ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2007, Vol. 81, No. 4, pp. 510514. Pleiades Publishing, Ltd.

., 2007.
Original Russian Text A.N. Vulfson, O.O. Borodin, 2007, published in Zhurnal Fizicheskoi Khimii, 2007, Vol. 81, No. 4, pp. 600605.

CHEMICAL THERMODYNAMICS
AND THERMOCHEMISTRY

A Thermodynamic Analysis of the Solubility of Gases in Water

at High Pressures and Supercritical Temperatures
A. N. Vulfson and O. O. Borodin
Moscow State Institute of Electronics and Mathematics and Institute of Petroleum and Gas Problems,
Russian Academy of Sciences, Moscow, Russia
E-mail: vulfson@ipug.ru; matan@miem.edu.ru
Received January 24, 2006

AbstractA one-parameter form of the Henry law is suggested to describe the solution of real gases in water
over a fairly wide range of temperature and pressure variations. The thermodynamic derivation of the Henry
law is based on the Vant Hoff model of concentrated solutions of gases. The analytic approach developed in
this work is a variant of rigorous thermodynamic theory that refines and generalizes the KrichevskiiKazar-
novskii equation. The thermodynamic theory suggested is compared with the experimental data on the solution
of methane and nitrogen in water.
DOI: 10.1134/S0036024407040024

Substantial deviations from the Henry law are conveniently be described using the virial expansion in
observed for the solution of gases in liquids in the powers of pressure with four coefficients [7],
region of high pressures. The first empirical model that
pv g /RT = 1 + B' ( T ) p + C' ( T ) p + D' ( T ) p ,
2 3
generalized the Henry law and established proportion- (1)
ality between the solubility and fugacity of pure gases
was suggested in [1]. The problem of the solubility of a where p is the pressure; T is the temperature; vg is the
gas in water formulated thermodynamically [2, 3] molar volume; R is the universal gas constant; and B',
should be solved for two cases: (1) the critical temper- C', and D' are the virial coefficients.
ature of a soluble gas Tc is higher than the temperature The B'(T) and C'(T) virial coefficients of (1) were
of the existence of liquid water, T < Tc, and (2) the crit- calculated for nonpolar gases by linear expansion in the
ical temperature of a soluble gas Tc is lower than the acentricity factor (see [8] for more details). The calcu-
temperature of the existence of liquid water T > Tc. In lations were performed as recommended in [3]. The
the first case, the solubility of the gas in water is calcu- D'(T) virial coefficient was adjusted to minimize the
lated using one of the variants of the vaporliquid equi- error in the compressibility Z = pvg/RT calculated by
librium method (see [2, 3] for more details). In the sec- (1) with respect to the compressibility calculated using
ond case, the solubility of the gas in water can be cal- the most complete WebbBenedictRubinStarling
culated using either the KrichevskiiKazarnovskii [4] equation of state (see [9, 10] for more details).
or KrichevskiiIlinskaya [5] equation. These equa-
tions are, however, semiempirical in character and not Table 1. Second, third, and fourth virial coefficients as
well grounded [6]. functions of temperature for nitrogen and methane
The thermodynamic method developed in this work T, K B' 103, atm1 C' 106, atm2 D' 109, atm3
applies to the second case. The suggested approach is
based on the Vant Hoff model of a molecular solution Nitrogen
of an arbitrary concentration in a nonvolatile solvent. 298.1 0.17837 2.42359 1.1
The results based on the phase equilibrium condition 323.1 0.00674 2.02472 1.2
lead to the general form of the Henry law. We will show 348.1 0.13916 1.68310 1.14
that the general form of the Henry law reduces to a one-
373.1 0.23495 1.39902 1.0
parameter form for solutions of moderate concentra-
tions. This form is similar to the KrichevskiiKazar- Methane
novskii equation. 293.1 1.85292 0.84430 18.0
313.1 1.44572 1.43726 11.0
The equation of state of a free gas. A real gas with
the critical temperature lower than the main tempera- 333.1 1.12607 1.69439 7.0
ture range of the existence of water 0C < t < 100C can 353.1 0.87196 1.76662 4.0

510
 A THERMODYNAMIC ANALYSIS OF THE SOLUBILITY OF GASES IN WATER 511

The calculated second, third, and fourth virial coef- where X(*) > 0 is the function known from either the-
ficients of (1) are listed in Table 1 for nitrogen N2 and oretical considerations or experimental data. Clearly,
methane CH4 as functions of temperature. for infinitely dilute solutions at c
1 and X(*) = 1, (6)
Note that (1) is valid at 0 < p < 500 atm for nitrogen becomes the well-known Vant Hoff equation. Under
and 0 < p < 250 atm for methane over the temperature solution conditions (5), the Vant Hoff equation of state
ranges specified. These limits can be extended if a of a solution of an arbitrary concentration (Eq. (6))
larger number of virial equation coefficients are used. takes the form identical with the quasi-ideal gas equa-
tion,
Let g(T, p) be the molar Gibbs energy of a pure gas;
this value is identical with its chemical potential. We *v qs /RT = X ( * ). (7)
then have
We can conveniently introduce the x(*) osmotic
p
activity function of the solute for the class of Vant
g ( T, p ) g ( T, p0 ) = v g d p, (2) Hoff solutions of arbitrary concentrations (6). This
function is determined by the equation
p0
d 1 x ( * )
under isothermal conditions at a fixed T value. Here, --------- ln x ( * ) = ------ X ( * ), lim -------------- = 1. (8)
p0 is a fixed pressure. Let us also define the fugacity of d* * * 0 *
a gas f (T, p) as Importantly, according to (8), the x(*) osmotic activity
f ( T, p ) g ( T, p ) g ( T, p0 ) of a Vant Hoff solution of an arbitrary concentration
ln -------------------- = -------------------------------------------------, only depends on the osmotic pressure *. At infinite
f ( T, p0 ) RT dilution, as * 0, osmotic activity tends to the
(3)
f ( T, p ) osmotic pressure of the solution, x(*) *. Substi-
lim ------------------ = 1. tuting (8) into (7) yields the Vant Hoff equation for a
p0 p
solution of an arbitrary concentration in the form
Substituting (1) into (3) and taking (2) into account,
d
we obtain v qs = RT --------- ln x ( * ). (9)
d*
1 1
f ( T , p ) = p exp B' ( T ) p + --- C' ( T ) p + --- D' ( T ) p .
2 3
The chemical potential of a solute in a Vant Hoff
2 3 solution is known to take a form similar to that obtained
(4) for the Gibbs energy of a pure gas. The thermodynamic
Equation (4) explicitly describes the fugacity of a potential of the dissolved gas as an aqueous solution
gas with virial equation of state (1). component is given by the equation gs = gs(T, *).
Using (9) in (2), we therefore obtain
The equations of state of pure water and a dissolved
*
gas. Let Nw and Ngs be the numbers of moles of water
and a gas dissolved in it and vw and vgs be their molar
volumes. In what follows, we assume that water is
gs ( T , * ) gs ( T , *0 ) = v gs d*
*0
absolutely incompressible, that is, vw = const. This (10)
*
allows us to omit insignificant details complicating the d x ( * )
discussion.
d*
= RT --------- ln x ( * ) d* = RT ln --------------,
x ( *0 )
The concentration of the dissolved gas in mole frac- 0*
tions is c = Ngs/Nw. Clearly, dissolved gas molecules are
distributed over the whole accessible solution volume for a moderately dilute Vant Hoff solution (6) under
Vs, which can be identified with the volume of pure isothermal conditions. Here, *0 is the osmotic pressure
water. Therefore, fixed at the given temperature. It follows that the
osmotic activity x(*) corresponding to (8) is propor-
V s = Nwv w, N gs v gs = N w v w , v gs = v w /c. (5) tional to the classic Lewis activity.
According to (5), the gas dissolves in water without A useful example of a moderately dilute Vant Hoff
increasing the volume of the liquid, which corresponds solution is a solution with the virial equation of state.
to the Guggenheim model of solution according to the Using expansion (7) with two virial coefficients, we
absolute absorption type (see [11] for details). obtain
Molecular solutions of arbitrary concentrations are *v * *
described within the framework of the general equation -------------gs- = 1 + -----0-, X ( * ) = 1 + -----0-,
of state [12] RT pw pw
(11)
*
*v
-------------w- = cX ( * ), lim X ( * ) = 1, x ( * ) = * exp -----0- ,
(6) p
RT * 0 w

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 81 No. 4 2007

512 VULFSON, BORODIN

0
where p w is a constant parameter in pressure units. f ( T, p ) c( T, p )
lim ------------------ = 1, lim --------------------- = 1,
0 p0 p p 0 c* ( T , p )
Clearly, 1/ p w is an analogue of the second virial coef- (19)
ficient in expansion (1) of the equation of state of a real * ( T , p ) RT x* ( T , p )
lim --------------------- = -------, lim --------------------- = 1.
gas in powers of pressure. Under solution conditions p 0 c* ( T , p ) v w p0 0 * ( T , p )
(5), one-parameter virial equation (11) becomes
Equations (18) and (19) lead us to conclude that
* c RT
-----0- = -------------- , = ------------- , (12) f ( T, p )
1 c 0 lim ---------------------
pw pw v w p 0 c* ( T , p )
(20)
where is the dimensionless function of temperature. f ( T, p ) p c( T, p )
A similar relation was used to describe the hydration of = lim ------------------ ----------------- --------------------- = H ( T ),
p0 p c ( T , p ) c* ( T , p )
solutes (see [13] for details). Equation (12) can conve-
niently be rewritten using the pseudoconcentration c* f ( T, p )
lim ---------------------
c* = c/ ( 1 c ), * = p w c*.
0
(13) p0 x* ( T , p )
(21)
f ( T , p ) c* ( T , p ) * ( T , p ) vw
Note that the
0
pw
virial parameter in (12) and (13) is not = lim --------------------- --------------------- --------------------- = ------- H ( T ).
p 0 c* ( T , p ) * ( T , p ) x* ( T , p ) RT
known and, within the framework of thermodynamic
theory, can only be determined from experimental data. Substituting (21) into (17) yields
The phase equilibrium condition and general form
vw
of the Henry law for a nondiluted Vant Hoff solution. ------- H ( T )x ( * ) = f ( T , p ). (22)
The concentration of the dissolved gas will be deter- RT
mined from the thermodynamic phase equilibrium con- Equation (22) is the general form of the Henry law
dition between a free gas and the gas dissolved in water. for the solution of a real gas in water in the approxima-
In the approximation of a nonvolatile liquid, this equa- tion of the absence of vaporization and on the assump-
tion takes the form tion that the dissolved gas forms a moderately dilute
gs ( T , * ) = g ( T , p ). (14) Vant Hoff solution (6). According to (22), the osmotic
activity of a gas in solution x(*) is proportional to the
Clearly, this equation also holds at p = p0. fugacity of the free gas f (T, p). In particular, for an infi-
Let us subtract the equation obtained above from nitely dilute Vant Hoff solution, x(*) = * according
(14) to obtain the main thermodynamic equation in to (8). It follows that
terms of Planck thermodynamic potentials,
H ( T )c = f ( T , p ). (23)
gs ( T , * ) gs ( T , *0 ) g ( T, p ) g ( T, p0 )
--------------------------------------------------------- = -------------------------------------------------, (15) The first work where Eq. (23) was suggested was likely
RT RT [1].
where *0 = *(T, p0) is the temperature-dependent The one-parameter form of the Henry Law. In the
special case of equation of state (11), the general form
osmotic pressure of the gas corresponding to the pres- of the Henry law (Eq. (22)) reduces to
sure p0. Substituting (3) and (10) into (15) yields
f ( T, p0 ) f ( T, p ) 1 vw
ln --------------------- = -----0- * ( T , p ) + ln ------- H ( T ). (24)
- x ( * ) = f ( T , p ).
------------------- (16) * ( T , p ) pw RT
x ( 0* )
The passage to the p0 0 limit transforms (16) into Using (13) in (24) yields

f ( T, p0 ) f ( T, p )
- x ( * ) = f ( T , p ).
lim ------------------- (17) ln --------------------- = ( T )c* ( T , p ) + ln H ( T )
p0 0 x ( *0 ) c* ( T , p )
c( T, p ) RT
(25)
Without using particular forms of the equations of c* ( T , p ) = -------------------------------------
- , ( T ) = -------------.
1 ( T )c ( T , p ) 0
pw v w
state of free gases and solutions of gases in a nonvola-
tile liquid, let us define the Henry parameter H(T) as
Equation (25) is the one-parameter form of the Henry
p
H ( T ) = lim -----------------. (18) law that corresponds to the solution of a real gas in
p 0 c( T, p ) water with the formation of a nondiluted Vant Hoff
Using fugacity definition (3) and bearing in mind that solution with virial equation of state (11).
the equilibrium concentration c(T, p) 0 as p 0, According to thermodynamic theory, the tempera-
we can, in accordance with (8) and (13), write the limits ture dependence of the Henry parameter H(T) over a

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 81 No. 4 2007

 A THERMODYNAMIC ANALYSIS OF THE SOLUBILITY OF GASES IN WATER 513

Table 2. Coefficients of (26) for the solution of nitrogen and methane in water ( is the deviation)
Gas t, C aH bH cH dH
N2 173 162.723 8435.7 21.5655 0.00843921 0.94
CH4 280 181.516 9114.8 25.0467 0.000143485 1.8

Table 3. Molar solubilities of nitrogen and methane in water (c 103) as functions of temperature and pressure
Nitrogen Methane
p, MPa
298.1 K 323.1 K 348.1 K 293.1 K 313.1 K 331.1 K 353.1 K
2.53 0.279 0.219 0.204 0.602 0.482 0.393 0.361
5.07 0.541 0.428 0.397 1.204 0.883 0.747 0.691
10.13 1.015 0.812 0.760 1.951 1.566 1.365 1.261
15.2 2.529 2.048 1.815 1.702
20.27 1.812 1.469 1.391 3.035 2.449 2.208 2.112
25.33 3.372 2.786 2.513 2.401
30.4 2.458 2.035 1.938 3.099 2.802 2.722
40.53 3.653 3.348 3.188
50.66 3.566 2.987 2.877 3.983 3.677 3.581
60.8 4.328 4.047 3.918
81.06 4.925 4.192 4.065
101.33 5.741 4.916 4.765

limited temperature range can be approximated as Equation (27) then takes the form1

ln H = a H + b H /T + c H ln T + d H T . (26)
The coefficients of (26) for nitrogen and methane
were determined from the experimental data reported in
[14]; they are listed in Table 2.
A comparison of the one-parameter Henry law form
with experimental data. Let T0 and p0 be constants cor-
responding to normal conditions, that is, 25C and
1 atm, respectively. The one-parameter Henry law form
then gives
f ( T , p ) c* ( T 0, p 0 )
ln ---------------------- ------------------------- = ( T )c* ( T , p )
f ( T 0, p 0 ) c* ( t, p )
f c *00 c* H * .
- = ( c 00
ln ------- ----- * ) -----
- ln ------ 0 c 00 (28)
f 00 c* c *00 H 0
Let c = c(T, p) be a known discrete set of experimental
data. The temperature, pressure, and concentration val-
ues can be used to calculate f and c*. The c00 and H/H0
values are tabulated in [3] and [14], respectively, and
the f00 value is determined by (4). Let us represent the
experimental data on the solubility of gases graphically
at various temperatures and pressures. In conformity
with (28), let the y = ln( f c *00 / f00c*) and x = c*/ c *00 val-
ues be plotted as ordinates and abscissas, respectively.
If the one-parameter Henry law (Eq. (28)) is satisfied
with a small error, all experimental points at the given
temperature fall close to a family of straight lines with

H(T ) the slope c *00 and y-intercept ln(H/H0) 0 c *00 . The 0

ln -------------- - ( T 0 )c* ( T 0, p 0 ) , (27)
H(T0) value can be varied to adjust the family of straight lines

(28) and minimize the difference between the theoreti-

c( T, p )
c* ( T , p ) = -------------------------------------
- , ( T ) = -------------.
1 ( T )c ( T , p )
To simplify equations, let us use the notation
c00 = c(T0, p0), c *00 = c*(T0, p0), f00 = f (T0, p0),
H0 = H(T0), 0 = (T0).
RT
cal values and the measured dissolved gas concentra-
0
pw v w tions. The experimental data on the solubility of nitro-
gen and methane were reported in [14] (Table 3).
1 This implicit equation can be solved iteratively, and the Henry
law can naturally be selected to represent zeroth approximation.
The first approximation (28) is then the equation in which c*/ c *00
is replaced with the relative pressure p/p0. The first approxima-
tion obtained this way is an analogue of the KrichevskiiKazar-
novskii equation [6].

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 81 No. 4 2007

514 VULFSON, BORODIN

f c00 for nitrogen over the temperature range 25C < t < 75C
ln ------- ---------
-
f 00 c up to pressures of p = 500 atm and for methane over the
temperature range 10C < t < 80C up to pressures of
1.2 p = 250 atm. At higher pressures, discrepancies
between thermodynamic theory and experimental
data are likely caused by the inaccuracy of virial
equation (1).
0.9 To summarize, the suggested Vant Hoff model of a
solution of a gas of an arbitrary concentration can effec-
3 tively be used to construct both the general and one-
parameter Vant Hoff law equations corresponding to
the solution of real gases in water over fairly wide tem-
0.6 2 perature and pressure ranges. The calculations per-
formed provide convincing evidence in favor of the
conclusions drawn in this work concerning the solution
1 of gases with low critical temperatures that cannot be
condensed over the temperature range of the existence
0.3 of water. The analytic approach developed can be con-
sidered a variant of rigorous thermodynamic theory that
refines the KrichevskiiKazarnovskii [4] and Krichev-
skiiIlinskaya [5] equations.

0 250 500 750 1000

c*/c*00
Fig. 1. Nitrogen N2 solubilities in water according to one-
parameter Henry law (28) with c00 = 1.19 105 and 0 =
80 and experimental data [14] at (1) 25, (2) 50, and
(3) 75C.
f c00
ln ------- ----------
f 00 c
1.0
0.5
0 1 3
2 4
0 100 200
c*/c*00
Fig. 2. Methane CH4 solubilities in water according to one-
parameter Henry law (28) with c00 = 2.48 105 and 0 =
40 and experimental data [14] at (1) 20, (2) 40, (3) 60, and
(4) 80C.
The data presented in Table 3 and theoretical
straight lines (28) with the parameters c00 = 1.19 105
and 0 = 80 for N2 and c00 = 2.48 105 and 0 = 40 for
CH4 are shown in Figs. 1 and 2. We see that (28) cor-
rectly describes the arrangement of six points for each
of the gases under consideration on the experimental
adsorption isotherms. It follows that, according to
Table 3, the one-parameter Henry law (Eq. (28)) holds
ACKNOWLEDGMENTS
The authors thank A.N. Dmitrievskii for valuable
comments and his attention to this work.
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