APRIL, 1928 PHYSICAL REVIEW VOLUME 31

T H E ENTROPY AND T H E R M O D Y N A M I C POTENTIALS OF REAL

GASES AND M I X T U R E S OF REAL GASES, AND A MASS
ACTION LAW FOR CHEMICAL REACTION BETWEEN
REAL GASES
I. GENERAL T H E R M O D Y N A M I C RELATIONS.*
BY JAMES A. BEATTIE
ABSTRACT
Thermodynamic quantities for mixtures of real gases.—Using the two assump-
tions, that at infinitely low pressures the energies of real gases are additive and
the equilibrium pressure is given by the product of the total pressure into the mol
fraction, there are deduced general thermodynamic equations for the energy, heat
content, entropy, thermodynamic potentials of gas mixtures and the chemical
potential of a gas in a mixture in terms of the independent variables p and T, and
V and r.
Mass action law for real gases.—Two forms of the mass action law are deduced
depending upon the choice of p and T, or V and T as the independent variables.

1. INTRODUCTION
T N T H I S paper there is developed by the use of two assumptions a general
-** method, which leads to equations for the energy, entropy, and heat content
of mixtures of compressed real gases. By use of these results, expressions
are derived for the thermodynamic potentials Fy ,T and FPtr of mixtures,
and for the Gibb's chemical potential /x of the individual gases composing a
mixture. From the latter there is then developed a general mass-action law
for a chemical reaction between real gases. In the succeeding paper there
will be obtained, by means of a new equation of state, integrated expressions
for all of the above quantities.
It is well known that the mass action equation derived with the aid of the
perfect-gas law and Dalton's partial-pressure law, is not valid for gas
equilibria at higher pressures. Recently Gillespie1 by a consideration of the
Gibb's chemical potential has derived a general relation for the effect of
pressure on gaseous chemical equilibria at constant temperature. This mass
action equation which is based on the assumption that Dalton's law of partial
pressure can be applied to real gases at infinitely low pressures is

lnKf = lnKp+(l/RT) 'Zhi j * [(dV/dndTtP.nt.n,t...-RT/p]dp\ (1)

where Kf is the equilibrium constant of the reaction at an infinitely low pres-

sure, Kp the value at the pressure p, v\ the number of mols of Substance 1 in
* Contribution from the Research Laboratory of Physical Chemistry, Massachusetts
Institute of Technology, No. 209.
1
Gillespie, Jour. Amer. Chem. Soc. 47, 305 (1925); 48, 28 (1926).
680
 THERMODYNAMICS OF REAL GASES 681

the stoichiometric equation for the chemical reaction, and (d V/dni)T ,v ,»a ,n,, • • •
the partial molal volume of Gas 1 in the equilibrium mixture. This latter
quantity is obtained by differentiation of the equation of state for mixtures
of the gases taking part in the chemical reaction [i.e./(/>., V1T,ni1n2y • • •) == 0]«
In general the integral of Equation (1) must be evaluated graphically. Later
Gillespie2 has transformed this expression into one which is more readily
integrable.
In a series of papers, 3 van Laar and Lorenz have obtained expressions
for the energy, entropy, and the thermodynamic quantities derivable from
them, including a mass-action law which they applied to chemical equilibria
in condensed systems.
Keyes4 has given an equation for the entropy and energy of a mixture of
gases obeying his equation of state, and has deduced from it a mass action
equation for non-ideal gases.

2. T H E ENERGY AND ENTROPY OF MIXTURES OF REAL GASES.

Let us suppose that a given mixture of gases undergoes a change in state
at constant composition from one pressure and temperature (pi, Tx) to
another (p2, T2). The change in energy and entropy can be calculated along
any reversible path. For the present calculation the path considered is:
(1) change the pressure from pi to an infinitely low pressure at constant
temperature Ti, (2) heat or cool the mixture at constant volume (or pressure)
from Ti to JT2, and (3) increase the pressure at the temperature T% from the
low value to p%\ each of the steps being carried out reversibly. Thus all pres-
sure variations are brought about isothermally, and all temperature varia-
tions are carried out at infinitely low pressures. 5 The assumptions used in
the following derivations^are summarized in Section 3.
The variations of the energy and entropy with pressure can be obtained
by integrating the appropriate differential equations. The application of this
method for the energy presents no unusual difficulty, but in the integration
of the Maxwell Relations for the effect of pressure or of change in volume on
the entropy, the integral becomes infinite at the lower limit because of the
presence of a term containing In p or In V. In the present method the
lower limit of the entropy is replaced by the expression for the entropy of a
mixture of perfect gases, and this contains a term which combines with the
infinite term of the integral to give a finite value.
We can use either V and T, or p and T as the independent variables and
this leads to two formulations.
2
Lurie and Gillespie, Jour. Amer. Chem. Soc. 49, 1146 (1927).
3
van Laar and Lorenz, the fundamental equations are developed in Zeits. anorg. u. allg.
Chem. 145, 239 (1925).
4
Keyes, Jour. Amer. Chem. Soc. 49, 1393 (1927).
6
van Laar and Lorenz, loc. cit., have used a similar method in the case of the energy. For
the entropy of mixtures, however, they corrected the equation for the entropy of a mixture of
perfect gases by a consideration of the space occupied by the molecules of the real gas.
682 JAMES A. BE ATT IE

(a) When V and T are the independent variables. For these independent
variables we make use of the general relations for the variation of the energy
and entropy of any fluid with the volume
(dU/dV)T=T(dp/dT)v-p (2)

(dS/dV)T=(dp/dT)v (3)
Integration of (2) and (3) along an isothermal gives

U-U*= f [T(dp/dT)v~-p]dV (4)

Jv*

S-S*= f (dp/dT)vdV (5)

J v*
where U and S are the energy and entropy of the system at the volume V,
and U* and S* the values at V*, all being taken at the same temperature.
The asterisk affixed to a symbol is used to denote its value at an infinitely
low pressure.
If the system under consideration is a mixture of real gases, U* and S*
can be replaced by the equations for the energy and entropy of mixtures of
perfect gases.6 Hence

U*= £<»i\ I Cv.dT+Uoi (6)

S* = Z { n i [" j Cv.dT/T+Soi 1 1 + D(*i2an7*/»i) (7)

In the above equations n\ is the number of mols of Gas 1 in the mixture, V is

the total volume of the mixture, Cvi* the molal constant volume heat
capacity of pure Gas 1 at infinitely low pressures (which in general cannot be
replaced by the corresponding constant, perfect-gas value), and Uoi and 50i
the molal energy and entropy constants of this gas at the temperature To,
which may be any arbitrarily chosen "standard temperature."
Substituting (6) and (7) in (4) and (5), we obtain

U= f [T(dp/dT)v-p]dV+ X>rai) (8)

Jv*
rv
5 = 1 (dp/dT)vdV+ £ ( » i * k ^ * / » 0 + ]£(»i*i) (9)
Jv*
6
Gibbs, Scientific Papers, Longmans, Green and Co., New York (1906), Vol. I, pp.
150 et seq.
 THERMODYNAMICS OF REAL GASES 683

where the quantities U\ and $i are defined by the relations

Cv.dT+Uo! (10)
To

rT *
*x = CVldT/T+S0i (11)

They may be considered as the molal energy and entropy constants of Sub-
stance 1 at the temperature T.
Equation (9) can be written in the form

[(dp/dT)v- T,n1R/V]dV+ 2^nlI0nV/n1)+ £(»i5i) (12)

00

by adding and subtracting the term ^(niR In V), where V is the volume of
]T) ni mols of mixture, and replacing the lower limit F* by °o . This is made
possible by the fact that at low densities the pressure of real gases can be
expanded in a converging power series of the inverse volume and hence
the difference between p and ^T,tiiRT/V is a series beginning with a term
K/V2 and containing higher powers of 1/V. Thus the integrand of Equ-
ation (12) approaches zero with sufficient rapidity so that as F* increases

Limit
f [(dp/dT)v- X>ii?/F]JF=0
J v*
and hence lower limit F* can be replaced by oo as is done in (12). Also for the
same reason the lower limit F* of the integral in Equation (8) can be replaced
by oo . Equations (8) and (9) then become after reversing the upper and lower
limits

U= f [p-T(dp/dT)v]dV+ I>iO (13)

Jy

S= f [^iR/V-idp/d^vW+^intl^V/nO+J^intsO (14)
Jy
For the study of the variations of U and 5 at constant temperature, the
quantities Ui, u2 • • •, and Su s2, • • •, are constant, and if also the composition
of the mixture does not change, the terms ^(tiiUi) and X X ^ i ) a r e both
constant.
(b) When p and T are the independent variables. For these independent
variables we make use of the heat content H, and the other Maxwell relation
(dH/dp)T = -T(dV/dT)p+V (15)

(dS/dp)T=-(dV/dT)p (16)
684 JAMES A. BEATTIE

Integration of (15) and (16) gives

H-H*= f [-T(dV/dT)p+V]dp (17)

S-S* = f ~(dV/dT)pdp (18)

J p*

Applying these equations to mixtures of real gases, we can use equations

corresponding to (6) and (7) for H* and 5*, the independent variables now-
being p and T

#*= E { »i[ j Cp^r+ffoil j (19)

S* = E { nj f C*PldT/T+S0J\- ^(mKhip+xi/RTo) (20)

where iJ 0 i and 50i are the molal heat content and entropy constants for Sub-
stance 1 at the temperature T0, and xi is its mol fraction in the mixture.
Substitution of (19) and (20) in (17) and (18) gives

H= fP[-T(dV/dT)p+V]dp+^l(n1h1) (21)
J p*

S=- ^ ~{dV/dT)vdp- J^(n1Rlnp*x1)+ E ( w i ' ) (22)

J p*
in which hi and Si' are denned by relations corresponding to (10) and (11),

C*PldT+H0x (23)

*i' = f C^dT/T+RlnRTo+Soi (24)

By use of an argument somewhat similar to that which led to (12) we

can write (22) in the form

5= f* [T,*iR/p-(W/dT)p]dp- E(»iiflnj>*i)+ E ( ^ i ' ) (25)

Jo
where p is the total pressure of the mixture, and we can also replace the lower
limit, p*, of the integral in (21) by 0, giving

H= C[V-T(dV/dT)p]dp+ X(»i*0 (26)

•/ o
 THERMODYNAMICS OF REAL GASES 685

For a consideration of the isothermal variations of H and S with pressure

the quantities hi, h2, • • • , and s/, s2 , • • • , are evidently constant, and for
constant temperature and composition, the terms X)(wi&i) and ^(niSi') are
constant.
There have now been derived four equations which may be classified as
follows: general expressions for the variation of U and S with V and T,
Equations (13) and (14); general expressions for the variation of H and S
with p and T, Equations (26) and (25).
When it is desired to study the isothermal variations of these quantities
with V, or with p, the same equations are applicable, with certain quantities,
namely tii, n2, • • • , Si, s2, • • • , Sif, s2', • • • , and hi, h2, • • • , constant. If
further the composition also does not change, the terms ^2(fiiUi), ^(niSi),
]C(^i 5 iO and ]>3(ni^i) are constant.
It may be mentioned that the partial molal entropy of a gas in a mixture
can be readily obtained by differentiation of Equation (14) or (25) with re-
spect to ni] similarly the partial molal energy and heat content result from
the differentiation of (13) and (26) with respect to n\. The method of carry-
ing out such differentiations is indicated in Section 5 of this paper.
3. ASSUMPTIONS USED IN THE DERIVATIONS OF SECTION 2.
The derivations of the general equations of the preceding section rest on
only two assumptions:
(a) At infinitely low total pressure, the equilibrium pressure of a gas in a
gaseous mixture is equal to the product of its mol fraction into the total
pressure.
(b) At infinitely low total pressure, the energy of a mixture of gases is
the sum of the energies of the component gases when each is at the temper-
ature and occupies the total volume of the mixture.
For the derivation of the isothermal equations, only the assumption (a)
is necessary. 7 Eqs. (6) and (19) are a direct consequence of assumption (b),
and it is easy to show8 that (7) and (20) follow from (a) and (b). In order to
carry out the solution of the general equations to a numerical result it is
necessary to have:
(c) An equation of state for mixtures of real gases of the form
f(p,V,T,ni,n2, • • • ,) = 0
for which the integral of pd V can be evaluated either directly or by graphical
means. It is to be noted that when evaluating the derivatives (dV/dT)p and
(dp/dT)v from this equation of state, the variables nu n2, - - - , are to be
held constant.
(d) The constant volume molal heat capacity at infinitely low pressures
CV* for all the pure gases as functions of the temperature. (From CV* and the
equation of state of the pure gases Cp* can be calculated.)
7
It was particularly emphasized by Gillespie, loc. cit., that this assumption alone is
sufficient for the mass-action law at constant temperature.
8
Cf. for instance Gibbs, loc. cit-
6S6 JAMES A. BE ATTIE

(e) Data necessary to determine the entropy and energy (or heat content)
constants for the pure gases, at the standard temperature r 0 , which might be
for instance 0°C.
For the numerical solution of the isothermal equations, it is necessary to
have (c) an equation of state for mixtures and (e) the entropy and energy
(or heat content) constants for the pure gases at the temperature under
consideration.
For a mixture of constant composition it is necessary to have only one
value of the entropy, energy, or heat content for some state of the system
in order to calculate the value at any other temperature and pressure by
means of the equations given.

4. T H E THERMODYNAMIC POTENTIALS

(a) When V and T are the independent variables. The thermodynamic

potential FV,T is defined by the relation
FVtT=U-TS (27)

and using the values for U and S given by Eqs. (13) and (14) we obtain
after simplification

FV,T= f (p~^iRT/V)dV-yZ[n1RTln(V/n1)]+^(n1F1)(2S)
Jv
for the general variation of the thermodynamic potential of a gas mixture with
pressure and temperature. The quantity F\ is defined by the relation

F^Ui-Tsi. (29)

For all isothermal variations of Fv ,T, the functions Fi, F2, • • • , are constant,
and if in addition the composition is not varied then the term ]T)(wi^i) is
constant.
(b) When p and T are the independent variables. The thermodynamic
potential
FP)T = H-TS (30)

can be expressed as a function of p and T by the use of Eqs. (25) and (26)
giving

FP.T= f\v-J2niRT/p)dp+J2(niRTlnpx1)+y£(n1F1') (31)

for the general variation of this thermodynamic potential of a gas mixture,

where TV is defined by the relation

Fi'=*hi-Ts!' (32)
f
As before F\, F2 , • • •', are constant for isothermal variations, and]T}(wi7V)
is constant for processes at constant temperature and composition.
 THERMODYNAMICS OF REAL GASES 687

5. T H E CHEMICAL POTENTIAL

The chemical potential (the so-called partial molal thermodynamic

potential) of a gas in a mixture can be obtained from either of the two
thermodynamic potentials by differentiation, thus

Hl=(dFv,T/dni)v,Ttnt,nt,.-. J Atl=(^i7p,r/^l)p,r,n2,n8,-.. (33)

Using for Fy ,T and FPiT the values given in (28) and (31) we obtain the
relations

Ml = (p—±± UV\ -RTln \-RT+F! (34)

dniLJv\ V / Jv,T,n2,n3 %

>i = —~r C(v- ^niRT)dp\ +RT\npxx+F1f (35)

Carrying out the indicated differentiation of the integral gives

Ml= (_L_ )dV-RTln—+RT+Fl (36)

Jy \dfli V / fli

rp/dV
RT\
/*i= )dp+RTlnpxl+Fl/ (37)
Jo \<9^i p /
for the chemical potential 9 of Substance 1 in a mixture of gases. The first
expression is used when the independent variables are V and 7\ and the second
when they are p and T.
6. T H E MASS ACTION LAW FOR REAL GASES
From either of the functions Fy ,T or FP>T the mass-action law can be
derived. When a chemical reaction is at equilibrium, the variation of Fy ,T
at constant volume and temperature is zero with respect to a displacement
of the equilibrium caused by a small variation in composition. The same is
true for FPtT at constant pressure and temperature. From a consideration of
the relations (33) it is evident that both of these methods lead to the same
expression for the mass action law, namely
2>W = 0 (38)
in which the summation is taken over all of the gases in the reacting mixture,
v\ is the number of mols of Gas 1 appearing in the chemical equation express-
ing the reaction, and /xi is the chemical potential of the Substance 1 given
by either of the two equations (36) or (37) depending upon the choice of inde-
pendent variables.
9
The fugacity /i of a gas (c.f. Lewis and Randall, Thermodynamics, McGraw-Hill Book
Co., New York (1923), p. 191) is related to th chemical potential through the equation m—RT
in/i-fiY.
688 JAMES A. BE ATTIE

We thus obtain

^{VlIv {^T^P)dv } ~ 2(^ r l n 3 + ^ c " l ( F l + j R r ) ] = 0 (39)

^ { Vl I Xin ~) d p } + 2 > l i m n ^ + EWV) = 0 (40)

for the mass-action expression in terms of the variables V and T, or p and T.
The mass-action equation is usually written for the variation of the equi-
librium constant Kp defined by the relation
lnKp = J^ivMpxi)
which when introduced into (39) and (40) gives

~H["i<Fi+RT)] (41)
Kl
1 _ ( r'/dV RT\ ) 1 _

for the general variation of Kp with temperature and pressure. The temper-
ature functions F\ and TV are given in Eqs. (29) and (32).
Usually only the isothermal variation of Kp with pressure is desired. As
the pressure approaches zero we obtain from (41) and (42)

ln*P„= H("MRT)---j:HF1+RT)} (43)

Kl

In*,,-—-=-2>i/Y) (44)
Kl
and substitution of these values into (41) and (42) gives

#*>, V S»i^r/ * r ^ l Jy \dni v) )

In—^- £<U ( -)dp} (46)

These expressions give the variation of Kp with pressure at constant temper-

ature. I t is to be noted that (46) is the same as (1), the mass action law
deduced by Gillespie by means of a consideration of the equilibrium of a
gas through a semi-permeable membrane. At constant temperature, (45)
and (46) can be used to calculate Kp for any pressure from one value a t a
given pressure.
 THERMODYNAMICS OF REAL GASES 689

7. SUMMARY OF THE EQUATIONS DEDUCED

Symbols: p, total pressure; V, total volume of the mixture; T, Kelvin
temperature; n\ and X\, number of mols and the mol fraction of Substance 1
in the mixture; v±, number of mols of Substance 1 in the stoichiometric
equation for a chemical reaction, being negative if the substance disappears
in the reaction. Cv* and CPl*, molal heat capacities at constant volume and
pressure of pure Substance 1 when the pressure is very small, (i.e. approaches
zero). U, energy; S, entropy; H, heat content. Fv,T, thermodynamic poten-
tial at constant V and T\ FP<T, thermodynamic potential at constant p and
T; /xi, chemical potential of Substance 1 in the mixture. Kp, the equilibrium
constant of a chemical reaction in terms of partial pressures of the reacting
gases; KPo, the equilibrium constant at zero pressure. Z70i, Sou and iJ 0 i are
the energy, entropy, and heat content constants for Substance 1 at some
arbitrarily chosen "Standard temperature." Ui, Si, si', hi, Fi, and TV are the
energy, entropy, heat content and thermodynamic potential "constants"
for Substance 1 at the temperature T. They are given by the relations

C^dT+Uoi (10) Sl'= I CPldT/T+R\nRT0+S> (24)

rT * (29)
5i= CVldT/T+SQi (11) Fi^Ui-Ts!

Ai= C^dT+Hoi (23) iY = A i - 7 V (32)

(a) When V and T are the independent variables,

U= f [p-T{dp/dT)y]dV+Y,in1u1) (13)
Jv

FV,T= f (p-^f—)dV- ll(^^T\n~\+J2(niFi) (28)

r^/dp RT\ V
ms= J (-f- )dV-RTln \-RT+F1 (36)

— EMwn] (4D
Kl
l n ^ 0 = Y,{vl\nRT)—--Y,[vi(,Fi+RT)\ (43)
RT
690 JAMES A. BEATTIE

• *p. V T.nxRT) RT^\ Jv\dni V/ )

(b) When p and T are the independent variables

»-f1>-7l-l
<-) I# + E(»i*i) (26)

5=- I| T »> ;i
.T-^-(- - X> 1 .Rln^- 1 ) + £ ( » i ' i ' ) (25)
Jo L ^ \dT/p.
FptT=S V
I \~ -~~-)dP+ H{nlRT\npxl)+ 2>i/Y) (31)

Ml== )dp+RTlnpxi+Fi' (37)

J o \dftl ^ /
1 _ ( rv/dV RT\ \ 1 _

E E( F ) (42)
*•"•-
^
- i ?
1 ^ (
{" J. t
r /dV
- y
RT
/ T s " ''
p

Note: The partial differentials (dp/dT)v and (dV/dT)p are taken at

s (46)
W.UrrrM
constant ni, n2, - • • ; dp/dni is taken at constant temperature and volume;
and d V/dni is taken at constant pressure and temperature. All of the deriva-
tives can be evaluated from the equation of state for mixture of gases.
CAMBRIDGE, M A S S .
November 23, 1927.