9

9.5

(a) Start with eqn. 9.2-13

ln

fi
1
= ln i =
xi P
RT

P=

V = ZRT P

V =

LM RT N F dP I OPdV ln Z
MN V GH N JK PQ
i V

RT
a
NRT
N 2a
NRT
Ni N j aij
2 =
2 =

V b V
V Nb V
V Nibi
V2

P
RT
NRT
=

Ni V V Nibi V Nibi

=
N

ab f 2VN a

j ij

RT
NRTbi 2 N j aij
+

V Nb (V b)2
V2

2 x j aij
RT
RTbi
P
=
+

2
V
Ni V
V2
(V b)

f
1
ln i = ln i =
xi P RT

ZRT P

LM
N

OP
Q

ZRT P

ZRT P

V =

Z
Bi

= ln
+
Z B ( Z B)
ln i = ln

2 x j aij

V =

V
1
RT ln
V b
RT

LM RT RT RTb
MM V V b (V b)
N
RTbi

(V b) V =

RTV

2 x j aij

ZRT P

ln Z

V2

F where B = Pb I
H
RT K

ln Z

fi
Bi
=
ln(Z B)
xi P Z B

2 x j aij
j

RTV

(b) For a pure van der Waals fluid (Eqn. 7.4-13)

ln

V2

OP
PPdV ln Z
Q

V =

2 x j aij
j

fi
a
= ( Z 1) ln Z Bi i
P
RTV

and, by definition of the activity coefficient

f i = xi f i i

R|
2 x A U
|V
B
f = x P expS
ln(Z B)
Z
|W
|T Z B
A
f = P expRS( Z 1) lna Z B f UV
ZW
T
j

ij

mixture

ii

pure fluid i

so

fi
=
xi f i

RS
|T

LMF 2 x A I
JK
NGH
expk( Z 1) lna Z B f a A f Z p

exp Bi (Z B) ln( Z B)

j ij

ii

OPUV
Q|W

mixture

=i

pure fluid

Note that the compressibilities in pure fluid and mixture will generally be different at the same T
and P.