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PINGS
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
(8)
(17)
Aij actually measures the deviation from Guggenheims naive mixture assumption [8]. Two
special cases should be noted:
(9)
Aij=O
GENERALDERIVATION
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)
Therefore,
= f;g(PJexp(
(20)
ykp =
f;(P)
But
P - P;
(19)
(18)
i=j
- k
(Bk - (VP))
- Aij + A,)] k G i
(22)
(13)
(& ii1jil
exp
LB
RT j
POWER-SERIES
EXPANSION
(16)
862
,
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))
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
xkpk
ykk=
k=Ii-
(Y&U
+
I,P; - P,,
and
yk =
l+
pRI
$$
k<l
(30)
Y
863
c. J.
PINGS
X!$Lk
I+
p$
(Bk
Case ZZ
P:,
(Vf))
YA =
_2z.+?(I-$)I
(31)
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.
864
A perturbationon RaoultsLaw
system at 160F
B H20 = - 604.24 cm3/mole
B CM4= - 22.64
BH20-CH4 = 39.03
A = 274
(k&)
= 18.1 cm3/mole
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
449.7
792
1054
oG410t
0.0276
0.023 1
AB
RT{l - [VA/(%/~)])
2p[1 - (PA/p)]*
_ BA -
2c1-
(vi?>
(40)
(pA/p)I
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
;: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