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Abstract-Four conditions sufficient for the applicability of Raoult’s 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 Raoult’s Law value of vapour pressure or mole fraction.

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c. J.

PINGS

(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

by the introduction by definition of Aij

ff(P) N ff(PJ

(8)

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

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)

ff(p)

xkp; exp

[

(12)

VP) -

RT

= x&

B,P;

exp RT

(21)

(20) and (21):

Therefore,

= f;g(PJexp(

(20)

fugacities :

ykp =

f;(P)

But

P - P;

(19)

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)

i=j

- k

(Bk - (VP))

- Aij + A,)] k G i

(22)

(13)

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

following expression, which is applicable to the

gas phase of a pure component.

f:(e) = p

exp

LB

RT j

POWER-SERIES

EXPANSION

(16)

the computation of the composition of a gas

phase in equilibrium with a liquid phase of known

862

,

Equations available :

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

(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))

RI

Case II

Given :

p,

Yl,lv

Given :

Equation available :

1

Determine :

Yl9 Y2

Yl

Using

u

(Yk),,

Case I

..*

pR,

(24)

Yl+lP Y1+2,

RT

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

I

Yk

X!$Lk

I+

p$

(Bk

Case ZZ

P:,

(Vf))

YA =

_2z.+?(I-$)I

(31)

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.

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

their critical temperatures equation (10) is useful

for pressure up to several times the critical pressure.

AGREEMENTWITH EXPERIMENT

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

CC14-N2systemat 75C.

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

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

0.0237

0.048

oGo474

0.240

OW237

0.476

om119

0.958

449.7

792

1054

oG410t

0.0276

0.023 1

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

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

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

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.

;: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.

866

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