9

9.6

As a preliminary note that, from Eqns. (6.4-27 and 28)

LMT F P I POPdV
MN GH T JK PQ
LMF P I R OPdV
MNGH T JK V PQ

V = ZRT P

H (T , P) H IG (T , P) = RT ( Z 1) +

V =

and

V = ZRT P

S (T , P) S IG (T , P) = R ln Z +

V =

vdw E.O.S. P =

RT
a
so

V b V2

FG P IJ = R ; T FG P IJ
H T K V b H T K
FG P IJ R = R R ;
H T K V (V b) V
V

P=
V

RT
RT
a
a

+ 2 = 2
V b (V b) V
V

V = ZRT P

H (T , P) H IG (T , P) = RT ( Z 1) +

V =

and

a
a
RTA
dV = RT (Z 1) = RT ( Z 1)
2
V
Z
V

V = ZRT P

S (T , P) S IG (T , P) = R ln Z +

V =

LM R R OPdV
NV b V Q
ZRT P

= R ln Z + R ln

(V b)
= R ln( Z B)
V V =

Now on to solution of problem.

RT
(a) V ex = V mix
xi V i =
Z mix
xi Z i = mix V
P
Zmix = compressibility of mixture at T and P
Zi = compressibility of pure fluid i at T and P
Will leave answer to this part in this form since the analytic expression for Zi and Zmix
(solution to cubic) is messy. Though it can be analytically and symbolically with a computer
algebra program such as Mathcad, Mathematica, Maple, etc.)
RT
RTAmix
RTAi
(b) H ex = H mix
xi H i =

xi RT Zi 1
Zmix 1
Zmix
Zmix
i

L
MN a

OP
Q

FG x A IJ RTA
HZK Z
F x A A IJ
= RT bZ x Z g + RT G
H Z Z K
= a H PV f x a H PV f
= b H x H g PbV
xV g
F x A A IJ RTbZ
= RT bZ x Z g + RT G
H Z Z K
F x A A IJ
= + RT G
H Z Z K
b

= RT Zmix xi Zi + RT

mix

i i

mix

mix

U ex

mix

mix

mix

mix

mix

mix

i i

mix

mix

i i

mix

(c)

i i

i i

i i

mix

mix

mix

xi Zi

S mix xi Si R xi ln xi
= S ex

a
= R lnaZ
= R lnaZ

a f
f
f R x lnaZ B f + ln x
f R x ln x aZ B f

= P ln Zmix Bmix R X i ln Zi Bi R xi ln xi

= R ln

mix

Bmix

mix Bmix
Zmix Bmix

Zi Bi
i

xi

(d) G ex = H ex TS ex = RT Zmix xi Zi + RT
RT ln

FG x A A IJ
H Z Z K
i i

mix

mix

Zmix Bmix

Zi Bi
i

xi

Aex = U ex T S ex = + RT

FG x A A IJ RT ln Z B
H Z Z K
aZ B f
i i

mix

mix

mix

mix
xi
i