because the
poly(ethylene glycol) samples used were found to be monodispersed.
The interaction term of the conventional F l o r y - H u g g i n s equation was empirically modified to
take deviations from random mixing into account by introducing an exponent parameter ~ij. The
interaction parameter g~j was empirically expressed as a function of dextran molecular weight.
 T. Furuya et al. / Fluid Phase Equilibria 103 (1995) 119-141 135

Further, a F distribution function was used to express the molecular weight distribution of
DEX. Also the Laguerre-Gauss quadrature method was used to choose pseudocomponents of
DEX to apply a continuous thermodynamic approach. The modified Flory-Huggins equation
proposed here coupled with the continuous thermodynamic approach can be used to correlate
the liquid-liquid equilibria and the molecular weight distribution in both phases with fairly
good agreement with the experimental data.

Acknowledgments

We gratefully acknowledge the financial support provided by the Grant-in-Aid for Encourage-
ment of Young Scientists (1993, 05 750 676), The Ministry of Education, Science and Culture,
Japan. We also thank Mr. K. Nakada and Ms. J. Zhu for their support in this work.

List of symbols

alj constant in Eq. (18)

blj constant in Eq. (18)
F(I) distribution function
G Gibbs free energy
I distributed variable (taken here as molecular weight)
m molar volume ratio of polymer to water
M molecular weight
Mn number-average molecular weight
Mw weight-average molecular weight
n amount of substance (mol)
R gas constant (J mol ~ K -~)
T temperature (K)
s number of quadrature points
W weight fraction

Greek letters

7 parameters used in distribution function

~6 exponent in Eq. (13)
F gamma function
chemical potential
0-2 variance
Flory-Huggins interaction parameter between components i and j
z5 constant in Eq. (18)
volume fraction
(D quadrature point weighting factor
136 T. Furuya et al. / Fluid Phase Equilibria 103 (1995) 119-141

Subscripts

i, j components i and j
1 dextran (DEX)
2 poly(ethylene glycol) (PEG)
3 water

Superscripts

BOT bottom phase (DEX-rich phase)

TOP top phase (PEG-rich phase)
pure pure component

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Appendix

Table AI
Molecular weight distribution of DEX used in this experiment

DEX T40 DEX T70 DEX 140 DEX T500(a) DEX TS00(b)

Molecular dW/d log M Molecular dW/d log M Molecular dW/d log M Molecular dW/d log M Molecular d W/d log M
weight weight weight weight weight

400630 1 . 0 4 7 7 × 10 2 1313286 1.3472 x 10 4 3346018 3 . 9 5 2 5 x 10 3 25478782 9 . 7 2 8 8 × I0 - 5 11846010 4 . 0 7 5 7 x 10 3

268060 2 . 7 4 9 5 x 10 - 2 284085 2 . 3 6 4 2 × 10 - 2 1828502 1.3118 × 10 . 2 14358751 2 . 1 7 3 3 x 10 3 6513323 2.1913 x I0 2
202175 5 . 6 1 7 3 x 10 - 2 190923 3.0101 x 10 ~ 1051746 4 . 1 4 2 7 x 10 - 2 8380416 1 . 0 2 0 2 × 10 2 3729102 6 . 0 1 1 7 × 10 2
152481 1.2448 x 10 -~ 128414 6 . 6 8 3 9 x 10 ~ 633983 1.2361 x 10 - I 5057348 2 . 9 7 7 7 x 10 2 2217768 1.2211 × 10
118064 2 . 3 9 9 4 x 10-~ 90524 1.0766 398753 3 . 4 8 2 6 x 10 t 3150570 6 . 7 1 3 4 x 10 2 1366698 2.2201 × 10 -~
92116 3 . 9 2 7 8 x 10 ~ 63813 1.2614 260552 6 . 3 9 3 2 x 10 - I 2022864 1.2378 x 10 1 870603 3.8691 x 10 -~
71870 5 . 5 8 5 3 x 10 - I 46500 1.1756 176098 7 . 3 5 2 0 x 10 i 1336463 2 . 0 8 0 9 x 10 i 571860 6 . 3 4 7 5 × 10 i
56074 7 . 1 1 2 8 x 10 ~ 36848 9.6817 x lO-I 122572 8 . 2 9 5 2 x 10 i 907108 3 . 3 8 8 6 x 10 i 386390 9 . 1 3 0 5 × 10 i
46272 8.3069 × 10-i 29200 7 . 4 3 1 2 × 10 - t 87480 8 . 9 9 2 0 x 10 1 631499 5 . 3 0 1 4 x 10 -~ 267893 1.0286
39229 9 . 2 1 9 3 x 10 i 23139 5.4051 x 10 ~ 63742 8 . 1 9 0 4 x 10 -~ 450194 7.7601 x 10 i 190128 8 . 7 1 6 9 x 10 - t
33257 9 . 8 6 0 6 x 10 i 18149 3 . 7 1 8 4 x 10 i 47209 6.6881 x 10 -~ 328126 1.0075 137786 6 . 9 9 4 3 x 10 t
28195 1.0181 13948 2 . 4 4 0 0 x 10 t 35386 5 . 2 0 5 7 x 10 ~ 244117 1.0779 101715 5.8743 x 10 - I
23903 1.0156 10718 1 . 5 1 4 0 × 10 i 26726 3 . 9 7 3 4 x 10 - I 185082 9 . 3 0 0 5 x 10 1 76300 4 . 3 8 9 9 x 10 i
20265 9 . 7 4 2 3 x 10 L 8237 8 . 8 8 8 4 x 10 2 20251 2 . 9 8 8 9 x 10 ~ 142775 7 . 2 0 8 0 × 10 i 58017 2 . 7 1 4 5 x 10 - t
16901 8 . 9 4 0 6 x 10 t 6329 4.9481 x 10 2 15328 2.2192 x 10-' 111882 5 . 7 2 3 4 x 10 ' 44610 1.5043 x 10 -L
14019 7.8610× 10 t 4864 2.4850× 10 2 11538 1.6089 x 10 - t 88916 4.5891 × 10 i 34599 8 . 0 4 5 3 x 10 2
11629 6.6111 x 10 t 3738 1.0062x 10 -2 8600 1.1355 x 10 i 71552 3.3727× 10 - I 27004 4.6727 × I0 2
9647 5 . 2 7 8 6 x 10 t 2873 2 . 8 2 3 8 x 10 3 6320 7 . 8 5 4 9 x 10 . 2 58207 2 . 2 3 2 6 × 10 21156 2 . 9 8 9 4 x 10 2
8002 4 . 0 0 1 0 x 10 t 2207 1.9297 x 10 3 4559 4 . 8 9 8 7 × 10 - 2 47793 1.3508 × 10 16598 1.9760 x 10 2
6637 2 . 8 8 1 4 x 10 -~ 1696 1 . 0 6 4 0 x 10 3 3214 2 . 5 7 1 3 x 10 2 39541 7 . 9 7 6 0 x 10 2 13007 1.2997 x 10 2
5505 1 . 9 9 8 0 x 10 i 1303 7 . 3 8 7 6 x 10 . 4 2205 1.0152 x 10 2 32913 4 . 7 3 2 7 × 10 . 2 10157 9 . 1 1 0 0 x 10 - 3
4567 1 . 3 2 6 0 x 10 ~ 1001 8 . 1 4 5 7 x 10 . 4 1466 2 . 9 4 1 7 × 10 3 27518 2 . 9 4 5 8 × 10 2
3789 8 . 3 4 3 3 x 10 2 940 7 . 4 2 2 3 x 10 4 23071 1.6668 x 10 2
3142 5.3016x 10 2 19366 1.0936x 10 2
2607 3 . 3 3 8 8 × 10 2 16251 8 . 4 0 5 9 × 10 3
2162 1 . 9 3 1 6 × 10 2
1793 7.9031 × 10 . 3
1487 4 . 6 3 7 3 × 10 3
138 T. Furuya et al./ Fluid Phase Equilibria 103 (1995) 119-141

Table A2
Molecular weight distribution of DEX T 4 0 in t h e t o p a n d b o t t o m phases for the DEX T40 PEG4000 water aqueous two-phase s y s t e m a t 20~C

Feed: DEX T 4 0 6.01 w t . % Feed: DEX T 4 0 6.51 w t . % Feed: DEX T40 7.00 wt.% Feed: DEX T40 7.50 wt.%
PEG4000 8.98 w t . % PEG4000 9.50 wt.% PEG4000 10.02 w t . % PEG4000 10.50 w t . %

Molecular Top Bottom Top Bottom Top Bottom Top Bottom

weight dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M

400630 6 . 2 9 5 6 × 10 3 7.0170× I0 3 7.1632× 10 3

268060 1.5015 × 10 2 1.8025 × 10 - ~ 2 . 2 6 4 8 × 10 2 2 . 2 2 1 0 x 10 2
202175 2 . 3 5 5 4 × 10 3 3 . 8 4 0 2 × 10 - 2 6.1890x 10 5 5 . 4 6 1 2 × 10 2 4.6596x 10 4 6.0296× 10 2 5.8926× 10 2
152481 8.0051 × I 0 3 8 . 5 5 9 7 × IO 2 2.1081 x 10 4 1.2664× 10 -~ 1.9171 x 10 4 1.3256× 10 ~ 1.3126× 10 1
118064 2 . 5 8 0 8 x 10 2 1.5465 × 10 1.4246 x I0 3 2 . 3 4 7 8 × 10 ~ 3 . 6 6 2 8 × 10 - 5 2 . 4 7 1 8 x 10 t 2 . 0 3 9 0 x 10 4 2 . 4 5 9 6 × 10 i
92116 6 . 4 0 5 5 x 10 2 2 . 3 5 6 3 × 10 9 . 3 6 7 5 × 10 3 3 . 7 0 7 7 × 10 ~ 1.4096 × 10 :~ 3 . 9 2 1 3 x 10 - t 6 . 4 4 0 2 x 10 4 3 . 9 3 3 8 × 10 1
71870 1 . 2 9 1 4 × 10 ~ 3 . 1 2 2 5 x 10 2 . 7 5 1 3 x 10 2 5.064(I x 10 ~ 6 . 1 8 8 6 × 10 -:~ 5 . 4 2 3 9 × 10 t 1.9385 x 10 3 5 . 5 0 4 6 × 10 1
56074 2.1841 × 10 -~ 3 . 7 0 6 7 x 10 -~ 6 . 0 4 8 5 x 10 -" 6 . 1 5 7 4 x 10 -~ 1.677(I × 10 2 6 . 7 2 9 6 × 10 ~ 6 . 0 0 4 8 x I0 3 6 . 8 8 8 9 × I0
46272 3 . 2 0 8 3 × 10 ~ 4 . 0 8 2 9 x 10 1.0873x10 ~ 6.8631 × 1 0 -~ 3.6015x10 2 7.6786×10 1 1.5276×10 2 7.9593x10 1
39229 4 . 2 9 1 7 x 10 ~ 4 . 2 6 2 3 x 10 1.6954x 10 ~ 7 . 2 1 6 7 x 10 ~ 6.5806× 10 - 2 8.2514x 10 1 3.I600× 10 2 8 . 6 5 8 7 × 10 1
33257 5 . 3 2 5 7 x 10 ~ 4.2641 × 10 -~ 2.3846x 10-~ 7 . 2 4 9 8 x 10 ~ 1.0640× 10 t 8.4701 × 10 i 5.6140× 10 2 9.0170× 10 i
28195 6.2072x10 ~ 4.1132x10 3 . 0 9 0 7 x 10 ~ 6.9631 × 10-~ 1.5391 × 10 t 8 . 3 3 9 8 × 10 1 8 . 8 1 5 3 × 10 2 9.0200x 10 i
23903 6 . 7 9 1 9 x 10 ~ 3.8221 × 10 3.7037×10 t 6.4914 ×10-1 2.0394x10 t 7.8740×10 1 1.2635x10 i 8.6644x10 i
20265 7 . 0 2 6 4 x 10 ~ 3 . 4 2 5 8 x 10 4 . 1 2 2 8 × 10 ~ 5.7845 × 10 t 2 . 4 8 6 7 × 10 i 7.1786× 10 1 1.6481 × 10 i 7.9696x 10 i
16901 6 . 8 8 7 6 x 10 t 2 . 9 4 6 0 × 10 4 . 2 7 3 0 x 10 ~ 4 . 9 5 4 5 x 10 t 2 . 7 8 4 7 x 10 ~ 6 . 2 0 4 4 x 10 ~ 1.9548 x 10 ~ 6 . 9 7 3 7 x 10 -~
14019 6.3751 x 10 -~ 2.4377x10 -~ 4 . 1 5 0 8 x 10 ~ 4.0650× 10 -~ 2.8780x 10 ~ 5 . 1 2 8 9 x 10 ~ 2 . 1 2 4 7 x 10 ~ 5 . 8 1 5 2 x 10
11629 5.5986×10 t 1.9294×10 3.7745x 10 ~ 3.1716×10 ~ 2.7708×10 ~ 4.0162x10 ~ 2.1195x10 ~ 4.5994x 10
9647 4 . 6 5 8 0 × 10 ~ 1.4685 × 10 3.2361 x 10 ~ 2 . 3 6 3 9 × 10 ~ 2 . 4 7 4 8 x 10 ~ 3 . 0 0 1 4 x 10 -~ 1 . 9 5 6 0 x 10 ~ 3 . 4 3 2 4 x 10
8002 3 . 6 8 3 8 × I 0 -~ 1 . 0 6 7 3 × I 0 -~ 2 . 6 0 5 6 × 10 ~ 1 . 6 7 3 4 × 10 ~ 2 . 0 7 5 4 × 10 -~ 2 . 1 2 8 5 x 10 t 1.6863 x 10 t 2.4361 x 10
6637 2 . 7 7 7 3 × 10 ~ 7 . 5 6 3 4 × 10 2 1.9911 × I0 ~ 1.1432 × I 0 ~ 1.6481 × 10 ~ 1.4585 x 10 ~ 1.3687 x 10 ~ 1.6367 x 10 - t
5505 2 . 0 2 0 4 x 10 1 5 . 2 7 6 5 x 10 2 1.4604 x 10 ~ 7 . 3 0 6 6 × 10 2 1.2440 x 10 ~ 9 . 7 5 7 2 x 10 2 1.0562 × 10 ~ 1.0478 x I 0 -~
4567 1.4224x 10 -~ 3.5514x 10 . 2 1 . 0 2 7 0 × 1 0 -~ 4.4167×10 -2 8 . 9 9 4 7 x 10 2 6.2433×10 2 7 . 8 3 9 9 × 10 2 6 . 4 9 5 6 x 10 2
3789 9 . 7 4 6 9 x 10 2 2 . 4 2 5 6 x 10 2 7.1132×10 2 2.4362×10 2 6.3133×10 2 4.0065× 10 2 5.6201 × 1 0 2 4.4254× 10-2
3142 6.5396× 10 2 1.6333 x 10 2 4.7330× 10 2 1.1849 × 10 2 4.3477× 10 2 2 . 4 9 2 5 × 10 2 3.9162x 10 2 3.2031 x 10 2
2607 4 . 3 8 7 2 x 10 2 1 . 1 3 6 9 x 10 z 3.1832× 10 2 5 . 1 8 2 5 x 10 3 2.9349× 10 2 1.5491 × 10 2 2.7219× 10 ~ 2.3350× 10 2
2162 2 . 9 9 1 4 x 10 2 8 . 1 3 6 0 x 10 3 2.1817×10 2 2.1711 x l O 3 1.9539x10 2 9.8093× 10 3 1.9205× 10 2 1.7070× 10 2
1793 5 . 9 7 1 0 × 10 - 3 1.2318 × 10 - 2
1487 1.2335 × 10 2

Table A3
Molecular weight distribution of DEX T 7 0 in t h e t o p a n d b o t t o m phases for the DEX T70 PEG4000 water aqueous two-phase system at 20°C

Feed: D E X T 7 0 5 . 4 9 w t . % Feed: DEX T70 6.00 wt.% Feed: DEX T 7 0 6.51 w t . % Feed: DEX T70 7.00 wt.%
PEG4000 8.53 w t . % PEG4000 9.00 wt.% PEG4000 9.50 wt.% PEG4000 10.02 w t . %

Molecular Top Bottom Top Bottom Top Bottom Top Bottom

weight dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M

1313280 8.3099× I0 s 1.3617 × 10 - 4 1.7644 × I 0 - 4 1.9090 × 10 4

284088 6 . 6 2 3 0 × 10 s 2 . 0 5 3 6 x 10 2 4 . 4 2 5 2 x 10 5 2 . 8 8 0 6 × 10 - z 3 . 0 7 5 6 × 10 - 2 2 . 9 0 8 2 × 10 2
190928 1 . 1 0 3 2 x 10 2 2 . 7 8 5 7 x 10 ~ 1.8882 × 10 3 3.2851 x 10 L 1.5216 × 10 - 4 3 . 3 8 1 3 x 10 -~ 3 . 2 8 6 2 x 10
128419 6.0181 × 10 2 6.0203x 10 1 1.3203 × 10 2 6 . 7 6 5 7 × 10 - I 2 . 3 1 5 2 x 10 . 3 6 . 9 5 7 0 x 10 -~ 1.5357 × 10 4 6 . 8 8 1 7 × lO
90526 1.6811 × 10 - I 9.0556x 10 1 5 . 1 4 4 5 × 10 2 1.0332 1.3998 x 10 2 1.0803 2 . 6 0 2 9 x 10 . 3 1.0810
71703 1.1379
63815 2.9164x10 i 9.6011 x l O i 1.1566x10 i 1.1349 4.2943 x I0 -2 1.2100 1.4157 x 10 2 1.2399
46502 3 . 6 7 2 8 × 10 ~ 7 . 9 6 3 0 x 10 ~ 1 . 7 7 4 6 × 10 1 9 . 7 4 5 2 × 10 t 8.2563 × I0 2 1.0679 3 . 6 4 9 7 x 10 2 1.1143
36852 3 . 7 8 4 7 x 10 i 5 . 8 6 6 2 x 10 ~ 2 . 1 2 4 4 x I0 ~ 7 . 2 7 1 9 x 10 t 1.1692 × 10 i 8 . 1 7 6 8 x 10 i 6 . 2 0 4 6 × 10 2 8 . 7 4 0 8 x 10
31559 2 . 1 7 7 8 × 10 -~
29204 3 . 4 3 2 8 x 10 -~ 4 . 0 5 6 7 x 10 ~ 2 . 1 5 9 9 x 10 ~ 5 . 0 4 8 5 x 10 -~ 1.3519 x 10 -~ 5.7832x 10 i 8 . 2 5 8 5 x I0 2 6 . 3 0 4 3 x I0 - I
25010 1.3740 x 10 i
 T. Furuya et al. / Fluid Phase Equilibria 103 (1995) 119-141 139

Table A3 (continued)

Feed: DEX T70 5.49 wt.% Feed: DEX T70 6.00 wt.% F e e d : D E X T 7 0 6.51 w t . % Feed: DEX T70 7.00 wt.%
PEG4000 8.53 wt.% PEG4000 9.00 wt.% PEG4000 9.50 wt.% P E G 4 0 0 0 10.02 w t . %

Molecular Top Bottom Top Bottom Top Bottom Top Bottom

weight dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M

23144 2 . 7 9 9 3 × 10 - l 2 . 6 6 4 2 × 10 - I 1.9355 × 10 - I 3 . 2 9 9 2 x 10 i 1.3544 × 10 -1 3 . 8 5 4 5 x 10 - I 9 . 2 2 2 3 × 10 - 2 4 . 2 6 3 0 × 10 1

21417 9 . 2 6 6 8 × 10 2
18154 2.1126x10 1 1.6894x 10 ~ 1.5658z10 -I 2.0646×10 -t 1.1826x 10 1 2.4449×10 1 8.9019×10 2 2.7318x 10-1
13952 1.4668 x 10 1 1.0315x 10 1 1.1512x 10 t 1.2383 × 10 - I 9 . 3 0 9 4 × 10 - 2 1.4634× 10 -1 7.5740× 10 2 1.6381 × 10 1
10722 9 . 4 2 1 9 x 10 2 6 . 0 5 3 6 x 10 2 7 . 9 0 5 0 × 10 - 2 7 . 0 1 9 6 × 10 2 6 . 6 9 6 5 × 10 2 8 . 4 7 5 7 × 10 2 5 . 7 7 5 8 × 10 2 9 . 4 6 1 2 × 10 - 2
8240 5 . 7 2 5 2 × 10 2 3 . 6 5 5 7 × 10 2 5 . 0 8 4 9 x 10 2 3 . 9 0 1 3 x 10 - 2 4 . 5 1 7 7 x 10 - 2 4.3531 × 10 2 4 . 0 5 9 9 x 10 2 5 . 2 3 5 8 x 10 z
6333 3 . 2 7 9 8 × 10 2 2.3011 x 10 2 3 . 2 0 8 2 x 10 2 2 . 0 2 6 4 × 10 - 2 2 . 9 3 7 6 × 10 - 2 2 . 4 5 1 6 × 10 - 2 2 . 7 2 6 7 × 10 - 2 2 . 8 8 1 7 x 10 - 2
4867 1 . 7 2 2 2 x 10 2 1.4241 × 10 2 2 . 0 1 7 4 x 10 2 1.0902 × 10 2 1.8925 × 10 z 1 . 2 6 7 6 x 10 2 1.8026 x 10 - 2 1.6077 x 10 - 2
3740 7 . 8 8 1 6 x 10 3 1 . 0 5 1 4 × 10 - 2 1.2889 x 10 - 2 5 . 5 1 1 7 x 10 - 3 1.2540 x 10 - 2 6 . 4 8 6 7 x 10 - 3 1 . 2 1 9 4 x 10 2 8.8811 x 10 - 3
2874 3.2871 x 10 - 3 9 . 0 3 2 7 x 10 - 3 8 . 6 5 7 0 × 10 - 3 2 . 6 3 1 5 x 10 - 3 9 . 0 7 8 4 x 10 - 3 2 . 0 2 6 5 x 10 - 3 8.9021 × 10 - 3 4 . 7 0 3 5 × 10 - 3
2209 8 . 3 9 6 5 × 10 - 3 2 . 0 7 2 8 x 10 - 3 1 . 3 9 7 6 x 10 - 3 3 . 6 6 7 0 x 10 - 3

Table A4
Molecular weight distribution of DEX 140 in t h e t o p a n d b o t t o m phases for the DEX 140 PEG4000 water aqueous two-phase system at 20°C

Feed: DEX 140 5.03 w t . % Feed: DEX 140 5 . 5 2 w t . % Feed: DEX 140 6 . 0 0 w t . % Feed: DEX 140 6 . 5 2 w t . %
PEG4000 8.00 wt.% PEG4000 8.57 wt.% PEG4000 9.00 wt.% PEG4000 9.51 w t . %

Molecular Top Bottom Top Bottom Top Bottom Top Bottom

weight dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M dW]d log M dW/d log M

3346018 1.1608 x 10 3 5 . 7 1 9 3 x 10 4
1828502 9 . 1 8 2 0 x 10 3 1.0024 x 10 - 2 8 . 6 8 6 5 × 10 3 8 . 1 0 0 0 x 10 - 3
1051746 3 . 9 4 7 9 x 10 2 3 . 9 5 7 6 x 10 - : 3 . 8 1 3 4 x 10 2 3 . 7 7 6 5 x 10 - 2
633983 1 . 2 4 4 7 x 10 1 1 . 1 9 2 9 x 10 i 1.1829 x 10 t 1.2077 x 10 - t
398753 5 . 5 3 6 3 x 10 - 3 3 . 3 1 1 9 x 10 1 3 . 2 9 0 7 x 10 i 3.2381 x 10 i 3.2652x 10 - t
260552 3 . 0 0 4 0 x 10 2 5 . 9 6 4 8 x 10 -~ 1.7614 × 10 - 3 6 . 2 3 3 4 x 10 1 1.2906 x 10 4 6 . 2 5 1 0 x 10 - I 6.2322x 10 -~
199966 6 . 4 7 3 5 x 10
176098 8 . 8 5 4 9 × 10 - 2 6 . 3 8 6 9 × 10 - I 1.6303 x 10 2 7 . 2 2 7 7 × 10 ~ 1.4283 x 10 - 3 7 . 3 6 1 5 x 10 ~ 7 . 3 2 0 9 x 10 i
122572 1.8088 × 10 - I 6.3977x 10 t 5 . 1 0 1 3 x 10 z 7.7521 x 10 -~ 1 . 2 5 0 9 x 10 2 8.1698×10 t 1.5694x 10-3 8.2162x10 t
97644 8.0731 x 10
87480 2 . 7 9 4 3 x 10 - I 6 . 2 6 2 5 x 10 I 1 . 1 1 2 0 x 10 I 7 . 9 9 5 0 x 10 - I 4 . 2 5 6 1 x 10 2 8 . 7 2 0 9 x 10 i 1 . 3 2 2 6 x 10 - 2 8 . 9 1 8 7 x 10 i
63742 3 . 2 2 9 7 x 10 ~ 5 . 1 0 6 3 x 10 -~ 1 . 6 3 4 0 x 10 I 6 . 7 2 7 9 x 10 i 8 . 3 9 7 4 x 10 - 2 7.6181 x 10 ~ 3.7561 x 10 2 7 . 9 8 6 8 x 10 - I
57578 3 . 2 3 0 9 × 10 -~
47209 3 . 1 0 8 3 × 10 - I 3.6656× 10 - I 1.8966 × 10 t 4 . 9 4 3 3 x 10 1 1.1770x 10 - I 5.7274x 10 ~ 6.6183x10 -: 6.1589x10
42835 1.9163 × 10 1
35386 2 . 7 2 7 2 × lO 1 2 . 5 6 8 3 × I0 ~ 1.8821 × 10 -~ 3 . 4 3 4 8 x 10 - I 1.3428 x 10 i 4.0430x 10 - I 8.7627x 10 2 4.4371 x 10 -~
32204 1 . 3 6 3 4 x 10 1
26726 2.2736× 10 t 1.7393 x 10 I 1.7218 × 10 ~ 2 . 3 7 7 8 × 10 -1 1.3481 x 10 1 2 . 7 8 3 3 x 10 - I 9 . 8 4 5 9 x 10 2 3 . 0 8 7 6 × 10 - I
20251 1 . 8 3 4 4 × 10 1 1.2562 × 10 i 1 . 4 7 2 2 x 10 -~ 1.6002 × 10 - I 1.2295 x 10 ~ 1.8856x I0 -t 9 . 7 1 4 5 x 10 2 2 . 1 3 5 3 x 10 -1
15328 1 . 4 2 0 4 x 10 ~ 8 . 3 1 7 3 × 10 - 2 1.1889 × 10 - I 1 . 1 0 3 4 x 10 t 1.0396 x 10 -~ 1.2256x I0 i 8 . 8 1 0 8 x 10 2 1.4416x I0 1
11538 1.0801 x 10 1 5.9926× 10 2 9 . 1 3 7 3 x 10 _2 7.1640× 10 2 8 . 3 0 3 9 x 10 - 2 7 . 7 7 1 6 x 10 2 7 . 3 2 4 5 x 10 - 2 9 . 7 3 4 4 x 10 2
8600 7 . 5 9 6 9 x 10 _2 3 . 7 7 9 2 × 10 2 6 . 7 1 9 0 × 10 2 4 . 6 3 6 0 x 10 - 2 6.1132x 10 2 4.8232x 10-2 5.6232x 10 2 6.1853x 10-2
6320 5 . 2 4 9 6 × 10 _2 2 . 7 7 7 9 × 10 2 4 . 4 4 8 2 x 10 2 2 . 8 2 9 7 × 10 - 2 4.2219x 10 2 2.9171 x 10 - 2 3.9866X 10 2 3 . 5 4 2 3 x 10 - 2
4559 3 . 1 9 8 3 × 10 2 1 . 2 9 4 2 x 10 - 2 2 . 6 7 2 3 × 10 2 1.9121 x 10 2 2.5919x 10 - 2 1.3216x 10 2 2 . 4 6 0 5 x 10 - 2 1.8643 x 10 2
3214 1 . 7 8 1 6 x 10 2 7 . 4 5 7 3 × 10 3 1.3748 × 10 - 2 6 . 1 5 7 2 × 10 3 1.2709x 10 - z 6 . 5 0 1 6 X 10 3 1.2667 x 10 - 2 1 . 1 9 7 2 X 10 2
2509 4 . 7 6 9 9 × 10 - 3 4 . 2 5 2 3 x 10 3
2205 8 . 8 5 3 2 x 10 3 4 . 4 3 9 5 x 10 3 4 . 2 1 4 0 × 10 3 4 . 1 6 8 9 x 10 3 7.5342x 10 - 3
1466 4 . 9 6 2 4 x 10 3 1.5277 x 10 - 3 1 . 0 8 4 6 × 10 3 1.3493 × 10 - 3 1.1793 X 10 - 3 2 . 7 4 6 9 x 10 3
140 T. Furuya et al. / P;luid Phase Equilibria 103 (1995) 119 141

Table A5
Molecular weight distribution of DEX T500(a) in t h e t o p a n d b o t t o m phases for the DEX T500(a) PEG4000 water aqueous two-phase system at
20C

Feed: DEX T500(a) 4.28 wt.% Feed: DEX T500(a) 4.50 wt.% Feed: DEX T 5 0 0 ( a ) 5.01 w t . % Feed: DEX T500(a) 6.00 wt.%
PEG4000 7.31 w t . % PEG4000 7.50 wt.% PEG4000 8.00 wt.% PEG4000 9.01 w t . %

Molecular Top Bottom Top Bottom Top Bottom Top Bottom

weight dW/d log M dW/d log M dW/d log M dlV/d log M dW/d log M dW/d log M dW/d log M dW/d log M

25235899 5 . 8 2 2 2 x 10 5 4 . 8 5 8 9 x 10 4 1.2909 x 1 0 - ' ;

14294957 1.1542 × 10 3 1.9453 x 10 3 1.2701 x I 0 3 1.0277 x 10 3
8383433 8 . 9 1 2 7 × 10 ~ 9 . 1 0 9 7 x 10 ~ 7 . 7 8 2 0 x 10 3 7 . 8 6 3 7 x 10 3
5082058 2 . 8 9 2 2 x 10 2 2 . 8 0 4 9 x 10 2 2 . 5 9 4 7 x 10 2 2 . 5 5 4 7 x 10 2
3179384 6.6086x 10 2 6.3919x 10 2 5 . 9 7 6 4 x 10 2 6 . 0 3 1 0 x 10 2
2049464 1 . 2 5 4 6 x 10 ~ 1.181/1 x 10 i 1.1393 x 10 t 1.1297 x 10
1359062 2 . 1 4 7 5 x 10 1 2.11391) x 10 1.9821 x 10 i 1.9599 x 10 t
925648 3 . 5 0 1 3 x 10 3 3 . 4 7 5 7 x 10 i 1.0344× 10 ~ 3.3514x 10 i 3 . 2 9 9 9 x 10 ~ 3.2821 × 10
646496 1.8525 x 10 2 5.3191 x 10 i 4 . 2 0 5 2 × 10 3 5 . 3 3 4 3 x 10 t 2 . 1 7 5 5 x 10 4 5 . 2 6 0 5 x 10 t 5 . 2 2 9 4 x 10 i
462281 5 . 7 4 9 0 x 10 2 7 . 4 5 3 3 x 10 ~ 1.8791 × 10 2 7.67117 x 10 2 . 1 6 3 0 × 10 3 7 . 8 0 6 8 x 10 ~ 7 . 7 6 7 6 x 10 1
337889 1.2557x 10 ~ 9.0276x 10 ~ 5 . 6 1 8 8 × 10 2 9 . 6 5 5 5 x 10 8 . 4 2 4 8 x 10 ~ 1.0174 1.0183
291115 9.2244x 10 ~ 1.0050
252046 1.9006 x 10 ~ 8 . 9 0 0 4 x 10 ~ 1.0620 x 10 ~ 9 . 8 2 5 7 x 10 2 . 5 3 9 6 x I0 2 1.0740 8 . 7 5 3 0 x 10 4 1.0932
191567 2 . 0 7 2 5 x 10 ~ 7 . 0 8 5 4 x 10 ~ 1.3666 x 10 ~ 8.1/363 × 10 4 . 4 2 2 2 × 10 2 9 . 0 4 1 2 × 10 ~ 4 . 0 3 2 3 x 10 3 9 . 4 4 9 0 x 10 1
148121 1.9141 x 10 ~ 5 . 1 5 9 3 x 10 -~ 1.4254 x 10 ~ 5 . 8 4 5 7 x 10 5 . 8 0 1 6 x 10 2 6 . 7 7 5 8 × 10 i 8 . 0 7 2 8 x 10 3 7.3500x 10-
116324 1.7384x 10 ~ 3.8815x 10 ~ 1.4160x10 ~ 4.3968x10 6 . 8 7 3 0 x 10 2 5.2131 x 10 i 1.3193 x 10 2 5 . 8 6 4 7 x 10
92636 1.5203 × 10 ~ 2 . 9 8 2 7 × 10 ~ 1.3260 × 10 ~ 3 . 3 5 8 9 x 10 7 . 3 7 6 6 x 10 --2 4 . 0 1 5 6 × 10 i 1 . 8 3 1 0 x 10 -" 4 . 6 5 6 5 x 10 1
74691 1.1883 x 10 ~ 2 . 1 3 1 8 x 10 ~ 1.1006 x 10 ~ 2.37111/x 10 6 . 8 2 3 4 x 10 - 2 2 . 8 4 8 5 × 10 t 2 . 1 3 0 9 x 10 2 3 . 3 9 7 0 x 10 i
67344 2 . 1 6 2 5 x 10 2
60873 8 . 1 5 4 7 x 10 2 1.3746× 10 -~ 7 . 9 7 7 7 × 10 2 1.5033 x I0 5 . 4 1 6 5 x 10 2 1.7902x 10 1 2.1216x 10 2 2.1730x 10 i
50069 4 . 9 9 5 3 x 10 - 2 8.5101 x 10 -~ 5 . 1 5 1 3 x 10 -~ 8 . 8 4 3 3 x 10 2 3 . 8 3 0 7 x 10 2 1.0458 × 10 i 1.8180x 10 2 1.2776x 10 i
41495 2 . 8 6 8 8 x 10 2 5 . 2 1 4 0 x 10 2 3 . 2 1 7 8 x 10 2 5 . 0 2 9 4 x 10 2 2 . 5 6 0 2 x 10 2 5 . 8 3 8 8 × 10 2 1.4499 x 10 2 7 . 1 6 9 0 x 10 2
34596 1.6067 x 10 - 2 3 . 7 0 0 0 x 10 -" 2 . 0 0 7 2 x 10 -~ 3 . 1 9 9 8 x 10 2 1.6951 x 10 2 3 . 1 8 6 3 × I0 2 1.1227 x I0 2 4 . 0 7 8 6 x 10 2
28971 8 . 9 4 8 7 x 10 3 2.7646x 10 -~ 1.3941 x 10 -~ 2 . 0 0 3 3 x 10 2 1.1715 x 10 - 2 1.7582× 10 2 8 . 9 5 1 5 x 10 3 2 . 5 8 1 7 x 10 2
24328 5.2441 × 10 3 2 . 3 5 7 6 x 10 2 9 . 0 2 6 9 × 10 3 1.3907 x 10 2 8 . 5 8 5 7 x 10 3 1.0086×10 ~ 7 . 0 6 2 2 x I 0 -3 6 . 1 1 8 8 x 10 - 3
20453 3.5701 x 10 3 2 . 0 2 3 3 x I0 2 6 . 6 7 3 8 x 10 ~ 1.0960 x 10 2 5 . 9 7 9 5 x 10 3 7 . 1 8 0 4 x 10 3 5 . 6 4 0 6 x 10 3 4.0441 x 10 3
17190 2.0599 × I0 -3 2.1841 x 10 - 2 4 . 3 3 2 6 x 10 ~ 9 . 5 9 2 7 x 10 3 4.57112 x 10 • 4 . 1 9 5 2 × 10 3 4 . 4 8 6 6 x 10 3

Table A6
Molecular weight distribution of DEX T 5 0 0 ( b ) in t h e t o p a n d b o t t o m phases for the DEX T500(b) PEG6000 water aqueous t w o - p h a s e s y s t e m at
20C

Feed: DEX T500(b) 2.50 wt.% F e e d : D E X T 5 0 0 ( b ) 3.1/0 w t . % Feed: DEX T500(b) 3.50 wt.% Feed: DEX T500(b) 4.00 wt.%
PEG6000 5.50 wt.% PEG6000 6.00 wt.% PEG6000 6.50 wt.% PEG6000 7.00 wt.%

Molecular Top Bottom Top Bottom Top Bottom Top Bottom

weight dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M

11948412 9.9734x10 4 4.0985x l0 3 3 . 5 3 5 5 x 10 3 4.0788× l0 3 3.6774x l0 3

6479236 3 . 6 9 3 7 x 10 3 1.9067 x 10 . 2 1.7985 x 10 2 1.8641 × 10 - 2 1.9318 x 10 2
3661977 9 . 8 2 4 7 x 10 - 3 5 . 4 2 4 4 x 10 2 5 . 1 8 3 9 × 10 2 5 . 1 7 8 4 × 10 2 5 . 4 0 0 5 x 10 2
2151790 7.4716x 10 3 1.1456x 10 i 1.1127x10 i 1.0873×10 t 1.1328x10 i
1311254 2.4322x 10 - 3 2.1699x 10 1 8.6994×10 a 2.1136×10 i 2.0928×10 t 2.1400x10
826604 4.0027x 10 4 3.8890x lO.i 8 . 7 8 0 6 x 10 3 3.8159x10 i 5 . 7 0 3 6 x 10 3 3 . 7 8 7 0 x 10.-~ 3 . 0 6 9 2 x 10 3 3 . 7 9 4 4 x 10
537699 4.0262x 10 3 6.3915x 10 1 4 . 2 9 7 5 x 10 3 6 . 3 4 2 7 x 10 ~ 6.3284x I0 3 6.3011 x l O ~ 4 . 1 9 4 3 x 10 - 3 6.2977x10
360025 3.0168 x 10 - 2 8.7982 x 10 -~ 9 . 9 3 1 7 x 10 ~ 9.06/11 x 10 i 6 . 6 0 5 0 x 10 - 3 9 . 0 5 9 2 × 10 i 4 . 8 9 4 6 x 10 3 9 . 0 2 9 3 x 10 - I
279660 9 . 3 0 8 7 x 10 1 9 . 9 2 1 4 x 10 ~ 1.0016 9 . 9 7 3 2 x 10
247505 9.0091 x 10 - 2 9 . 0 1 5 3 x 10 ~ 2.3701 x 10 2 9.8391 x I 0 t 1.1637 x 10 2 9.9751 x 10 ~ 3 . 8 1 0 6 x 10 3 9 . 9 4 4 6 x 10 t
174268 1.4048 x 10 1 6 . 7 8 8 5 x 10 t 4 . 5 0 7 2 x 10 2 7 . 9 1 8 5 x 10 ~ 1.6995 x 10 2 8 . 2 4 1 6 × 10 i 4 . 4 6 1 7 x 10 - 3 8 . 2 8 9 8 x 10 i
125354 1 . 6 9 5 6 x 10 ~ 4.8841 x 10 t 6 . 8 3 0 7 x 10 -~ 6 . 0 3 4 7 × 10 ~ 2.5619 × I0 2 6 . 5 0 3 4 x 10 i 7 . 8 0 1 4 x 10 3 6 . 6 2 5 5 x I0
 T. Furuya et al. / Fluid Phase Equilibria 103 (1995) 119 141 141

Table A6 (continued)

Feed: DEX T500(b) 2.50 wt.% Feed: DEX T500(b) 3.00 wt.% Feed: DEX T500(b) 3.50 wrY, Feed: DEX T500(b) 4.00 wt.%
PEG6000 5.50 wt.% PEG6000 6.00 wt.% PEG6000 6.50 wt.% PEG6000 7.00 wtY,,

Molecular Top Bottom Top Bottom Top Bottom Top Bottom

weight dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M dW/d log M

91889 1.8536x 10 t 3.6976x 10 i 8 . 9 5 6 4 x l 0 -~ 4.6958 x l0 ~ 3.8357 × l0 2 5.2628 x l0 ~ 1.4379× 10 2 5 . 4 3 1 8 x 10 L

75400 9 . 4 4 0 4 x 10 2
68472 1.6312 x 10 i 2.4526x 10 i 9 . 2 8 7 0 x 10 2 3 . 1 6 7 3 x 10 t 4 . 5 9 7 3 x 10 2 3 . 6 6 4 3 x 10 t 2.(1869 x 10 2 3 . 8 8 7 9 x 10 t
51735 1.1367 x 10 t 1 . 3 5 8 9 x 10 7 . 5 1 0 5 x 10 2 1.7397 × 10 ~ 4 . 2 4 3 7 x 10 2 2 . 0 9 2 2 x 10 t 2 . 3 2 3 8 x 10 2 2 . 2 9 6 9 x 10
39538 6 . 7 9 8 8 x 10 2 6 . 6 4 5 7 x 10 2 5 . 0 4 4 9 x 10 2 8 . 0 7 2 4 x 10 2 3.2271 x 10 2 1.0681 x 10 ~ 1.9724 x 10 2 1.1992 × 10
30486 3 . 7 8 0 0 x 10 2 3 . 3 8 7 3 x 10 2 3 . 0 8 9 8 x 10 2 3 . 5 5 3 7 x 10 2 2 . 1 6 3 8 x 10 -~ 5 . 1 6 4 7 x 10 2 1 . 4 9 2 4 x 10 2 6.4031 x 10 2
23658 2 . 0 7 9 7 x 10 2 1 . 8 4 9 6 x 10 -' 1 . 8 7 1 6 x 10 2 1.7248 x 10 2 1.3486 x 10 2 2 . 6 4 8 8 x 10 2 1.0077 x 10 2 3 . 3 2 2 9 x 10 2
18430 1.2527 x 10 2 1.2410x 10 2 1.1682 x 10 2 7 . 3 8 2 6 x 10 ~ 8 . 3 0 6 5 x 10 3 1.3805 x 10 2 6 . 6 4 9 4 x 10 3 2 . 0 6 2 9 x 10 2
1 4 3 78 7 . 4 4 0 6 x 10 3 9 . 0 0 0 4 x 10 3 7.6922x10 a 4.6198x 10 3 5.1103x10 3 7.8949x 10 ~ 4 . 0 3 2 6 x 10 ~ 1.4713xl0 2
11204 5 . 0 9 5 5 x 10 ~ 5 . 0 7 6 9 x 10 3 2 . 7 9 9 3 x 10 ~ 2 . 5 6 1 0 x 10 3 9 . 8 0 2 8 x 10 3
8699 3 . 6 4 8 8 x 10 3 3 . 4 9 8 2 x 10 ~ 1.1794x 10 3 1.0846x 10 3 4 . 6 7 9 4 x 10 3