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Chemical Engineering Science, 1962, Vol. 17, pp. 861-866. Pergamon Press Ltd., London.

Printed in Great Britain.

A perturbation on Raoults Law


c. J.

PINGS

California Institute of Technology, Pasadena, California


(Received 22 December 1961)
Abstract-Four
conditions sufficient for the applicability of Raoults Law are stated. A generalized
expression for phase equilibrium is derived by relaxing three of those conditions by accounting for the
liquid-phase molal volume and by describing the gas phase by the virial equation of state. This expression is then expanded in a power series about the Raoults Law value of vapour pressure or mole
fraction.

INTRODUCTION

FOR gaseous systems at moderate pressures, deviations from perfect gas behaviour are well accounted
for by the second virial coefficient. This particular
equation of state has been especially useful since
HQ~SXFELDERet al. [l] presented a systematic
tabulation of intermolecular potential parameters
necessary for estimating the second virial coefficient
from a Lennard-Jones model. PITZER and CURL [2]
and PRAUSNITZand BENSON[3] have made suggestions for estimating the second virial coefficient for
pure components and for mixtures by extensions
of the techniques of the law of corresponding
states.
It would be expected that the second virial coefficient might well appear in l?rst-order corrections
to relationships describing the equilibrium conditions that would exist between a gas phase and either
a solid or liquid phase. It is the purpose of this
paper to demonstrate that for certain classes of
systems an improved description of the vapour
pressure of a liquid phase, or the solubility of a
condensed phase in a gaseous phase, can be obtained
by correcting the Raoults Law expression with a
term which includes second virial coefficient inforROWLINSON [4] and PRAUSNITZ and
mation.
BENSON[3] have discussed similar expressions, but
their results have usually been restricted to binary
systems and perhaps were not as tractable for
numerical computation as the expressions developed
in the present paper.
D

RAOULTSLAW
A systematic derivation of Raoults Law will
serve as a useful point of departure for a develop
ment of the modified equations. Consider a twophase system, one of which is a gas phase, the other
being either liquid or solid. For the sake of
generality we will refer to the latter in this paper as
the condensed phase. Assume that there are n components in the gas phase and 1 components in the
condensed phase (l < n). The necessary and
sufficient conditions for phase equilibrium [5,6] are
the following:
f$u = f$c
(1)
T(U)= T(C)
(2)
p(e) = p(c)
(3)
Now making the following four assumptions:
I. The condensed phase is ideal.
II. Condensed-phase volume is negligible.
III. The gas phase is ideal.
IV. All the pure components in the gas phase are
described by the perfect gas law.
These four assumptions are translated into the
following four analytical statements :

(5)
III.
IV.
861

fP = y&7
;(e) = p

(6)
(7)

C. J. PINGS

Subsequent formulas will be simplified somewhat


by the introduction by definition of Aij

Equation (5) leads to the following conclusion:


ff(P) N ff(PJ

(8)

If equations (4) and (6) to (8) are now substituted


into equation (1) one obtains the following expression which is a generally accepted version of
Raoults Law :
y,P = x&

(17)
Aij actually measures the deviation from Guggenheims naive mixture assumption [8]. Two
special cases should be noted:

(9)

Aij=O
GENERALDERIVATION

We propose to relax assumptions II, III


but retain assumption I. Assumptions III
will be improved upon by assuming that
phase is described by the virial equation
truncated at the second virial coefficient.

Bik - Bij +

and IV,
and IV
the gas
of state

Bjk

if

j$it1j$IYiYjBij(T)

[Aa - Aij + Ajk]

ff(p)

xkp; exp
[

(12)

VP) -

RT

= x&

B,P;
exp RT

(21)

Equation (1) may then be used to equate equations


(20) and (21):

Therefore,
= f;g(PJexp(

(20)

the following expression for the condensed phase


fugacities :

ykp =

f;(P)

(10) A combination of equations (13) and (16) yields

But

P - P;

(19)

Equation (15) is then conveniently re-expressed :

Condition II will be relaxed by assuming a constant,


but non-zero, value for the molal volume of the
.hquid phase. The pressure dependence of the condensed phase fugacity is then given by the equation
(11) instead of equation (8).
*,
f$)(P) = f$)(PJexp( V,)+
(11)
f$C)(PJ = f;g(p;)

(18)

Bk + Aik- Ai, + Ajk

i=j

- k

(Bk - (VP))

i$l ,tl YiYj(b

- Aij + A,)] k G i

(22)

(13)

For each component present in both the gaseous


and
condensed phase (k < l) there exists an exFor a gas phase represented by equation (lo), the
pression
of the type of equation (22) giving the y,s
following two equations describe the partial molal
and
P as a function of the mole fractions in the
volume and the fugacity of component k [7].
condensed phase. However, the right-hand side of
each such expression contains the unknown yks
and P. Rigorous solution would presumably
require iterative techniques. Of course, equations
(22) are explicit in the x,s if all of the gas-phase
fk = Ykp exp
YiYjCBik Bij + Bjkl) Cl51
mole fractions are given.
(14)

(& ii1jil

As a special case of the last equation we have the


following expression, which is applicable to the
gas phase of a pure component.
f:(e) = p

exp

LB
RT j

POWER-SERIES
EXPANSION

(16)

One utilization of equation (22) would be for


the computation of the composition of a gas
phase in equilibrium with a liquid phase of known

862
,

A perturbation on Raoults Law


Equations available :

composition. It would appear useful to contemplate


approximations which would avoid the iteration
alluded to in the previous paragraph. It is worthwhile to try a power-series expansion about the
Raoults Law behaviour. Specifically one might
expand the Y,s and P about their Raoults Law
values in a power series in the perturbing parameters
(& - (VP))) and Aij. We do not contemplate here
the retention of terms beyond those in the first
power, particularly since the virial expansion in
equation (10) was only carried to first-order terms.
Thus we suggest:

Determine

:
p, Yl,

Y2 1.. Yl-1

Using
I,

k< 1

(y,),, =+

p,,=

(25)

k=l

(26)

l-cyk
1+1

= I +a(Bk -

ap

(B, -

(vr))) R1

in the following expressions:

(Vf) - 0) +

(23)

P=

1 _

aYk
a(B,

(I/k(c)))

(Bk-(vp)-O)+
R1

@k

(vt>)

I+

,$+I

1-

._-

y,

@i

pRi

k=l+l

2k=$+lyk

l-

-f

pR,+

y;

(27)

k=l+l
I,
Yk

pk;Tpl

+ f

(Bk

< vy))

+ P,,+ + 2j3 - 2& - 2p,,& k < 1 (28)


RI

Case II

Given :
p,

Yl,lv

Given :

Y1+2 .*. Yn-1

Equation available :
1

Determine :
Yl9 Y2

Yl

Using
u

(Yk),,

Case I

..*

pR,

(24)

Yl+lP Y1+2,

RT

In the treatment of the actual expansion it is


necessary to contend with two classes of problems
depending on the stipulation of the independent
variables. In certain cases, called here Case I, the 1
equations (22) could be used to compute (I - 1)
composition parameters in the gas phase, plus the
pressure. This would presume knowledge of the
(n - I)Y,s of the components present only in the
gas phase.
For another group of problems, called here Case
II, with the pressure given, the I equations could be
used to compute Zy,s. In this case the given information must include, in addition to the pressure, values
of (n - 1 - I)Y,s of the components present only
in the gas phase. In this case we will assume that the
components are so ordered that component n is the
one unspec$ed. The actual expansions, along with
a summary of variables, is given below for the two
cases.

xkpk

ykk=

k=Ii-

(Y&U
+

I,P; - P,,

and
yk =

l+

pRI

$$

k<l

(30)

Y
863

c. J.

PINGS

In the following expansion


I
Yk

X!$Lk

I+

p$

(Bk

Case ZZ
P:,
(Vf))

YA =

2p + P+ - 24, - 2P& k < l

_2z.+?(I-$)I

(31)

resulting in the improved approximation to Yi, . . . yr


plus Y
(32)
In these expansions, symbols have been introduced for various summations:
1

i=l

(33)
j=l

(34)

(35)

(36)

l/) =

i=l+l

yiyjs;

(37)

j=t+l

APPLICATIONTO A BINARYSYSTEM
It would seem worthwhile to explicitly reduce the
above expansions for one common case of frequent
practical interest, namely a binary system with only
one component in the condensed phase. We thus
consider an A-B binary with A present in .both
phases (xA = 1) and B present in the gas phase only.
Reducing the preceding expansions for n = 2, I = 1
the following are obtained:
Case I
p=-

P;
1 -YB

1 _P;;(BA-<V~)
RT
---

-_ YB

1 - YB
~~;AAB

RT

Yt
1-y,

(38)

(39)

DISCUSSION
We emphasize that the results presented in
equations (27), (28) and (31) are still based on an
assumption of ideality in the condensed phase. It
would be reasonable to expect therefore that these
first-order perturbations on Raoults Law will be of
greatest utility in describing systems where gas-phase
imperfections dominate the deviation from Raoults
Law. One obvious group of systems which meet this
requirement are those having only one component
in the condensed phase. For a system with more
than one component in the liquid or solid phase, the
corrections provided by equations (27), (28) and (3 1)
may be small compared to errors stemming from
condensed-phase imperfections. Nevertheless we
have presented the general expressions in such form
that they will cover multi-component condensed
phases. These equations should at least serve as a
guide to interpolative description of such systems.
Of course, we could have formally accounted for
condensed-phase imperfection by introduction of
activity coefficients; one needs only to everywhere
replace xk by yk& in equations (27), (28) and (31).
The expressions resulting from the inclusion of the
activity coefficients would actually be of considerable
value if one wished to determine liquid-phase activity
coeficients from measurements of the compositions
of co-existing gas and liquid phases.

In addition to the limitations discussed above with


respect to the condensed phase, note should be taken
of the range of applicability of the gas-phase corrections. Equations (27), (28) and (31) should not be
useful at pressures greater than those for which
equation (10) is a good approximation to the PVT
behaviour.
However, inspection of generalized
charts of volumetric behaviour of pure substances
[l] reveals that for many systems this first-order
correction to the perfect gas law provides a good
approximation of actual behaviour for pressures up

864

A perturbationon RaoultsLaw

to the vapour pressure. For substances well above


their critical temperatures equation (10) is useful
for pressure up to several times the critical pressure.
AGREEMENTWITH EXPERIMENT

We report below the application of equation (39)


to two separate systems for which data are available: H,O-CH4 at 160F [9] and N,-Ccl, at 75C
[3]. Both of these are reasonable approximations
to the systems n = 2,Z = 1, that is two-phase, two
component, with only one component in the condensed phase.
For the computation on the H20-CH, system,
AH20,CH4P
BH2and BcH4 were estimated by assuming
applicability of a Stockmayer potential for water
and a Lennard-Jones 6-12 potential for methane.
Similar estimates for the CC&N,
system were
obtained by assuming applicability of Lennard-Jones
6-12 potentials for both species. Intermolecular
potential parameters were obtained from the tables
in HIRSCHFELDER
et al. [l]. Conventional combining
rules were used to estimate the distance and energy
parameters characterizing the interaction between
unlike species. Values for the second virial coefficients were then obtained from reduced tabulations [l]. Vapour pressures and molal volumes
were obtained from KEENANand KEYES [lo] and
LANGE [I 11. Data used are summarized below:
H,O-CH4

system at 160F
B H20 = - 604.24 cm3/mole
B CM4= - 22.64
BH20-CH4 = 39.03

FIG. 1. Gas-phase compositionvs. pressure in the


CC14-N2systemat 75C.

For these two systems Table 1 and Fig. 1 present


the calculation of gas-phase composition using
equation (39). Estimates based on Raoults Law
are included for comparison. In these two cases,
substantial improvement is realized by inclusion of
the first-order correction terms to Raoults Law. In
the case of the H,O-CH4 system at 160F, one
would not expect equations (38) or (39) to be particularly useful above about 2000 p.s.i.a. because of
the obvious departure of the behaviour of methane
[12] from equation (10).

A = 274
(k&)

= 18.1 cm3/mole

Pi,, = 4.741 p.s.i.a.


Ccl,-N,

system at 75C
B cc14 = - 584.3 cm3/mole
B,, = 3.387
B CC14-Nz

89.96

A = 201
<k@, ) = 96.5 cm3/mole
P, 4
cc14 = 14.02 p.s.i.a.

COMPUTATION
OF INTERMOLECULAR
PARAMETER

In a previous paragraph we mentioned the possibility of using the basic expressions derived in this
paper as a guide to study of activity coefficients in
the liquid phase. A very similar application would
be the use of the expressions for the experimental
deduction of the interaction parameters Aij from
observation of vapour pressure plus the composition
of the two phases. As an example for the n = 2,
I = 1 system discussed previously, equation (39)
can be explicitly solved for AAB.
865

c.
Table 1.
P
(p.s.i.a.)

J.

Computation

PINGS

of gas-phase composition

Raoults Law
Relative
Y
error

Y
Experimental

200
1000
2000
4000

0.0248*
00x88
000350
0.0023

HzO-CHI system at 160F


0.0237
0.048
oGo474
0.240
OW237
0.476
om119
0.958

449.7
792
1054

oG410t
0.0276
0.023 1

Nz-CC14 system at 75C


0.0312
0,314
0.0177
0.559
0.0133
0.737

AB

RT{l - [VA/(%/~)])
2p[1 - (PA/p)]*

_ BA -

2c1-

(vi?>

(40)

(pA/p)I

Using this expression for the CClb-N, system at


75C and 1054 p.s.i.a., we compute &c14-N2
= 232 cmj/mole compared with the value 210 cm3/
mole estimated from intermolecular parameters.
NOTATION
Bt3 Contribution
, Bk
fk
ipi,k
I
;
pat

to second virial coefficient arising from


interaction between molecule i and molecule j
Second virial coefficient of component k
Fugacity of component k
Integers denoting species
Integer denoting last species in condensed phase
Integer denoting last species in system
Pressure
Vapour pressure of component i
Universal gas constant

0.0246
oGo560
000322
OGO203

0.010
0.050
0087
0.143

omQ7
0.0271
0.0227

om7
0.019
0.018

t YCCI,.

* YH20.

Equation (39)
Relative
Y
error

T Absolute temperature
V Molal volume
vk Partial molal volume of component k
Xt Mole fraction of component i in a condensed phase
YC Mole fraction of component i in the gas phase
45 & - t(Bt + Bj)
See equation (33)
See equation (34)
;
See equation (35)
Ti See equation (36)
See equation (37)
*
Yk Activity coefficient of component k
Superscripts
c Refers to condensed phase
g Refers to gas phase
o Refers to pure component
Subscripts
A Refers to component A
i, j, k Indices designating components
I Last component in condensed phase
n Last component in system
Rl Indicates Raoults Law value of a property

REFERENCE

HI
PI

HIRKHFELDER J. O., CIJRTI~~C. F. and BIRD R. B., Molecular Theory of Gasesandliquids.


PITZER K. S. and CURL R. F., J. Amer. Chem. Sot. 1957 79 2369.
PRAUSNITZ J. M. and BENSONP. R., Amer. Inst. Chem. Engrs. J. 1959 52 161.

John Wiley, New York 1954.

;:3 ROWLIN~ONJ. S., Liquids and Liquid Mixtures. Academic Press, New York 1959.
[51

LEWIS

G. N. and RANDALLM., Thermodynamics and The Free Energy of Chemical Substances. McGraw-Hill, New
York 1923.
161 EPSTEINP. S., Textbook of Thermodynamics. John Wiley, New York 1937.
[71 PINGS C. J., Chem. Engng. Sci. 1961 16 181.
E. A., Mixtures. Oxford University Press 1952.
PI GUGGENHEIM
[91 OLDS R. H., SAGE B. H. and LACEYW. N., Zndust. Engng. Chem. 1942 34 10 1223.
WI KEENAN J. H. and KEYESF. G., Thermodynamic Properties of Steam. John Wiley, New York 1936.
illI LANGEN. A., Handbook of Chemistry. Ohio Handbook Publishers 1956.
u21 SAGE B. H. and LACEYW. N., Thermodynamic Properties of the Lighter Paraffin Hydrocarbons and Nitrogen. American
Petroleum Institute, New York 1950.

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