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

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

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

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

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

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 .

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

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)

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

(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)

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.

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)

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)

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

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

(9)

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)

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)

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)

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

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)

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

(15)

(16)

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 )

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)

3.1. 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.

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.

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).

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.

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

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

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).

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)

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:

+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

71

Table 6

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

Substance

vo /cm3 g1

ARD/%

Bias/%

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

KelleyBueche)

(This work, for Gerhardt et al. equation)

(This work, for KelleyBueche equation)

0.6873

0.6914

a

b

Values not determined in this work.

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

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

2Xi

Xi (1+),Xj =

/ i

(A2)

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

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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