High Temperature, Vol. 40, No. 2, 2002, pp. 203–206. Translated from Teplofizika Vysokikh Temperatur, Vol.

40, No. 2, 2002, pp. 231–234.

Original Russian Text Copyright © 2002 by Sabirzyanov, Il’in, Akhunov, Gumerov.

THERMOPHYSICAL PROPERTIES
OF MATERIALS

Solubility of Water in Supercritical Carbon Dioxide

A. N. Sabirzyanov, A. P. Il’in, A. R. Akhunov, and F. M. Gumerov
Kazan State University of Technology, Kazan, 420015 Tatarstan, Russian Federation
Received February 28, 2000

Abstract—A new experimental circulation facility is developed to investigate the solubility of liquids in super-
critical fluids at a pressure of up to 35 MPa and temperatures from 293 to 423 K. The solubility of water in
supercritical carbon dioxide is experimentally investigated on the 313 and 323 K isotherms in the pressure range
from 8 to 20 MPa. Empirical parameters of intermolecular interaction are obtained in the Soave approximation,
which enables one to describe the solubility with an error that does not exceed the experimental error.

INTRODUCTION Standard pressure gages 13 and 14 are used to measure

The processes of supercritical fluid extraction find
an ever growing application in various branches of
industry [1]. The use of supercritical fluids in extraction
processes is based on the high sensitivity of solubility
to insignificant changes in temperature and pressure in
the vicinity of the critical point of a pure solvent [2].
This enables one, on the one hand, to carry out a super-
fractionation of the starting mixture and, on the other
hand, accomplish a complete regeneration of the
extractant by way of simple reduction of pressure, with-
out additional consumption of energy, with subsequent
repeated use of the extractant. The repeated use of the
extractant implies a supercritical extraction cycle in a
circulation facility. One of the conditions for the
energy-related optimization of such a cycle is the
reduction to a minimum of the exergy loss. To carry out
an exergetic analysis of the extraction cycle, one must
have exact knowledge of the solubility of the target
component in a fluid solvent. Diluted waste water solu-
tions represent one of the most widespread extraction
systems in various branches of industry. Therefore, it is
the main objective of this study to experimentally per-
form the supercritical extraction cycle and obtain
desired experimental data on the solubility of water in
supercritical carbon dioxide which is most extensively
used in fluid extraction processes.
EXPERIMENT
Our experimental circulation facility and experi-
mental procedure are described in detail in [3]. Figure 1
shows the schematic of the facility operating at pres-
sures up to 35 MPa and temperatures of 293–423 K.
The experimental facility is based on a membrane com-
pressor 3 (MK-80-3.5/350 type) manufactured by AO
Kazan’kompressormash and intended to compress
gases up to a pressure of 35 MPa. The operating exper-
imental pressure is set within ±0.1 MPa with a gas pass-
ing through a pressure regulator 5 (ADN-0063M1 type)
also manufactured by AO Kazan’kompressormash.
the pressure in the extraction cell and separator. The
preassigned process temperature is maintained by a
thermostatting bath 15 into which the housing of the
extraction cell is immersed. The error of maintaining
the process temperature is ± 0.05 K. The temperatures
of the fluid in the extraction cell and of the gas in the
separator are measured by Chromel–Alumel thermo-
couples inserted directly into the medium being mea-
sured through the housings of the units using special
sealing means. The error in measuring temperature is
estimated at ± 0.1 K. The solvent flow rate is controlled
by a valve 12 in the range of 0.3–0.4 kg/h. If necessary,
the receiver may be additionally pumped without inter-
fering with the process, which allows one to continue
the process for as long as is necessary. The time of
experiment is defined by the required ratio of the mass
of solvent to that of solute. The quantity of the solvent
passed through the liquid being dissolved is measured
by the weighing method. For this purpose, a receiving
cylinder 8 is placed on an electronic balance 18
(VM-150 type) manufactured by AO Massa-K (St. Peters-
burg), which is used to determine the weight of the cyl-
inder before and after the experiment with an error of
± 0.05 kg. The initial and final amount of the liquid
being dissolved is determined with an error of ±10–5 kg
by weighing on a CAS electronic analytical balance.
The amount of liquid dissolved in the fluid is calculated
from the material balance. The solubility of the liquid
is determined in molar fractions. Liquid carbon dioxide
99.8% pure, prepared in accordance with the GOST
(State Standard) 8050-85 (by POZIS-gaz, Zeleno-
dol’sk), and distilled water were used in the experi-
ments. We have estimated the mean-square relative
error of the method for measuring the solubility in the
developed circulation facility within 7.2%. Figure 2
gives a comparison of our results obtained on the 313 K
isotherm with the results of [4] also obtained in the cir-
culation facility. The consistency of the results is
observed within a total error of 14%. The experimental

0018-151X/02/4002-0203$27.00 © 2002 MAIK “Nauka /Interperiodica”

204 SABIRZYANOV et al.

14 13
17
7
2
16
1
6 11 16
12 16

15
6

16

5
10

18 4
8 19

Fig. 1. Schematic of the experimental circulation facility: (1) extractor; (2) separator; (3) membrane compressor; (4) receiver;
(5) pressure regulator; (6) filter; (7, 11) thermostat; (8) receiving cylinder; (9) fine filter; (10) intermediate cylinder; (12) throttle
valve; (13, 14) pressure gages; (15) thermostatting bath; (16) thermocouples; (17) entrainment separator; (18) balance; and
(19) backup cylinder.

data on the solubility of water in supercritical ëé2
obtained by us are given in Tables 1 and 2 and Fig. 3.
The behavior of differential solubility (∂y/∂P)T of
water in supercritical carbon dioxide is consistent with
the predictions of the quantitative theory of solubility of
substances in supercritical fluids [5]. The strong varia-
tion of solubility in a relatively narrow range of pres-
sures in the vicinity of the critical temperature of pure
solvent points to the possibility of repeated use of one
portion of supercritical carbon dioxide as extractant in
the processes of treatment of dilute aqueous solutions.
THEORY
Bartle et al. [6] suggested and tested a model
enabling one to describe the solubility of low-volatile
and incompressible substances in supercritical fluids,
ln y = ln ( P v /P ) – ln φ 2 + PV m /RT ,
where y is the solubility of substances in molar frac-
tions, Pv is the saturation pressure of the substance
being dissolved at a given temperature T of the system,
P is the pressure in the system, φ2 is the fugacity coef-
ficient of the solute in the fluid, Vm is the reduced molar
volume of a pure solute, and R is the universal gas con-
stant.
The saturation pressure of water was determined
from the tables in [7]. The fugacity coefficient of the
solute in the fluid phase may be calculated by one of the
cubic multiparameter equations of state. We used the
Soave two-parameter equation of state [8], which is
extensively used to calculate the phase equilibria in the
liquid–supercritical fluid systems,
P = RT / ( v – b ) – a/ ( v – b ). (2)
In Eq. (2), v is the specific volume and a and b are
parameters of the Soave equation for mixture, that are
determined as follows:
(1)
a = ∑∑y y a i j ij , (3)
j i

HIGH TEMPERATURE Vol. 40 No. 2 2002

 SOLUBILITY OF WATER IN SUPERCRITICAL CARBON DIOXIDE 205

y, molar fractions Û, molar fractions

0.01 0.01

0.001 0.001
1 1
2 2

8 12 16 20 24 8 12 16 20 24
P, MPa ê, MPa

Fig. 2. The solubility of water in supercritical carbon diox- Fig. 3. The solubility of water in supercritical carbon diox-
ide on the T = 313 K isotherm: (1) [4] and (2) our results. ide: (1) 313 and (2) 323 K; the solid lines indicate calculation.

The substitution of variables A = aP/R2T 2, B =

b = ∑∑y y b i j ij , (4) bP/RT, and Z = Pv /RT reduces the initial Soave equa-
tion (2) to the cubic form relative to Z:
j i

Z – Z + ( A – B – B )Z – AB = 0.
3 2 2
where yi and yj are the molar fractions of the ith and jth (11)
components of the mixture in any of the equilibrium
phases, respectively. The parameters of the Soave equa- We can write the final expression for the calculation
tion for pure components are combinations of the criti- of the fugacity coefficient of the components [9],
cal pressure and temperature,
ln φ i = ( Z – B )B i /B – ln ( Z – B )
a ii = α i ( T )0.42748R T cri /P cri ,
2 2
(5)
(12)
b ii = 0.086664RT cri /P cri , (6)
+ ln ( 1 + B/Z ) B i /B – 2 ∑y a i ij /a A/B,
j

2
α i ( T ) = 1 + m i  1 – -------- ,
T where j is the number of another substance, whose
(7)
 T cri interaction with molecules is taken into account in cal-
culating the fugacity coefficient of the ith component.
2
The individual parameters of water and carbon dioxide
m i = 0.480 + 1.574ω i – 0.176ω i . (8) needed for calculation are given in Table 3.

Here, Pcr i , Tcr i, and ωi are the critical pressure, temper- The fitting empirical parameters of intermolecular
ature, and the acentric factor of the ith component. interaction kij and ηij are determined at a fixed temper-
Thus, the value of a may be calculated by the thermo-
dynamic similarity method, because the acentric factor Table 1. Solubility of water in supercritical carbon dioxide
ω is the similarity parameter. The cross parameters tak- (molar fractions ×103) at a temperature of 313 K
ing into account the peculiar features of the pair inter-
action of dissimilar molecules are calculated in accor- P, MPa 8.31 9.12 10.26 12.36 15.4 17.96 20.54
dance with the van der Waals combination rules with y × 103 0.53 1.05 4.14 4.50 5.75 6.07 5.96
the introduction of the empirical corrections kij and ηij,

a ij = ( 1 – k ij ) a ii a jj , (9) Table 2. Solubility of water in supercritical carbon dioxide

(molar fractions ×103) at a temperature of 323 K
b ii + b jj P, MPa 8.51 9.12 10.34 14.19 16.41 18.44 20.26
b ij = ( 1 – η ij ) -----------------
-. (10)
2 y × 103 2.51 5.25 7.17 8.51 9.08 9.27 10.20

HIGH TEMPERATURE Vol. 40 No. 2 2002

206 SABIRZYANOV et al.

Table 3. Individual parameters of substances temperature dependence of the intermolecular interac-

tion parameters may be explained. The chemical forces
Vm × 103, depend stronger on temperature than the physical
Substance Tcr , K Pcr , MPa ω
m3/kmol forces, because they are defined by the ordering of mol-
ecules in the solution. An increase in temperature inten-
CO2 304.2 [10] 7.382 [10] 0.225 [10] – sifies the motion of molecules, and this hampers the
Water 647 [10] 22.03 [10] 0.344 [10] 18.092 [11] mutual orientation of molecules which is necessary for
forming a hydrogen bond.
Table 4. Parameters of intermolecular interaction in the wa-
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kij 0.2592 –3.381 × 10–3 Gases as Solvents), Moscow: Nauka, 1974.
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HIGH TEMPERATURE Vol. 40 No. 2 2002