Journal of Solution Chemistry, Vol. 16, No.

12, 1987

Solubility and Thermodynamics of Carbon

Dioxide in Aqueous Ethanol Solutions
M i g u e l A. P o s t i g o ~ a n d M i g u e l K a t z ~'z
Received November 13, 1986; Revised April 8, 1987

Solubilities of carbon dioxide in aqueous ethanol solutions, determined at

15, 20, 25, 30 and 35~ at atmospheric pressure, show a minimum at each
temperature. Thermodynamics functions for the solution process were cal-
culated and compared with the predictions of the Pierotti gas solubility
theory. The abnormal behavior of these solutions is demonstrated.

KEY WORDS: Solubility; carbon dioxide; Henry's coefficients; ethanol;

water; thermodynamic quantities; Pierotti's theory.

1. I N T R O D U C T I O N
Solubilities of gases in pure liquids and in mixed solvents are of
considerable industrial and theoretical importance. In the present work,
solubilities of carbon dioxide in mixtures of ethanol and water were
measured at five different temperatures over the complete concentration
range. O'Connell and Prauznitz (a) and Boublik and Hala (2> have
analyzed solubilities in mixed solvents from purely thermodynamic
viewpoints and have derived semi-theoretical correlations. O'Connell (3>
pointed out the limitations of the thermodynamic treatment and
proposed an equation, the form of which was suggested by Kirkwood
and Buff<~ solution theory. In this case, it is necessary to have activity
coefficients data for the gas free solvent mixtures; such data are often
unavailable. Tiepel and Gubbins (s) have proposed an analysis by using a
statistical mechanical perturbation theory. In this work, the Pierotti (6~
gas solubility theory was applied and some thermodynamic properties of
these solutions were calculated.

'C&edra de Flslcoqumuca, lnstituto de Ingemena Qmrmca e Instituto de Flslca,

Facultad de Ciencias Exactas y Technolog~a, Universidad N. de Tucuman, Avda. In-
dependencia 1800, Tucuman (4000), R. Argentina.

~Fo whom correspondence should be addressed.

1015
0095-9782/87/1200-1015505.00/0 9 1987 Plenum PuNishing Corporation
1016 Postigo and Katz

,5! / / : i
/,./XS /
,i,.
....
...':./S

Fig. 1. Ostwald's coefficientsL for carbon dioxide as a functionof mole fraction

of ethanol at differenttemperatures.. 99 experimentalvalues; Eq. (4).

2. E X P E R I M E N T A L
Solubility measurements were carried out by using the same ap-
paratus as that used previously. The full description of the apparatus
and mode of operation have been given elsewhere. (7) A 250ml Erlen-
meyer flask calibrated with doubly distilled water is connected to a pres-
sure transducer which in turn is connected to a digital multimeter (Fluke
8000A). The apparatus was calibrated with a manometer containing
dibutylphtalate. Degassed ethanol was introduced into the flask through
a hypodermic syringe and connected to a 50 ml burette. The flask was
submerged in a thermostatic bath. The errors in the measurements were
10 Pa in pressure and 0.02 K in temperature.
The solvent mixture of the desired composition was boiled in a
degassing vessel with a reflux condenser at reduced pressure to remove
dissolved gases. The composition of mixed solvents was determined by
measuring their refraction indices at 25~ with an Abbe refractometer.
The errors in the compositions of the mixtures is approximately +0.001
mole fraction. The refraction indices and densities of ethanol-water
solutions were obtained from known data. (8)
Carbon Dioxide in Aqueous Ethanol Solutions 1017

l hlM Pa

tl/'~" "'

7/ \ \ \
e \\\

'~176
I
0
. .~
0.5 I
X2

Fig. 2. Henry's constants for ethanol-water mixtures as a function of mole fraction

of ethanol a different temperatures. 9 9 9 experimental values; x calculated from
Eq. (16) at 25~

3. RESULTS
The Bunsen coefficient o~is defined as the volume of gas, reduced
to standard conditions, which is absorbed by unit volume of the solvent
at the temperature of the measurement from a gas at standard pressure.
It is calculated from

o~= [(Po -fx)Vo - (P -f2)(Vo - V)]273.15

(1)
(P-f2)VT

where Po is the initial gas pressure and P the final; Vo is the initial
volume of gas and V the volume of the solution; f~ is the vapor pressure
of water at temperature T and f2 the vapor pressure of the solution at the
same temperature, calculated by Raoult's law.
The solubilities are expressed in terms of Ostwald coefficients
and Henry's constants. The Ostwald coefficient L is defined as the ratio
of the volume of absorbed gas to the volume of absorbing liquid and is
related to the Bunsen coefficient by
1018 Postigo and Katz

L = ~T/273.15 (2)
where T is the working temperature.
Henry's constant for a gas dissolved in the mixed solvent is
defined as the ratio of the fugacity of the gas to its mole fraction in the
mixed solvent, and is related to the Ostwald coefficient by O)

h= RT9 + 101308 (3)

L(xlM1 + x2M2)

where p is the density of the solution, xl and xz are the mole fractions of
water and ethanol and MI and M2 are the molecular weights, respec-
tively. Henry's constant h is expressed in Pascal. Ostwald and Henry
coefficients are calculated from experimental data for a at five different
temperatures. Values of the solubility of carbon dioxide in water and in
ethanol are shown in Table I, together with literature values for com-
parison.
Table II shows the values of the L coefficients at the five tempera-
tures for the solubility of carbon diodixe in aqueous solutions with the
error in L estimated to be 1%. The Ostwald coefficients L for the mix-
ture can be expressed as a function of ethanol mole fraction with an
equation of the type:

L = xIL1 + x2L2 + XlX2 Z aj(2xz - 1) j-1 (4)

The method of least squares was used to determine the coefficients aj

which are summarized in Table III along with the standard error of fit at
the five temperatures. In Fig. 1, L is plotted as function of the ethanol
concentrations at the five temperatures. Schowalter and Fergusog x3) ob-
tained similar curve at 15~
Fig. 2 shows Henry's law constants at the five temperatures,
which present a more pronounced maximum at higher temperature.
Thermodynamic functions of the solution process of carbon
dioxide in water-ethanol mixtures were calculated from the solubility
measurements. The standard chemical potential of solution <14)is given
by:
A~t~ = R T l n L (5)
According to Ben Naim, (is) Eq. (5) can be considered to represent the
free energy change for the process of transferring the solute from a fixed
position in the vapor phase to a fixed position in the liquid at constant
temperature and pressure. The corresponding enthalpy and entropy
Carbon Dioxide in Aqueous Ethanol Solutions 1019

T a b l e I . H e n r y ' s C o e f f i c i e n t s f o r C a r b o n D i o x i d e in
Ethanol-Water Solutions a

Solvent 15~ 20~ 25~

Exp. Lit. Exp. Lit. Exp. Lit.

Water 123.7 124.9 b 143.3 145.1 b 165.6 165.5 c
Ethanol 13.5 --- 14.8 --- 15.9 15.8 c

Solvent 30~ 35~

Exp. Lit. Exp. Lit.

Water 188.8 188.4d 211.7 212.6 b
Ethanol 17.5 --- 19.0 ---

a Units: MPa. bRef. 10. CRef. 11. dReL 12.

T a b l e I I . O s t w a l d ' s C o e f f i c i e n t s f o r C a r b o n D i o x i d e in
Aqueous Ethanol Solutions

15~ 20~ 25~ 30~ 35~

x2 L x2 L x2 L x2 L x2 L

0.046 0.974 0.055 0.755 0.065 0.584 0.043 0.542 0.050 0.429
0.081 0.927 0.108 0.651 0.102 0.512 0.076 0.447 0.099 0.311
0.125 0.905 0.164 0.635 0.165 0.464 0.123 0.364 0.144 0.269
0.183 0.950 0.255 0.710 0.213 0.496 0.174 0.351 0.185 0.279
0.215 0.998 0.267 0.782 0.256 0.571 0.242 0.443 0.206 0.303
0.258 0.085 0.348 0.980 0.331 0.743 0.330 0.649 0.275 0.422
0.300 1.191 0.426 1.202 0.430 1.025 0.362 0.736 0.410 0.810
0.375 1.401 0.463 1.310 0.455 1.101 0.456 1.052 0.495 1.069
0.476 1.708 0.506 1.443 0.540 1.365 0.498 1.158 0.531 1.179
0.550 1.943 0.629 1.842 0.611 1.574 0.607 1.487 0.569 1.308
0.631 2.187 0.670 1.963 0.658 1.708 0.660 1.629 0.657 1.548
0.707 2.414 0.741 2.165 0.711 1.856 0.738 1.827 0.760 1.803
0.795 2.671 0.804 2.343 0.809 2.112 0.813 1.990 0.821 1.943
1020 Postigo and Katz

T a b l e l ] I . Coefficients and Standard Deviations o f Eq. (4) D e t e r m i n e d

b y Least Squares for C a r b o n Dioxide in Water-Ethanol Solutions

~ a1 a2 a.3 a4 103~

15 - 1.173 2.34 - 1.02 0.70 7

20 -1.839 2.51 -1.64 0.60 6
25 -2.044 2.54 -2.38 - 4
30 - 1.704 2.80 -2.70 0.15 7
35 -1.561 3.02 -2.33 0.70 4

changes for the process o f fixed-position transfer are

AH ~ = A g ~ + TAS ~ (6)

AS o = -(aAtx~ (7)

T h e c h e m i c a l potential for transfer o f carbon dioxide f r o m water

to ethanol solution m a y be written as:
AIX~ = Ag~ - Ag~ (8)
and the standard enthalpy and entropy o f transfer are:

A ~
= T2[O(__.~)/~T]p (9)

= - (aa~t~'r/a 73p (lO)

T h e Ostwald coefficients for c a r b o n dioxide in water and in aqueous

ethanol solutions h a v e b e e n fitted at the five temperatures b y
- R T l n Lo = ao + boT + coT 2 (11)

-RTln L = a + bT + cT = (12)

AI.t~ = (a - ao) + (b - bo)T + (c - co)T2 (13)

= (a - ao) - (c - co)T 2 (14)

ASa = - ( b - bo) - 2(c - co)T (15)

T h e values obtained for the constants o f Eq. (11) and (12) are
Carbon Dioxide in Aqueous Ethanol Solutions 1021

A p ~ r / J tool !

2oooL .~V
/

-iooo~
I
I
i

-2coo,

Fig. 3. Ap-~rof solution for carbon dioxide as a

function of mole fraction of ethanol at different temperatures.

! /,,N~r/k j mot 1 !
,

I
10 308,15~ . . . . . ~ I

f | ""'~ ~"-'-"~o

// / // 29815"1<
' / " / ' / "/ //

-10 8,15K

-2C i
/

Fig. 4. ~ of solution of carbon dioxide as a

function of mole fraction of ethanol at different temperatures.
1022 Postigo and Katz

T a b l e I V . C o n s t a n t s f r o m E q s . (11) a n d (12) a n d S t a n d a r d
Deviations for Carbon Dioxide in Water-Ethanol Solutions

x2 a b c

0.000 -29722 141.7 -0.1358 10

o. 1oo - 12905 221.2 -0.1373 20
0.200 -115556 633.7 -0.8061 40
0.300 - 168731 1026.7 - 1.5349 60
0.400 -158831 989.3 -1.5304 75
0.500 -136025 852.4 -1.3357 58
0.600 - 118898 745.2 - 1.1747 48
0.700 -106903 667.6 - 1.0540 40
0.800 -94357 584.3 -0.9192 33
0.900 -66890 400.9 -0.6164 23
1.000 1066 -51.6 0.1338 10

a Units: a, J-mol-1; b, J-K-l-mol-1; c, J-K-2-mo1-1.

Table V. Physical Parameters a

Substance (x eij/k ej/k g 1031ct '

CO 2 0.3732 b . . . . . . . . . 26.5 b

C2HsOH 0.4321 c 282 d 288 d 1.69 c ---

H20 0.2750 c 419 d 76 d 2.84 c ___

a ~ hard sphere diameter of molecule, nm; e, energy parameter in Lennard Jones type
potential function, J; k, Boltzmarm , s constant, J - K -1; Ix, dipole moment, D; ~ ,,
polarizability of the molecule, m 3. bRef. 18. CRef. 17. dRef. 11.

summarized in Table IV.

4. D I S C U S S I O N
F i g . 1 s h o w s t h a t p l o t o f L vs. m o l e f r a c t i o n o f e t h a n o l i n t h e l o w
c o n c e n t r a t i o n r a n g e d i s p l a y a m i n i m u m at a p p r o x i m a t e l y xz = 0.15. A t
l o w t e m p e r a t u r e s , t h e s o l u b i l i t y is g r e a t e r . B e n N a i m a n d B a e r (is) h a v e
d e t e r m i n e d t h e s o l u b i l i t y o f a r g o n i n w a t e r - e t h a n o l m i x t u r e s at d i f f e r e n t
t e m p e r a t u r e s a n d at c o n c e n t r a t i o n s b e t w e e n 0 . 0 1 5 a n d 0.25 m o l f r a c t i o n
Carbon Dioxidein Aqueous Ethanol Solutions 1023

AS~r/j K-lmol 1

/ , /0.5 : , 1
//,'/.
//A 93'15K"

-6

-100

Fig. 5. ASg of solutionof carbon dioxide as a

functionof mole fraction of ethanol at differenttemperatures.
ethanol. They observed a maximum in the solutility at low concentra-
tions o f ethanol, then a minimum and finally an increase, as in our
system. Tokunaga ~ determined the solubility of oxygen and nitrogen
in ethanol-water solutions at 0~ and 20~ and obtained similar results
as for argon.
Fig. 3 shows Alag in a form similar to Fig. 2. Plots of ~ and
AS~ (Figs. 4 and 5) vs. the mole fraction of ethanol show similar trends
with a minimum that is more pronounced at low temperatures. No satis-
factory explanation of these phenomena can be given. The interpreta-
tion of solubility data in these systems is rather complicated, because we
are dealing with a non-ideal, hydrogen bond, three component systems.
A gas solubility theory presented by Pierotti (6) was extended to the
systems of mixed solvents treated here. According to Pierotti

in hVM___gc +--gi (16)

RT RT RT

Here, gc is the reversible work associated with the creation of a cavity in

which a gas molecule can be accommodated, g~ is the interaction energy
of the gas molecule in its cavity due to various intermolecular inter-
actions, and VM is the molar volume of the solution. Sada, et al. (1~ has
reported the equation needed to calculate gc and gi. The physical
parameters used in this work are shown in Table V.
1024 Postigo and Katz

It can be seen in Fig. 2 that the general behavior o f the Henry

coefficients are given by Eq. (16), but the m a x i m u m (which is thought
to be due to h y d r o g e n bonds) cannot be reproduced by Pierotti's curve
at 25~ It is below the experimental data and only tends to the ex-
perimental values at higher ethanol concentrations.

ACKNOWLEDGMENT
The present work was financed by a S U B C Y T Research Grant.

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