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J.

of Supercritical Fluids 97 (2015) 6373

Contents lists available at ScienceDirect

The Journal of Supercritical Fluids


journal homepage: www.elsevier.com/locate/supflu

Viscosity and density of poly(ethylene glycol) and its solution with


carbon dioxide at 353.2 K and 373.2 K at pressures up to 15 MPa
Masayuki Iguchi a,1 , Yuya Hiraga b , Kazuhiro Kasuya b , Taku Michael Aida b ,
Masaru Watanabe a,b , Yoshiyuki Sato a , Richard Lee Smith Jr. a,b,
a
Graduate School of Engineering, Research Center of Supercritical Fluid Technology, Tohoku University, Aramaki Aza Aoba 6-6-11, Aoba-ku,
Sendai 980-8579, Japan
b
Graduate School of Environmental Studies, Research Center of Supercritical Fluid Technology, Tohoku University, Aramaki Aza Aoba 6-6-11, Aoba-ku,
Sendai 980-8579, Japan

a r t i c l e

i n f o

Article history:
Received 12 July 2014
Received in revised form 9 October 2014
Accepted 9 October 2014
Available online 23 October 2014
Keywords:
Carbon dioxide
Poly(ethylene glycol)
Viscosity
Density
Molecular weight
Free volume viscosity model

a b s t r a c t
Few viscosity and density data have been reported for CO2 poly(ethylene glycol) solutions, even though
many vaporliquid equilibrium data exist in the literature. In this work, viscosity and density of pure
poly(ethylene glycol) (PEG, M = 3000, 8300, 20,000 g mol1 ) at atmospheric pressure were measured.
Viscosities of PEG 3000 and PEG 8300 solutions with CO2 were measured with a torsional vibrating
viscometer at 353.2 K and 373.2 K over the range of CO2 pressures from 5 MPa to 15 MPa. The densities of
CO2 PEG solutions were calculated with the perturbed-chain statistical associating uid theory equation
of state. From shear viscosity measurements, PEG 3000 and PEG 8300 were conrmed to be Newtonian
and PEG 20000 was conrmed to be non-Newtonian. The viscosity reduction ratio for PEG solutions
saturated with CO2 was found to be independent of the PEG molecular weight (400 M 8300 g mol1 ).
A simple equation is proposed that can correlate CO2 PEG solution viscosity reduction ratio to within
0.08 in absolute units. The CO2 PEG solution viscosities could be correlated with free volume models to
within 14% using the tted value of CO2 occupied volume.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Poly(ethylene glycol) or PEG, is a polymer that has ethylene
oxide as its repeating unit and a molecular weight that is less than
20,000 g mol1 [1]. For PEG that has a molecular weight greater
than 20,000 g mol1 , the polymer is referred to as poly(ethylene
oxide) or PEO. In the polymer chain of PEG, methylene groups
are hydrophobic whereas the ether oxygen and terminal hydroxyl
groups are hydrophilic, which gives PEG its amphiphilic character.
Physical properties of PEG vary greatly with its molecular weight. At
room temperature, PEG that has a molecular weight of 400 g mol1
(PEG 400) is a liquid, while PEG 1500 is a waxy solid and PEG 6000
is a crystalline plastic. PEG is widely used in food and pharmaceutical industries due to its unique characteristic properties that

Corresponding author at: Graduate School of Environmental Studies, Research


Center of Supercritical Fluid Technology, Tohoku University, Aramaki Aza Aoba 66-11, Aoba-ku, Sendai 980-8579, Japan. Tel.: +81 22 795 5863.
E-mail address: smith@scf.che.tohoku.ac.jp (R.L. Smith Jr.).
1
Present address: Research Center for Compact Chemical System, National Institute of Advanced Industrial Science and Technology, Nigatake 4-2-1, Miyagino-ku,
Sendai 983-8551, Japan.
http://dx.doi.org/10.1016/j.supu.2014.10.013
0896-8446/ 2014 Elsevier B.V. All rights reserved.

include: (i) high solubility in both aqueous and organic solvents, (ii)
no known immunogenicity, antigenicity and toxicity effects, and
(iii) high exibility and hydration of the polymer chain [2].
Carbon dioxide (CO2 ) readily dissolves into PEG, while PEG is
practically insoluble in the vapor phase of CO2 [37]. A large amount
of CO2 can be dissolved into PEG compared with other gases such
as propane and nitrogen [6]. Dissolution of CO2 into the PEG phase
causes a decrease in the melting point of PEG (ca. 20 K) [4,8,9],
a signicant reduction in the PEG viscosity (5080%) [8,1012],
a reduction in the CO2 PEG interfacial tension [13], and swelling
of the PEG [9,1416]. These characteristics of CO2 PEG solutions
have been applied to particle formation processes [1719], biphasic
reaction systems [20,21], membrane materials for gas separations
[22,23].
Fundamental studies of CO2 PEG solutions have been carried
out to understand the molecular interactions with microscopic
and macroscopic methods. Using microscopic methods, the interaction between CO2 and PEG was investigated by infrared (IR)
spectroscopy [15,24], near-IR spectroscopy [14,16], and ab initio
calculations [16]. The IR peak of CO2 bending shift to lower wavelengths in CO2 PEG solutions indicates interaction between CO2
and PEG [15]. The ab initio calculations show that the oxygen

64

M. Iguchi et al. / J. of Supercritical Fluids 97 (2015) 6373

Nomenclature
a
shift factor or viscosity reduction ratio
a0 /sa1 , a1 adjustable parameters in Eq. (1)
b0 , b1 /K adjustable parameters in Eq. (2)
c/g ml1 polymer concentration in mixture
c0 /cm3 g1 , c1 /cm3 g1 K1 adjustable parameters in Eq. (3)
d0 /mPa s cmd1 gd1 , d1 , d2 adjustable parameters in Eq. (5)
f
free volume fraction
H/mPa s scaling value in Eq. (2) set equal to unity
k
coverage factor
kij
correction factor for binary segment interaction
parameter
kB /J K1 Boltzmann constant
number of segments per chain
m
M/g mol1 molecular weight
n /g mol1 number average molecular weight
M
v /g mol1 viscosity average molecular weight
M
w /g mol1 weight average molecular weight
M
p/MPa pressure
Sw
swelling ratio
T/K
temperature
up /MPa standard uncertainty of pressure
standard uncertainty of temperature
uT /K
Uc ()/% combined expanded uncertainty of viscosity
Uc ()/% combined expanded uncertainty of viscositydensity product
Uc ()/% combined expanded uncertainty of density
v/cm3 g1 specic volume
V/cm3
volume
vf /cm3 g1 free specic volume
vo /cm3 g1 occupied specic volume
wi
weight fraction of component i
Greek symbols
V/cm3 volume change
/J
depth of pair potential
volume fraction of component i
i
/mPa s viscosity
0 /mPa s zero-shear rate viscosity
/kg2 m4 s1 viscositydensity product
/s
1
shear rate
/kg m3 density
/A
segment diameter
/rad s1 frequency
Superscripts
o
atmospheric pressure

atom of PEG donates electrons to the carbon atom of CO2 , which


reveals a Lewis acidbase type of interaction between CO2 and PEG
[16]. Using macroscopic methods, the thermodynamic properties
of CO2 PEG solutions have been reported that include vaporliquid
equilibria (VLE) [39,1416,2531], solidliquid equilibria (SLE)
[4,8,9], densities [11,13,32], viscosities [8,1012] and interfacial
tensions [13]. Most research has focused on VLE with few reports
being available for other properties. CO2 solubility in PEG increases
with pressure and slightly decreases with an increase in temperature [36,8,16,29]. The solubility of CO2 in PEG 200 is lower than
that of PEG of higher molecular weight (ca. 400 g mol1 ). For PEG
that has a molecular weight above 400 g mol1 , the CO2 solubility
in PEG does not change much with the PEG molecular weight [4,6].
The solubility of PEG 1500 in CO2 phase is below 0.05 wt% at 328 K
and 40 MPa [15], so that PEG solubility in CO2 can be considered

to be negligible for PEG of higher molecular weight. The density of


CO2 PEG solutions decreases up to around 10 MPa [11,32], and then
slightly increases with CO2 pressure [11,13]. Due to the few data
that have been reported (M = 400, 600 and 2000 g mol1 ) [11,13,32],
the density behavior of CO2 PEG solutions with pressure is not still
well understood. For the viscosity of CO2 PEG solutions, measurements have been reported for molecular weights of 200 g mol1
[10,12], 400 g mol1 [10,11], 600 g mol1 [10], 6000 g mol1 [8] and
20,000 g mol1 [8]. The viscosity of PEG in the presence of CO2
decreases with an increase in CO2 pressure and does not change
much at pressures at higher than 20 MPa. However, PEG viscosity
in the presence of CO2 has not been reported for moderate molecular weights (600 < M < 6000 g mol1 ) and the viscosity reduction
that can be obtained with CO2 is of importance in technological
applications.
Rheology of CO2 PEG solutions is needed in many practical
applications. Shear viscosities of pure PEG and pure PEO have been
reported at molecular weights from 200 g mol1 to 4 106 g mol1
as shown in Table 1 [3341]. At the lower molecular weight
(M 1500 g mol1 ), PEG behaves as a Newtonian uid while PEG of
high molecular weight behaves as a non-Newtonian uid. The shear
rate dependence of viscosity for PEG that has an average molecular
weight from 2000 g mol1 to 20,000 g mol1 has not been studied
in detail. In the literature, measurements of CO2 PEG 6000 and
CO2 PEG 20000 solution viscosities have been reported assuming
that PEG behaves as a Newtonian uid [8].
In this work, the rheological behavior of PEG that has
average molecular weights of 3000 g mol1 , 8300 g mol1 and
20,000 g mol1 is veried. Subsequently, this work focuses on PEG
3000 and PEG 8300 among the PEGs of moderate molecular weight.
The objectives in this work were to measure the viscosity of
CO2 PEG 3000 and CO2 PEG 8300 solutions and to study the inuence of the PEG molecular weight on solution viscosity.
Viscosities of CO2 PEG 3000 and CO2 PEG 8300 solutions were
measured with a torsional vibrating viscometer. The principle of
the torsional vibrating viscometer is the dampening of an oscillating electromechanical resonator immersed in the liquid [42,43].
The viscometer gives the viscositydensity product [43], so that a
density value is required to obtain the solution viscosity. In this
work, atmospheric densities of the pure PEG 3000 and pure PEG
8300 were measured with a vibrating tube densimeter and highpressure densities of CO2 PEG 3000 and CO2 PEG 8300 solutions
were calculated using an equation of state based on the perturbedchain statistical associating uid theory (pc-SAFT EoS). The pc-SAFT
EoS is one of the models that has been widely applied to calculate
thermodynamic properties of polymer systems [44]. The density
calculation method was evaluated with measured values of PEG
2000 solution with CO2 [32].
In PEG, although polymeric steric hindrances prevent the formation of intra-hydrogen bonds, inter-hydrogen bonds form between
the terminal hydroxyl groups, and the hydrogen atom in the terminal group and the oxygen atom in the polymer chain. Results
of studies made with IR spectroscopy show that the hydrogen
bonds in PEG 2000 only form within the terminal hydroxyl groups
[45,46]. The hydroxyl end groups of PEG have little inuence on the
CO2 solubility in PEG of higher molecular weight (M > 200 g mol1 )
[4,6], which is consistent with measured partition coefcients for
n-mers between vapor and liquid phases [7,47]. For VLE calculations with the SAFT EoS for PEG that has a molecular weight above
2000 g mol1 , there is no distinct difference between calculation
results with or without the association term [6]. Therefore, for PEG
of higher molecular weight (M 2000 g mol1 ), hydrogen bond formation can be neglected in the VLE calculations with the pc-SAFT
EoS [44].
This work examines models based on free volume theory to
calculate the viscosity reductions of PEG in the presence of CO2 .

M. Iguchi et al. / J. of Supercritical Fluids 97 (2015) 6373

65

Table 1
Available literature for the rheological behavior of molten poly(ethylene glycol) and poly(ethylene oxide).
M range/g mol1

Range

w /103
M

n /103
M

/s
1

1.0
6.318.6a
17.5340a
22.0
292
610, 932
4000

0.21.5

3.6
9.3
20.4
55
<305, <466

5300
<1002 103

Rheological behavior

Source

Newtonian
Newtonian
Newtonian
Non-Newtonian
Non-Newtonian
Non-Newtonian
Non-Newtonian
Non-Newtonian

[33,34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]

/rad s1

660

0.125
0.1500
0.01100
0.5103

v /103 .
Value of M

The concept of free volume has been widely applied to transport


phenomena in liquids [48,49]. Viscosity models that use free volume theory include the Doolittle equation [50], the Cohen and
Turnbull equation [48] and the equation proposed by Allal et al.
[51,52]. The Gerhardt et al. equation [53] is a commonly applied
free volume model for CO2 polymer solution viscosities [5358].
Gerhardt et al. proposed an equation for viscosity reduction for
dissolved CO2 in polymers by modifying the free volume fraction of
mixture in the KelleyBueche equation [53]. However, this model
has not been applied to CO2 PEG solution viscosities. This work
applies the models of Gerhardt et al. and KelleyBueche [59] to
CO2 PEG 3000, CO2 PEG 6000 and CO2 PEG 8300 systems and
compares the results in terms of the viscosity reduction ratio.
Free volume viscosity models use the occupied volume of CO2
that is determined from the density of a crystal state, whereas the
occupied volume of a polymer is obtained from its molten state
viscosity [5358,60]. In this work, values of the occupied volume
of CO2 in free volume viscosity models are examined.
2. Materials and methods
2.1. Materials
Poly(ethylene glycol) with an average molecular weight of
3000 300 and poly(ethylene glycol) with an average molecular weight of 8300 1000 g mol1 were obtained from Wako Pure
Chemical Industries, Ltd. (Tokyo). PEG having an average molecular weight of 20,000 g mol1 was obtained from Sanyo Chemical
Industries, Ltd. (Nagoya). The water content of each polymer was
0.2 wt% for PEG 3000, 0.1 wt% for PEG 8300 and 0.2 wt% for PEG
20000 as determined by weight loss according to JIS K 0068:2001.
In all experiments, PEG and CO2 (>99.99 vol%, Showa Tansan Co.,
Ltd.) were used as received. Dried pure PEG 3000 used in the atmospheric viscosity and density measurements was prepared at 313 K
under reduced pressure overnight.
2.2. Atmospheric viscosity of pure PEG
2.2.1. Shear viscosity measurement and correlation
Static and dynamic shear viscosities of the various pure PEGs
at atmospheric pressure were measured with a rheometer (Haake,
RheoStress 6000) equipped with cone plate geometry. A gap spacing of 0.105 mm was maintained for PEG 3000 with a diameter of
60 mm and a cone angle of 2 . For PEG 8300 and PEG 20000, a gap
spacing of 0.105 mm was maintained with a diameter of 35 mm
and a cone angle of 2 . Temperature was controlled to within 0.1 K,
and stability of the measured values was checked by the change of
shear stress with time being within 0.01%.
Static shear viscosities were measured at temperatures from
353.2 K to 373.2 K at every 10 K for PEG 3000 and at 353 K for PEG
8300 and PEG 20000 over the range of shear rates from 0.1 to several
thousand s1 . Dynamic shear viscosity of each PEG was measured

over the same temperature range as that used in the static shear
viscosity measurements. All dynamic viscosity measurements were
performed under a stress of 100 Pa. Static viscosity measurements
were performed in two cycles and then dynamic viscosities were
measured in two cycles under isothermal conditions. The cycle
started from low to high shear rates or frequencies, and then from
high to low shear rates. Some viscosity data in the range of low
and high shear rates were cutoff due to the limited resolution of
the apparatus. The combined expanded uncertainties with a level
of 0.95 (k = 2) were estimated to be 10.4% for PEG 3000 and 6.0% for
PEG 8300 and PEG 20000 (Methods S1 and Table S1, Supplementary
material).
For Newtonian uids, a zero-shear rate viscosity was determined as an average value of static shear viscosities at different
shear rates. For non-Newtonian uids, the zero-shear rate viscosity was obtained by tting static shear viscosity data to the Cross
model [61] using LevenbergMarquardt algorithm with analytical
derivatives [62]. The Cross model is given by the following equation:
0
o =
(1)
1 + a0 ()
a1
where 0 is the zero-shear rate viscosity, a0 and a1 are adjustable
parameters that were obtained by tting the viscosity data.
2.2.2. Viscosity measurement and correlation
Atmospheric viscosities of pure PEG 3000 were measured with a
Stabinger viscometer (Anton Paar, SVM3000). Stability of the measured values was evaluated by the change in viscosity being less
than 0.07% over a 1 min interval. Measurements were performed in
duplicate from 343.15 K to 373.15 K. Each series of measurements
included two cycles that consisted of measurements made from
low to high temperature that was followed by measurements made
from high to low temperature. The combined expanded uncertainty
with a level of 0.95 (k = 2) was estimated to be 1.0% (Methods S1 and
Table S1, Supplementary material).
To correlate the viscosities at atmospheric pressure, the following empirical equation was used [63]:
ln

 o 
H

= b0 +

b1
T

(2)

where H is a constant set equal to 1 mPa s, and b0 and b1 are


adjustable parameters that were obtained by tting the experimental data.
2.3. Atmospheric pure PEG density measurement and correlation
Densities of pure PEG 3000 and pure PEG 8300 at atmospheric
pressure were measured with a vibrating tube densitometer
equipped with a Stabinger viscometer at temperatures from
343.15 K to 373.15 K with a temperature step of 10 K. Stability of
measured values was determined by the change in density being

66

M. Iguchi et al. / J. of Supercritical Fluids 97 (2015) 6373

(f)
(k)

(b)

(j)

(e)
(k)

(d)

(h)
(a)

(c)

(g)

T
(i)

Fig. 1. Schematic diagram of the viscosity measurement apparatus: (a) carbon dioxide cylinder; (b) regulator; (c) syringe pump; (d) chiller; (e) pressure sensor; (f) viscometer;
(g) measurement cell; (h) electrical heater; (i) temperature probe; (j) rocking stand; (k) valves.

less than 0.1 kg m3 over a 1 min interval. Measurements were performed in duplicate and each series of measurements included the
low to high temperature and the high to low temperature segments.
The combined expanded uncertainties with a level of 0.95 (k = 2)
were estimated to be 1.4 kg m3 for PEG 3000 and 1.6 kg m3 for
PEG 8300 (Methods S1 and Table S1, Supplementary material).
Atmospheric density data were correlated with the following
empirical equation:
1000
= vo = c0 + c1 T
o

(3)

Parameters in Eq. (3), c0 and c1 , were determined by tting the


density data.
2.4. Viscosity of CO2 PEG solutions
2.4.1. Viscosity measurement
Viscosities of PEG 3000 and PEG 8300 in the presence of CO2
were measured with the apparatus as shown in Fig. 1. The viscosity sensor consisted of a torsional vibrating viscometer (XL7-100N,
Hydramotion) that gives the viscositydensity product in terms of
energy loss or loss factor [64]. The measurement cell (70 ml) was
connected to a gas pressure line. Pressure of CO2 was controlled
by a regulator for measurements at 5 MPa and by a syringe pump
(D500, ISCO) for measurements at high pressures. Pressure was
measured with an online pressure gauge (KDM30, Krone). Temperature was measured by a platinum resistance thermometer (Pt100,
Netsushin) in the wall of the cell. Temperature of the solution was
calibrated by measuring the difference between the inside and the
wall of the cell (Methods S2, Supplementary material). Mixing of
samples was carried out by gentle and slow rocking of the apparatus
that could be rotated by hand.

Viscosity measurements were made at 353.2 K and 373.2 K for


PEG 3000 and at 353.2 K for PEG 8300 over the range of CO2
pressures from 0 MPa to 15 MPa. The PEG was loaded into the cell
at room temperature and then heated up to temperatures above
343.2 K to melt the PEG. After the PEG was completely melted,
the viscometer was mounted to a ange on the cell, and atmospheric viscosities were measured at given temperatures. The cell
was purged by pressurized CO2 several times, and then the system
was pressurized up to the desired conditions. Values of the loss
factor were recorded continuously and nal reported values were
determined after the change of the loss factor was within 0.001 over
a time period of a few hours. Time for equilibration of the CO2 PEG
solutions was reduced by slowly rocking the cell and by placing the
cell near horizontal position to enhance the dissolution CO2 into the
solution. Measurements for each sample were carried out within a
three-day period.
The reference condition for the viscositydensity product was
set equal to 353.15 K and 0.1 MPa. The viscositydensity product
at the reference condition was determined from measured values
of the Stabinger viscometer for PEG 3000 and from measured values from the rheometer for PEG 8300. For PEG 3000, the combined
expanded uncertainties with a level of 0.95 (k = 2) were estimated
to be 4.0% for atmospheric conditions, 4.6% for 5 MPa, 4.7% for
10 MPa and 4.6% for 15 MPa (Methods S1 and Table S1, Supplementary material). For PEG 8300, the combined expanded uncertainties
were estimated to be 10.4% for 5 MPa and 13.7% for 10 MPa (Methods S1 and Table S1, Supplementary material).
The viscosity of pure PEG and its solutions with CO2 were determined from the measured product of viscosity and density using
the following equation:
=

()
103


(4)

M. Iguchi et al. / J. of Supercritical Fluids 97 (2015) 6373

where () represents the viscositydensity product that was


obtained from the measured loss factor of the apparatus, and 
refers to either the measured density for pure PEG or to the calculated density for CO2 PEG solution as described in Section 2.4. For
PEG 3000, the combined expanded uncertainties of the measured
viscosity with a level of 0.95 (k = 2) were estimated to be 4.0% for
atmospheric conditions, 5.0% for 5 MPa and 10 MPa, and 5.6% for
15 MPa (Methods S1, Supplementary material). For PEG 8300, the
combined expanded uncertainties were estimated to be 10.6% for
5 MPa and 13.9% for 10 MPa (Methods S1, Supplementary material).
Possible decomposition of PEG during the measurements was
checked by measuring the pure PEG viscosity after heating at a
given temperature for the maximum period of time (3 d). The PEG
3000 viscosity decreased by 1.9% after heating at 353.2 K for three
days, which is lower than the uncertainty of the measurements.
Thus, at the experimental conditions, negligible decomposition was
found to occur. However, the viscosity of PEG 3000 after heating at 373.2 K and that of PEG 8300 after heating at 353.2 K for a
three-day period decreased by 14.7% and 9.7%, respectively, which
indicates that decomposition can occur during the measurement of
PEG depending on the treatment or measurement conditions. For
the viscosities of CO2 PEG 3000 at 373.2 K, the calculated uncertainties are probably underestimated due to composition variations
caused by the measurement conditions.
2.4.2. Viscosity calculation
Calculation of the viscosity reduction ratio or shift factor is based
on the modied KelleyBueche equation as given by Eq. (5) [53]:
 = d0 (c)d1 exp

d 
2

(5)

where d0 , d1 and d2 are characteristic parameters, c is the concentration of polymer in the mixture and f is the free volume fraction.
The value of d2 refers to the numerical factor of free volume overlap as interpreted by Cohen and Turnbull [48,49], which should be
below 1. The exponent of the polymer concentration (d1 ) is in the
range of 34 for entangled polymer systems and is set equal to
unity for non-entangled polymers [57]. The free volume fraction is
dened as follows [50]:
f =

vf
v v0
=
v0
v0

(6)

where v is the specic volume, and vf and vo are the free volume
and the occupied volume, respectively. For the case of vf  vo , Eq. (6)
can be rewritten as f = vf /v. Due to the lack of validation for vf  vo in
CO2 polymer solutions, this work used Eq. (6) for the free volume
fraction.
The shift factor for scaling of the viscosity of the pure polymer
at atmospheric pressure to that of the CO2 PEG solution (ap,c ) can
be expressed with Eq. (5) as follows:
mixture (T, p, w)
ap,c
=
opolymer (T, po )

(1 wCO2 )

vopolymer
vmixture




exp

d2,polymer
d2,mixture

fmixture
fpolymer


(7)

where wCO2 represents the weight fraction of CO2 in the polymer,


and the subscripts mixture and polymer refer to the CO2 PEG solution and the pure PEG, respectively. The superscript o refers to
atmospheric conditions. In this work, the value of d1 was set equal
to unity for PEG 3000 that is less than its value for the critical molecular weight of PEG (3400 g mol1 ) [65]. For PEG that has a molecular
weight larger than the critical molecular weight, the d1 value was
set equal to 3. The values of d2,mixture and d2,polymer were set equal

67

to unity [53,57]. The method described in Section 2.6 was used to


calculate the values of wCO2 and vopolymer /vmixture .
Gerhardt et al. proposed a free volume fraction for mixtures that
used the occupied specic volume of the mixture (vo,mixture ) and the
specic volume of the mixture (vmixture ) [53]. In the Gerhardt et al.
equation, the free volume fraction of the mixture was represented
as follows:
vf,mixture
vmixture vo,mixture
fmixture =
(8)
=

vo,mixture

vo,mixture

vo,mixture = wCO2 vo,CO2 + wPEG vo,PEG

(9)

The free volume fraction of the mixture for the KelleyBueche


equation used the volume fraction (i ) and the free volume fraction
(fi ) of each component in the mixture as follows [59]:
fmixture = CO2 fCO2 + polymer fpolymer
wi vi
vmixture
vmixture vo,i
fi =
vo,i
i =

(10)
(11)
(12)

where vi is the specic volume and vo,i is the occupied specic


volume of component i.
The characteristic parameter vo for PEG 3000 and PEG 6000 was
determined by tting viscosity data and calculated densities from
Eq. (3) using Eq. (7) when the reference condition was chosen to
be 353.15 K and 0.1 MPa. Then, the value of d0 in Eq. (5) was determined from the viscosity at the reference condition. The measured
densities of PEG 8300 were used for those of the PEG 6000, since the
density difference of PEG 6000 and PEG 8300 can be estimated to
within the uncertainty of the present measurements (Section 3.2).
In the analysis with the free volume fraction, the vo value for PEG
8300 in Eq. (12) was set equal to that for PEG 6000. The value of
vo for CO2 was set equal to 0.589 cm3 g1 which was obtained by
extrapolation of the crystalline density to absolute zero temperature [66].
2.5. Calculation of CO2 solubility in PEG
Solubilities of CO2 in PEG 3000 and PEG 8300 at 353.2 K were
calculated from an empirical equation as follows:
100 wCO2 = 1.602 p 3.236 102 p2 +2.387 104 p3

(13)

The equation was obtained by tting data of PEG molecular


weights from 1500 g mol1 to 8000 g mol1 [4,6,8]. All CO2 PEG
solubility data could be correlated with Eq. (13) to within 2% of
the CO2 solubility value (Fig. S2, Supplementary material).
2.6. Density calculation of CO2 PEG solutions
Liquid densities of CO2 PEG solutions were calculated with the
perturbed-chain statistical associating uid equation of state (pcSAFT EoS) for non-associating systems [67]. The mixture liquid
density was estimated from the measured density of pure PEG at
atmospheric pressure (o ) and the density ratio of CO2 PEG solution to pure PEG (/o ), which was calculated by the pc-SAFT EoS
as follows:
 = o


o

(14)

The pc-SAFT EoS parameters for the pure components used in


this work are given in Table 2. The PEG parameters were determined by tting high-pressure densities of pure PEGs [68], and VLE
and atmospheric densities of benzenePEG solutions [69] because
the energy parameter of the EoS tends to be insensitive to the liquid density [44]. In general, pure parameters were simultaneously

68

M. Iguchi et al. / J. of Supercritical Fluids 97 (2015) 6373

Table 2
Pure component parameters in the pc-SAFT EoS for poly(ethylene glycol), benzene and carbon dioxide.
Substance

/A

/kB /K

Poly(ethylene glycol)
Benzenec
Carbon dioxidec

44.749M
2.4653
2.0729

3.0608
3.6478
2.7852

234.87
287.35
169.21

a
b
c

ARD/% (bias/%)
a

wPEG b

liquid b

0.63 (+0.05)

2.45 (+0.41)

0.43 (0.43)

Experimental densities of pure PEG taken from Zoller and Walsh [68].
Calculations with the value of kij set equal to zero. Experimental data for the liquid composition and density of benzenePEG mixture taken from Booth and Devoy [69].
Values reported by Gross and Sadowski [67].

Table 3
Values of kij for poly(ethylene glycol) and carbon dioxide systems for the pc-SAFT
EoS.
M/g mol1

kij

ARD wPEG /%

Bias wPEG /%

Source

1500
3000
6000
8300

0.0191
0.0210
0.0171
0.0185

0.55
0.36
0.67
0.36

0.05
<0.01
+0.13
<0.01

[4]
Eq. (13)
[8]
Eq. (13)

determined by tting pure density and binary component data.


Pure parameters of the EoS can depend on the number and type of
selected binary data [70]. In this work, benzenePEG solution was
chosen as a binary mixture that could be described by the SAFT EoS
without tting (kij = 0) according to the study of Pedrosa et al. [71].
Further information of the tting methods, data sources and the
results are described in the Appendix and in the Supplementary
material (Table S1 and Figs. S3S6).
The binary parameters for  and between CO2 and PEG in the
mixtures were determined as follows:
CO2 PEG = PEGCO2 =

1
(CO2 + PEG )
2

CO2 PEG = PEGCO2 = (1 kij )

CO2 PEG

(15)
(16)

where kij is a correction factor for binary segment interaction


parameter of unlike chains. The kij values of CO2 PEG solutions
were determined by tting experimental VLE data for PEG 1500 [4]
and PEG 6000 [8], and calculated data are given by Eq. (13) for PEG
3000 and PEG 8300 in Table 3. Calculation results of CO2 PEG solutions are shown in the Supplementary material (Figs. S7S10). In
the VLE calculations, it was assumed that the PEG does not dissolve
into the vapor phase.
2.7. Parameter determination and evaluation
Adjustable parameters in Eqs. (1)(3), (5), (7), (13) and (16) were
determined by minimizing the following objective function (f(Y)):
f (Y ) =

2
n 

Ycal,i Yexp,i
i=1

(17)

Uc (Yexp,i )

where Y refers to the viscosity, density, shift factor or CO2 solubility,


and Uc (Y) is the combined expanded uncertainty of Y. In Eq. (17),
n is the number of measurements and the subscripts cal and exp
refer to calculated and experimental values, respectively.
Correlations were evaluated according to denitions of the bias
and average relative deviation (ARD) as follows:
1
Bias = 100
n
n

i=1

Ycal,i
1
Yexp,i

i=1

(18)

Ycal,i

ARD = 100

Yexp,i 1

Fig. 2. Measured static and dynamic shear viscosities at 353.2 K and 0.1 MPa
for poly(ethylene glycol) of different molecular weights: unlled symbols, static
viscosities; lled symbols, dynamic viscosities; circles, 3000 g mol1 ; squares,
8300 g mol1 , triangles, 20,000 g mol1 . Lines for PEG 3000 and PEG 8300 are average values of the static viscosities. The line for PEG 20000 was calculated with Eq.
(1). Error bars represent estimated combined expanded uncertainties of the shear
viscosity (Supplementary material).

(19)

3. Results and discussion


3.1. Atmospheric viscosity of PEG
Static and dynamic shear viscosities at 353.2 K for the PEGs of
different molecular weights are shown in Fig. 2. PEG 3000 and PEG
8300 were found to behave as Newtonian uids, while PEG 20000
was found to be non-Newtonian. Shear viscosities of PEG 3000 at
363.2 K and 373.2 K were found to be independent of the shear
rates (Fig. S11, Supplementary material). Shear viscosities of PEG
20000 decreased at shear rates above 50 s1 , which agrees with the
results of Trml et al. [38]. Shear viscosities of PEG 20000 could
be correlated with Eq. (1) to within 0.2% in ARD and less than 0.1%
in bias value with parameters 0 = 27,640 mPa s, a0 = 1.9296 106
and a1 = 1.6996. The zero-shear rate viscosities of PEG 3000, PEG
8300 and PEG 20000 were in accordance with average values of
the complex viscosity of each PEG to within 2%. This indicates that
the CoxMerz relationship used for the PEGs in this work was
equivalent for measured viscosities among the different types of
viscometers (cone and plate rheometer, Stabinger viscometer and
torsional vibrating viscometer).
Fig. 3 shows reported zero-shear rate viscosities for PEG of
different molecular weights at 353.2 K. The molecular weight
dependence of the PEG viscosities measured in this work was similar to that reported in the literature [3638,72]. The PEG 20000
viscosity reported by Kukova et al. is much lower than the value
reported by this work, Parivalko et al. [36], Teramoto et al. [37]
and Trml et al. [38]. These differences can be attributed to the
shear thinning of PEG 20000 as shown in Fig. 2 and possibly due
to viscosity reduction caused by reaction during pretreatment or
measurements.

M. Iguchi et al. / J. of Supercritical Fluids 97 (2015) 6373

69

Table 4
Atmospheric viscosities and densities of poly(ethylene glycol) 3000 measured with the different viscometers.a
T/K

/kg m3

/mPa s
Un-dried

343.2
353.2
363.2
373.2

Rheometer

Torsional vibrating

Stabinger

135.4
104.7
84.97

165.1
126.5b
99.55
79.37

126.5
98.38
78.46

Dried

Un-dried

Dried

169.3
127.9
99.52
79.45

1085.6
1077.4
1069.3
1061.2

1084.9
1077.0
1069.0
1061.1

a
Standard uncertainties are uT = 0.1 K for the rheometer and torsional vibrating viscometer, and 0.02 K for the Stabinger viscometer, and combined expanded uncertainties
with a 0.95 level of condence (k = 2) are Uc () = 10.4% for the rheometer, 4.0% for the torsional vibrating viscometer and 1.0% for the Stabinger viscometer, and Uc () = 1.4 kg m3
(Supplementary material).
b
Measured value with the Stabinger viscometer.

Fig. 3. Atmospheric zero-shear rate viscosities of poly(ethylene glycol) of different


molecular weights at 353 K: , This work; , Cruz et al. [72]; , Kukova et al. [8];
+, Parivalko et al. [36]; , Teramoto et al. [37]; , Trml et al. [38]; line, correlation of Teramoto et al. [37]. Error bars represent estimated combined expanded
uncertainties of the zero-shear rate viscosity (Supplementary material).

Table 4 shows measured viscosities and densities of PEG 3000


at atmospheric pressure of this work. The viscosities of un-dried
PEG 3000 measured with the Stabinger viscometer could be represented by Eq. (2) within an ARD of 0.3% and bias less than
+0.1% with parameters b0 = 4.0732 and b1 = 3147.1. Fig. 4 shows
a relative deviation plot for PEG 3000 viscosities measured in this
w=
work and for literature values [72]. The literature values (M
2816 g mol1 , wH2 O = 0.7 wt%) shown in Fig. 4 were estimated
from the reported kinematic viscosities [72] and the measured densities of PEG 3000 in this work. The viscosities of un-dried PEG 3000
measured with the different viscometers were in accordance with

Fig. 5. Liquid densities of (a) poly(ethylene glycol) 2000, (b) 3000 and (c) 8300 in
the presence of carbon dioxide versus pressure. Symbols: , 2000 g mol1 at 374.3 K
[32]; , 3000 g mol1 at 353.2 K; , 8300 g mol1 at 353.2 K. Lines: solid lines, Eq.
(14); dash lines, the pc-SAFT EoS. Pure component parameters and the values of kij
for the EoS are given in Tables 2 and 3, respectively.

their uncertainties. The viscosity of un-dried PEG 3000 was lower


by about 1% than that of dried PEG (wH2 O = 0.2 wt%). The literature values of the PEG viscosities [72] were about 12% larger than
those of this work, which might be attributed to differences in the
molecular weight of PEG.
3.2. Atmospheric density of PEG
Measured atmospheric densities of PEG 3000 are shown in
Table 4. Measured values of un-dried PEG 3000 agreed with those
of dried PEG 3000 within the uncertainty of the measurements.
This indicates the effect of 0.2 wt% water content in PEG 3000 on
densities is below 1.4 kg m3 . The parameters in Eq. (3) for PEG
3000 were determined as c0 = 6.8202 101 and c1 = 6.9762 104
by tting data of both samples, using which the obtained values of
ARD and bias were below 0.1%. For PEG 8300, ARD and bias values were obtained as below 0.1% using the parameters in Eq. (3) as
c0 = 6.8601 101 and c1 = 6.8346 104 . The measured values of
PEG 3000 and PEG 8300 were between values of PEG 1470 and PEG
18500 [68] (Fig. S12, Supplementary material), and the densities
increased with the molecular weight of PEG.
3.3. Density of CO2 PEG solutions

Fig. 4. Relative deviation plot for atmospheric viscosities of poly(ethylene glycol)


3000. Symbols: circles, Stabinger viscometer; diamonds, cone and plate rheometer; down triangles, torsional vibrating viscometer; , reported values [72]; lled
symbols, un-dried sample; unlled symbols, dried sample. Error bars represent estimated combined expanded uncertainties of the viscosity (Supplementary material).

Densities of CO2 PEG solutions were calculated from the pcSAFT EoS as shown in Fig. 5 along with literature data. The
calculation method for liquid mixture densities for CO2 PEG 2000
solutions has been evaluated by Funami et al. [32]. Due to the lack
of VLE data for PEG 2000CO2 system, binary interaction parameters for PEG 1500CO2 were used in the density calculations.

70

M. Iguchi et al. / J. of Supercritical Fluids 97 (2015) 6373

Table 5
Viscositydensity product, density and viscosity for poly(ethylene glycol) solutions
saturated with carbon dioxide at 353.2 K and 373.2 K.a
T/K

p/MPa

/kg2 m4 s1

/kg m3 b

/mPa s

M = 3000 g mol
353.2
5.0
353.2
10.0
15.0
353.2
5.0
373.2
M = 8300 g mol1
353.2
5.0
353.2
10.0

87.1395
61.4204
50.3371
61.7483

1078.72
781.124

1073.4
1070.0
1068.8
1057.6

1074.3
1070.8

81.18
57.40
47.10
58.39

1004
729.5

a
Standard uncertainties are uT = 0.1 K and up = 0.1 MPa, and combined expanded
uncertainties with a 0.95 level of condence (k = 2) are Uc () = 2.0%, Uc () = 4.64.7%
and Uc () = 5.05.6% for PEG 3000, and Uc () = 10.413.7% and Uc () = 10.613.9%
for PEG 8300 (Supplementary material).
b
Calculated values with Eq. (14).

Atmospheric densities calculated directly by the pc-SAFT EoS were


underestimated by 1% for both PEGs. Therefore, in the mixture density calculations used in this work, a density change ratio with CO2
pressure was adopted as a correction for atmospheric densities calculated by the pc-SAFT EoS (Eq. (14)). The calculated CO2 PEG 2000
solution densities agreed with the experimental values to within
1.0% (Fig. S13, Supplementary material), and so the standard uncertainty of the solution density was estimated to be 1.0%.
Calculated liquid densities for CO2 PEG solutions decreased
with pressure for values of up to about 1020 MPa. At higher
pressures, the calculated liquid densities increased with pressure.
This trend of density with pressure has been observed for CO2 PEG
400 solutions [11], and is probably due to the interplay between the
CO2 solubility in PEG and the swelling of the PEG caused by CO2 .
The density change ratio with CO2 pressure was described by
the weight fraction of CO2 in the PEG (wCO2 ), the volume of pure
PEG (VPEG ) and the volume change in the presence of CO2 (V) as
follows (Methods S4, Supplementary material):
CO2 +PEG
PEG

1
(1 wCO2 )(1 + V/VPEG )

(20)

where V/VPEG is denoted as the swelling ratio (Sw). The decrease


in solution density at low pressure can be attributed to the volume
expansion of the PEG solution with dissolved CO2 . Due to a relatively large amount of dissolved CO2 in the PEG at high pressure,
the solution density increased as pressure was increased.
The density behavior at high pressure was investigated by
calculating the swelling ratio with Eq. (20) (Fig. S14, Supplementary material). In this work, the calculated swelling ratio for
CO2 PEG 1500 solutions increased monotonically with pressure
up to 30 MPa, however, the rate of increase of the swelling ratio
decreased at pressures above 10 MPa. The behavior of calculated
swelling ratios at low pressure is in accordance with the study of
Pasquali et al. [9,15]. At high pressure (p > 10 MPa), Pasquali et al.
reported different trends for the PEG 1500 swelling ratio with an
increase in CO2 pressure: (i) monotonic increase of Sw with increasing pressure up to 20 MPa [15] and (ii) small change of Sw with
increasing pressure up to 25 MPa [9]. In this work, the calculated
swelling ratios at high pressure depended on pressure and so further studies on volumetric-related properties of CO2 PEG solutions
are needed in the future.
3.4. Viscosity of CO2 PEG solutions
Viscosities of CO2 PEG solutions are given in Table 5 including
the measured viscositydensity product and the calculated density with Eq. (14). The measured viscosity of CO2 PEG solutions
decreased with an increase in CO2 pressure in a similar trend as

Fig. 6. Viscosity reduction ratio for dissolved carbon dioxide in poly(ethylene glycol)
solution of different molecular weight at temperatures between 347.8 and 353.2 K.
This work: , 3000 g mol1 at 353.2 K; , 8300 g mol1 at 353.2 K. Literature: +,
400 g mol1 at 347.8 K [11]; , 6000 g mol1 at 353.2 K [8]. Lines: black solid line,
Eq. (21); red line, Gerhardt et al. equation; blue line, KelleyBueche equation; solid
line, the equation with the literature value of vo,CO2 ; dashed line, the equation with
the tted value of vo,CO2 to CO2 PEG solution viscosities at 353.2 K (M = 3000, 6000
and 8300 g mol1 ). Parameters in the equations are given in Table 6. Error bars represent estimated combined expanded uncertainties of the viscosity reduction ratio
(Supplementary material).

other CO2 PEG solutions [8,11]. At 15 MPa and 353.2 K, the reduction in the CO2 PEG solution viscosity by CO2 was 62% compared
with that of the pure PEG.
Viscosity reduction ratio in the presence of CO2 is dened as
the ratio of the CO2 PEG solution viscosity to that of pure PEG at a
given temperature. When there is no CO2 dissolution into the PEG,
the viscosity reduction ratio is equal to unity. Fig. 6 shows viscosity
reduction ratios of CO2 PEG solutions for different PEG molecular
weights (M = 400, 3000, 6000 and 8300 g mol1 ) at temperatures
between 347.8 K and 353.2 K. In Fig. 6, the CO2 solubility in the PEG
was determined by calculation with the pc-SAFT EoS for PEG 3000
at 353. 2 K and for PEG 8300 at 353.2 K, and from the literature
for other PEGs [5,8]. Although the viscosities of CO2 PEG 20000
solutions are available at temperatures from 353. 2 K to 393.2 K in
the literature [8], the reported values were excluded in the gure,
since the effect of shear rate on PEG 20000 viscosity and temperature treatment of the samples are unknown (Fig. 3). The viscosity
reduction ratio for dissolved CO2 in the PEG between 347.8 K and
353.2 K can be reduced to a simple curve for PEGs of different molecular weights from 400 g mol1 to 8300 g mol1 as a function of the
weight fraction of CO2 in the PEG solution as follows:

ap,c = exp 5.7777 wCO2 1.7214 101 (wCO2 )2


+6.3273 103 (wCO2 )3

(21)

Eq. (21) can represent the viscosity reduction ratio of CO2 PEG
solutions to within 0.08 of the ap,c value. The reduction in viscosity ratio caused by CO2 dissolution into PEG was found to be
independent of the PEG molecular weight.
In Fig. 6, the viscosity reduction ratio for CO2 PEG 3000 solutions at 353.2 K was predicted with the Gerhardt et al. equation
and the KelleyBueche equation from parameters given in Table 6.
Results for PEG 6000 and PEG 8300 solutions with CO2 are shown in
the Supplementary material (Figs. S15 and S16). Calculated values
of the molar occupied volume (vo M/cm3 mol1 ) was in decreasing
order of PEG 6000 > PEG 3000 > CO2 , which agrees with the order
estimated from the chemical structure. Both equations overestimated the viscosity reduction by 40% for the CO2 PEG solutions.
The overestimation of the viscosity reduction values by the theory might be caused by large values of the calculated free volume

M. Iguchi et al. / J. of Supercritical Fluids 97 (2015) 6373

71

Table 6
Characteristic parameters for free volume viscosity models for poly(ethylene glycol) 3000, 6000 and 8300, and carbon dioxide.
Substance

d0 /mPa s cmd1 gd1

vo /cm3 g1

ARD/%

Bias/%

Poly(ethylene glycol) 3000


Poly(ethylene glycol) 6000
Poly(ethylene glycol) 8300

0.5595
5.8594
1.1558 101

0.7839
0.7717
0.7717a

0.7
1.2

0.2
0.5

Carbon dioxide

n.d.b

0.589

([66], for equations of Gerhardt et al. and


KelleyBueche)
(This work, for Gerhardt et al. equation)
(This work, for KelleyBueche equation)

0.6873
0.6914
a
b

Value set equal to PEG 6000.


Values not determined in this work.

fraction of the CO2 PEG solutions. Prediction of viscosity reduction


was made with value of vo,CO2 determined from the crystal density
(Section 2.4). The vo,CO2 was also determined by tting the viscosity data of CO2 PEG solutions (M = 3000, 6000 and 8300 g mol1 ) at
353.2 K with each equation (Table 6). The viscosity reduction could
be correlated to within an ARD of 6.4% for PEG 3000, 9.2% for PEG
6000 and 14.2% for PEG 8300 using the Gerhardt et al. equation.
Similar results were obtained with the KelleyBueche equation.
The use of tted vo,CO2 improved the prediction of the viscosity
reduction ratio for the CO2 PEG solutions (Figs. 6, S15 and S16,
Supplementary material). From the results in this study, it can be
concluded that the value of vo,CO2 for the viscosity reduction calculation should be determined by tting viscosity data, while the
calculation method for the free volume fraction seems to have little
effect on the viscosity reduction ratio.
4. Conclusions
New viscosity data for CO2 PEG solutions are reported for
3000 g mol1 and 8300 g mol1 of molecular weight at 353.2 K and
373.2 K over the range of CO2 pressures from 5 MPa to 15 MPa.
Shear viscosity measurements show that PEG 3000 and PEG 8300
behave as Newtonian uids whereas PEG 20000 behaves as a
non-Newtonian uid. Comparing the viscosity reduction ratio provided by CO2 among PEGs of different molecular weights (M = 400,
3000, 6000 and 8300 g mol1 ), it can be concluded that the viscosity reduction ratio is independent of PEG molecular weight at
a given temperature. A simple relationship can correlate the viscosity reduction ratio in terms of the weight fraction of CO2 in
PEG solutions for PEG molecular weight being from 400 g mol1
to 8300 g mol1 within 0.08 in absolute units. The equation of Gerhardt et al. or KelleyBueche overestimates the viscosity reduction
ratio of the CO2 PEG solutions by up to 40%, but can correlate the
data to within 14% when a tted value of the CO2 occupied volume
is used.
Acknowledgement
The authors would like to acknowledge partial nancial support
of the Ministry of Education, Science, Sports and Culture for support
of this work.
Appendix A.
A.1. Pure parameters of poly(ethylene glycol) for the pc-SAFT EoS
Pure parameters (m,  and ) of PEG were determined according
to the method proposed by Gross and Sadowski [44]. In this work,
it was assumed that only segment number (m) is dependent on the
molecular weight and that it can be represented as a linear function
of the molecular weight. Pure parameters were determined by minimizing the following objective function (f(m/M, , /kB )) using the

LevenbergMarquardt method with numerical derivatives [62]:

f (m/M, , /kB ) =


418 

PEG,cal,i PEG,exp,i
i=1

9

j=1

Uc (PEG,exp,i )

L
L
wPEG,cal,j
wPEG,exp,j

L
Uc (wPEG,exp,i
)

CL

6 H6 +PEG,cal,k

Uc (CL

6 H6 +PEG,exp,k

6 H6 +PEG,exp,k

k=1

CL

(A1)

L
where PEG is the density of pure PEG, wPEG
is the PEG composition
in the liquid phase of benzenePEG mixture and CL H +PEG is
6 6
the liquid density of benzenePEG mixture. In the calculations
for benzenePEG mixtures, it was assumed that the PEG does
not dissolve into the vapor phase and that the binary interaction
parameter was set equal to unity (kij = 0). The composition in liquid
phase was determined by the isofugacity of benzene in vapor and
liquid phases. The derivatives of the parameters were obtained by
using central differences:

Y
Xi

=
Xj =
/ i

Xi (1+ ),Xj =
/ i

2 Xi

Xi (1+ ),Xj =
/ i

(A2)

where X refers to the pure parameters, Y represents the density of


pure PEGs and its mixture with benzene in the liquid phase, or the
PEG composition in the liquid phase in the benzenePEG mixture.
The value of that represents the difference was set equal to
1010 . Initial values of the pure parameters were estimated from
the values of diethyl ether reported by Gross and Sadowski [67].
The effect of initial values on determination for the pure parameters was investigated by using values reported by Martn et al. [28]
as initial values. The obtained parameters (m/M = 44.927,  = 3.0571
and /kB = 234.57) were slightly different from those values used in
this work when the initial values were set equal to diethyl ether
(m/M = 44.749,  = 3.0608 and /kB = 234.87). However, the ARD values calculated with these different parameters were in accordance
to within 0.02%. Thus, there is little inuence on initial values for
the pure parameters determined in this work.
Verication of the calculation with the pc-SAFT EoS was made
by calculation for the critical point of methane (Tc = 191.4006 K,
pc = 4.6751 MPa and c = 0.14285), carbon dioxide (Tc = 310.2768 K,
pc = 8.0639 MPa and c = 0.13186) and benzene (Tc = 572.3948 K,
pc = 5.53721 MPa and c = 0.13039) which were reported by Privat
et al. [73]. The critical temperature, pressure and reduced density
are denoted as Tc , pc and c , respectively.

72

M. Iguchi et al. / J. of Supercritical Fluids 97 (2015) 6373

Appendix B. Supplementary data


Supplementary material related to this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.supu.
2014.10.013.

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