Advanced Thermodynamics KP8108

Solutions to Selected Problems

(a companion to J. M. Prausnitz, R. N. Lichtenthaler
and E. G. de Azevedo Molecular Thermodynamics,
2nd ed.)
Prof. Bjrn Hafskjold, Dep. of Chemistry (NTNU)
Assoc. Prof. Tore Haug-Warberg, Dep. of Chem. Eng. (NTNU)
May 16, 2007
ii
Contents
Problem 2.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Problem 2.5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Problem 2.6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Problem 2.7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Detailed derivation of Eqs. (3-53) and (3-54) . . . . . . . . . . . . . . . . . . . . 5
Problem 3.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Problem 3.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Problem 3.7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Problem 3.9 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Problem 5.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Iteration 1: y
1
= 0.01 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Iteration 2: y
1
= 3.4835 10
3
. . . . . . . . . . . . . . . . . . . . . . . . 15
Problem 5.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Problem 5.16 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Problem 5.17 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Iteration 1: y
3
= 0 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Iteration 2: y
3
= 1.04 10
4
. . . . . . . . . . . . . . . . . . . . . . . . . 26
Problem 6.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Problem 6.16 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
Problem 7.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Problem 7.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
Problem 10.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Method 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Method 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Problem 10.6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Problem 10.9 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Question a . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Question b . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Question c (method I) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Question c (method II) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
Problem 11.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Problem 11.6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
Problem 11.9 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
Problem 12.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
Problem 12.4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
Problem 12.7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
iii
iv
Chapter 2
Problem 2.2
For the given equation of state, P
_
V
n
b
_
= RT, and by using the Maxwell relation
2
A/TV =

2
A/VT, we nd:
_
S
V
_
T
=
_
P
T
_
V
=
R
V
n
b
=
P
T
.
For an isothermal change:
S =
_ _
S
V
_
T
dV =
_
R
V
n
b
dV = nRln
_
V
2
nb
V
1
nb
_
= nRln
_
P
1
P
2
_
.
Alternatively, from
2
G/TP =
2
G/PT, we nd:
_
S
P
_
T
=
_
V
T
_
P
=
nR
P
.
This formula integrates to the same expression for S as above. For U we know the
dierential dU = TdS pdV and hence (U/V)
T
= T(S/V)
T
P. Using the rst of
the Maxwell rules from above we get
_
U
V
_
T
= T
_
P
T
_
V
P = 0.
Consequently, U = 0. Alternatively, we can write (U/P)
T
= T(S/P)
T
P(V/P)
T
which gives:
_
U
P
_
T
= T
_
S
P
_
T
P
_
V
P
_
T
= T
_
V
T
_
P
P
_
V
P
_
T
=
RT
P
+
RT
P
= 0.
Again we nd that U = 0. For the next derivative we shall use H = U + PV and
_
H
P
_
T
=
_
U
P
_
T
+ V + P
_
V
P
_
T
= 0 +
nRT
P
+ nb P
nRT
P
2
= nb.
1
For an isothermal change:
H =
_ _
H
P
_
T
dP =
_
nbdP = nb (P
2
P
1
) .
The changes in Gibbs energy (G) and Helmholtz energy (A) are found from the denitions
of G and A, and the results above:
G = H TS = nb (P
2
P
1
) nRT ln
_
P
1
P
2
_
,
A = U TS = nRT ln
_
P
1
P
2
_
.
Problem 2.5
Because entropy is constant it would be natural to express the result as an explicit function
of S . However, this is not feasible because the equation of state is expressed in terms of T
and V. We shall therefore use implicit dierentiation and rst write entropy as a function
of volume and temperature, dierentiate, use some of the Maxwell relations, and then put
the dierential of S (V, T) equal to zero:
dS =
_
S
V
_
T
dV +
_
S
T
_
V
dT =
_
P
T
_
V
dV +
C
V
T
dT = 0
Thermodynamically, the exhaust temperature does not depend on the gas ow rate through
the turbine, and for convenience we choose one mole of gas as the basis for the calculation.
With the van der Waal equation, we nd for one mole of gas:
P =
RT
v b

a
v
2

_
P
T
_
V
=
R
v b
Inserted into the expression for dS = 0 this gives the following dierential equation be-
tween v and T at constant entropy:
dv
v b
=
c
V
R
dT
T
This is the adiabatic equation of state for a van der Waal gas. Integration at constant c
v
gives
ln
_
v
2
b
v
1
b
_
=
c
V
R
ln
_
T
2
T
1
_
where T
2
and v
2
are unknown. It is given that the nal pressure is atmospheric, and by using
the equation of state, we could express v
2
by P
2
. This is, however, a little cumbersome, but
since the exhaust pressure is low, we try rst by approximating the exhaust gas is an ideal
gas. This gives:
ln
_
T
2
T
1
_
=
R
c
V
ln
_

_
v
ig
2
b
v
1
b
_

_

R
c
V
ln
_
RT
2
P
2
(v
1
b)
_
2
where we have approximated v
ig
2
b v
ig
2
= RT
2
/P
2
. Rearrangement gives
ln
_
T
2
T
1
_
=
R
c
V
ln
_
T
1
T
2
_

R
c
V
ln
_
RT
1
P
2
(v
1
b)
_
=
R
c
V
_
1 +
R
c
V
_ ln
_
RT
1
P
2
(v
1
b)
_
=
R
c
P
ln
_
RT
1
P
2
(v
1
b)
_
where we have made use of c
ig
P
= c
ig
V
+ R. With the given numbers, we nd
ln
_
T
2
(350 + 273) K
_
=
8.314 J K
-1
mol
-1
33.5J K
-1
mol
-1
ln
_
82.06cm
3
atm mol
-1
K
-1
(350+273) K
1 atm (600-45) cm
3
mol
-1
_
= 1.123
T
2
= 623 exp(1.123) = 203 K
Checking the ideal-gas assumption:
V
ig
2
=
RT
2
P
2
=
82.06 cm
3
atm mol
-1
K
-1
203 K
1 atm
= 16700 cm
3
mol
-1
V
vdw
2
= 16400 cm
3
mol
-1
Note: The van der Waal result was found by an iterative solution of the cubic equation in
V at 203 K and 1 atm. If we want to improve the ideal-gas assumption, we may insert
V
vdw
2
= 16400 cm
3
mol
-1
into the equation above:
ln
_
T
2
T
1
_
=
R
c
V
ln
_

_
v
vdw
2
b
v
1
b
_

_
=
8.314 J K
-1
mol
-1
25.2 J K
-1
mol
-1
ln
_
(16400 45) cm
3
mol
-1
(600-45) cm
3
mol
-1
_
= 1.117
T
2
= 623 exp(1.117) = 204 K
Problem 2.6
The virial expansion of the compression factor is
z =
Pv
RT
= 1 +
B
v
+
C
v
2
+
The compression factor for the van der Waal gas is
z
vdw
=
v
RT
_
RT
v b

a
v
2
_
=
1
1
b
v

a
RT
1
v
We recognize the rst term on the right-hand side as the sum of a geometric series:
1
1
b
v
= 1 +
b
v
+
_
b
v
_
2
+
3
Ordering the van der Waal compression fcator in increasing powers of
1
v
gives
z
vdw
= 1 +
_
b
a
RT
_
1
v
+
_
b
v
_
2
+
and we conclude that
B = b
a
RT
.
Problem 2.7
We start by recovering one result from Problem 2.2:
_
U
P
_
T
= T
_
V
T
_
P
P
_
V
P
_
T
.
From the given equation of state, the volume is
z =
Pv
RT
= 1 +
BP
RT
v =
RT
P
_
1 +
BP
RT
_
=
RT
P
+ a
b
T
2
From this we nd:
_
V
T
_
P
=
R
P
+
2b
T
3
_
V
P
_
T
=
RT
P
2
_
U
P
_
T
= T
_
R
P
+
2b
T
3
_
P
_

RT
P
2
_
=
2b
T
2
Integration at the constant temperature then gives:
U() =

_
0
_
U
P
_
T=
dP =
2b

2

4
Chapter 3
Detailed derivation of Eqs. (3-53) and (3-54)
Start with this denition of the chemical potential:

i
=
_
A
n
i
_
V
Applied to Eq. (3-50) the denition leads to

i
=

_
V
_

_
_
P
n
i
_
T,V,n
j

RT
V
_

_
dV RT

n
i

j
_
n
j
ln
_
P

V
n
j
RT
__
+ u

i
Ts

i
(1)
We note that j = 1 is the only term that survives the dierentiation of the sum. This term is

n
i
_
n
i
ln
_
P

V
n
i
RT
__
= ln
_
P

V
n
i
RT
_
1 (2)
Furthermore, the standard state of component i is pure ideal gas at temperature T and
pressure P

= 1 bar. The chemical potential of i in this state is

i
= g

i
= u

i
+ RT Ts

i
(3)
Eqs. 2 and 3 into 1 gives

i
=

_
V
_

_
_
P
n
i
_
T,V,n
j

RT
V
_

_
dV RT
_
ln
_
P

V
n
i
RT
_
1
_
+

i
RT

i
=

_
V
_

_
_
P
n
i
_
T,V,n
j

RT
V
_

_
dV RT ln
_
P

V
n
i
RT
_
(4)
The relation between the chemical potential and fugacity is

i
= RT ln
_
f
i
f

i
_
(5)
The fugacity of the standard state is P

= 1 bar. The fugacity is further expressed by the

fugacity coecient as
f
i
=
i
P
i
=
i
y
i
P

i
=
f
i
y
i
P
(6)
5
Combination of Eqs. 4, 5, and 6 yields
RT ln
_

i
y
i
P
P

_
=

_
V
_

_
_
P
n
i
_
T,V,n
j

RT
V
_

_
dV RT ln
_
P

V
n
i
RT
_
RT ln
i
=

_
V
_

_
_
P
n
i
_
T,V,n
j

RT
V
_

_
dV RT ln
_
P

V
n
i
RT
_
RT ln
_
y
i
P
P

_
=

_
V
_

_
_
P
n
i
_
T,V,n
j

RT
V
_

_
dV RT ln
_
PV
nRT
_
=

_
V
_

_
_
P
n
i
_
T,V,n
j

RT
V
_

_
dV RT ln z (3-53)
For a pure component, the chemical potential is

i
=
G
n
i
=

i
+ RT ln
_
f
i
f

i
_
=

i
+ RT ln
_
f
i
P
_
+ RT ln
_
P
f

i
_
RT ln
_
f
i
P
_
pure i
=
i

i
RT ln
_
P
f

i
_
=
G
n
i

n
i
RT ln
_
P
P

_
(7)
The Gibbs energy is taken from Eq. (3-51) in the book:
G
n
i
=

_
V
_
P
n
i

RT
V
_
dV RT ln
_
P

V
n
i
RT
_
+
PV
n
i
+ u

i
Ts

i
(8)
Note that
G

n
i
= h

i
Ts

i
= u

i
+ RT Ts

i
(9)
and
PV
n
i
= RTz (10)
6
Eqs. 8, 9, and 10, inserted into 7, combine to:
RT ln
_
f
i
P
_
pure i
=
G
n
i

n
i
RT ln
_
P
P

_
=

_
V
_
P
n
i

RT
V
_
dV RT ln
_
P

V
n
i
RT
_
+
PV
n
i
+ u

i
Ts

_
u

i
+ RT Ts

i
_
RT ln
_
P
P

_
=

_
V
_
P
n
i

RT
V
_
dV RT ln
_
PV
n
i
RT
_
+
PV
n
i
RT
=

_
V
_
P
n
i

RT
V
_
dV RT ln z + RTz RT
=

_
V
_
P
n
i

RT
V
_
dV RT ln z + RT(z 1) (3-54)
Note: There is probably an easier way to understand this equation. It is illogical to bring
in expressions for both A and G and pretend they are independent functions. The elegant
solution would be to bring in the homogeneous properties of P = P(T, V, N) and develop
Eq. 3-54 directly from Eq. 3-53. Suggestions are welcome.
Problem 3.2
The gas mixture is illustrated in Figure 1. If we consider the gas to be a pseudo pure
A, B
x
A
= 0.25, x
B
= 0.75
P = 50 bar
T = 373 K

A
= 0.65,
B
= 0.90
Figure 1: Properties of the gas mixture.
substance, the relation between the chemical potential and the fugacity would be

M
=

M
+ RT ln
_
f
M
f

M
_
where

M
and f

M
are the chemical potential and the fugacity, respectively, in the standard
state. This would correspond to a molar Gibbs energy for the mixture, G
M
=
M
. On the
7
other hand, the molar Gibbs energy for the mixture is given by
G
m
=

i
x
i
where the chemical potential of each component is

i
=

i
+ RT ln
_
f
i
f

i
_
=

i
+ RT ln
_

i
P
i
f

i
_
Here,
i
is the fugacity coecient of component i. Equating G
M
and G
m
gives

M
+ RT ln
_
f
M
f

M
_
=

i
x
i

i
+ RT

i
x
i
ln
_

i
P
i
f

i
_
(11)
which we can use to express f
M
in terms of the component properties. We should, however,
rst make a remark on the relation between the standard states. The

M
is not the same as

i
even if they refer to the same pressure, because

M
contains the properties of an ideal
mixture:

M
=

i
x
i

i
+ RT

i
x
i
ln x
i
(12)
The standard fugacities, which are usually taken to be ideal gas at 1 bar pressure, are the
same: f

M
= f

i
. Equations 11 and 12 give:

i
x
i

i
+ RT

i
x
i
ln x
i
+ RT ln
_
f
M
f

M
_
=

i
x
i

i
+ RT

i
x
i
ln
_

i
P
i
f

i
_
ln
_
f
M
1 bar
_
=

i
x
i
ln
_

i
P
i
1 bar
_

i
x
i
ln x
i
With the given data, we nd:
ln
_
f
M
1 bar
_
= 0.25 ln (0.65 0.25 50) + 0.75 ln (0.90 0.75 50)
0.25 ln 0.25 0.75 ln 0.75 = 3.725 3
f
M
= 1 exp(3.7253) = 41.5 bar
Problem 3.3
The two situations are shown schematically in Figure 2. Equilibrium between gas and
liquid at 1 bar may be expressed as

gas
C
2
H
6
(1bar) =
liq
C
2
H
6
(x
C
2
H
6
= 0.33 10
4
)
The same equilibrium at 35 bar may be expressed as

gas
C
2
H
6
(35bar) =
liq
C
2
H
6
(x
C
2
H
6
= x)
8
gas gas
H
2
O, C
2
H
6
H
2
O, C
2
H
6
P = 1 bar P = 35 bar
P
H
2
O
= 0.0316 bar P
H
2
O
= 0.0316 bar
P
C
2
H
6
1 bar P
C
2
H
6
35 bar
T = 298 K T = 298 K
liquid liquid
H
2
O, C
2
H
6
H
2
O, C
2
H
6
x
H
2
O
1.0 x
H
2
O
1.0
x
C
2
H
6
= 0.33 10
4
x
C
2
H
6
=?
Figure 2: The two equilibrium situations.
where x
C
2
H
6
is the unknown denoted by x. In the gas phase, the eect of a change in the
chemical potential at constant temperature is
d
i
= v
i
dP
where v
i
is the partial molar volume of component i. Since there is so little water in the gas
phase, we assume it to be pure C
2
H
6
, in which case we can neglect the eect of a change
in composition, and v
i
is the molar volume of C
2
H
6
, i.e. v
i
= v
C
2
H
6
. The molar volume is
given by the equation of state,
v =
RT
P
_
1 aP bP
2
_
where a = 7.6310
3
bar
1
and b = 7.2210
5
bar
2
. Integration of the chemical potential
at constant T gives

gas
C
2
H
6
(35bar)
gas
C
2
H
6
(1bar) =
35 bar
_
1 bar
_

C
2
H
6
dP
_
T
dP = RT
35 bar
_
1 bar
_
1
P
a bP
_
dP
= RT
_
ln
_
35 bar
1 bar
_
a 34 bar
1
2
b
_
35
2
1
2
_
bar
2
_
In the liquid phase, the change in chemical potential is the sum of two contributions; one
due to the pressure change, and one due to the composition change. The eect of the change
in pressure is d
C
2
H
6
= v
C
2
H
6
dP, where v
C
2
H
6
is the partial molar volume of ethane in the
liquid. Since the liquid is practically incompressible, it may be assumed to be constant
over the pressure change in question here, and in any case the contribution is negligibly
small for the liquid. The eect of the change in composition is d
C
2
H
6
= RTd ln a
C
2
H
6
,
where a
C
2
H
6
= f
C
2
H
6
/ f

C
2
H
6
is the activity of ethane. We have to assume that the activity
9
coecient of ethane, dened by
C
2
H
6
= a
C
2
H
6
/x
C
2
H
6
, is constant over the concentration
range considered here, which leads to

liq
C
2
H
6
(x)
liq
C
2
H
6
(x = 0.33 10
4
)
=
35 bar
_
1 bar
v
C
2
H
6
dP + RT
x
C
2
H
6
=x
_
x
C
2
H
6
=0.3310
4
d ln
C
2
H
6
+ RT
x
C
2
H
6
=x
_
x
C
2
H
6
=0.3310
4
d ln x
C
2
H
6
RT
x
C
2
H
6
=x
_
x
C
2
H
6
=0.3310
4
d ln x
C
2
H
6
= RT ln
_
x
0.33 10
4
_
Equating the changes in the chemical potential of the gas and liquid phases give
RT ln
_
x
0.33 10
4
_
= RT
_
ln(35) 7.63 10
3
34
1
2
7.22 10
5
_
35
2
1
2
_
_
ln
_
x
0.33 10
4
_
= ln(35) 7.63 10
3
34
1
2
7.22 10
5
_
35
2
1
2
_
= 3.2517
x = 0.33 10
4
exp(3.2517) = 8.53 10
4
Problem 3.7
Throttling is an isenthalpic process, and we shall therefore consider the conservation of
enthalpy in this problem. Since the equation of state is given explicitly in the volume as
function of P and T, we nd the enthalpy from the following relation:
H =
P
_
0
_
V T
_
V
T
_
P,n
T
_
dP +

i
n
i
h
0
i
where h
0
i
is the molar enthalpy of pure i at the actual temperature. The given volumetric
data for the mixture leads to
_
V T
_
V
T
_
P,n
T
_
= a +
b
T
where a = 5 10
5
m
3
mol
1
and b = 0.2 m
3
K mol
1
. Integration leads to the molar
enthalpy
h =
_
a +
b
T
_
P +

i
x
i
h
0
i
where x
i
is the mole fraction of component i. The condition h
in
= h
out
gives
_
a +
b
T
in
_
P
in
+

i
x
i
h
0
i,in
=
_
a +
b
T
out
_
P
out
+

i
x
i
h
0
i,out
_
a +
b
T
in
_
P
in
=
_
a +
b
T
out
_
P
out
+

i
x
i
_
h
0
i,out
h
0
i,in
_
10
We have h
0
i,out
h
0
i,in
= c
0
P,i
(T
out
T
in
) and c
0
P
=
_
i
x
i
c
0
P,i
= 33.5 J mol
1
K
1
. Solving for P
in
gives
P
in
=
_
a +
b
T
out
_
P
out
+ c
0
P
(T
out
T
in
)
_
a +
b
T
in
_
=
_
5 10
5
m
3
mol
1
0.2m
3
Kmol
1
/200K
_
10
5
Pa + 33.5Jmol
1
K
1
(200K 300K)
_
5 10
5
m
3
mol
1
0.2m
3
Kmol
1
/300K
_
= 55.9 10
5
Pa = 55.9 bar
Problem 3.9
The internal energy of mixing is (using one mole as basis):

mix
u = u
M
x
1
u
1
x
2
u
2
Since the van der Waal equation is explicit in P:
P =
RT
v b

a
v
2
,
it is convenient to nd the internal energy from
u =

_
v
_
P T
_
P
T
_
V,n
T
_
dv +

i
x
i
u
0
i
where
P T
_
P
T
_
V,n
T
=
RT
v b

a
v
2

RT
v b
=
a
v
2
Note that the mixing must be assumed to occur at constant pressure, not at constant volume,
which means that we must use dierent volumes for the lower integration limit for the
mixture and the two pure components. The molar internal energy for the mixture and each
of the pure components are:
u
M
= a
M

_
v
M
dv
v
2
+

i
x
i
u
0
i
=
a
M
v
M
+

i
x
i
u
0
i
u
1
=
a
1
v
1
+ u
0
1
u
2
=
a
2
v
2
+ u
0
2
The change in internal energy for the mixture is

mix
u =
a
M
v
M
+

i
x
i
u
0
i
+ x
1
_
a
1
v
1
u
0
1
_
+ x
2
_
a
2
v
2
u
0
2
_
=
a
M
v
M
+
x
1
a
1
v
1
+
x
2
a
2
v
2
11
With the given data, we nd
a
M
=

j
x
i
x
j

a
i
a
j
(1 k
i j
)
= 0.5
2
10
6
_
1.04 + 2

1.04 4.17(1.0 0.1) + 4.17

_
bar cm
6
mol
2
= 2.24 10
6
bar cm
6
mol
2
v
M
=

i
x
i
v
i
= 0.5(32.2 + 48.5) cm
3
mol
1
= 40.35 cm
3
mol
1

mix
u =
_

2.24
40.35
+
0.5 1.04
32.2
+
0.5 4.17
48.5
_
10
6
bar cm
6
mol
2
cm
3
mol
1
= 363 J mol
1
12
Chapter 5
Problem 5.2
The question here is whether the fugacity of CO
2
in the compressed gas is higher than
the fugacity at saturation conditions. The actual temperature is lower than the triple-point
temperature, and the condensed phase in equilibrium with the vapour, if it exists, is solid.
To nd the saturation pressure, we consider how it changes from the vapour pressure of
pure CO
2
(component 1) to its new value after injection of H
2
(component 2) until the total
pressure is 60 bar. We therefore consider a charging process as illustrated in Figure 3. The
H
2
is inert in this case, in the sense that it does not dissolve in the solid phase. The change
CO
2
(g) CO
2
(g) + H
2
(g)
P

CO
2
= 0.1392 bar (g) P
CO
2
+ P
H
2
= 60 bar
T = 173 K T = 173 K
CO
2
(s) (s) CO
2
(s)
T = 173 K T = 173 K
Figure 3: Available data for the state changes.
in chemical potential of CO
2
in the gas phase is

1
(g) = RT
c
_

d ln f
1
= RT
_
ln f
1
_
c

(13)
where f
1
is the fugacity of CO
2
. The fugacity of pure CO
2
vapour can be assumed to be
equal to its vapour pressure (the saturation pressure of 0.1392 bar is quite low), but please
validate this assumption by numerical calculations. The fugacity of CO
2
in the compressed
state must be calculated somehow, and we shall be using
f
1
=
1
y
1
P
where
1
and y
1
are the the fugacity coecient and the mole fraction of CO
2
, respectively,
and P is the total pressure (equal to 60 bar). The fugacity coecient is estimated from van
13
der Waals equation:
z =
Pv
RT
=
v
v b

a
RTv
(14)
The mixing rules are
a =

j
y
i
y
j

a
i
a
j
b =

i
y
i
b
i
The fugacity coecient of component 1 in the mixture is calculated from Eq. 3-70 in Praus-
nitz et al.:
ln
1
= ln
v
v b
+
b
1
v b

2

a
1
_
j
y
j

a
j
RTv
ln z (15)
Numerical values for the van der Waals parameters may be found in several textbooks, e.g.
in P. W. Atkins, Physical Chemistry, 6th edition, Oxford, 1998:
a/atm cm
6
mol
2
b/cm
3
mol
1
CO
2
(1) 3.64010
6
42.67
H
2
(2) 0.247610
6
26.61
Alternatively we may use the corresponding state principle and calculate a = 27(RT
c
)
2
/64P
c
and b = RT
c
/8P
c
from critical data. Do this on your own and compare the results with the
table. Because the mole fraction of CO
2
is low, at most 0.01, we make a small error if
we choose the van der Waal parameters to be those of pure H
2
, but for the time being we
determine the mixture parameters on the basis of 1 mole% CO
2
.
Iteration 1: y
1
= 0.01
This gives:
a =(0.01
2
3.640 10
6
+ 2 0.01 0.99

3.640 10
6
0.2476 10
6
+0.99
2
0.2476 10
6
) atm cm
6
mol
2
=2.618 3 10
5
atm cm
6
mol
2
b =(0.01 42.67 + 0.99 26.61) cm
3
mol
1
=26.77 cm
3
mol
1
At 60 bar, the molar volume in Eq. 14 (note that we have to solve a cubic equation in v) is
v = 250.69 cm
3
mol
1
and z = 1.048. Inserted into Eq. 15:
ln
1
= ln
_
250.69
250.69 26.77
_
+
42.67
250.69 26.77

3.640 10
6
_
0.01

3.640 10
6
+ 0.99

0.2476 10
6
_
250.69 82.0567 173
ln 1.048
= 0.292

1
= exp(0.292) = 0.7468
14
Inserting the last result into Eq. 13 gives the change in chemical potential of CO
2
in the gas
phase:

1
(g) = 83.1439 cm
3
bar mol
-1
K
-1
173 K ln
_
0.7468 y
1
60 bar
0.1392 bar
_
= 14428 cm
3
bar mol
-1
ln (321.9y
1
)
The change in chemical potential for CO
2
in the solid phase is

1
(s) =
c
_

v
s
dP = v
s
60 bar
_
0.1392 bar
dP = 27.6 cm
3
mol
1
(60 0.1392) bar
= 1652.16 cm
3
bar mol
-1
Here, we have assumed that the solid is incompressible and that H
2
does not dissolves in
the solid. At equilibrium, in the compressed state, we have
1
(g) =
1
(s) which gives
14428 cm
3
bar mol
-1
ln (321.9y
1
) = 1652.16 cm
3
bar mol
-1
y
1
=
1
321.9
exp
_
1652.16
14428
_
= 3.4835 10
3
At this point, we conclude that Iteration 1 is slightly o, and try another calculation:
Iteration 2: y
1
= 3.4835 10
3
This gives
a = (0.0035
2
3.640 10
6
+ 2 0.0035 0.9965

3.640 10
6
0.2476 10
6
+ 0.9965
2
0.2476 10
6
) atm cm
6
mol
2
= 2.5254 10
5
atm cm
6
mol
2
b = (0.0035 42.67 + 0.9965 26.61) cm
3
mol
1
= 26.67 cm
3
mol
1
and v = 251.17 cm
3
mol
1
, and z = 1.048. Inserting these numbers into Eq. 15 gives:
ln
1
= ln
_
251.17
251.17 26.77
_
+
42.67
251.17 26.77

3.640 10
6
_
0.0035

3.640 10
6
+ 0.9965

0.2476 10
6
_
251.17 82.0567 173
ln 1.048
= 0.282

1
= exp(0.282) = 0.7543
A small change in
1
from 0.7468 to 0.7543 is observed. The improved value of the change
in chemical potential for the gas phase is calculated (once more) from Eq. 13):

1
(g) = 83.1439 cm
3
bar mol
-1
K
-1
173 K ln
_
0.7543 y
1
60 bar
0.1392 bar
_
= 14428 cm
3
bar mol
-1
ln (325.1y
1
)
15
The solid phase chemical potential is the same as above, and we nd
y
1
=
1
325.1
exp
_
1652.16
14428
_
= 3.4492 10
3
We consider Iteration 2 to be good, and accept this as the nal result. To conclude the
calculation, we need a material balance, using one mole material in total as basis:
n
CO
2
(g) + n
CO
2
(s) + n
H
2
(g) = 1 mol (16)
n
H
2
(g) = 0.99 mol (17)
The mole fraction of CO
2
in the gas phase is
y
CO
2
=
n
CO
2
(g)
n
CO
2
(g) + n
H
2
(g)
= 0.00345 (18)
Solution of Eqs. 1618 gives the amount of precipitated CO
2
:
n
CO
2
(s) = 0.0066 mol
Problem 5.3
The situation is shown in Figure 4. The question is whether some of the CO
2
will condense
into liquid or solid, or not. This depends on the pressure and temperature in the gas during
the isenthalpic expansion. In the following, we will denote CH
4
by 1 and CO
2
by 2. The
30 mol% CO
2
(g)
70 mol% CH
4
(g)
70 bar, 313 K
CO
2
(s) or CO
2
(l)?
CH
4
(g)
1 bar, T=?
Figure 4: The given process.
critical point of CO
2
is at P
c
= 73.8 bar and T
c
= 304.2 K. The triple point is at P
T
= 5.18
bar and T
T
= 216.8 K. If the gas cools to a temperature in the range between the critical
point and the triple point, some CO
2
may possibly condense to a liquid, if it cools to
T < 216.8 K, it may condense to a solid. Because the equation of state is given as a
virial expansion in molar density, it is most convenient to express the enthalpy of the gas as
H =

_
V
_
P T
_
P
T
_
V,n
T
_
dV + PV +

i
n
i
u
0
i
where n
i
is the number of moles of component i and u
0
i
is the molar internal energy of pure
i in the ideal gas state at the actual temperature. The strategy is to nd how H depends
16
on V and T, then constrain H to be constant, and nally to use this constraint to nd the
isenthalpic equation of state for the gas. This equation will tell us how much the gas cools
on expanding. The given data for the mixture are of the form
z
mix
=
Pv
RT
= 1 +
B
mix
v
(19)
where
B
mix
=

j
y
i
y
j
B
i j
(20)
and y
i
is the mole fraction of component i. Each B
i j
is of the form
B
i j
= a
i j
+
b
i j
T
+
c
i j
T
2
,
which means B
mix
will be on the same form,
B
mix
= a +
b
T
+
c
T
2
where
a =

j
y
i
y
j
a
i j
= (0.7
2
42.5 + 2 0.7 0.3 41.4 + 0.3
2
40.4) cm
3
mol
-1
= 41.85 cm
3
mol
-1
b =

j
y
i
y
j
b
i j
= (0.7
2
16.75 + 2 0.7 0.3 19.50 + 0.3
2
25.39) 10
3
cm
3
K mol
-1
= 18.683 10
3
cm
3
K mol
-1
c =

j
y
i
y
j
c
i j
= (0.7
2
25.05 + 2 0.7 0.3 37.3 + 0.3
2
68.7) 10
5
cm
3
K
2
mol
-1
= 34.124 10
5
cm
3
K
2
mol
-1
We then nd for one mole of gas
P T
_
P
T
_
V,n
T
=
R
v
2
_
b +
2c
T
_
and for the molar enthalpy:
h =
R
v
_
aT + 2b +
3c
T
_
+

i
y
i
h
0
i
(21)
We note that the ideal-gas contribution to enthalpy is (constant c
P
assumption):

i
y
i
h
0
i
= c
0
P
T
where
c
0
P
=

i
y
i
c
0
P,i
= (0.7 35.8 + 0.3 37.2) J mol
-1
K
1
= 36.22 J mol
-1
K
1
17
The energy constraint tells that h is constant and solving Eq. 21 for v gives:
v(T) =
R
_
aT + 2b +
3c
T
_
h c
0
P
T
(22)
At the upstream conditions,
B
mix
=
_
41.85
18.683 10
3
313

34.124 10
5
313
2
_
cm
3
mol
-1
= 52.672 cm
3
mol
-1
and from Eq. 19:
70 bar v
83.1439 bar cm
3
mol
-1
K
1
313 K
= 1
52.672 cm
3
mol
-1
v
which gives v
1
= 308.24 cm
3
mol
-1
. The constant enthalpy in Eq. 21 can now be deter-
mined to
h
1
=
8.314 J mol
-1
K
-1
_
41.85 313 2 18.683 10
3

334.12410
5
313
_
K cm
3
mol
-1
308.24 cm
3
mol
-1
+ 36.22 J mol
-1
K
1
313 K
= 9800 J mol
-1
The question is whether the temperature-pressure relationship will be such that the gas is
cooled to a temperature below the condensation point for CO
2
, or in other words, will the
fugacity CO
2
in the gas be higher than the equilibriumvalue in contact with pure CO
2
? The
fugacity of CO
2
in the expanding gas is given by
f
2
=
2
y
2
P,
which should be compared with the fugacity for saturated gas in equilibrium with liquid or
solid:
f
sat
2
= P
sat
2
exp
_
v
l
P
RT
_
(3.5)
The saturation pressure of pure CO
2
is
ln P
sat
(bar) = 10.807
1980.24
T
(23)
and v
l
is the molar volume of pure CO
2
(l). The fugacity coecient is given by
ln
2
=
2
v

j
y
j
B
2j
ln z
mix
Most likely the Poynting correction is quite small, and the fugacity coecient is probably
less than 1. This implies that CO
2
is more volatile in the compressed gas than in the pure
form (where
2
1), and if we nd that if the gas is unsaturated in pure form, no CO
2
will
condense. Under this assumption, we solve Eqs. 19, 20, 22, 23 and calculate the data shown
in Table 1: The outlet pressure of 1 bar is reached before the temperature drops below the
18
Table 1: Saturation pressure(s) of CO
2
.
T/K v/cm
3
mol
1
B/cm
3
mol
1
P/bar P
2
/bar P
sat
2
/bar
271 35182 -73.6 0.639 0.192 33.1
... ... ... ... ... ...
304 400.6 -56.5 54.2 16.26 73.2
304.2 398 -56.4 54.5 16.36 73.8
305 387.9 -56.1 55.9 16.78 74.8
... ... ... ... ... ...
313 308.2 -52.7 70 21 (N/A)
T, K
270 280 290 300
P
,

b
a
r
0
20
40
60
80
100
P
2
sat
P
2
Figure 5: Saturation pressure and partial pressure of CO
2
.
triple point temperature, and any condensed CO
2
will be in liquid form. We note that from
the table P = P P
sat
2
is negative, which means the Poynting correction is less than unity.
The eect of the inert gas is therefore to reduce the saturation fugacity as compared with
the saturation pressure. A plot of P
2
and P
sat
2
is given in Figure 5. The gure shows that
the saturation pressure is higher than the actual partial pressure of CO
2
, and consequently
that CO
2
(l) will not condense. To improve the assumption of the ideal gas phase we need
to estimate the molar volume of liquid CO
2
. Data from Reid et al. indicate that
l
(T = 293
K) = 0.777 g cm
3
. The molecular weight of CO
2
is M = 44.01 g mol
1
. This gives
v
l
=
M

=
44.01 g mol
-1
0.777 g cm
3
= 56.6 cm
3
mol
-1
Assuming that the liquid density varies only a little with temperature, the saturation fugac-
ity is easily calculated:
f
sat
2
= P
sat
2
exp
_
56.6 cm
3
mol
-1
P
83.1439 cm
3
bar mol
-1
K
-1
T
_
19
The fugacity coecient in the gas phase is
ln
2
=
2
v

j
y
j
B
2j
ln z
mix
=
2
v
_
a
2
+
b
2
T
+
c
2
T
2
_
ln
_
1 +
B
mix
v
_
(24)
where
a
2
=

j
y
j
a
2j
= (0.7 41.4 + 0.3 40.4) cm
3
mol
-1
= 41.1 cm
3
mol
-1
b
2
=

j
y
j
b
2j
= (0.7 19.50 + 0.3 25.39) 10
3
cm
3
K mol
-1
= 21.267 10
3
cm
3
K mol
-1
c
2
=

j
y
j
c
2j
= (0.7 37.3 + 0.3 68.7) 10
5
cm
3
K
2
mol
-1
= 46.72 10
5
cm
3
K
2
mol
-1
The results for the fugacity may now be calculated from Eqs. 19, 20, 2224, and some of
the results are given in Table 2: A plot of f
2
and f
sat
2
is shown in Figure 6. The gure
Table 2: Fugacities of CO
2
.
T/K
2
f
2
/bar f
sat
2
/bar
271 1.365 0.262 30.52
... ... ... ...
304 0.826 13.43 70.14
304.2 0.824 13.48 70.45
305 0.816 13.69 71.69
... ... ... ...
313 0.741 15.57 (N/A)
conrms that no CO
2
(l) will be formed.
Problem 5.16
This problem is similar to problem 5.2. We consider a process as illustrated in Figure 7.
The ethylene is inert in the sense that it does not dissolve in the solid phase. Like in Problem
5.2, we compute the change in chemical potential for naphtalene in the gas phase as

1
(g) = RT
c
_

d ln f
1
= RT
_
ln f
1
_
c

The fugacity of pure napthalene vapour can be assumed to be equal to the vapour pres-
sure, 2.8010
4
bar, because the vapour pressure is low. The fugacity of napthalene in the
compressed state is determined as
f
1
=
1
y
1
P (25)
20
T, K
270 280 290 300
f
,

b
a
r
0
20
40
60
80
100
f
2
sat
f
2
Figure 6: Saturation fugacity and fugacity of CO
2
.
Naphtalene (g) (1) Naphtalene (g)
+ Ethylene (g) (2)
P

1
= 2.80 10
4
bar
1
(g) P
1
+ P
2
= 30 bar
P
1
= ?
T = 308 K T = 308 K
Naphtalene (s)
1
(s) Naphtalene (s)
T = 308 K T = 308 K
Figure 7: Naphtalene dissolving in ethylene.
with the usual notation. The change in chemical potential for naphtalene in the solid phase
is

1
(s) =
c
_

v
s
dP = v
s
30 bar
_
2.8010
4
bar
dP
The molar volume of the solid is given by the density and the molecular weight:
v
s
=
M

=
128.2 g mol
-1
1.145 g cm
3
= 112.0 cm
3
mol
-1
This gives

1
(s) = 112.0 cm
3
mol
-1
(30 2.80 10
4
) bar = 3360 cm
3
bar mol
-1
21
At equilibrium in the compressed state, we must have

1
(g) =
1
(s) (26)
We now consider the two cases, (a) The vapour is an ideal gas, and (b) the gas obeys the
virial expansion truncated after the second term.
a) With the ideal gas law

1
(g) = RT ln
_
P
1
2.80 10
4
bar
_
= 3360 cm
3
bar mol
-1
P
1
= 2.80 10
4
bar exp
_
3360 cm
3
bar mol
-1
83.1439 cm
3
bar mol
-1
K
-1
308 K
_
= 3.19 10
4
bar
y
1
=
P
1
P
=
3.19 10
4
bar
30 bar
= 1.06 10
5
b) With the virial expansion truncated after the second term. The virial expansion reads
z =
PV
nRT
= 1 + B
n
V
P =
RT
V
_
n +
B
V
n
2
_
(27)
The second virial coecient is given by the van der Waals result,
B = b
a
RT
(28)
where
a =

j
y
i
y
j

a
i
a
j
b =

i
y
i
b
i
It is convenient to write the expression for b as
b =

j
y
i
y
j
b
i j
where
b
i j
=
1
2
_
b
i
+ b
j
_
,
because we can then use Eq. (5-29) in Prausnitz et al.:
ln
1
=
2
v
(y
1
B
11
+ y
2
B
12
) ln z (29)
with
B
i j
= b
i j

a
i
a
j
RT
(30)
and
B =

j
y
i
y
j
B
i j
(31)
22
We will need the numerical values for a and b, which we nd from the critical values:
a =
27(RT
c
)
2
64P
c
b =
RT
c
8P
c
The critical values (See e.g. Reid et al.) are listed in Table 3, which also gives the computed
values for a and b. The values for a
i j
, b
i j
, and B
i j
are given in Table 4. We now make a
Table 3: Critical data for napthalene and ethylene.
T
c
/K P
c
/atm a/cm
6
atm mol
2
b/cm
3
mol
1
Naphtalene (1) 748.4 40.0 3.9810
7
191.91
Ethylene (2) 282.4 49.7 4.5610
6
58.28
Table 4: Interaction parameters for napthalene and ethylene.
Combination a
i j
/cm
6
atm mol
2
b
i j
/cm
3
mol
1
B
i j
/cm
3
mol
1
b/cm
3
mol
1
11 3.9810
7
191.91 -1382.9 191.91
12 1.3510
7
125.10 -409.06 58.28
22 4.5610
6
58.28 -122.15
guess for the mole fraction of naphtalene to obtain a rst estimate of the viral coecient
B. We can for example assume that P
1
is little aected by the presence of ethylene which
gives the starting value
y
1
=
P

1
P
=
2.80 10
4
bar
30bar
= 9.3 10
6
(Other qualied guesses include the answer from a) or y
1
= 0.) The equations 2531 give
an iterative procedure to nd y
1
:
B = y
2
1
B
11
+ 2y
1
(1 y
1
) B
12
+ (1 y
1
)
2
B
22
P
RT
v
2
v B = 0
z = 1 +
B
v
ln
1
=
2
v
(y
1
B
11
+ (1 y
1
) B
12
) ln z
RT ln
_

1
Py
1
P

1
_
=
B, v, z and
1
are estimated from the previous y
1
and a better estimate is obtained in the
last equation. With B
i j
from Table 4, =3360cm
3
bar/mol, T = 308K, P = 30bar and
P

1
= 2.8 10
4
bar the two rst iterations give the values shown in Table 5. We can therefore
conclude that y
1
= 2.80 10
5
.
23
Table 5: Iteration sequence.
iteration 1 iteration 2
B -122.155 -122.166
v 705.893 705.876
z 0.826949 0.826930

1
0.379462 0.379441
y
1
2.8044710
5
2.8046210
5
Problem 5.17
This problem is also similar to problem5.2. Instead of considering the cooling, we consider
compressing water vapour by adding air at 263 K. This is illustrated in Figure 8. Like in
H
2
O (g) (3) N
2
(1) + O
2
(2) (g)
+ H
2
O (g)
P

1
= 1.95 torr
3
(g) P = 30 bar
y
3
= ?
T = 263 K T = 263 K
H
2
O (s)
3
(s) H
2
O (s)

s
= 0.92 g cm
3

Figure 8: Available data for the state changes.

Problem 5.16, we compute the change in chemical potential for water vapour in the gas
phase as

3
(g) = RT
c
_

d ln f
3
= RT
_
ln f
3
_
c

= RT ln
f
3
P

3
The fugacity of pure water vapour is again assumed to be equal to the vapour pressure, 1.95
torr =
1.95
760
atm = 2.5710
3
atm = 2.6010
3
bar, because the vapour pressure is low. The
fugacity of water vapour in the compressed state is
f
3
=
3
y
3
P.
The change in chemical potential for ice is

3
(s) =
c
_

v
s
dP = v
s
30 bar
_
2.6010
3
bar
dP
24
The molar volume of ice is the molecular weight divided by the density:
v
s
=
M

=
18.0 g mol
-1
0.92 g cm
3
= 19.57 cm
3
mol
-1
This gives

1
(s) = 19.57 cm
3
mol
-1
(30 2.60 10
3
) bar = 587.1 cm
3
bar mol
-1
At equilibrium in the compressed state, we must have

1
(g) =
1
(s)
We have to determine the second virial coecient, the compression factor, and the fugacity
coecient:
B
mix
=

j
y
i
y
j
B
i j
z
mix
=
Pv
RT
= 1 +
B
mix
v
ln
3
=
2
v

j
y
j
B
3j
ln z
mix
A material balance for N
2
(g), O
2
(g), and H
2
O (g) gives
y
1
= 0.8(1 y
3
), y
2
= 0.2(1 y
3
)
Again, we have to solve the problem by iteration, which is considered below.
Iteration 1: y
3
= 0
This is for the saturated vapour. With the numerical values given in the problem, we nd
B
mix
=
_
0.8(1 y
3
)
_
2
B
11
+ 2 0.8(1 y
3
) 0.2(1 y
3
)B
12
+ 2 0.8(1 y
3
)y
3
B
13
+
_
0.2(1 y
3
)
_
2
B
22
+ 2 0.2(1 y
3
)y
3
B
23
+ y
3
y
3
B
33
=
_
0.8
2
25 + 2 0.8 0.2 15 + 0.2
2
12
_
cm
3
mol
-1
= 21.3 cm
3
mol
-1
30 bar v
83.1451 cm
3
bar mol
-1
K
-1
263 K
= 1
21.3 cm
3
mol
-1
v
v = 706.9 cm
3
mol
-1
z
mix
= 1
21.3 cm
3
mol
-1
706.9 cm
3
mol
-1
= 0.9699
ln
3
=
2
706.9 cm
3
mol
-1
(0.8 63 0.2 72) cm
3
mol
-1
ln (0.9699) = 0.1528

3
= 0.8583
The maximum permissible moisture content is therefore
y
3
=
2.60 10
3
0.8583 30
exp
_
587.1
83.1451 263
_
= 1.04 10
4
If we are in doubt concerning the accuracy of this result, we can make another iteration as
shown below.
25
Iteration 2: y
3
= 1.04 10
4
This gives
B
mix
=
_
0.8(1 y
3
)
_
2
B
11
+ 2 0.8(1 y
3
) 0.2(1 y
3
)B
12
+ 2 0.8(1 y
3
)y
3
B
13
+
_
0.2(1 y
3
)
_
2
B
22
+ 2 0.2(1 y
3
)y
3
B
23
+ y
3
y
3
B
33
=
_
0.8(1 1.04 10
4
)
_
2
B
11
+ 2 0.8(1 1.04 10
4
) 0.2(1 1.04 10
4
)B
12
+ 2 0.8(1 1.04 10
4
) 1.04 10
4
B
13
+
_
0.2(1 1.04 10
4
)
_
2
B
22
+ 2 0.2(1 1.04 10
4
)1.04 10
4
B
23
+ 1.04 10
4
1.04 10
4
B
33
= 0.6399B
11
+ 0.3199B
12
+ 1.6638 10
4
B
13
+ 0.0400B
22
+ 4.1596 10
5
B
23
+ 1.0816 10
8
B
33
= 21.289 cm
3
mol
-1
30 bar v
83.1439 cm
3
bar mol
-1
K
-1
263 K
= 1
21.289 cm
3
mol
-1
v
v = 706.9 cm
3
mol
-1
z
mix
= 1
21.289 cm
3
mol
-1
706.9 cm
3
mol
-1
= 0.9699
ln
3
=
2
706.9 cm
3
mol
-1
(0.8 63 0.2 72) cm
3
mol
-1
ln (0.9699) = 0.1528

3
= 0.8583
The maximum permissible moisture content is therefore
y
3
=
2.60 10
3
0.8583 30
exp
_
587.1
83.1451 263
_
= 1.04 10
4
26
Chapter 6
Problem 6.2
An azeotrope is a liquid mixture that does not change composition when it evaporates. If
we plot a liquid-vapour phase diagram for a mixture that forms an azeotrope, it will look
like shown in Fig. 6-12 in the textbook (for a P x -diagram) or in Fig. 6-22 (for a T x
-diagram). The point is that in the minimum or maximum of the curves in either of the
diagrams, the bubble-point and dew-point lines go through the same point. In order to nd
the bubble-point and dew-point lines, we have to consider the phase equilibrium shown in
Figure 9. In this gure, we have arbitrarily chosen to illustrate the change in chemical
potential of component 1 from pure state to the mixed state. The change in chemical
Pure 1 (g) Mixture 1+2 (g)
P
s
1

1
(g) P
1
+ P
2
= P
T T
Pure 1 (l)
1
(l) Mixture 1+2 (l)
T T
Figure 9: Schematic illustration of a mixing process.
potential for component 1 in the gas phase is

1
(g) = RT
mixture
_
pure 1
d ln f
1
= RT ln
_
P
1
P
s
1
_
= RT ln
_
y
1
P
P
s
1
_
where we have used the given information that the gas phase may be considered ideal. In
the liquid phase, the change in chemical potential is

1
(l) =
pure 1 at P
_
pure 1 at P
s
1
v
1
dP + RT
mixture
_
pure 1 at P
d ln a
1
(32)
27
where v
1
is the molar volume of pure component 1. The rst term in Eq. 32 is the Poynting
correction, which we will neglect here. The change
1
(l) is then

1
(l) = RT ln a
1
= RT ln (
1
x
1
)
where
1
is the activity coecient for component 1. By equating the changes in chemical
potentials, we get
RT ln
_
y
1
P
P
s
1
_
= RT ln (
1
x
1
)
y
1
P
P
s
1
=
1
x
1
From the given expression for the excess Gibbs energy for the mixture, we nd (using Eqs.
(6-46) and (6-47) in the textbook):
ln
1
=
A
RT
x
2
2
ln
2
=
A
RT
x
2
1
For the azeotrope, x
1
= y
1
which gives the bubble-point at the azeotrope
x
1
P
P
s
1
= exp
_
A
RT
x
2
2
_
x
1
P
P
s
1
= exp
_
A
RT
x
2
2
_
(33)
The same consideration for component 2 gives
P
P
s
2
= exp
_
A
RT
x
2
1
_
(34)
Dividing Eq. 33 by Eq. 34 and using the information that
P
s
2
P
s
1
= 1.649, gives
P
s
2
P
s
1
= exp
_
A
RT
_
x
2
2
x
2
1
_
_
= 1.649

A
RT
_
x
2
2
x
2
1
_
= ln 1.649 =
1
2
In other words, for an azeotrope to occur, the requirement is that for any value of x
1
in the
range 0 x
1
1, A must satisfy
A
RT
=
1
2
_
x
2
2
x
2
1
_ =
1
2
_
(1 x
1
)
2
x
2
1
_ =
1
2 (1 2x
1
)
A plot of the allowed values of A/RT is shown in Figure 10. This means that for e.g.
A
RT
= 1, there will be an azeotrope at x
1
= 0.25. To illustrate this, we can construct a P x
28
x
1
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
A
/
R
T
-20
-10
0
10
20
Figure 10: The lines show allowed values of A/RT.
diagram as follows: The total vapour pressure (the bubble-point pressure) is the sum of the
partial pressures:
P = P
1
+ P
2
= P
s
1
exp
_
A
RT
x
2
2
_
x
1
+ P
s
2
exp
_
A
RT
x
2
1
_
x
2
If we set
A
RT
= 1, we nd
P
P
s
1
= exp
_
x
2
2
_
x
1
+
P
s
2
P
s
1
exp
_
x
2
1
_
x
2
The dew-point line is given by
y
1
=
P
1
P
=
P
s
1
exp
_
A
RT
x
2
2
_
x
1
P
s
1
exp
_
A
RT
x
2
2
_
x
1
+ P
s
2
exp
_
A
RT
x
2
1
_
x
2
Again setting
A
RT
= 1 as an example, we nd
y
1
=
exp
_
x
2
2
_
x
1
exp
_
x
2
2
_
x
1
+
P
s
2
P
s
1
exp
_
x
2
1
_
x
2
The bubble-point and dew-point curves are shown in Figure 11 for this particular case. We
now have to consider the question of liquid-liquid miscibility. This is illustrated in Figure
12, showing the change in Gibbs energy on mixing as function of composition for four
dierent values of A;
A
RT
= 0, 1, 2, 3. The Gibbs energy of mixing is given by

mix
G =
mix
G
ideal
+ G
excess
= RT
2

i=1
x
i
ln x
i
+ Ax
1
x
2
(35)
29
x
1
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
P
/
P
1
*
0.8
1.0
1.2
1.4
1.6
1.8
b
u
b
b
le
-
p
o
i
n
t

li
n
e d
e
w
-
p
o
i
n
t

l
i
n
e
gas
2-phase
liquid
azeotrope
Figure 11: Bubble- and dew-point lines for
A
RT
= 1.
Miscibility occurs for all compositions if

mix
G
x
2
1
0 for all x
1
If we use this condition for the model in Eq. 35, we nd

2
x
2
1
[RT (x
1
ln x
1
+ x
2
ln x
2
) + Ax
1
x
2
] =
RT
x
1
x
2
2A 0
A
RT

1
2x
1
x
2
The values of
1
2x
1
x
2
are plotted in Figure 13, together with the conditions on A shown in
Figure 10. We see that the minimum value of
1
2x
1
x
2
occurs at x
1
= 0.5, when
1
2x
1
x
2
= 2. The
conclusion is that azeotropes may occur for completely miscible liquids ifA 2RT. For
such values of A, an azeotrope will occur in the ranges
0 x
1

3
8
and
1
2
< x
1
1
Problem 6.16
The situation is illustrated in Figure 14, showing the partial pressures as given by Henrys
and Raoults laws. Henrys law,
P
i
= H
i, j
x
i
applies in the limit of zero solute concentration, x
i
0, and Raoults law,
P
i
= P
s
i
x
i
applies in the limit of pure solvent, x
i
1. The problem here is to determine the vapour
pressure at x
1
= 0.5 and the corresponding vapour composition,
y
1
=
P
1
P
30
x
1
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

m
i
x
G
/
R
T
-0.8
-0.6
-0.4
-0.2
0.0
0.2

mix
G
ideal
/RT+3x
1
x
2

mix
G
ideal
/RT+2x
1
x
2

mix
G
ideal
/RT+x
1
x
2

mix
G
ideal
/RT
Figure 12: Change in Gibbs energy of mixing. Complete miscibility occurs if

2

mix
G
x
2
1
0.
Between the limits of dilute solution and pure solvent, we have to use a model to estimate
the vapour pressure. Assuming ideal gas phase, the partial pressure is given by
P
i
= P
s
i

i
x
i
(36)
We have four given pieces of information, P
s
1
, P
s
2
, H
1,2
, and H
1,2
. Because
1
and
2
are re-
lated by the Gibbs-Duhem equation, the model for g
E
(and
i
) may contain two parameters
to be determined. We can also understand that at least two parameters are required because
the properties of the two components are not symmetric, as seen for instance by the ratios
H
1,2
P
s
1
and
H
2,1
P
s
2
. The van Laar model satises this, and we set
ln
1
=
A

_
1 +
A

x
1
B

x
2
_
2
ln
2
=
B

_
1 +
B

x
2
A

x
1
_
2
Using this model with Eq. 36 in the limit x
i
0 gives
ln
1
= A

= ln
_
H
1,2
P
s
1
_
= ln
_
2 bar
1.07 bar
_
= 0.6255
ln
2
= B

= ln
_
H
2,1
P
s
2
_
= ln
_
1.60 bar
1.33 bar
_
= 0.1848
For an equimolar mixture, we nd
ln
1
=
A

_
1 +
A

_
2
=
0.6255
_
1 +
0.6255
0.1848
_
2
= 0.0325
1
= 1.0330
ln
2
=
B

_
1 +
B

_
2
=
0.1848
_
1 +
0.1848
0.6255
_
2
= 0.1101
2
= 1.1164
31
x
1
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
A
/
R
T
-20
-10
0
10
20
Figure 13: Allowable values of A/RT (solid line) and upper limit for complete miscibility
in the liquid phase (dashed line).
This gives
P
1
= 1.07 bar 1.0330 0.5 = 0.5527 bar
P
2
= 1.33 bar 1.1164 0.5 = 0.7424 bar
P = P
1
+ P
2
= 1.2951 bar
The vapour (dew-point) composition is
y
1
=
0.5527 bar
1.2951 bar
= 0.4268
Data generated with this model are shown in Figure 15. Alternatively, we can use the
three-sux Margules equation,
ln
1
=
1
RT
_
(A + 3B) x
2
2
4Bx
3
2
_
ln
2
=
1
RT
_
(A 3B) x
2
1
+ 4Bx
3
1
_
Using this model with Eq. 36 in the limit x
i
0 gives
ln
1
=
A B
RT
= ln
_
H
1,2
P
s
1
_
= ln
_
2 bar
1.07 bar
_
= 0.6255
ln
2
=
A + B
RT
= ln
_
H
2,1
P
s
2
_
= ln
_
1.60 bar
1.33 bar
_
= 0.1848
A
RT
=
0.6255 + 0.1848
2
= 0.4052
B
RT
=
0.1848 0.6255
2
= 0.2204
32
x
1
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
P
,

b
a
r
0.0
0.5
1.0
1.5
2.0
P
1
P
2
H
e
n
r
y
's

l
a
w
R
a
o
u
lt's
la
w
2.00
1.07
1.60
1.33
H
e
n
r
y
's

la
w
R
a
o
u
lt's
la
w
Figure 14: The given information.
x
1
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
P
,

b
a
r
0.0
0.5
1.0
1.5
2.0
P
1 P
2
P
Bubble-point line
Dew-point line
2.00
1.07
1.60
1.33
Figure 15: Partial pressures and total vapour pressure computed from the van Laar model.
For an equimolar mixture, we nd
ln
1
= (0.4052 3 0.2204) 0.5
2
+ 4 0.2204 0.5
3
= 0.0462
1
= 1.0473
ln
2
= (0.4052 + 3 0.2204) 0.5
2
4 0.2204 0.5
3
= 0.1564
1
= 1.1693
This gives
P
1
= 1.07 bar 1.0473 0.5 = 0.5603 bar
P
2
= 1.33 bar 1.1693 0.5 = 0.7776 bar
P = P
1
+ P
2
= 1.3379 bar
Tha vapour (dew-point) composition is
y
1
=
0.5603 bar
1.3379 bar
= 0.4188
Data generated with this model are shown in Figure 16.
33
x
1
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
P
,

b
a
r
0.0
0.5
1.0
1.5
2.0
P
1 P
2
P
Bubble-point line
Dew-point line
2.00
1.07
1.60
1.33
Figure 16: Partial pressures and total vapour pressure computed from the three-sux Mar-
gules equation.
34
Chapter 7
Problem 7.1
The situation is shown in the P x diagram, Figure 1 for the mixture A-CS
2
. From the
x
A
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
P
,

k
P
a
0
2
4
6
8
10
12
14
P
A
P
CS
2
P
Figure 17: Plot of the partial pressures and total pressure for the mixture A-CS
2
. The curves
are based on the van Laar model.
given information, we can determine the activity coecient at x
1
= 0.5 and T = 283 K:
P
A
= P
s
A

A
x
A

A
=
P
A
P
s
A
x
A
=
8 kPa
13.3 kPa 0.5
= 1.2030
ln
A
= 0.1848
The given solubility parameters suggest that we use regular solution theory. The relation to
the van Laar model,
ln
1
=
A

_
1 +
A

x
1
B

x
2
_
2
ln
2
=
B

_
1 +
B

x
2
A

x
1
_
2
35
is
A

=
v
1
RT
(
1

2
)
2
B

=
v
2
RT
(
1

2
)
2
where v
i
and
i
are the molar volume and the solubility parameter, respectively, of compo-
nent i. With the given information, we nd that
v
A
=
V
n
A
=
VM
A
m
=
M
A

A
=
160 g mol
-1
0.8 g cm
-3
= 200 cm
3
mol
-1
A

=
v
A
v
CS
2
=
200 cm
3
mol
-1
61 cm
3
mol
-1
A

= ln
A
_
1 +
A

_
2
= 0.1848
_
1 +
200
61
_
2
= 3.3832
Assuming that v
1
(
1

2
)
2
is independent of the temperature, we nd
v
A
_

A

CS
2
_
2
@(T = 298 K) = v
A
_

A

CS
2
_
2
@(T = 283 K) = A

RT

A
=
CS
2

_
A

RT
v
A
= 20.5 (J cm
-3
)
1
2

_
3.3832 8.3145 J mol
-1
K
-1
283 K
200 cm
3
mol
-1
= 20.5 (J cm
-3
)
1
2
6.3 (J cm
-3
)
1
2
We will return to the question of which sign to choose, but for the time being assume that
the correct sign is -. This gives the complete set of properties shown in Table 6. For the
Table 6: Solubility parameters.
A CS
2
Toluene
Solubility parameter at 298 K, (J cm
-3
)
1
2
14.2 20.5 18.2
Liquid molar volume at 298 K, cm
3
mol
-1
200 61 107
Saturation pressure at 283 K, kPa 13.3 1.73 25.5
mixture A-T (Toluene), we now nd
A

=
v
A
RT
(
A

T
)
2
=
200 cm
3
mol
-1
8.3145 J mol
-1
K
-1
283 K
(14.2 18.2)
2
J cm
-3
= 1.36
B

=
v
T
RT
(
A

T
)
2
=
107 cm
3
mol
-1
8.3145 J mol
-1
K
-1
283 K
(14.2 18.2)
2
J cm
-3
= 0.7276
36
At x
A
= x
T
= 0.5:
ln
A
=
A

_
1 +
A

x
A
B

x
T
_
2
=
1.36
_
1 +
1.360.5
0.72760.5
_
2
= 0.1652

A
= 1.1796
ln
T
=
B

_
1 +
B

x
T
A

x
A
_
2
=
0.7276
_
1 +
0.72760.5
1.360.5
_
2
= 0.3088

T
= 1.3618
P
A
= P
s
A

A
x
A
= 13.3 kPa 1.1796 0.5 = 7.84 kPa
P
T
= P
s
T

T
x
T
= 25.5 kPa 1.3618 0.5 = 17.36 kPa
P = P
A
+ P
T
= 7.84 kPa + 17.36 kPa = 25.20 kPa
y
A
=
P
A
P
=
7.84 kPa
25.20 kPa
= 0.31
The full phase diagram is shown in Figure 2. An alternative representation of the data is
x
A
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
P
,

k
P
a
0
5
10
15
20
25
30
P
A
P
T
P
B
u
b
b
le
-
p
o
in
t lin
e
D
e
w
-p
o
in
t lin
e
Figure 18: P x diagram for the mixture A-Toluene at 283 K.
shown in Figure 3. The alternative positive sign for
_
A

RT
v
A
would give

A
= 20.5 (J cm
-3
)
1
2
+ 6.3 (J cm
-3
)
1
2
= 26.8 (J cm
-3
)
1
2
This would correspond to a change in molar internal energy on vaporization (Eq. (7-33) in
the textbook) of

vap
u
A
=
2
A
v
A
= 26.8
2
J cm
-3
200 cm
3
mol
-1
= 143.6 kJ mol
-1
The density of 0.8 g cm
3
indicates that A is a hydrocarbon. Typical values for the enthalpy
of vaporization of a hydrocarbon is 30-50 kJ mol
1
. The value corresponding to
A
= 26.8
(J cm
-3
)
1
2
is therefore not acceptable.
37
x
A
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
y
A
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Figure 19: Vapour-liquid equilibria for the mixture A-Toluene at 283 K.
Problem 7.3
We denote n-Hexane by 1 and benzene by 2. Using regular solution theory and the given
data
A

=
v
1
RT
(
1

2
)
2
=
132 cm
3
mol
-1
8.3145 J mol
-1
K
-1
323 K
(14.9 18.8)
2
J cm
-3
= 0.7476
A

=
v
1
v
2
=
132 cm
3
mol
-1
89 cm
3
mol
-1
= 1.4831
B

=
_
A

_
1
= 0.6742
B

=
B

= 0.6742 0.7476 = 0.5041

we nd:
ln
1
=
A

_
1 +
A

x
1
B

x
2
_
2
=
0.7476
_
1 + 1.4831
0.3
0.7
_
2
= 0.2795

1
= 1.3224
ln
2
=
B

_
1 +
B

x
2
A

x
1
_
2
=
0.5041
_
1 + 0.6742
0.7
0.3
_
2
= 0.0761

2
= 1.0791
38
At the given composition, we then nd
P
1
= P
s
1

1
x
1
= 0.533 bar 1.3224 0.3 = 0.2115 bar
P
2
= P
s
2

2
x
2
= 0.380 bar 1.0791 0.7 = 0.2870 bar
P = P
1
+ P
2
= 0.2115 bar + 0.2870 bar = 0.4985 bar
and nally
K
1
=
y
1
x
1
=
P
1
Px
1
=
0.2115 bar
0.4985 bar 0.3
= 1.414
K
2
=
y
2
x
2
=
P
2
Px
2
=
0.2870 bar
0.4985 bar 0.7
= 0.822
39
40
Chapter 10
Problem 10.3
This problem can be solved in several ways.
Method 1
Inspired by the Hildebrand-Scott plots (Figure 10-11 in the textbook), we may estimate the
solubility from a correlation of the type
ln x
H
2
= A
i
+ B (37)
where x
H
2
is the mole fraction (solubility) of H
2
,
i
is the solubility parameter for the
solvent, and A and B are (temperature dependent) constants. To determine A and B , we use
data for CH
4
and CO. Air is a mixture of 78%N
2
, 21%O
2
, and 1%Ar. In terms of solubility
properties, Ar is like O
2
(see Table 7-1 in the textbook), and we take the composition to be
78% N
2
and 22% O
2
. For the mixed solvent (air), we replace
1
in Eq. 37 by

i
where
i
is the volume fraction of component i . The sum includes all components, but we
assume the solubility of H
2
to be so low that its contribution can be neglected. The volume
fraction is dened as

i
=
x
i
v
i
_
j
x
j
v
j
We will need data for the solubility parameter, dened by Eq. (7-33) in the textbook:

i
=
_

vap
u
v
_1
2
i
where
vap
u is the change in internal energy on complete vaporization, i.e. to an ideal gas
state. Data are given for
vap
h, which is related to
vap
u by

vap
u =
vap
h
vap
(Pv)
vap
h RT
Data for the various properties are given in Table 7, all data at 90 K. The values for A and
B in Eq. 37 are determined from Table 8. which gives A = 0.435 (J cm
3
)

1
2
, B = 0.982.
(If we instead use the data from Table 7-1 in the textbook, we nd A = 0.461 (J cm
3
)

1
2
,
41
Table 7: Physical properties of gases.
From given data From Table 7-1
Comp.

vap
h
J mol
1

vap
u
J mol
1
v
i
cm
3
mol
1

i
(J cm
3
)
0.5
v
i
cm
3
mol
1

i
(J cm
3
)
0.5
CH
4
8750 8000 35.6 15.0 35.3 15.1
CO 5530 4780 37.0 11.4 37.1 11.7
N
2
5110 4360 37.5 10.8 38.1 10.8
O
2
6550 5800 27.9 14.4 28.0 14.7
Table 8: Solubility parameters.
Component x
H
2
ln x
H
2

i
/(J cm
3
)
0.5
CH
4
5.4910
4
-7.507 15.0
CO 2.6310
3
-5.941 11.4
B = 0.598.) We shall, however, see below that, due to a numerical coincidence, we shall
not need these numbers. The average solubility parameter for liquid air at 90 K is calculated
from the data in Table 9. which gives

= 11.4 (J cm
3
)
1
2
. (If we instead use the data from
Table 7-1, we nd

= 11.5 (J cm
3
)
1
2
.) We note that this is the same solubility parameter
as for CO, and according to this method, we would expect the solubility in air to be the
same as in CO,
x
H
2
= 2.63 10
3
Using data from Table 7-1 gives
x
H
2
= 2.7 10
3
We might be concerned about the vapour pressure and how well the vapour is represented
by an ideal gas. The normal boiling points for N
2
and O
2
are listed in Table 10. At 90 K, we
must therefore expect the vapour pressure to be above 1 atm (1.013 bar), and the solubility
will be smaller than the value found above. The saturation pressure for each component at
90 K can be found from the Clausius-Clapeyron equation:
P
s
i
(T) = P
s
i
(T
b
) exp
_

vap
h
R
_
1
T

1
T
b
__
Using this, we nd the values listed in Table 4. To compute the vapour pressure of liquid
air at 90 K, we rst determine the activity coecients from the van Laar model (we neglect
Table 9: Solubility parameters for liquid air
Component x
i
v
i
/cm
3
mol
1

i

i
/(J cm
3
)
0.5
N
2
0.78 37.5 0.827 10.8
O
2
0.22 27.9 0.173 14.4
42
Table 10: Normal boiling point.
Component T
b
/K P
s
i
/bar
CH
4
111.5 1.106
CO 83 1.89
N
2
77 3.209
O
2
90 1.013
H
2
in the liquid phase because x
H
2
is low):
ln
N
2
=
A

_
1 +
A

x
N
2
B

x
O
2
_
2
ln
O
2
=
B

_
1 +
B

x
O
2
A

x
N
2
_
2
where
A

=
v
N
2
RT
_

N
2

O
2
_
2
=
37.5 cm
3
mol
-1
8.3145 J mol
-1
K
-1
90 K
(10.8 14.4)
2
J cm
-3
= 0.6495
B

=
v
O
2
RT
_

N
2

O
2
_
2
=
27.9 cm
3
mol
-1
8.3145 J mol
-1
K
-1
90 K
(10.8 14.4)
2
J cm
-3
= 0.4832
which gives
ln
N
2
=
0.6495
_
1 +
0.64950.78
0.48320.22
_
2
= 0.0195

N
2
= 1.0197
ln
O
2
=
0.4832
_
1 +
0.48320.22
0.64950.78
_
2
= 0.330

O
2
= 1.391
and nally
P
N
2
= P
s
N
2

N
2
x
N
2
= 3.209 bar 1.0197 0.78 = 2.55 bar
P
O
2
= P
s
O
2

O
2
x
O
2
= 1.013 bar 1.391 0.22 = 0.31 bar
P = P
N
2
+ P
O
2
+ P
H
2
= 2.55 bar + 0.31 bar + 1.00 bar = 3.86 bar
We conclude that the pressure is relatively low, and that the gas phase is ideal.
43
Method 2
Using the two-sux Margules expansion for the excess Gibbs energy, see Chapter 10-6 in
the textbook leading to Eq. (10-54):
ln H
H
2
,air
= x
N
2
ln H
H
2
,N
2
+ x
O
2
ln H
H
2
,O
2
a
N
2
,O
2
x
N
2
x
O
2
where a
N
2
,O
2
is estimated by (see footnote on p. 615 in the textbook)
a
N
2
,O
2

_

N
2

O
2
_
2
_
v
N
2
+ v
O
2
_
2RT
=
(10.8 14.4)
2
J cm
-3
(37.5 + 27.9) cm
3
mol
-1
2 8.3145 J mol
-1
K
-1
90 K
= 0.566
Data for Henrys constant H
H
2
,N
2
are found in Table 10-4 in the textbook:
T/K H
H
2
,N
2
/bar
79 456
95 345
Interpolated to 90 K; H
H
2
,N
2
= 380 bar; ln H
H
2
,N
2
= 5.940. We have no data for H
H
2
,O
2
, and
estimate it from the correlation found under Method 1:
ln x
H
2
= ln
_
P
H
2
H
H
2
,O
2
_
= A
O
2
+ B
ln H
H
2
,O
2
= ln P
H
2
A
O
2
B = 0 + 0.435 14.4 + 0.982 = 7.246
This gives:
ln H
H
2
,air
= 0.78 5.940 + 0.22 7.246 0.566 0.22 0.78 = 6.130
H
H
2
,air
= 460 bar
x
H
2
=
1 bar
460 bar
= 2.2 10
3
Problem 10.6
We are supposed to use the Orentlicher correlation,
ln
f
2
x
2
= ln H
(P
s
1
)
2,1
+
A
RT
_
x
2
1
1
_
+
v

2
_
P P
s
1
_
RT
(6.1)
with the following data for H
2
in N
2
around 77 K taken from Table 10-4 in the textbook:
T/K H
(P
s
1
)
2,1
/bar v

2
/cm
3
mol
1
A/J mol
1
68 547 30.4 704
79 456 31.5 704
44
The normal boiling point of N
2
is 77 K, which means that P
s
1
= 1 atm = 1.013 bar. By
linear interpolation, we nd for T = 77 K: H
(P
s
1
)
2,1
= 473 bar and v

2
= 31.3 cm
3
mol
1
. We
then nd from Eq. (10.1):
ln
f
2
x
2
= ln 473 +
704 J mol
-1
8.3145 J mol
-1
K
-1
77 K
_
(1 x
2
)
2
1
_
ref Eq.6.2 (38)
+
31.3 cm
3
mol
1
(100 1.013) bar
83.1451 bar cm
3
mol
-1
K
-1
77 K
= 6.6430 + 1.0996
_
x
2
2
2x
2
_
ln x
2
= ln f
2
6.6430 1.0996
_
x
2
2
2x
2
_
The fugacity of hydrogen in the gas phase is
f
2
=
2
P
2
= 0.88 (100 1.013) bar = 87.1 bar
ln f
2
= 4.4672
We now set up an iterative solution method, starting with x
2
= 0:
Guessed x
2
ln x
2
from Eq. (6.2) New value of x
2
0 -2.1758 0.114
0.114 -1.9404 0.144
0.144 -1.8826 0.152
0.152 -1.8666 0.155
0.155 -1.8620 0.155
Conclusion: The solubility is x
2
= 0.16.
Problem 10.9
Question a
We consider the expressions for the fugacities of nitrogen (component 2) in n-butane (com-
ponent 1) in gas and liquid:
f
g
2
= H
2,1
x
2
f
l
2
=
l
2
x
2
P
in the limit of x
2
0. At equilibrium, the two fugacities are equal, i.e.
H
2,1
=
l
2
P (39)
The fugacity coecient in the liquid phase must be determined from the Peng-Robinson
equation of state. The Peng-Robinson equation of state reads (Eq. (12-59) in the textbook):
P =
RT
v b

a(T)
v(v + b) + b(v b)
(40)
45
where the coecients for each of the components are:
a(T) = a(T
c
)(T)
a(T
c
) = 0.45724
(RT
c
)
2
P
c
(T) =
_
1 +
_
1
_
T/T
c
__
2
(41)
= 0.37464 + 1.54226 0.26992
2
b = 0.07780
RT
c
P
c
The following physical properties are found in Reid et al. (the last ve columns are com-
puted from Eq. 41:
Component T
c
/K P
c
/bar
n-butane 425.2 38.0 0.199 0.6709
N
2
126.2 33.9 0.039 0.4344
Component (T = 250K)
a(T
c
)
10
6
cm
6
bar mol
2
a(T=250K)
10
6
cm
6
bar mol
2
b
cm
3
mol
1
n-butane 1.3374 15.039 20.113 72.38
N
2
0.6773 1.485 1.006 24.08
The mixing rules are:
a =

j
x
i
x
j

a
i
a
j
(1 k
i j
)
b =

i
x
i
b
i
where k
11
= k
22
= 0 and k
12
= 0.0867. The expression for the fugacity coecient is:
ln
k
=
b
k
b
_
Pv
RT
1
_
ln
P(v b)
RT

a
2

2bRT
_
2
_
i
x
i
a
ik
a

b
k
b
_
ln
v + (1 +

2)b
v + (1

2)b
In the limit of x
2
0, we get the following relation:
H
2,1
= lim
x
2
0
_
f
2
x
2
_
= lim
x
2
0
(
2
P)
The following results are found from Eq. 42:
a = a
1
b = b
1
P = P
s
1
= 0.392 bar
v = v
s
1
= 93.035 cm
3
mol
-1
ln
2
=
b
2
b
1
_
P
s
1
v
s
1
RT
1
_
ln
P
s
1
(v
s
1
b
1
)
RT

a
1
2

2b
1
RT
_
2a
12
a
1

b
2
b
1
_
ln
v
s
1
+ (1 +

2)b
1
v
s
1
+ (1

2)b
1
46
The value of the fugacity coecient is:
ln
l
2
=
24.08 cm
3
mol
-1
72.38 cm
3
mol
-1
_
0.392 bar 93.035 cm
3
mol
-1
83.145 bar cm
3
mol
-1
K
-1
250 K
1
_
ln
0.392 bar (93.035 72.38) cm
3
mol
-1
83.145 bar cm
3
mol
-1
K
-1
250 K

20.113 10
6
cm
6
bar mol
-2
2

2 72.38 cm
3
mol
-1
83.145 bar cm
3
mol
-1
K
-1
250 K

_
2

1.006 20.113 10
6
(1 0.0867) cm
6
bar mol
-2
20.113 10
6
cm
6
bar mol
-2

24.08 cm
3
mol
-1
72.38 cm
3
mol
-1
_

_
ln
_
93.035 + (1 +

2)72.38
_
cm
3
mol
-1
_
93.035 + (1

2)72.38
_
cm
3
mol
-1
= 7.0002

l
2
= exp(7.0002) = 1097
From Eq. 39 we then nd H
2,1
= 1097 0.392 bar = 430 bar
Question b
The partial molar volume is dened as
v
2
=
_
V
n
2
_
P,T,n
1
Since the equation of state is not explicit in v, It is more convenient to consider how the
pressure varies when we vary T, P, n
1
, and n
2
:
dP =
_
P
T
_
V,n
1
,n
2
dT +
_
P
V
_
T,n
1
,n
2
dV +
_
P
n
1
_
V,T,n
2
dn
1
+
_
P
n
2
_
V,T,n
1
dn
2
At constant P, T, and n
1
, we have
dP =
_
P
V
_
T,n
1
,n
2
dV +
_
P
n
2
_
V,T,n
1
dn
2
= 0
so under these conditions,
v
2
=
(P/n
2
)
V,T,n
1
(P/V)
T,n
1
,n
2
47
We can now evluate the dierentials of P in the limit x
2
0. From Eq. 40:
P =
nRT
V nb

n
2
a(T)
V
2
+ 2Vnb n
2
b
2
P
n
2
=
(V nb) n

RT nRT(nb

b)
(V nb)
2

_
V
2
+ 2Vnb n
2
b
2
_
(2nn

a + n
2
a

) n
2
a[2V(n

b + nb

) (2nn

b
2
+ 2n
2
bb

)]
_
V
2
+ 2Vnb n
2
b
2
_
2
=
RT(Vn

+ n
2
b

)
(V nb)
2

V
2
n(2n

a + na

) + 2Vn
2
(bn

a + nba

nb

a) + bn
4
(ba

+ 2b

a)
_
V
2
+ 2Vnb n
2
b
2
_
2
=
RT(vn

+ nb

)
n (v b)
2

v
2
(2n

a + na

) + 2v(bn

a + nba

nb

a) + b(bna

+ 2nb

a)
n
_
v
2
+ 2vb b
2
_
2
P
V
=
nRT
(V nb)
2

_
V
2
+ 2Vnb n
2
b
2
_
0 n
2
a(2V + 2nb)
_
V
2
+ 2Vnb n
2
b
2
_
2
=
RT
n (v b)
2
+
2a(v + b)
n
_
v
2
+ 2vb b
2
_
2
Here,
n

=
n
n
2
= 1
a

=
a
n
2
=

n
2
_
n
2
1
a
1
+ 2n
1
n
2

a
1
a
2
(1 k
12
) + n
2
2
a
2
(n
1
+ n
2
)
2
_
=
(n
1
+ n
2
)
2
_
2n
1

a
1
a
2
(1 k
12
) + 2n
2
a
2
_

_
n
2
1
a
1
+ 2n
1
n
2

a
1
a
2
(1 k
12
) + n
2
2
a
2
_
2 (n
1
+ n
2
)
(n
1
+ n
2
)
4
=
1
n
__
2x
1

a
1
a
2
(1 k
12
) + 2x
2
a
2
_
2
_
x
2
1
a
1
+ 2x
1
x
2

a
1
a
2
(1 k
12
) + x
2
2
a
2
__
na

= 2
_
x
1

a
1
a
2
(1 k
12
)(1 2x
2
) x
2
1
a
1
+ x
2
a
2
(1 x
2
)
_
= 2x
1
_
x
1
a
1
+

a
1
a
2
(1 k
12
)(x
1
x
2
) + x
2
a
2
_
b

=
b
n
2
=

n
2
_
n
1
b
1
+ n
2
b
2
n
1
+ n
2
_
=
(n
1
+ n
2
) b
2
(n
1
b
1
+ n
2
b
2
)
(n
1
+ n
2
)
2
=
1
n
(b
2
x
1
b
1
x
2
b
2
)
nb

= x
1
(b
2
b
1
)
In the limit x
2
0, the expressions reduce to
na

= 2
_
a
1
+

a
1
a
2
(1 k
12
)
_
nb

= b
2
b
1
48
P
n
2
=
RT(v
1
+ b
2
b
1
)
n (v
1
b
1
)
2

v
2
1
_
2a
1
+ 2
_
a
1
+

a
1
a
2
(1 k
12
)
__
n
_
v
2
1
+ 2v
1
b
1
b
2
1
_
2

2v
1
_
b
1
a
1
+ 2b
1
_
a
1
+

a
1
a
2
(1 k
12
)
_
a
1
(b
2
b
1
)
_
n
_
v
2
1
+ 2v
1
b
1
b
2
1
_
2

b
1
_
b
1
2
_
a
1
+

a
1
a
2
(1 k
12
)
_
+ 2a
1
(b
2
b
1
)
_
n
_
v
2
1
+ 2v
1
b
1
b
2
1
_
2
=
RT(v
1
+ b
2
b
1
)
n (v
1
b
1
)
2
2
v
2
1

a
1
a
2
(1 k
12
) + v
1
_
2b
1

a
1
a
2
(1 k
12
) a
1
b
2
_
+ b
1
_
b
1

a
1
a
2
(1 k
12
) + a
1
b
2
_
n
_
v
2
1
+ 2v
1
b
1
b
2
1
_
2
=
RT(v
1
+ b
2
b
1
)
n (v
1
b
1
)
2
2

a
1
a
2
(1 k
12
)
n
_
v
2
1
+ 2v
1
b
1
b
2
1
_ + 2
a
1
b
2
(v
1
b
1
)
n
_
v
2
1
+ 2v
1
b
1
b
2
1
_
2
P
V
=
RT
n (v
1
b
1
)
2
+
2a
1
(v
1
+ b
1
)
n
_
v
2
1
+ 2v
1
b
1
b
2
1
_
2
Evaluated with the given data:
P
n
2
=
83.145 bar cm
3
mol
-1
K
-1
250 K (93.035 + 24.08 72.38) cm
3
mol
-1
n (93.035 72.38)
2
cm
6
mol
-2

20.113 1.006 10
6
(1 0.0867) cm
6
bar mol
-2
n
_
93.035
2
+ 2 93.035 72.38 72.38
2
_
cm
6
mol
-2
+
2 20.113 10
6
cm
6
bar mol
-2
24.08 cm
3
mol
-1
(93.035 72.38) cm
3
mol
-1
n
_
93.035
2
+ 2 93.035 72.38 72.38
2
_
2
cm
12
mol
-4
=
1763 bar
n
P
V
=
83.145 bar cm
3
mol
-1
K
-1
250 K
n (93.035 72.38)
2
cm
6
mol
-2
+
2 20.113 10
6
cm
6
bar mol
-2
(93.035 + 72.38) cm
3
mol
-1
n
_
93.035
2
+ 2 93.035 72.38 72.38
2
_
2
cm
12
mol
-4
=
25.38 bar cm
-3
mol
n
The partial molar volume is then
v

2
=
1763 bar/n
25.38 bar cm
-3
mol/n
= 69.5 cm
3
mol
-1
49
Question c (method I)
The parameter in the two-sux Margules equation is dened by
ln
2
=
A
RT
x
2
1
The activity coecient
2
refers to pure component 2 as reference state (
2
= 1when
x
2
= 1). In this problem, the properties are given at x
2
= 0, and we must change the refer-
ence state for component 2. Alternatively, we might think that we could instead consider
component 1 and use
ln
1
=
A
RT
x
2
2

A
RT
=
ln
1
x
2
2
= lim
x
2
0
ln
1
x
2
2
This wil, however, also raise a problem because ln
1
0 in this limit. The change of
reference state is made with use of the Gibbs-Duhem equation at constant P and T:
x
1
d ln
1
+ x
2
d ln
2
= 0
d ln
2
=
x
1
x
2
d ln
1
=
A
RT
x
1
x
2
2x
2
dx
2
=
A
RT
2(1 x
2
)dx
2
We may note that if we use pure component 2 as reference state, we nd
ln
2
=
x
2
_
x
2
=1
d ln
2
=
A
RT
2
x
2
_
x
2
=1
(1 x
2
)dx
2
=
A
RT
2
_
(x
2
1)
1
2
(x
2
2
1)
_
=
A
RT
x
2
1
We now use pure componnet 1 as reference state:
ln

2
=
x
2
_
x
2
=0
d ln
2
=
A
RT
2
x
2
_
x
2
=0
(1 x
2
)dx
2
=
A
RT
2
_
x
2

1
2
x
2
2
_
=
A
RT
(2x
2
x
2
2
)
In this limit we may therefore write
f
2
= f
2
(x
2
= 0)a
2
= H
2,1

2
x
2

f
2
x
2
= H
2,1

2
ln
f
2
x
2
= ln H
2,1
+ ln

2
= ln H
2,1

2A
RT
x
2
+
A
RT
x
2
2
(42)
If we consider ln
f
2
x
2
as function of x
2
and expand around x
2
= 0 at constant P and T, we get
ln
f
2
x
2
=
_
ln
H
2,1
x
2
x
2
_
x
2
=0
+
_

_
ln
f
2
x
2
x
2
_

_
P,T,x
2
=0
x
2
+ ...
= ln H
2,1
+
_
ln H
2,1
x
2
_
P,T,x
2
=0
x
2
+ ... ref Eq.9.5 (43)
50
Comparing Eq. 42 with and using Eq. 39, we nd

2A
RT
=
_
ln H
2,1
x
2
_
P,T,x
2
=0
=
_

x
2
(ln
2
+ ln P)
_
P,T,x
2
=0
=
_
ln
2
x
2
_
x
2
=0
Note that the dierentiation with respect to x
2
reprsents the eect of variation in composi-
tion only, and that P and Tare held constant (P = P
s
1
). We must consider both x
1
and x
2
as
variables. If P and T are constants while the composition varies, the volume has to vary.
The molar volume of the mixture may be expressed as
v = v

1
x
1
+ v

2
x
2
= v

1
+ ( v

2
v

1
)x
2
Question c (method II)
An alternative expression for the fugacity of N
2
is
f
2
=

2
x
2
f
0
2
Since the solubility of N
2
in n-butane is small, pure solvent is chosen as reference state
(indicated with the asterisk),

2
= 1. The parameter in the two-sux Margules equation is
dened by
ln

2
=
A
RT
(x
2
1
1) =
A
RT
(1 + x
1
)x
2
Combining Eqs. 39 and gives
f
2
x
2
=

2
f
0
2
=
2
P
ln
f
2
x
2
= ln

2
+ ln f
0
2
+ ln
2
+ ln P
Expanding ln
f
2
x
2
in powers of x
2
and equating the coecients of the linear terms, gives

2A
RT
=
_
ln
2
x
2
_
P=P
s
1
,x
2
=0
The expression for ln
2
is
ln
2
=
b
k
b
_
Pv
RT
1
_
ln
P(v b)
RT

a
2

2bRT
_

_
2
_
i
x
i
a
ik
a

b
k
b
ln
v + (1 +

2)b
v
+ (1

2)b
_

_
This depends on x
2
in a complex way. It is assumed in Eq. that P and T are constant (the
temperature is held constant and the pressure variation gives rise to the term
v

2
RT
(P P
s
1
)).
Under these conditions, v has to vary when x
2
varies. Using the chain rule, we get
d ln
2
dx
2
=
ln
2
x
2
+
ln
2
x
1
dx
1
dx
2
+
ln
2
v
dv
dx
2
It is understood here that all dierentials are at constant P and T so that
f
2
=

2
x
2
H
2,1
=
2
x
2
P
51
or

2
=
2
P
H
2,1
ln

2
= ln(
2
P) lnH
2,1
For small values of x
2
we may expand
f
2
= f
2
(x
2
= 0)a
2
= H
(P
s
1
)
2,1

2
x
2

f
2
x
2
= H
(P
s
1
)
2,1

2
ln
f
2
x
2
= ln H
(P
s
1
)
2,1
+ ln

2
= ln H
(P
s
1
)
2,1

2A
RT
x
2
+
A
RT
x
2
2
(9.4)
If we consider ln
f
2
x
2
as function of x
2
and expand around x
2
= 0 at constant P and T, we get
ln
f
2
x
2
=
_

_
ln
H
(P
s
1
)
2,1
x
2
x
2
_

_
P,T,x
2
=0
+
_

_
ln
f
2
x
2
x
2
_

_
P,T,x
2
=0
x
2
+ ...
= ln H
(P
s
1
)
2,1
+
_

_
ln H
(P
s
1
)
2,1
x
2
_

_
P,T,x
2
=0
x
2
+ ... (9.5)
Comparing Eq. 42 with and using Eq. 39, we nd

2A
RT
=
_

_
ln H
(P
s
1
)
2,1
x
2
_

_
P,T,x
2
=0
=
_

x
2
(ln
2
+ ln P)
_
P,T,x
2
=0
=
_
ln
2
x
2
_
x
2
=0
Note that the dierentiation with respect to x
2
represents the eect of variation in compo-
sition only, and that P and Tare held constant (P = P
s
1
). We must consider both x
1
and x
2
as variables. If P and T are constants while the composition varies, the volume has to vary.
The molar volume of the mixture may be expressed as
v = v

1
x
1
+ v

2
x
2
= v

1
+ ( v

2
v

1
)x
2
52
Chapter 11
Problem 11.1
We consider a solvent (component 1) with a solute (component 2). The change in chemical
potential of component 1 as a result of changing the composition and temperature of the
liquid mixture is
d
1
(l) = s
1
(l)dT + RTd ln x
1
Suppose the liquid mixture is in equilibrium with a solid, which is assumed to be pure
solvent. The corresponding change in chemical potential for the solid is
d
1
(s) = s
1
(s)dT
If equilibrium is established after the change, the two changes in chemical potential must
be equal:
s
1
(l)dT + RTd ln x
1
= s
1
(s)dT
or
RTd ln x
1
= [s
1
(l) s
1
(s)] dT =
fus
s
1
dT =

fus
h
1
T
dT (44)
Equation 44 is the basic equation for freezing-point depression. Integration from pure
solvent to an actual mixture composition of x
1
gives
[ln x
1
]
x
1
1
=

fus
h
1
R
_
1
T
_
T
T

ln x
1
=

fus
h
1
R
_
1
T

1
T

_
where T

is the melting point of pure solvent. This equation can be solved for T:
1
T
=
1
T

fus
h
1
ln x
1
Since the mixture is rich in benzene, and the melting points of the two components are not
very dierent, we may assume that benzene freezes out rst, and consider it as the solvent
(component 1):
1
T
=
1
278.7 K

8.3145 J mol
-1
K
-1
9843 J mol
-1
ln 0.95 = 0.003631
T = 275.4 K
The phase diagram for the system is shown in Figure 20.
53
x
1
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
T
,

K
260
280
300
320
340
360
Figure 20: Liquidus curve for the naphtalene-benzene system. Benzene is component 1.
Problem 11.6
Also in this case we consider a solvent (component 1) and a solute (component 2). Since the
necessary information for computing the activity coecients is available, we may assume
a nonideal mixture in this case. The expression for T is, by analogy to problem 11.1:
1
T
=
1
T

fus
h
1
ln a
1
=
1
T

fus
h
1
(ln
1
+ ln x
1
)
In this case, it is not clear which of the components will freeze out rst at the given compo-
sition. Even if there is much less benzene than n-heptane in the mixture, the freezing point
of benzene is so much higer than that of n-heptane that it might still freeze out rst. To be
sure, we can construct the phase diagram like in Problem 11.1, except that here, we use the
van Laar model for the activity coecients:
ln
1
=
A

_
1 +
A

x
1
B

x
2
_
2
ln
2
=
B

_
1 +
B

x
2
A

x
1
_
2
A

=
v
1
RT
(
1

2
)
2
B

= A

v
2
v
1
A

=
v
1
v
2
The phase diagram for this system is shown in Figure 21. We see from the gure that
x
1
= 0.1 is at the benzene-rich side of the eutectic point. We therefore consider benzene as
54
x
1
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
T
,

K
160
180
200
220
240
260
280
300
Figure 21: Liquidus curve for the n-heptane-benzene system. Benzene is component 1.
the solvent (component 1) and nd:
A

=
89 cm
3
mol
-1
8.3145 J mol
-1
K
-1
T
(18.8 15.1)
2
J cm
-3
=
146.54 K
T
B

= A

148 cm
3
mol
-1
89 cm
3
mol
-1
=
243.69 K
T
A

=
89 cm
3
mol
-1
148 cm
3
mol
-1
= 0.6014
ln
1
=
A

_
1 +
A

x
1
B

x
2
_
2
=
146.54 K
T
_
1 + 0.6014
0.1
0.9
_
2
=
128.76 K
T
ln
2
=
B

_
1 +
B

x
2
A

x
1
_
2
=
243.69 K
T
_
1 + 1.6629
0.9
0.1
_
2
=
0.9559 K
T
This gives the following expression for the freezing temperature:
1
T
=
1
278.7 K

8.3145 J mol
-1
K
-1
9843 J mol
-1
_
128.76 K
T
+ ln 0.1
_
_
1 +
8.3145 128.76
9843
_
1
T
=
1
278.7 K

8.3145
9843 K
ln 0.1
T =
1 +
8.3145128.76
9843
1
278.7 K

8.3145
9843 K
ln 0.1
= 200.39 K
Problem 11.9
The condition for equilibrium is
f
2
(g) = f
2
(l)
that is, the fugacity of the CO
2
(component 2) is the same in gas and liquid phases. At
194.3 K and x
2
= 0.05, the solution is undersaturated with respect to CO
2
. If the mole
55
fraction x
2
were equal to 0.25, the fugacity of the liquid would have been equal to that of
the solid, i.e.
f
2
(g) = f
2
(l) = f
2
(s) (45)
and the saturation pressure would in that case have been P
s
2
= 0.99 bar. In the actual case
with x
2
= 0.05, the fugacity must be lower than this, the vapour pressure must be lower
than 0.99 bar. We may therefore safely assume that the gas is ideal, and consequently
P
2
= f
2
(g) = f
2
(l) (46)
The fugacity in the liquid phase is the activity times the fugacity of a standard state,
f
2
(l) = a
2
f
L
2
=
2
x
2
f
L
2
(47)
where f
L
2
is the fugacity of (the hypothetical state) pure liquid CO
2
at T = 194.3 K. This
implies that the standard state corresponding to the activity coecient
2
is pure liquid
CO
2
. In order to use the information provided by Eq. 45, it is convenient, however, to use
pure solid CO
2
at T = 194.3 K as the standard state. This gives
f
2
(l) =
2
x
2
f
L
2
=
2
x
2
f
S
2
f
L
2
f
S
2
= f
2
(s) = f
S
2
= P
s
2
where f
S
2
is the fugacity of (pure) solid CO
2
at T = 194.3 K. Combining Eqs. 4547 gives
P
2
=
2
x
2
f
S
2
f
L
2
f
S
2
for x
2
= 0.05
P
s
2
=
2
x
2
P
s
2
f
L
2
f
S
2
for x
2
= 0.25
We rst determine the activity coecient from the data at x
2
= 0.25:

2
(x
2
= 0.25) =
1
x
2
f
S
2
f
L
2
=
0.56
0.25
= 2.24
The activity coecient at x
2
= 0.05 must be estimated from this value, which means that
we can use a model with at most one parameter. One such model is the two-sux Margules
equation:
ln
2
=
A
RT
x
2
1

A
RT
=
ln
2
x
2
1
=
ln 2.24
0.75
2
= 1.4337
Hence,
ln
2
(x
2
= 0.05) =
A
RT
0.95
2
= 1.4337 0.95
2
= 1.2939

2
(x
2
= 0.05) = 3.6471
The partial pressure of CO
2
at x
2
= 0.05 is therefore
P
2
= 3.6471 0.05 0.99 bar
1
0.56
= 0.322 bar
56
Chapter 12
Problem 12.3
The thermodynamic condition for equilibrium is

A
=

A
(48)
where
A
is the chemical potential of the alcohol. Prime and double prime refer to the
hexane phase and DMSO phase, respectively. The chemical potential in each phase is

A
=
o
A
+ RT ln x
A
+ RT ln
A
(49)
where
o
A
is the chemical potential in a reference state, x
A
is the mole fraction of the alcohol,
and
A
is the activity coecient of the alcohol. We note that the excess Gibbs energy is of
the form
g
E
= Ax
A
x
B
where A is a constant and x
B
is the mole fraction of the solvent (hexane or DMSO). This
leads to the following form for the activity coecient:
RT ln
A
= Ax
2
B
(50)
Combining Eqs. 4850 gives
RT ln x

A
+ A

_
x

B
_
2
= RT ln x

A
+ A

_
x

B
_
2
RT ln
_
x

A
x

A
_
= A

_
1 x

A
_
2
A

_
1 x

A
_
2
(51)
ln K = ln
_

_
lim
x

A
0
x

A
0
_
x

A
x

A
_
_

_
=
A

RT
The problem is now to nd the constants A

and A

at 30

C and 100 bar. For this, we use

the fact that Gibbs energy depends on temperature and pressure as
dG = VdP S dT
For the excess properties, we then nd
dg
E
= v
E
dP s
E
dT (52)
57
This can be used to compute the dierence in excess Gibbs energy when the conditions are
changed from 0

C and 1 bar to 30

C and 100 bar. The last term in Eq. 52 is, however,

not convenient because we do not have data for s
E
available. Instead we use the Gibbs-
Helmholtz equation for the temperature variation:
d(g
E
/T) = h
E
d(1/T)
The eect of the pressure change is (assuming constant excess volumes over the pressure
range in question):
g
E
= v
E
P
The eect of the temperature change is (assuming constant excess enthalpies over the tem-
perature range in question):

_
g
E
T
_
= h
E

_
1
T
_
Inserting the given numbers leads to for the hexane phase and the DMSO phase at the actual
pressure:
g
E
= 2400x

A
x

H
J mol
-1
+ 16x

A
x

H
cm
3
mol
-1
990 N cm
-2
= 2558.4x

A
x

H
J mol
-1
g
E
= 320x

A
x

D
J mol
-1
10x

A
x

D
cm
3
mol
-1
990 N cm
-2
= 221.0x

A
x

D
J mol
-1
Similarly at the actual temperature:
g
E
= 2558.4x

A
x

H
J mol
-1

303 K
273 K
+ 4800x

A
x

H
J mol
-1

_
1
303 K
273 K
_
= 2312.1x

A
x

H
J mol
-1
A

= 2312.1 J mol
-1
g
E
= 221.0x

A
x

D
J mol
-1

303 K
273 K
+ 600x

A
x

D
J mol
-1

_
1
303 K
273 K
_
= 179.4x

A
x

D
J mol
-1
A

= 179.4 J mol
-1
Used in Eq. 51, we then nd:
ln K =
(179.4 2312.1) J mol
-1
8.3145 J mol
-1
K
-1
303 K
= 0.8465
K = 0.429
Problem 12.4
The phase diagram (P T -diagram) is shown in Figure 22. The problem here is to deter-
mine the temperature at which the solid-liquid equilibrium pressure is 200 bar (indicated
with the dashed line in Figure 22. If we consider equilibrium between solid and liquid at a
certain P and T, given by equality in chemical potentails,

l
(P, T) =
s
(P, T)
58
T, K
265 270 275 280 285 290 295 300
P
,

b
a
r
0.004
0.006
0.008
50.000
100.000
150.000
200.000
Figure 22: P T diagram for benzene.
the equilibrium at P + dP and T + dT will be given by

l
(P + dP, T + dT) =
s
(P + dP, T + dT)
The corresponding changes in the chemical potentials must be the same in the two phases,
d
l
=
l
(P + dP, T + dT)
l
(P, T) = d
s
The change in chemical potential is given by
d
l
= v
l
dP s
l
dT
and similarly for the solid phase. This gives the following dierential equation for the
liquidus curve:
_
v
l
v
s
_
dP =
_
s
l
s
s
_
dT (53)
The molar volumes at 278.7 K may be found from the given densities:
v
l
=
M

l
=
78.1 g mol
-1
0.891 g cm
-3
= 87.65 cm
3
mol
-1
v
s
=
M

s
=
78.1 g mol
-1
1.010 g cm
-3
= 77.33 cm
3
mol
-1
v
l
v
s
= (87.65 77.33) cm
3
mol
-1
= 10.32 cm
3
mol
-1
(54)
At equilibrium, the change in entropy on fusion is equal to the change in enthalpy on fusion
divided by the melting temperature. The enthalpy on fusion is not given, but the enthalpies
on vaporization and sublimation may be deducted from the vapour pressure curves by com-
paring the given vapour-pressure equations with the Clausius-Clapeyron equation:
ln P = ln P
o

vap
h
R
_
1
T

1
T
o
_
59
This version of the Clausius-Clapeyron equation assumes that
vap
h is constant over the
temperature range in question, which is consistent with the given vapour-pressure equa-
tions. We nd

vap
h
R
= 1785 K

sub
h
R
= 2310 K
Enthalpy is a state function, and at the triple point we must have

fus
h =
sub
h
vap
h = (23101785) K83.145 bar cm
3
mol
-1
K
-1
= 43651 bar cm
3
mol
-1
(55)
Consistently with the assumption that
sub
h and
vap
h are constant over the temperature
range, we assume that also
fus
h is constant. This gives for the entropy of fusion at a
temperature T:

fus
s =

fus
h
T
=
43651 bar cm
3
mol
-1
T
(56)
The resukts 54 and 56 inserted into Eq. 53 gives:
10.32 cm
3
mol
-1
dP = 43651 bar cm
3
mol
-1
dT
T
P = P
o
+
43651 bar cm
3
mol
-1
10.32 cm
3
mol
-1
ln
T
T
o
= P
o
+ 4230 bar ln
T
T
o
The xed points P
o
and T
o
are given by the normal melting point: P
o
= 1.013 bar and
T
o
= 278.7 K, leading to
P = 1.013 bar + 4230 bar ln
T
278.7 K
At 200 bar, we then nd:
200 bar = 1.013 bar + 4230 bar ln
T
278.7 K
T = 278.7 Kexp
_
(200 1.013) bar
4230 bar
_
= 292.1 K
Problem 12.7
The stability of the mixture with respect to phase separation is expressed by
mix
g (see
Figures 12-14 and 12-15 in the textbook). The Gibbs energy on mixing for a binary mixture
is

mix
g = RT (x
1
ln x
1
+ x
2
ln x
2
) + g
E
(P, T) (57)
At 1 atm and 273 K, the excess Gibbs energy of the mixture is given as
g
E
(1 atm, 273 K) = RT 1.877 x
1
x
2
60
At a pressure P and 273 K, the excess Gibbs energy is
g
E
(P, 273 K) = g
E
(1 atm, 273 K) +
P
_
1 atm
v
E
dP
= RT 1.877 x
1
x
2
+
P
_
1 atm
x
1
x
2
(4.026 0.233 ln P)dP
= 82.0578 atm cm
3
mol
-1
K
-1
1.877 273 K x
1
x
2
+
_
4.026 cm
3
mol
-1
(P 1 atm) 0.233 cm
3
mol
-1
(Pln P P + 1 atm)
_
x
1
x
2
= (42048 4.026 0.233) atm cm
3
mol
-1
x
1
x
2
+ (4.026 + 0.233 0.233 ln P) cm
3
mol
-1
P x
1
x
2
= (42044 atm+ 4.259P 0.233Pln P) x
1
x
2
cm
3
mol
-1
(58)
Eq. 58 in 57 gives at 273 K:

mix
g = 22402 atm cm
3
mol
-1
(x
1
ln x
1
+ x
2
ln x
2
)
+ (42044 atm+ 4.259P 0.233Pln P) x
1
x
2
cm
3
mol
-1
This expression is plotted for two values of P, P = 10 atm and P = 2000 atm, in Figure
23. We observe that the function is symmetric around x
1
= x
2
= 0.5. To nd the minimum
x
1
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

m
i
x
g
,

J

m
o
l
-
1
-1800
-1600
-1400
-1200
-1000
-800
-600
-400
-200
0

mix
g
id

mix
g, P=10 atm

mix
g, P=2000 atm
Figure 23: Gibbs energy of (regular) mixing.
pressure at which the mixture separates, we have to nd the solution to

mix
g
x
2
1
= 0 at x
1
= 0.5
With g
E
(P, 273 K) of the form
g
E
(P, 273 K) = A(P)x
1
x
2
where
A(P) = (42044 atm+ 4.259P 0.233Pln P) cm
3
mol
-1
61
we rst nd

mix
g
x
1
= RT [ln x
1
ln(1 x
1
)] + A(1 2x
1
)
and then

mix
g
x
2
1
=
RT
x
1
(1 x
1
)
2A
Setting this expression equal to 0 at x
1
= 0.5 gives
A =
RT
2 0.5
2
=
82.0578 atm cm
3
mol
-1
K
-1
273 K
2 0.5
2
= 44804 atm cm
3
mol
-1
This corresponds to a pressure given by the equation
(42044 atm+ 4.259P 0.233Pln P) cm
3
mol
-1
= 44804 atm cm
3
mol
-1
which has the solution P = 1045 atm =1059 bar. At P = 1500 atm, the Gibbs energy of
mixing will have two minima (located symmetrically around x
1
= 0.5), given by

mix
g
x
1
= RT [ln x
1
ln(1 x
1
)] + A(P = 1500 atm)(1 2x
1
) = 0
This gives the following solution for x
1
:
A(P) = (42044 atm+ 4.259 1500 atm 0.233 1500atmln 1500)cm
3
mol
-1
= 45877 atm cm
3
mol
-1
which makes
82.0578 atm cm
3
mol
-1
K
-1
273 K[ln x
1
ln(1 x
1
)]
+45877 atm cm
3
mol
-1
(1 2x
1
) = 0
and nally
x

1
= 0.37, x

1
= 0.63
62