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. Bjørn 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: y1 = 0.01 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Iteration 2: y1 = 3.4835 × 10−3 . . . . . . . . . . . . . . . . . . . . . . . . 15
Problem 5.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Problem 5.16 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Problem 5.17 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Iteration 1: y3 = 0 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Iteration 2: y3 = 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 Vn − b = RT , and by using the Maxwell relation ∂2 A/∂T ∂V =
∂2 A/∂V∂T , we find: ! !
∂S ∂P R P
= = V = .
∂V T ∂T V n
−b T
For an isothermal change:
Z ! Z ! !
∂S R V2 − nb P1
∆S = dV = V
dV = nR ln = nR ln .
∂V T n
−b V1 − nb P2
Alternatively, from ∂2G/∂T ∂P = ∂2G/∂P∂T , we find:
! !
∂S ∂V nR
=− =− .
∂P T ∂T P P
This formula integrates to the same expression for ∆S as above. For U we know the
differential dU = T dS − pdV and hence (∂U/∂V)T = T (∂S /∂V)T − P. Using the first of
the Maxwell rules from above we get
! !
∂U ∂P
=T − P = 0.
∂V T ∂T V
Consequently, ∆U = 0. Alternatively, we can write (∂U/∂P)T = T (∂S /∂P)T − P(∂V/∂P)T
which gives:
! ! !
∂U ∂S ∂V
=T −P
∂P T ∂P T ∂P T
! !
∂V ∂V
=T −P
∂T P ∂P T
RT RT
=− +
P P
= 0.
Again we find that ∆U = 0. For the next derivative we shall use H = U + PV and
! ! !
∂H ∂U ∂V
= +V +P
∂P T ∂P T ∂P T
nRT nRT
=0+ + nb − P 2
P P
= nb.

1
For an isothermal change:
Z ! Z
∂H
∆H = dP = nbdP = nb (P2 − P1 ) .
∂P T

The changes in Gibbs energy (G) and Helmholtz energy (A) are found from the definitions
of G and A, and the results above:
!
P1
∆G = ∆H − T ∆S = nb (P2 − P1 ) − nRT ln ,
P2
!
P1
∆A = ∆U − T ∆S = −nRT ln .
P2

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 differentiation and first write entropy as a function
of volume and temperature, differentiate, use some of the Maxwell relations, and then put
the differential of S (V, T ) equal to zero:
! ! !
∂S ∂S ∂P CV
dS = dV + dT = dV + dT = 0
∂V T ∂T V ∂T V T

Thermodynamically, the exhaust temperature does not depend on the gas flow 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 find for one mole of gas:
!
RT a ∂P R
P= − 2 ⇒ =
v−b v ∂T V v − b

Inserted into the expression for dS = 0 this gives the following differential equation be-
tween v and T at constant entropy:
dv cV dT
=−
v−b R T
This is the adiabatic equation of state for a van der Waal gas. Integration at constant cv
gives ! !
v2 − b cV T2
ln = − ln
v1 − b R T1
where T 2 and v2 are unknown. It is given that the final pressure is atmospheric, and by using
the equation of state, we could express v2 by P2 . This is, however, a little cumbersome, but
since the exhaust pressure is low, we try first by approximating the exhaust gas is an ideal
gas. This gives:

R  vig
 
− b 
! !
T2 2 R RT 2
ln = − ln   ≈ − ln
T1 cV v1 − b cV P2 (v1 − b)

2
where we have approximated vig ig
2 − b ≈ v2 = RT 2 /P2 . Rearrangement gives
! ! !
T2 R T1 R RT 1
ln = ln − ln
T1 cV T2 cV P2 (v1 − b)
!
R RT 1
=−   ln
cV 1 + cRV P2 (v1 − b)
!
R RT 1
= − ln
cP P2 (v1 − b)

where we have made use of cigP = cig

V + R. With the given numbers, we find

8.314 J K-1 mol-1 82.06cm3 atm mol-1 K-1 (350+273) K

! !
T2
ln =− ln
(350 + 273) K 33.5J K-1 mol-1 1 atm (600-45) cm3 mol-1
= −1.123
∴ T 2 = 623 exp(−1.123) = 203 K

Checking the ideal-gas assumption:

ig RT 2 82.06 cm3 atm mol-1 K-1 203 K

V2 = = = 16700 cm3 mol-1
P2 1 atm
V2vdw = 16400 cm3 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
V2vdw = 16400 cm3 mol-1 into the equation above:

R  vvdw 8.314 J K-1 mol-1 (16400 − 45) cm3 mol-1

 
− b 
! !
T2 2
ln = − ln   = − ln
T1 cV v1 − b 25.2 J K-1 mol-1 (600-45) cm3 mol-1
= −1.117
∴ T 2 = 623 exp(−1.117) = 204 K

Problem 2.6
The virial expansion of the compression factor is
Pv B C
z= = 1+ + 2 + ···
RT v v
The compression factor for the van der Waal gas is
v  RT a 1 a 1
zvdw = − 2 = b
−
RT v − b v 1 − v RT v
We recognize the first term on the right-hand side as the sum of a geometric series:
!2
1 b b
=1+ + +···
1 − bv v v

3
 1
Ordering the van der Waal compression fcator in increasing powers of v
gives
!2
vdw
 a 1 b
z =1+ b− + + ···
RT v v

and we conclude that

a
B=b− .
RT

Problem 2.7
We start by recovering one result from Problem 2.2:
! ! !
∂U ∂V ∂V
= −T −P .
∂P T ∂T P ∂P T

From the given equation of state, the volume is

Pv BP
z==1+
RT RT
RT  BP  RT b
∴v= 1+ = +a− 2
P RT P T
From this we find:
!
∂V R 2b
= + 3
∂T P P T
!
∂V RT
=− 2
∂P T P
! !
∂U R 2b  RT  2b
= −T + 3 −P − 2 =− 2
∂P T P T P T

Integration at the constant temperature τ then gives:

Zπ !
∂U 2b
∆U(τ) = dP = − π
∂P T =τ τ2
0

4
Chapter 3

Detailed derivation of Eqs. (3-53) and (3-54)

Start with this definition of the chemical potential:
!
∂A
µi =
∂ni V
Applied to Eq. (3-50) the definition leads to
Z∞  !  " !#
 ∂P RT  ∂ X P◦ V
µi =  −  dV − RT n j ln + u◦i − T s◦i (1)
∂ni T,V,n j V  ∂ni j n j RT
V

We note that j = 1 is the only term that survives the differentiation of the sum. This term is
" !# !
∂ P◦ V P◦ V
ni ln = ln −1 (2)
∂ni ni RT ni RT
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
µ◦i = g◦i = u◦i + RT − T s◦i (3)
Eqs. 2 and 3 into 1 gives
Z∞  !  " ! #
 ∂P RT  P◦ V
µi =  −  dV − RT ln − 1 + µ◦i − RT
∂ni T,V,n j V ni RT
V
Z∞  !  !
◦  ∂P RT  P◦ V
µi − µi = 

 −  dV − RT ln
 (4)
∂ni T,V,n j V  ni RT
V

The relation between the chemical potential and fugacity is

!
◦ fi
µi − µi = RT ln ◦ (5)
fi
The fugacity of the standard state is P◦ = 1 bar. The fugacity is further expressed by the
fugacity coefficient as
fi = ϕi Pi = ϕi yi P
fi
ϕi = (6)
yi P

5
Combination of Eqs. 4, 5, and 6 yields

! Z∞  !  !
ϕi yi P  ∂P RT  P ◦ V
RT ln =  −  dV − RT ln
P◦ ∂ni T,V,n j V  ni RT
V
Z∞  !  ! !
 ∂P RT  P◦ V yi P
RT ln ϕi =  −  dV − RT ln − RT ln
∂ni T,V,n j V  ni RT P◦
V
Z∞  ! 
 ∂P RT   PV 
=  ∂n −  dV − RT ln
i T,V,n j V  nRT
V
Z∞  ! 
 ∂P RT 
=  −  dV − RT ln z (3-53)
∂ni T,V,n j V 
V

For a pure component, the chemical potential is

!
G ◦ fi
µi = = µi + RT ln ◦
ni fi
! !
◦ fi P
= µi + RT ln + RT ln ◦
P fi
! !
fi P
RT ln = µi − µ◦i − RT ln ◦
P pure i fi
!
G G◦ P
= − − RT ln (7)
ni ni P◦

The Gibbs energy is taken from Eq. (3-51) in the book:

Z∞ ! !
G P RT P◦ V PV
= − dV − RT ln + + u◦i − T s◦i (8)
ni ni V ni RT ni
V

Note that
G◦
= h◦i − T s◦i = u◦i + RT − T s◦i (9)
ni

and
PV
= RT z (10)
ni

6
Eqs. 8, 9, and 10, inserted into 7, combine to:
! !
fi G G◦ P
RT ln = − − RT ln
P pure i ni ni P◦
Z∞ ! !
P RT P◦ V PV
= − dV − RT ln + + u◦i − T s◦i
ni V ni RT ni
V
!
◦ ◦
P
− ui + RT − T si − RT ln
P◦
Z∞ ! !
P RT PV PV
= − dV − RT ln + − RT
ni V ni RT ni
V
Z∞ !
P RT
= − dV − RT ln z + RT z − RT
ni V
V
Z∞ !
P RT
= − dV − RT ln z + RT (z − 1) (3-54)
ni V
V

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
xA = 0.25, xB = 0.75
P = 50 bar
T = 373 K
ϕA = 0.65, ϕB = 0.90

Figure 1: Properties of the gas mixture.

substance, the relation between the chemical potential and the fugacity would be
!
⊖ fM
µM = µM + RT ln ⊖
fM

where µ⊖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 = µM . On the

7
other hand, the molar Gibbs energy for the mixture is given by
X
Gm = µi xi
i

where the chemical potential of each component is

! !
⊖ fi ⊖ ϕ i Pi
µi = µi + RT ln ⊖ = µi + RT ln
fi fi⊖

Here, ϕi is the fugacity coefficient of component i. Equating G M and Gm gives

! X !
⊖ fM ⊖
X ϕ i Pi
µM + RT ln ⊖ = xi µi + RT xi ln (11)
fM i i
fi⊖

which we can use to express f M in terms of the component properties. We should, however,
first make a remark on the relation between the standard states. The µ⊖M is not the same as
µ⊖i even if they refer to the same pressure, because µ⊖M contains the properties of an ideal
mixture: X X
µ⊖M = xi µ⊖i + RT xi ln xi (12)
i i

The standard fugacities, which are usually taken to be ideal gas at 1 bar pressure, are the
same: f M⊖ = fi⊖ . Equations 11 and 12 give:
! X !
X
⊖
X fM ⊖
X ϕ i Pi
xi µi + RT xi ln xi + RT ln ⊖ = xi µi + RT xi ln
i i
f M i i
fi⊖
! X ϕP  X
fM i i
∴ ln = xi ln − xi ln xi
1 bar i
1 bar i

With the given data, we find:

!
fM
ln = 0.25 × ln (0.65 × 0.25 × 50) + 0.75 × ln (0.90 × 0.75 × 50)
1 bar
−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 liq
µC2 H6 (1bar) = µC2 H6 (xC2 H6 = 0.33 × 10−4 )

The same equilibrium at 35 bar may be expressed as

gas liq
µC2 H6 (35bar) = µC2 H6 (xC2 H6 = x)

8
 gas gas
H2 O, C2 H6 H2 O, C2 H6
P = 1 bar P = 35 bar
PH2 O = 0.0316 bar PH2 O = 0.0316 bar
PC2 H6 ≈ 1 bar PC2 H6 ≈ 35 bar
T = 298 K T = 298 K

liquid liquid
H2 O, C2 H6 H2 O, C2 H6
xH2 O ≈ 1.0 xH2 O ≈ 1.0
xC2 H6 = 0.33 × 10−4 xC2 H6 =?

Figure 2: The two equilibrium situations.

where xC2 H6 is the unknown denoted by x. In the gas phase, the effect of a change in the
chemical potential at constant temperature is

dµi = v̄i dP

where v̄i is the partial molar volume of component i. Since there is so little water in the gas
phase, we assume it to be pure C2 H6 , in which case we can neglect the effect of a change
in composition, and vi is the molar volume of C2 H6 , i.e. v̄i = vC2 H6 . The molar volume is
given by the equation of state,

RT  
v= 1 − aP − bP2
P

where a = 7.63×10−3 bar−1 and b = 7.22×10−5 bar−2 . Integration of the chemical potential
at constant T gives
35
Z bar ! 35
Z bar
!
∂µC2 H6 1
µgas
C2 H6 (35bar)− µgas
C2 H6 (1bar)
= dP = RT − a − bP dP
TdP P
" !1 bar 1 bar
#
35 bar 1 
2 2

2
= RT ln − a 34 bar − b 35 − 1 bar
1 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 effect of the change
in pressure is dµC2 H6 = v̄C2 H6 dP, where v̄C2 H6 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 effect of the change in composition is dµC2 H6 = RT d ln aC2 H6 ,
where aC2 H6 = fC2 H6 / fC⊖2 H6 is the activity of ethane. We have to assume that the activity

9
coefficient of ethane, defined by γC2 H6 = aC2 H6 /xC2 H6 , is constant over the concentration
range considered here, which leads to
liq liq
µC2 H6 (x) − µC2 H6 (x = 0.33 × 10−4 )
35 xC2 H6 =x xC2 H6 =x
Z bar Z Z
= vC2 H6 dP + RT d ln γC2 H6 + RT d ln xC2 H6
1 bar xC2 H6 =0.33×10−4 xC2 H6 =0.33×10−4
xC2 H6 =x
Z  x 
≈ RT d ln xC2 H6 = RT ln
0.33 × 10−4
xC2 H6 =0.33×10−4

Equating the changes in the chemical potential of the gas and liquid phases give
" #
 x 
−3 1 −5

2 2
RT ln = RT ln(35) − 7.63 × 10 × 34 − × 7.22 × 10 35 − 1
0.33 × 10−4 2
 x 
−3 1 −5

2 2

ln = ln(35) − 7.63 × 10 × 34 − × 7.22 × 10 35 − 1 = 3.2517
0.33 × 10−4 2
∴ 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 find the enthalpy from the following relation:
ZP " ! #
∂V X
H= V −T dP + ni h0i
∂T P,nT i
0

where h0i is the molar enthalpy of pure i at the actual temperature. The given volumetric
data for the mixture leads to
" ! #
∂V b
V −T =a+
∂T P,nT T

where a = 5 × 10−5 m3 mol−1 and b = −0.2 m3 K mol−1 . Integration leads to the molar
enthalpy !
b X
h= a+ P+ xi h0i
T i

where xi is the mole fraction of component i. The condition hin = hout gives
! !
b X
0 b X
a+ Pin + xi hi,in = a + Pout + xi h0i,out
T in i
T out i
! !
b b X  
a+ Pin = a + Pout + xi h0i,out − h0i,in
T in T out i

10
We have h0i,out − h0i,in = c0P,i (T out − T in ) and c0P = xi c0P,i = 33.5 J mol−1 K−1 . Solving for Pin
P
i
gives
 
b
a+ T out
Pout + c0P (T out − T in )
Pin =  
a + Tbin
 
5 · 10−5 m3 mol−1 − 0.2m3 Kmol−1 /200K 105 Pa + 33.5Jmol−1 K−1 (200K − 300K)
=  
5 · 10−5 m3 mol−1 − 0.2m3 Kmol−1 /300K
= 55.9 · 105 Pa = 55.9 bar

Problem 3.9
The internal energy of mixing is (using one mole as basis):

∆mix u = u M − x1 u1 − x2 u2

Since the van der Waal equation is explicit in P:

RT a
P= − 2,
v−b v
it is convenient to find the internal energy from
Z∞ " ! #
∂P X
u= P−T dv + xi u0i
∂T V,nT i
v

where !
∂P RT a RT a
P−T = − 2− =− 2
∂T V,nT v−b v v−b v
Note that the mixing must be assumed to occur at constant pressure, not at constant volume,
which means that we must use different 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:
Z∞
dv X 0 aM X 0
u M = −a M + xi u i = − + xi ui
v2 i
vM i
vM
a1
u1 = − + u01
v1
a2
u2 = − + u02
v2
The change in internal energy for the mixture is
! !
aM X 0 a1 0 a2 0 a M x1 a1 x2 a2
∆mix u = − + xi ui + x1 − u1 + x2 − u2 = − + +
vM i
v1 v2 vM v1 v2

11
With the given data, we find
XX √
aM = xi x j ai a j (1 − ki j )
i j
h √ i
= 0.5 × 106 1.04 + 2 × 1.04 × 4.17(1.0 − 0.1) + 4.17 bar cm6 mol−2
2

2.24 × 106 bar cm6 mol−2

= X
vM = xi vi = 0.5(32.2 + 48.5) cm3 mol−1 = 40.35 cm3 mol−1
i
bar cm6 mol−2
!
2.24 0.5 × 1.04 0.5 × 4.17
∆mix u = − + + 106 = 363 J mol−1
40.35 32.2 48.5 cm3 mol−1

12
Chapter 5

Problem 5.2
The question here is whether the fugacity of CO2 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 find the saturation pressure, we consider how it changes from the vapour pressure of
pure CO2 (component 1) to its new value after injection of H2 (component 2) until the total
pressure is 60 bar. We therefore consider a charging process as illustrated in Figure 3. The
H2 is inert in this case, in the sense that it does not dissolve in the solid phase. The change

CO2 (g) CO2 (g) + H2 (g)

P∗CO2 = 0.1392 bar ∆µ (g) PCO2 + PH2 = 60 bar
T = 173 K −→ T = 173 K

CO2 (s) ∆µ (s) CO2 (s)

T = 173 K −→ T = 173 K

Figure 3: Available data for the state changes.

in chemical potential of CO2 in the gas phase is

Zc
d ln f1 = RT ln f1 c⋆
 
∆µ1 (g) = RT (13)
⋆

where f1 is the fugacity of CO2 . The fugacity of pure CO2 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 CO2 in the compressed
state must be calculated somehow, and we shall be using

f1 = ϕ1 y1 P

where ϕ1 and y1 are the the fugacity coefficient and the mole fraction of CO2 , respectively,
and P is the total pressure (equal to 60 bar). The fugacity coefficient is estimated from van

13
der Waal’s equation:
Pv v a
z= = − (14)
RT v − b RT v
The mixing rules are
XX √
a = yi y j ai a j
i j
X
b = yi bi
i

The fugacity coefficient of component 1 in the mixture is calculated from Eq. 3-70 in Praus-
nitz et al.: √ P √
v b1 2 a1 j y j a j
ln ϕ1 = ln + − − ln z (15)
v−b v−b RT v
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 cm6 mol−2 b/cm3 mol−1
CO2 (1) 3.640×106 42.67
H2 (2) 0.2476×106 26.61

Alternatively we may use the corresponding state principle and calculate a = 27(RT c )2 /64Pc
and b = RT c /8Pc from critical data. Do this on your own and compare the results with the
table. Because the mole fraction of CO2 is low, at most 0.01, we make a small error if
we choose the van der Waal parameters to be those of pure H2 , but for the time being we
determine the mixture parameters on the basis of 1 mole% CO2 .

Iteration 1: y1 = 0.01
This gives:
√
a = (0.012 × 3.640 × 106 + 2 × 0.01 × 0.99 × 3.640 × 106 × 0.2476 × 106
+ 0.992 × 0.2476 × 106 ) atm cm6 mol−2
= 2.618 3 × 105 atm cm6 mol−2
b = (0.01 × 42.67 + 0.99 × 26.61) cm3 mol−1
= 26.77 cm3 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 cm3 mol−1 and z = 1.048. Inserted into Eq. 15:
!
250.69 42.67
ln ϕ1 = ln +
250.69 − 26.77 250.69 − 26.77
√  √ √ 
2 3.640 × 106 0.01 × 3.640 × 106 + 0.99 × 0.2476 × 106
− − ln 1.048
250.69 × 82.0567 × 173
= −0.292
∴ ϕ1 = exp(−0.292) = 0.7468

14
Inserting the last result into Eq. 13 gives the change in chemical potential of CO2 in the gas
phase:
!
3 -1 -1 0.7468 × y1 × 60 bar
∆µ1 (g) = 83.1439 cm bar mol K × 173 K × ln
0.1392 bar
3 -1
= 14428 cm bar mol × ln (321.9y1 )
The change in chemical potential for CO2 in the solid phase is
Zc 60
Z bar
∆µ1 (s) = vs dP = vs dP = 27.6 cm3 mol−1 × (60 − 0.1392) bar
⋆ 0.1392 bar
= 1652.16 cm3 bar mol-1
Here, we have assumed that the solid is incompressible and that H2 does not dissolves in
the solid. At equilibrium, in the compressed state, we have ∆µ1 (g) = ∆µ1 (s) which gives
14428 cm3 bar mol-1 × ln (321.9y1 ) = 1652.16 cm3 bar mol-1
!
1 1652.16
y1 = exp = 3.4835 × 10−3
321.9 14428
At this point, we conclude that Iteration 1 is slightly off, and try another calculation:

Iteration 2: y1 = 3.4835 × 10−3

This gives
√
a = (0.00352 × 3.640 × 106 + 2 × 0.0035 × 0.9965 × 3.640 × 106 × 0.2476 × 106
+ 0.99652 × 0.2476 × 106 ) atm cm6 mol−2
= 2.5254 × 105 atm cm6 mol−2
b = (0.0035 × 42.67 + 0.9965 × 26.61) cm3 mol−1
= 26.67 cm3 mol−1
and v = 251.17 cm3 mol−1, and z = 1.048. Inserting these numbers into Eq. 15 gives:
!
251.17 42.67
ln ϕ1 = ln +
251.17 − 26.77 251.17 − 26.77
√  √ √ 
2 3.640 × 106 0.0035 × 3.640 × 106 + 0.9965 × 0.2476 × 106
− − ln 1.048
251.17 × 82.0567 × 173
= −0.282
∴ ϕ1 = exp(−0.282) = 0.7543
A small change in ϕ1 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):
!
3 -1 -1 0.7543 × y1 × 60 bar
∆µ1 (g) = 83.1439 cm bar mol K × 173 K × ln
0.1392 bar
3 -1
= 14428 cm bar mol × ln (325.1y1 )

15
The solid phase chemical potential is the same as above, and we find
!
1 1652.16
y1 = exp = 3.4492 × 10−3
325.1 14428
We consider Iteration 2 to be good, and accept this as the final result. To conclude the
calculation, we need a material balance, using one mole material in total as basis:

nCO2 (g) + nCO2 (s) + nH2 (g) = 1 mol (16)

nH2 (g) = 0.99 mol (17)

The mole fraction of CO2 in the gas phase is

nCO2 (g)
yCO2 = = 0.00345 (18)
nCO2 (g) + nH2 (g)
Solution of Eqs. 16–18 gives the amount of precipitated CO2 :

nCO2 (s) = 0.0066 mol

Problem 5.3
The situation is shown in Figure 4. The question is whether some of the CO2 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 CH4 by 1 and CO2 by 2. The

30 mol% CO2 (g) CO2 (s) or CO2 (l)?

70 mol% CH4 (g) CH4 (g)
70 bar, 313 K 1 bar, T=?

Figure 4: The given process.

critical point of CO2 is at Pc = 73.8 bar and T c = 304.2 K. The triple point is at PT = 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 CO2 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
Z∞ " ! #
∂P X
H= P−T dV + PV + ni u0i
∂T V,nT i
V

where ni is the number of moles of component i and u0i is the molar internal energy of pure
i in the ideal gas state at the actual temperature. The strategy is to find how H depends

16
on V and T , then constrain H to be constant, and finally to use this constraint to find 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
Pv Bmix
zmix = =1+ (19)
RT v
where XX
Bmix = yi y j Bi j (20)
i j

and yi is the mole fraction of component i. Each Bi j is of the form

bi j ci j
Bi j = a i j + + 2,
T T
which means Bmix will be on the same form,
b c
Bmix = a + + 2
T T
where
XX
a = yi y j ai j = (0.72 × 42.5 + 2 × 0.7 × 0.3 × 41.4 + 0.32 × 40.4) cm3 mol-1
i j
3 -1
= X
41.85
Xcm mol
b = yi y j bi j = −(0.72 × 16.75 + 2 × 0.7 × 0.3 × 19.50 + 0.32 × 25.39) × 103 cm3 K mol-1
i j
3 3 -1
= X X × 10 cm K mol
−18.683
c = yi y j ci j = −(0.72 × 25.05 + 2 × 0.7 × 0.3 × 37.3 + 0.32 × 68.7) × 105 cm3 K2 mol-1
i j

= −34.124 × 105 cm3 K2 mol-1

We then find for one mole of gas

! !
∂P R 2c
P−T = 2 b+
∂T V,nT v T

and for the molar enthalpy:

! X
R 3c
h= aT + 2b + + yi h0i (21)
v T i

We note that the ideal-gas contribution to enthalpy is (constant cP assumption):

X
yi h0i = c0P T
i

where
X
c0P = yi c0P,i = (0.7 × 35.8 + 0.3 × 37.2) J mol-1 K−1 = 36.22 J mol-1 K−1
i

17
The energy constraint tells that h is constant and solving Eq. 21 for v gives:
 
R aT + 2b + 3c T
v(T ) = 0
(22)
h − cP T
At the upstream conditions,

18.683 × 103 34.124 × 105

!
Bmix = 41.85 − − cm3 mol-1 = −52.672 cm3 mol-1
313 3132
and from Eq. 19:

70 bar × v 52.672 cm3 mol-1

= 1 −
83.1439 bar cm3 mol-1 K−1 × 313 K v

which gives v1 = 308.24 cm3 mol-1 . The constant enthalpy in Eq. 21 can now be deter-
mined to
 5

8.314 J mol-1 K-1 41.85 × 313 − 2 × 18.683 × 103 − 3×34.124×10
313
K cm3 mol-1
h1 =
308.24 cm3 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 CO2 , or in other words, will the
fugacity CO2 in the gas be higher than the equilibrium value in contact with pure CO2 ? The
fugacity of CO2 in the expanding gas is given by

f2 = ϕ2 y2 P,

which should be compared with the fugacity for saturated gas in equilibrium with liquid or
solid: !
sat sat vl ∆P
f2 = P2 exp (3.5)
RT
The saturation pressure of pure CO2 is
1980.24
ln Psat (bar) = 10.807 − (23)
T
and vl is the molar volume of pure CO2 (l). The fugacity coefficient is given by
2X
ln ϕ2 = y j B2 j − ln zmix
v j

Most likely the Poynting correction is quite small, and the fugacity coefficient is probably
less than 1. This implies that CO2 is more volatile in the compressed gas than in the pure
form (where ϕ2 ≈ 1), and if we find that if the gas is unsaturated in pure form, no CO2 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 CO2 .
T /K v/cm3 mol−1 B/cm3 mol−1 P/bar P2 /bar Psat
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)

100

80

P2sat
60
P, bar

40

20 P2

0
270 280 290 300
T, K

Figure 5: Saturation pressure and partial pressure of CO2 .

triple point temperature, and any condensed CO2 will be in liquid form. We note that from
the table ∆P = P − Psat2 is negative, which means the Poynting correction is less than unity.
The effect of the inert gas is therefore to reduce the saturation fugacity as compared with
the saturation pressure. A plot of P2 and Psat2 is given in Figure 5. The figure shows that
the saturation pressure is higher than the actual partial pressure of CO2 , and consequently
that CO2 (l) will not condense. To improve the assumption of the ideal gas phase we need
to estimate the molar volume of liquid CO2 . Data from Reid et al. indicate that ρl (T = 293
K) = 0.777 g cm3 . The molecular weight of CO2 is M = 44.01 g mol−1 . This gives

M 44.01 g mol-1
vl = = = 56.6 cm3 mol-1
ρ 0.777 g cm3
Assuming that the liquid density varies only a little with temperature, the saturation fugac-
ity is easily calculated:

56.6 cm3 mol-1 ∆P

!
sat sat
f2 = P2 exp
83.1439 cm3 bar mol-1 K-1 T

19
The fugacity coefficient in the gas phase is
!
2X 2 b2 c2 Bmix
 
ln ϕ2 = y j B2 j − ln zmix = a2 + + 2 − ln 1 + (24)
v j v T T v

where
X
a2 = y j a2 j = (0.7 × 41.4 + 0.3 × 40.4) cm3 mol-1
j

41.1 cm3 mol-1

= X
b2 = y j b2 j = −(0.7 × 19.50 + 0.3 × 25.39) × 103 cm3 K mol-1
j

−21.267 × 103 cm3 K mol-1

= X
c2 = y j c2 j = −(0.7 × 37.3 + 0.3 × 68.7) × 105 cm3 K2 mol-1
j

= −46.72 × 105 cm3 K2 mol-1

The results for the fugacity may now be calculated from Eqs. 19, 20, 22–24, and some of
the results are given in Table 2: A plot of f2 and f2sat is shown in Figure 6. The figure

Table 2: Fugacities of CO2 .

T /K ϕ2 f2 /bar f2sat /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)

confirms that no CO2 (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
Zc
d ln f1 = RT ln f1 c⋆
 
∆µ1 (g) = RT
⋆

The fugacity of pure napthalene vapour can be assumed to be equal to the vapour pres-
sure, 2.80×10−4 bar, because the vapour pressure is low. The fugacity of napthalene in the
compressed state is determined as
f1 = ϕ1 y1 P (25)

20
 100

80

f2sat
60
f, bar
40

20 f2

0
270 280 290 300
T, K

Figure 6: Saturation fugacity and fugacity of CO2 .

Naphtalene (g) (1) Naphtalene (g)

+ Ethylene (g) (2)
P∗1 = 2.80 × 10−4 bar ∆µ1 (g) P1 + P2 = 30 bar
−→ P1 = ?
T = 308 K T = 308 K

Naphtalene (s) ∆µ1 (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
Zc 30
Z bar
∆µ1 (s) = vs dP = vs dP
⋆ 2.80×10−4 bar

The molar volume of the solid is given by the density and the molecular weight:

M 128.2 g mol-1
vs = = = 112.0 cm3 mol-1
ρ 1.145 g cm−3

This gives

∆µ1 (s) = 112.0 cm3 mol-1 (30 − 2.80 × 10−4 ) bar = 3360 cm3 bar mol-1

21
At equilibrium in the compressed state, we must have

∆µ1 (g) = ∆µ1 (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
 P1 
∆µ1 (g) = RT ln = 3360 cm3 bar mol-1
2.80 × 10 bar
−4

3360 cm3 bar mol-1

!
−4
P1 = 2.80 × 10 bar × exp -1 -1
= 3.19 × 10−4 bar
3
83.1439 cm bar mol K 308 K
−4
P1 3.19 × 10 bar
y1 = = = 1.06 × 10−5
P 30 bar
b) With the virial expansion truncated after the second term. The virial expansion reads
PV n RT  B 2
z= =1+B ∴ P= n+ n (27)
nRT V V V
The second virial coefficient is given by the van der Waals result,
a
B=b− (28)
RT
where
XX √
a = yi y j ai a j
i j
X
b = yi bi
i

It is convenient to write the expression for b as

XX
b= yi y j bi j
i j

where
1 
bi + b j ,
bi j =
2
because we can then use Eq. (5-29) in Prausnitz et al.:
2
ln ϕ1 = (y1 B11 + y2 B12 ) − ln z (29)
v
with √
ai a j
Bi j = b i j − (30)
RT
and XX
B= yi y j Bi j (31)
i j

22
We will need the numerical values for a and b, which we find from the critical values:
27(RT c )2
a =
64Pc
RT c
b =
8Pc
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 ai j , bi j , and Bi j are given in Table 4. We now make a

Table 3: Critical data for napthalene and ethylene.

T c /K Pc /atm a/cm6 atm mol−2 b/cm3 mol−1
Naphtalene (1) 748.4 40.0 3.98×107 191.91
6
Ethylene (2) 282.4 49.7 4.56×10 58.28

Table 4: Interaction parameters for napthalene and ethylene.

Combination ai j /cm6 atm mol−2 bi j /cm3 mol−1 Bi j /cm3 mol−1 b/cm3 mol−1
11 3.98×107 191.91 -1382.9 191.91
12 1.35×107 125.10 -409.06 58.28
6
22 4.56×10 58.28 -122.15

guess for the mole fraction of naphtalene to obtain a first estimate of the viral coefficient
B. We can for example assume that P1 is little affected by the presence of ethylene which
gives the starting value
P∗1 2.80 · 10−4 bar
y1 = = = 9.3 · 10−6
P 30bar
(Other qualified guesses include the answer from a) or y1 = 0.) The equations 25–31 give
an iterative procedure to find y1 :
B = y21 B11 + 2y1 (1 − y1 ) B12 + (1 − y1 )2 B22
P 2
v −v−B = 0
RT
B
z = 1+
v
2
ln φ1 = (y1 B11 + (1 − y1 ) B12 ) − ln z
! v
φ1 Py1
RT ln = ∆µ
P∗1
B, v, z and φ1 are estimated from the previous y1 and a better estimate is obtained in the
last equation. With Bi j from Table 4, ∆µ=3360cm3 bar/mol, T = 308K, P = 30bar and
P∗1 = 2.8 · 10−4 bar the two first iterations give the values shown in Table 5. We can therefore
conclude that y1 = 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
φ1 0.379462 0.379441
−5
y1 2.80447·10 2.80462·10−5

Problem 5.17
This problem is also similar to problem 5.2. Instead of considering the cooling, we consider
compressing water vapour by adding air at 263 K. This is illustrated in Figure 8. Like in

H2 O (g) (3) N2 (1) + O2 (2) (g)

+ H2 O (g)
P∗1 = 1.95 torr ∆µ3 (g) P = 30 bar
−→ y3 = ?
T = 263 K T = 263 K

H2 O (s) ∆µ3 (s) H2 O (s)

ρ 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
Zc
f3
d ln f3 = RT ln f3 c⋆ = RT ln ∗
 
∆µ3 (g) = RT
P3
⋆

The fugacity of pure water vapour is again assumed to be equal to the vapour pressure, 1.95
torr = 1.95
760
atm = 2.57×10−3 atm = 2.60×10−3 bar, because the vapour pressure is low. The
fugacity of water vapour in the compressed state is

f3 = ϕ3 y3 P.

The change in chemical potential for ice is

Zc 30
Z bar
∆µ3 (s) = vs dP = vs dP
⋆ 2.60×10−3 bar

24
The molar volume of ice is the molecular weight divided by the density:
M 18.0 g mol-1
vs = = = 19.57 cm3 mol-1
ρ 0.92 g cm−3

This gives
∆µ1 (s) = 19.57 cm3 mol-1 (30 − 2.60 × 10−3 ) bar = 587.1 cm3 bar mol-1
At equilibrium in the compressed state, we must have
∆µ1 (g) = ∆µ1 (s)
We have to determine the second virial coefficient, the compression factor, and the fugacity
coefficient: XX
Bmix = yi y j Bi j
i j
Pv Bmix
zmix = =1+
RT v
2X
ln ϕ3 = y j B3 j − ln zmix
v j
A material balance for N2 (g), O2 (g), and H2 O (g) gives
y1 = 0.8(1 − y3 ), y2 = 0.2(1 − y3 )
Again, we have to solve the problem by iteration, which is considered below.

Iteration 1: y3 = 0
This is for the saturated vapour. With the numerical values given in the problem, we find
Bmix = 0.8(1 − y3 ) 2 B11 + 2 × 0.8(1 − y3 ) × 0.2(1 − y3 )B12 + 2 × 0.8(1 − y3 )y3 B13
 

+ 0.2(1 − y3 ) 2 B22 + 2 × 0.2(1 − y3 )y3 B23 + y3 y3 B33

 
 
= − 0.82 × 25 + 2 × 0.8 × 0.2 × 15 + 0.22 × 12 cm3 mol-1 = −21.3 cm3 mol-1
30 bar v 21.3 cm3 mol-1
= 1 −
83.1451 cm3 bar mol-1 K-1 × 263 K v
∴ v = 706.9 cm3 mol-1
21.3 cm3 mol-1
zmix = 1 − = 0.9699
706.9 cm3 mol-1
2
ln ϕ3 = -1
(−0.8 × 63 − 0.2 × 72) cm3 mol-1 − ln (0.9699) = −0.1528
3
706.9 cm mol
∴ ϕ3 = 0.8583
The maximum permissible moisture content is therefore
!
2.60 × 10−3 587.1
y3 = × exp = 1.04 × 10−4
0.8583 × 30 83.1451 × 263
If we are in doubt concerning the accuracy of this result, we can make another iteration as
shown below.

25
Iteration 2: y3 = 1.04 × 10−4
This gives

Bmix = 0.8(1 − y3 ) 2 B11 + 2 × 0.8(1 − y3 ) × 0.2(1 − y3 )B12 + 2 × 0.8(1 − y3 )y3 B13

 

+ 0.2(1 − y3 ) 2 B22 + 2 × 0.2(1 − y3 )y3 B23 + y3 y3 B33

 
h i2
= 0.8(1 − 1.04 × 10−4 ) B11 + 2 × 0.8(1 − 1.04 × 10−4 ) × 0.2(1 − 1.04 × 10−4 )B12
h i2
+ 2 × 0.8(1 − 1.04 × 10−4 ) × 1.04 × 10−4 B13 + 0.2(1 − 1.04 × 10−4 ) B22
+ 2 × 0.2(1 − 1.04 × 10−4 )1.04 × 10−4 B23 + 1.04 × 10−4 × 1.04 × 10−4 B33
= 0.6399B11 + 0.3199B12 + 1.6638 × 10−4 B13 + 0.0400B22 + 4.1596 × 10−5 B23
+ 1.0816 × 10−8 B33
= −21.289 cm3 mol-1
30 bar v 21.289 cm3 mol-1
= 1 − ∴ v = 706.9 cm3 mol-1
83.1439 cm3 bar mol-1 K-1 × 263 K v
21.289 cm3 mol-1
zmix = 1 − = 0.9699
706.9 cm3 mol-1

2
ln ϕ3 = -1
(−0.8 × 63 − 0.2 × 72) cm3 mol-1 − ln (0.9699) = −0.1528
3
706.9 cm mol
∴ ϕ3 = 0.8583

The maximum permissible moisture content is therefore

!
2.60 × 10−3 587.1
y3 = × exp = 1.04 × 10−4
0.8583 × 30 83.1451 × 263

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 find
the bubble-point and dew-point lines, we have to consider the phase equilibrium shown in
Figure 9. In this figure, 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)

P1s ∆µ1 (g) P1 + P2 = P
T −→ T

Pure 1 (l) ∆µ1 (l) Mixture 1+2 (l)

T −→ T

Figure 9: Schematic illustration of a mixing process.

potential for component 1 in the gas phase is

mixture
Z ! !
P1 y1 P
∆µ1 (g) = RT d ln f1 = RT ln s = RT ln
P1 P1s
pure 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

pure
Z1 at P mixture
Z
∆µ1 (l) = v1 dP + RT d ln a1 (32)
pure 1 at P1s pure 1 at P

27
where v1 is the molar volume of pure component 1. The first term in Eq. 32 is the Poynting
correction, which we will neglect here. The change ∆µ1 (l) is then

∆µ1 (l) = RT ln a1 = RT ln (γ1 x1 )

where γ1 is the activity coefficient for component 1. By equating the changes in chemical
potentials, we get
!
y1 P
RT ln = RT ln (γ1 x1 )
P1s
y1 P
= γ1 x1
P1s

From the given expression for the excess Gibbs energy for the mixture, we find (using Eqs.
(6-46) and (6-47) in the textbook):
A 2
ln γ1 = x
RT 2
A 2
ln γ2 = x
RT 1
For the azeotrope, x1 = y1 which gives the bubble-point at the azeotrope
x1 P A 2
 
= exp x x1
P1s RT 2

P  A 
= exp x2 (33)
P1s RT 2
The same consideration for component 2 gives
P A 2
 
= exp x (34)
P2s RT 1
P2s
Dividing Eq. 33 by Eq. 34 and using the information that P1s
= 1.649, gives

P2s  A 
2 2

= exp x − x1 = 1.649
P1s RT 2
A  2  1
∴ x2 − x21 = ln 1.649 =
RT 2
In other words, for an azeotrope to occur, the requirement is that for any value of x1 in the
range 0 ≤ x1 ≤ 1, A must satisfy
A 1 1 1
=  = h i=
RT 2 2
2 x2 − x1 2
2 (1 − x1 )2 − x1 2 (1 − 2x1 )

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 x1 = 0.25. To illustrate this, we can construct a P − x

28
 20

10

A/RT
0

-10

-20

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x1

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:

A 2 A 2
   
P = P1 + P2 = P1s exp x2 x1 + P2s exp x1 x2
RT RT
A
If we set RT
= 1, we find

P  
2
P2s  
= exp x2 x1 + exp x21 x2
P1s P1s

The dew-point line is given by

 
A 2
P1 P1s exp RT x2 x1
y1 = =    
P A 2
P1s exp RT x2 x1 + P2s exp RTA 2
x1 x2

A
Again setting RT
= 1 as an example, we find
 
exp x22 x1
y1 =   P2s
 
exp x22 x1 + P1s
exp x21 x2

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
A
different values of A; RT = 0, 1, 2, 3. The Gibbs energy of mixing is given by

2
X
ideal excess
∆mixG = ∆mix G +G = RT xi ln xi + Ax1 x2 (35)
i=1

29
 1.8
bu
bb liquid
le-
1.6 po
int
line
azeotrope

de
2-phase

w
1.4

-p
P/P1*

oi
nt
l
in
e
1.2
gas

1.0

0.8
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x1

A
Figure 11: Bubble- and dew-point lines for RT
= 1.

Miscibility occurs for all compositions if

∂2 ∆mixG
≥ 0 for all x1
∂x21
If we use this condition for the model in Eq. 35, we find
∂2 RT A 1
2
[RT (x1 ln x1 + x2 ln x2 ) + Ax1 x2 ] = − 2A ≥ 0 ∴ ≤
∂x1 x1 x2 RT 2x1 x2

The values of 2x11 x2 are plotted in Figure 13, together with the conditions on A shown in
Figure 10. We see that the minimum value of 2x11 x2 occurs at x1 = 0.5, when 2x11 x2 = 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
3 1
0 ≤ x1 ≤ and < x1 ≤ 1
8 2

Problem 6.16
The situation is illustrated in Figure 14, showing the partial pressures as given by Henry’s
and Raoult’s laws. Henry’s law,
Pi = Hi, j xi
applies in the limit of zero solute concentration, xi → 0, and Raoult’s law,

Pi = Pis xi

applies in the limit of pure solvent, xi → 1. The problem here is to determine the vapour
pressure at x1 = 0.5 and the corresponding vapour composition,
P1
y1 =
P

30
 0.2

0.0
∆mixGideal/RT+3x1x2

∆mixG/RT
-0.2
∆mixGideal/RT+2x1x2

-0.4
∆mixG
ideal
/RT+x1x2
-0.6
∆mixG
ideal
/RT

-0.8
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x1

∂2 ∆mix G
Figure 12: Change in Gibbs energy of mixing. Complete miscibility occurs if ∂x21
≥ 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

Pi = Pis γi xi (36)
We have four given pieces of information, P1s , P2s , H1,2 , and H1,2 . Because γ1 and γ2 are re-
lated by the Gibbs-Duhem equation, the model for gE (and γi ) 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
H1,2 H
Ps
and P2,1s . The van Laar model satisfies this, and we set
1 2

A′
ln γ1 =  ′
2
1 + BA′ xx21
B′
ln γ2 =  ′
2
1 + AB′ xx12

Using this model with Eq. 36 in the limit xi → 0 gives

! !
′ H1,2 2 bar
ln γ1 = A = ln = ln = 0.6255
P1s 1.07 bar
! !
′ H2,1 1.60 bar
ln γ2 = B = ln = ln = 0.1848
P2s 1.33 bar
For an equimolar mixture, we find
A′ 0.6255
ln γ1 =  2 =   = 0.0325 ∴ γ1 = 1.0330
′ 0.6255 2
1 + BA′ 1 + 0.1848
B′ 0.1848
ln γ2 =  2 =   = 0.1101 ∴ γ2 = 1.1164
′ 0.1848 2
1 + AB′ 1 + 0.6255

31
 20

10

A/RT
0

-10

-20

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x1

Figure 13: Allowable values of A/RT (solid line) and upper limit for complete miscibility
in the liquid phase (dashed line).

This gives

P1 = 1.07 bar × 1.0330 × 0.5 = 0.5527 bar

P2 = 1.33 bar × 1.1164 × 0.5 = 0.7424 bar
P = P1 + P2 = 1.2951 bar

The vapour (dew-point) composition is

0.5527 bar
y1 = = 0.4268
1.2951 bar
Data generated with this model are shown in Figure 15. Alternatively, we can use the
three-suffix Margules equation,
1 h i
ln γ1 = (A + 3B) x22 − 4Bx32
RT
1 h i
ln γ2 = (A − 3B) x21 + 4Bx31
RT
Using this model with Eq. 36 in the limit xi → 0 gives
! !
A−B H1,2 2 bar
ln γ1 = = ln = ln = 0.6255
RT P1s 1.07 bar
! !
A+B H2,1 1.60 bar
ln γ2 = = ln = ln = 0.1848
RT P2s 1.33 bar

A 0.6255 + 0.1848
= = 0.4052
RT 2
B 0.1848 − 0.6255
= = −0.2204
RT 2

32
 2.0 2.00

1.60 law
's
1.5 He nry
nry
's l He
1.33 P2 aw

P, bar
Ra
oul 1.07
1.0 t's
law
a w
u lt's l
Rao
P1
0.5

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x1

Figure 14: The given information.

2.0 2.00

1.60
1.5 P
Bubble-poi
1.33 nt line
P, bar

Dew-poin 1.07
1.0 t line

P1 P2
0.5

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x1

Figure 15: Partial pressures and total vapour pressure computed from the van Laar model.

For an equimolar mixture, we find

ln γ1 = (0.4052 − 3 × 0.2204) × 0.52 + 4 × 0.2204 × 0.53 = 0.0462 ∴ γ1 = 1.0473
ln γ2 = (0.4052 + 3 × 0.2204) × 0.52 − 4 × 0.2204 × 0.53 = 0.1564 ∴ γ1 = 1.1693
This gives
P1 = 1.07 bar × 1.0473 × 0.5 = 0.5603 bar
P2 = 1.33 bar × 1.1693 × 0.5 = 0.7776 bar
P = P1 + P2 = 1.3379 bar
Tha vapour (dew-point) composition is
0.5603 bar
y1 == 0.4188
1.3379 bar
Data generated with this model are shown in Figure 16.

33
 2.0 2.00

1.60
1.5 P Bubble-po
int lin e
1.33
P, bar

Dew-poin
t line 1.07
1.0

P1 P2
0.5

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x1

Figure 16: Partial pressures and total vapour pressure computed from the three-suffix Mar-
gules equation.

34
Chapter 7

Problem 7.1
The situation is shown in the P − x diagram, Figure 1 for the mixture A-CS2 . From the

14

12

10 P
PA
P, kPa

2 PCS
2

0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
xA

Figure 17: Plot of the partial pressures and total pressure for the mixture A-CS2 . The curves
are based on the van Laar model.

given information, we can determine the activity coefficient at x1 = 0.5 and T = 283 K:

PA = PAs γA xA
PA 8 kPa
∴ γA = s = = 1.2030
PA xA 13.3 kPa × 0.5
ln γA = 0.1848

The given solubility parameters suggest that we use regular solution theory. The relation to
the van Laar model,

A′
ln γ1 =  ′
2
1 + BA′ xx21
B′
ln γ2 =  ′
2
1 + AB′ xx12

35
is
v1
A′ = (δ1 − δ2 )2
RT
v2
B′ = (δ1 − δ2 )2
RT
where vi and δi are the molar volume and the solubility parameter, respectively, of compo-
nent i. With the given information, we find that

V V MA MA 160 g mol-1
vA = = = = = 200 cm3 mol-1
nA m ρA 0.8 g cm-3
A′ vA 200 cm3 mol-1
= =
B′ vCS2 61 cm3 mol-1
!2 !2
A′ 200
A′ = ln γA 1 + ′ = 0.1848 × 1 + = 3.3832
B 61

Assuming that v1 (δ1 − δ2 )2 is independent of the temperature, we find

vA δA − δCS2 2 @(T = 298 K) = vA δA − δCS2 2 @(T = 283 K) = A′ RT

r s
A′ RT 1 3.3832 × 8.3145 J mol-1 K-1 × 283 K
δA = δCS2 ± = 20.5 (J cm-3 ) 2 ±
vA 200 cm3 mol-1
1 1
= 20.5 (J cm-3 ) 2 ± 6.3 (J cm-3 ) 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 CS2 Toluene
-3 21
Solubility parameter at 298 K, (J cm ) 14.2 20.5 18.2
3 -1
Liquid molar volume at 298 K, cm mol 200 61 107
Saturation pressure at 283 K, kPa 13.3 1.73 25.5

mixture A-T (Toluene), we now find

vA
A′ = (δA − δT )2
RT
200 cm3 mol-1
= -1 -1
(14.2 − 18.2)2 J cm-3 = 1.36
8.3145 J mol K × 283 K
vT
B′ = (δA − δT )2
RT
107 cm3 mol-1
= (14.2 − 18.2)2 J cm-3 = 0.7276
8.3145 J mol-1 K-1 × 283 K

36
At xA = xT = 0.5:
A′ 1.36
ln γA =  2 =  = 0.1652
1.36×0.5 2
A′ x

1 + B′ xTA 1+ 0.7276×0.5
∴ γA = 1.1796

B′ 0.7276
ln γT =  2
=  = 0.3088
0.7276×0.5 2
B′ xT
 
1 + A′ xA 1 + 1.36×0.5
∴ γT = 1.3618

PA = PAs γA xA = 13.3 kPa × 1.1796 × 0.5 = 7.84 kPa

PT = PTs γT xT = 25.5 kPa × 1.3618 × 0.5 = 17.36 kPa
P = PA + PT = 7.84 kPa + 17.36 kPa = 25.20 kPa
PA 7.84 kPa
yA = = = 0.31
P 25.20 kPa
The full phase diagram is shown in Figure 2. An alternative representation of the data is

30
P B ub
25 bl e-
poi n
t lin
e
20 PT
D ew
P, kPa

- po
int li
15 ne

10

5
PA
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
xA

Figure 18: P − x diagram for the mixture A-Toluene at 283 K.

q
A′ RT
shown in Figure 3. The alternative positive sign for vA
would give
1 1 1
δA = 20.5 (J cm-3 ) 2 + 6.3 (J cm-3 ) 2 = 26.8 (J cm-3 ) 2

This would correspond to a change in molar internal energy on vaporization (Eq. (7-33) in
the textbook) of

∆vap uA = δ2A vA = 26.82 J cm-3 × 200 cm3 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 δA = 26.8
1
(J cm-3 ) 2 is therefore not acceptable.

37
 1.0

0.9

0.8

0.7

0.6

yA
0.5

0.4

0.3

0.2

0.1

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
xA

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

v1
A′ = (δ1 − δ2 )2
RT
132 cm3 mol-1
= -1 -1
(14.9 − 18.8)2 J cm-3 = 0.7476
8.3145 J mol K × 323 K
A′ v1 132 cm3 mol-1
= = = 1.4831
B′ v2 89 cm3 mol -1
!−1
B′ A′
= = 0.6742
A′ B′
B′ ′
B′ = A = 0.6742 × 0.7476 = 0.5041
A′

we find:

A′ 0.7476
ln γ1 =  ′
 2
= 2 = 0.2795
1 + BA′ xx21 1 + 1.4831 0.3
0.7
∴ γ1 = 1.3224
B′ 0.5041
ln γ2 =  2
=  = 0.0761
0.7 2
B′ x2
 
1 + A′ x1 1 + 0.6742 0.3
∴ γ2 = 1.0791

38
At the given composition, we then find

P1 = P1s γ1 x1 = 0.533 bar × 1.3224 × 0.3 = 0.2115 bar

P2 = P2s γ2 x2 = 0.380 bar × 1.0791 × 0.7 = 0.2870 bar
P = P1 + P2 = 0.2115 bar + 0.2870 bar = 0.4985 bar

and finally
y1 P1 0.2115 bar
K1 = = = = 1.414
x1 Px1 0.4985 bar × 0.3
y2 P2 0.2870 bar
K2 = = = = 0.822
x2 Px2 0.4985 bar × 0.7

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 xH2 = Aδi + B (37)

where xH2 is the mole fraction (solubility) of H2 , δi is the solubility parameter for the
solvent, and A and B are (temperature dependent) constants. To determine A and B , we use
data for CH4 and CO. Air is a mixture of 78% N2 , 21% O2 , and 1% Ar. In terms of solubility
properties, Ar is like O2 (see Table 7-1 in the textbook), and we take the composition to be
78% N2 and 22% O2 . For the mixed solvent (air), we replace δ1 in Eq. 37 by
X
δ̄ = Φi δi
i

where Φi is the volume fraction of component i . The sum includes all components, but we
assume the solubility of H2 to be so low that its contribution can be neglected. The volume
fraction is defined as
xi vi
Φi = P
j x jv j

We will need data for the solubility parameter, defined by Eq. (7-33) in the textbook:
! 21
∆vap u
δi =
v 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
1
B in Eq. 37 are determined from Table 8. which gives A = −0.435 (J cm−3 )− 2 , B = −0.982.
1
(If we instead use the data from Table 7-1 in the textbook, we find A = −0.461 (J cm−3 )− 2 ,

41
 Table 7: Physical properties of gases.
From given data From Table 7-1
∆vap h ∆vap u vi δi vi δi
Comp. J mol−1 J mol−1 cm3 mol−1 (J cm−3 )0.5 cm3 mol−1 (J cm−3 )0.5
CH4 8750 8000 35.6 15.0 35.3 15.1
CO 5530 4780 37.0 11.4 37.1 11.7
N2 5110 4360 37.5 10.8 38.1 10.8
O2 6550 5800 27.9 14.4 28.0 14.7

Table 8: Solubility parameters.

Component xH2 ln xH2 δi /(J cm−3 )0.5
CH4 5.49×10−4 -7.507 15.0
−3
CO 2.63×10 -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
1
from the data in Table 9. which gives δ̄ = 11.4 (J cm−3 ) 2 . (If we instead use the data from
1
Table 7-1, we find δ̄ = 11.5 (J cm−3 ) 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,
xH2 = 2.63 × 10−3

Using data from Table 7-1 gives

xH2 = 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 N2 and O2 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:
" !#
s s
∆vap h 1 1
Pi (T ) = Pi (T b ) exp − −
R T Tb

Using this, we find the values listed in Table 4. To compute the vapour pressure of liquid
air at 90 K, we first determine the activity coefficients from the van Laar model (we neglect

Table 9: Solubility parameters for liquid air

Component xi vi /cm3 mol−1 Φi δi /(J cm−3 )0.5
N2 0.78 37.5 0.827 10.8
O2 0.22 27.9 0.173 14.4

42
 Table 10: Normal boiling point.
Component T b /K Pis /bar
CH4 111.5 1.106
CO 83 1.89
N2 77 3.209
O2 90 1.013

H2 in the liquid phase because xH2 is low):

A′
ln γN2 =  2
A′ xN2
1+ B′ xO2

B′
ln γO2 =  2
B′ xO2
1+ A′ xN2

where
vN2
A′ = δN2 − δO2 2


RT
37.5 cm3 mol-1
= -1 -1
(10.8 − 14.4)2 J cm-3 = 0.6495
8.3145 J mol K × 90 K
vO2
B′ δN2 − δO2 2


=
RT
27.9 cm3 mol-1
= -1 -1
(10.8 − 14.4)2 J cm-3 = 0.4832
8.3145 J mol K × 90 K

which gives

0.6495
ln γN2 =  2 = 0.0195
1 + 0.6495×0.78
0.4832×0.22
∴ γ N2 = 1.0197
0.4832
ln γO2 =   = 0.330
0.4832×0.22 2
1 + 0.6495×0.78
∴ γ O2 = 1.391

and finally

PN2 = PNs 2 γN2 xN2 = 3.209 bar × 1.0197 × 0.78 = 2.55 bar
PO2 = POs 2 γO2 xO2 = 1.013 bar × 1.391 × 0.22 = 0.31 bar
P = PN2 + PO2 + PH2 = 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-suffix Margules expansion for the excess Gibbs energy, see Chapter 10-6 in
the textbook leading to Eq. (10-54):

ln HH2 ,air = xN2 ln HH2 ,N2 + xO2 ln HH2 ,O2 − aN2 ,O2 xN2 xO2

where aN2 ,O2 is estimated by (see footnote on p. 615 in the textbook)

δN2 − δO2 2 vN2 + vO2

aN2 ,O2 ≈
2RT
(10.8 − 14.4)2 J cm-3 (37.5 + 27.9) cm3 mol-1
= = 0.566
2 × 8.3145 J mol-1 K-1 × 90 K
Data for Henry’s constant HH2 ,N2 are found in Table 10-4 in the textbook:

T /K HH2 ,N2 /bar

79 456
95 345

Interpolated to 90 K; HH2 ,N2 = 380 bar; ln HH2 ,N2 = 5.940. We have no data for HH2 ,O2 , and
estimate it from the correlation found under Method 1:
!
PH 2
ln xH2 = ln = AδO2 + B
HH2 ,O2
ln HH2 ,O2 = ln PH2 − AδO2 − B = 0 + 0.435 × 14.4 + 0.982 = 7.246

This gives:

ln HH2 ,air = 0.78 × 5.940 + 0.22 × 7.246 − 0.566 × 0.22 × 0.78 = 6.130
HH2 ,air = 460 bar
1 bar
xH2 = = 2.2 × 10−3
460 bar

Problem 10.6
We are supposed to use the Orentlicher correlation,
 
∞ s
f2 (P1s ) A 2
  v̄2 P − P 1
ln = ln H2,1 + x1 − 1 + (6.1)
x2 RT RT

with the following data for H2 in N2 around 77 K taken from Table 10-4 in the textbook:
(P s ) 3
T /K H2,11 /bar v̄∞
2 /cm mol
−1
A/J mol−1
68 547 30.4 704
79 456 31.5 704

44
The normal boiling point of N2 is 77 K, which means that P1s = 1 atm = 1.013 bar. By
(P s ) 3
linear interpolation, we find for T = 77 K: H2,11 = 473 bar and v̄∞ −1
2 = 31.3 cm mol . We
then find from Eq. (10.1):

f2 704 J mol-1 h
2
i
ln = ln 473 + (1 − x2 ) − 1 ref Eq.6.2 (38)
x2 8.3145 J mol-1 K-1 77 K
31.3 cm3 mol−1 (100 − 1.013) bar
+
83.1451 bar cm3 mol-1 K-1 77 K
= 6.6430 + 1.0996 x22 − 2x2
 
ln x2 = ln f2 − 6.6430 − 1.0996 x22 − 2x2

The fugacity of hydrogen in the gas phase is

f2 = ϕ2 P2 = 0.88 × (100 − 1.013) bar = 87.1 bar

∴ ln f2 = 4.4672

We now set up an iterative solution method, starting with x2 = 0:

Guessed x2 ln x2 from Eq. (6.2) New value of x2

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 x2 = 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:

f2g = H2,1 x2
f2l = ϕl2 x2 P

in the limit of x2 → 0. At equilibrium, the two fugacities are equal, i.e.

H2,1 = ϕl2 P (39)

The fugacity coefficient 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):

RT a(T )
P= − (40)
v − b v(v + b) + b(v − b)

45
where the coefficients for each of the components are:

a(T ) = a(T c )α(T )

(RT c )2
a(T c ) = 0.45724
Pc
h  p i2
α(T ) = 1 + β 1 − T/T c (41)
β = 0.37464 + 1.54226ω − 0.26992ω2
RT c
b = 0.07780
Pc
The following physical properties are found in Reid et al. (the last five columns are com-
puted from Eq. 41:

Component T c /K Pc /bar ω β
n-butane 425.2 38.0 0.199 0.6709
N2 126.2 33.9 0.039 0.4344

a(T c ) a(T =250K) b

Component α(T = 250K) 106 cm6 bar mol−2 106 cm6 bar mol−2 cm3 mol−1
n-butane 1.3374 15.039 20.113 72.38
N2 0.6773 1.485 1.006 24.08

The mixing rules are:

XX √
a = xi x j ai a j (1 − ki j )
i j
X
b = xi bi
i

where k11 = k22 = 0 and k12 = 0.0867. The expression for the fugacity coefficient is:
" P # √
bk  Pv  P(v − b) a 2 i xi aik bk v + (1 + 2)b
ln ϕk = − 1 − ln − √ − ln √
b RT RT 2 2bRT a b v + (1 − 2)b
In the limit of x2 → 0, we get the following relation:
!
f2
H2,1 = lim = lim (ϕ2 P)
x2 →0 x2 x2 →0

The following results are found from Eq. 42:

a = a1
b = b1
P = P1s = 0.392 bar
v = v1s = 93.035 cm3 mol-1
√
b2 P1s v1s P1s (v1s − b1 ) v1s + (1 + 2)b1
! " #
a1 2a12 b2
ln ϕ2 = − 1 − ln − √ − ln √
b1 RT RT 2 2b1 RT a1 b1 v1s + (1 − 2)b1

46
The value of the fugacity coefficient is:

24.08 cm3 mol-1 0.392 bar × 93.035 cm3 mol-1

!
ln ϕl2 = −1
72.38 cm3 mol-1 83.145 bar cm3 mol-1 K-1 × 250 K
0.392 bar × (93.035 − 72.38) cm3 mol-1
− ln
83.145 bar cm3 mol-1 K-1 × 250 K
20.113 × 106 cm6 bar mol-2
− √
2 × 2 × 72.38 cm3 mol-1 × 83.145 bar cm3 mol-1 K-1 × 250 K
 √
 2 1.006 × 20.113 × 106 × (1 − 0.0867) cm6 bar mol-2 24.08 cm3 mol-1 

×  − 
20.113 × 106 cm6 bar mol-2 72.38 cm3 mol-1
h √ i
93.035 + (1 + 2)72.38 cm3 mol-1
× ln h √ i
93.035 + (1 − 2)72.38 cm3 mol-1
= 7.0002
∴ ϕl2 = exp(7.0002) = 1097

From Eq. 39 we then find H2,1 = 1097 × 0.392 bar = 430 bar

Question b

The partial molar volume is defined as

!
∂V
v2 =
∂n2 P,T,n1

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, n1 , and n2 :

! ! ! !
∂P ∂P ∂P ∂P
dP = dT + dV + dn1 + dn2
∂T V,n1 ,n2 ∂V T,n1 ,n2 ∂n1 V,T,n2 ∂n2 V,T,n1

At constant P, T , and n1 , we have

! !
∂P ∂P
dP = dV + dn2 = 0
∂V T,n1 ,n2 ∂n2 V,T,n1

so under these conditions,

(∂P/∂n2 )V,T,n1
v2 = −
(∂P/∂V)T,n1 ,n2

47
We can now evluate the differentials of P in the limit x2 → 0. From Eq. 40:
nRT n2 a(T )
P = − 2
V − nb V + 2Vnb − n2 b2
∂P (V − nb) n′ RT − nRT (−nb′ − n′ b)
=
∂n2 (V − nb)2
 
V 2 + 2Vnb − n2 b2 (2nn′ a + n2 a′ ) − n2 a[2V(n′ b + nb′ ) − (2nn′ b2 + 2n2 bb′)]
−
V 2 + 2Vnb − n2 b2 2

RT (Vn′ + n2 b′ )
=
(V − nb)2
V 2 n(2n′ a + na′ ) + 2Vn2(bn′ a + nba′ − nb′ a) + bn4 (−ba′ + 2b′ a)
−
V 2 + 2Vnb − n2 b2 2

RT (vn′ + nb′ ) v2 (2n′ a + na′) + 2v(bn′ a + nba′ − nb′ a) + b(−bna′ + 2nb′ a)

= −
n (v − b)2 n v2 + 2vb − b2 2


 
∂P nRT V 2 + 2Vnb − n2 b2 × 0 − n2 a(2V + 2nb)
= − −
∂V (V − nb)2 V 2 + 2Vnb − n2 b2 2


RT 2a(v + b)
= − 2
+
n (v − b) n v + 2vb − b2 2
2

Here,
∂n
n′ = =1
∂n2
√
∂ n21 a1 + 2n1 n2 a1 a2 (1 − k12 ) + n22 a2
" #
∂a
a′ = =
∂n2 ∂n2 (n1 + n2 )2
 √   √ 
(n1 + n2 )2 2n1 a1 a2 (1 − k12 ) + 2n2 a2 − n21 a1 + 2n1 n2 a1 a2 (1 − k12 ) + n22 a2 2 (n1 + n2 )
=
(n1 + n2 )4
1 h √   √ i
= 2x1 a1 a2 (1 − k12 ) + 2x2 a2 − 2 x21 a1 + 2x1 x2 a1 a2 (1 − k12 ) + x22 a2
nh
√ i
na′ = 2 x1 a1 a2 (1 − k12 )(1 − 2x2 ) − x21 a1 + x2 a2 (1 − x2 )
h √ i
= 2x1 −x1 a1 + a1 a2 (1 − k12 )(x1 − x2 ) + x2 a2
!
∂b ∂ n1 b1 + n2 b2
b′ = =
∂n2 ∂n2 n1 + n2
(n1 + n2 ) b2 − (n1 b1 + n2 b2 )
=
(n1 + n2 )2
1
= (b2 − x1 b1 − x2 b2 )
n
nb′ = x1 (b2 − b1 )
In the limit x2 → 0, the expressions reduce to
h √ i
na′ = 2 −a1 + a1 a2 (1 − k12 )
nb′ = b2 − b1

48
 2
h  √ i
∂P RT (v1 + b2 − b1 ) v1 2a1 + 2 −a1 + a1 a2 (1 − k12 )
= −
n (v1 − b1 )2
2
∂n2

n v21 + 2v1 b1 − b21
h  √  i
2v1 b1 a1 + 2b1 −a1 + a1 a2 (1 − k12 ) − a1 (b2 − b1 )
−  2
n v21 + 2v1 b1 − b21
h  √  i
b1 −b1 2 −a1 + a1 a2 (1 − k12 ) + 2a1 (b2 − b1 )
−  2
n v21 + 2v1 b1 − b21
RT (v1 + b2 − b1 )
=
n (v1 − b1 )2
√ h √ i h √ i
v21 a1 a2 (1 − k12 ) + v1 2b1 a1 a2 (1 − k12 ) − a1 b2 + b1 −b1 a1 a2 (1 − k12 ) + a1 b2
− 2  2
n v21 + 2v1 b1 − b21
√
RT (v1 + b2 − b1 ) a1 a2 (1 − k12 ) a1 b2 (v1 − b1 )
= 2
− 2   +2  2
n (v1 − b1 ) 2
n v1 + 2v1 b1 − b1 2
n v21 + 2v1 b1 − b21
∂P RT 2a1 (v1 + b1 )
= − +
∂V n (v1 − b1 )2 n v2 + 2v1 b1 − b2 2
 
1 1

Evaluated with the given data:

∂P 83.145 bar cm3 mol-1 K-1 × 250 K × (93.035 + 24.08 − 72.38) cm3 mol-1
=
∂n2 n (93.035 − 72.38)2 cm6 mol-2
√
2 × 20.113 × 1.006 × 106 × (1 − 0.0867) cm6 bar mol-2
−
n 93.0352 + 2 × 93.035 × 72.38 − 72.382 cm6 mol-2

2 × 20.113 × 106 cm6 bar mol-2 × 24.08 cm3 mol-1 × (93.035 − 72.38) cm3 mol-1
+
n 93.0352 + 2 × 93.035 × 72.38 − 72.382 2 cm12 mol-4


1763 bar
=
n
∂P 83.145 bar cm3 mol-1 K-1 × 250 K
= −
∂V n (93.035 − 72.38)2 cm6 mol-2
2 × 20.113 × 106 cm6 bar mol-2 × (93.035 + 72.38) cm3 mol-1
+
n 93.0352 + 2 × 93.035 × 72.38 − 72.382 2 cm12 mol-4

25.38 bar cm-3 mol

= −
n

The partial molar volume is then

1763 bar/n
v̄∞
2 = = 69.5 cm3 mol-1
25.38 bar cm-3 mol/n

49
Question c (method I)
The parameter in the two-suffix Margules equation is defined by
A 2
ln γ2 = x
RT 1
The activity coefficient γ2 refers to pure component 2 as reference state (γ2 = 1when
x2 = 1). In this problem, the properties are given at x2 = 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
A 2
ln γ1 = x
RT 2
A ln γ1 ln γ1
∴ = 2
= lim 2
RT x2 x2 →0 x
2

This wil, however, also raise a problem because ln γ1 → 0 in this limit. The change of
reference state is made with use of the Gibbs-Duhem equation at constant P and T :

x1 d ln γ1 + x2 d ln γ2 = 0
x1 A x1 A
d ln γ2 = − d ln γ1 = − 2x2 dx2 = − 2(1 − x2 )dx2
x2 RT x2 RT
We may note that if we use pure component 2 as reference state, we find
Zx2 Zx2 " #
A A 1 2 A 2
ln γ2 = d ln γ2 = − 2 (1 − x2 )dx2 = − 2 (x2 − 1) − (x2 − 1) = − x
RT RT 2 RT 1
x2 =1 x2 =1

We now use pure componnet 1 as reference state:

Zx2 Zx2 !
A A 1 2 A
ln γ2∗ = d ln γ2 = − 2 (1 − x2 )dx2 = − 2 x2 − x2 = − (2x2 − x22 )
RT RT 2 RT
x2 =0 x2 =0

In this limit we may therefore write

f2 = f2 (x2 = 0)a2 = H2,1 γ2∗ x2

f2
∴ = H2,1 γ2∗
x2
f2 2A A 2
ln = ln H2,1 + ln γ2∗ = ln H2,1 − x2 + x (42)
x2 RT RT 2

If we consider ln xf22 as function of x2 and expand around x2 = 0 at constant P and T , we get

 ∂ ln xf2 

!  
f2 H2,1 x2 2
ln = ln +   x2 + ...
x2 x2 x2 =0 ∂x2

P,T,x2 =0
!
∂ ln H2,1
= ln H2,1 + x2 + ... ref Eq.9.5 (43)
∂x2 P,T,x2 =0

50
Comparing Eq. 42 with and using Eq. 39, we find
! " # !
2A ∂ ln H2,1 ∂ ∂ ln ϕ2
− = = (ln ϕ2 + ln P) =
RT ∂x2 P,T,x2 =0 ∂x2 P,T,x2 =0 ∂x2 x2 =0

Note that the differentiation with respect to x2 reprsents the effect of variation in composi-
tion only, and that P and T are held constant (P = P1s ). We must consider both x1 and x2 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 = v̄∞ ∞ ∞ ∞ ∞
1 x1 + v̄2 x2 = v̄1 + (v̄2 − v̄1 )x2

Question c (method II)

An alternative expression for the fugacity of N2 is

f2 = γ2∗ x2 f20

Since the solubility of N2 in n-butane is small, pure solvent is chosen as reference state
(indicated with the asterisk), γ2∗ = 1. The parameter in the two-suffix Margules equation is
defined by
A 2 A
ln γ2∗ = (x1 − 1) = − (1 + x1 )x2
RT RT
Combining Eqs. 39 and gives
f2
= γ2∗ f20 = ϕ2 P
x2
f2
ln = ln γ2∗ + ln f20 + ln ϕ2 + ln P
x2

Expanding ln xf22 in powers of x2 and equating the coefficients of the linear terms, gives
" #
2A ∂ ln ϕ2
− =
RT ∂x2 P=Ps ,x2 =0
1

The expression for ln ϕ2 is

 P √ 
bk  Pv  P(v − b) a  2 i xi aik bk v + (1 + 2)b √ 
ln ϕ2 = − 1 −ln − √  − ln + (1 − 2)b
b RT RT 2 2bRT a b v
This depends on x2 in a complex way. It is assumed in Eq. that P and T are constant (the
v∞
temperature is held constant and the pressure variation gives rise to the term RT2 (P − P1s )).
Under these conditions, v has to vary when x2 varies. Using the chain rule, we get
d ln ϕ2 ∂ ln ϕ2 ∂ ln ϕ2 dx1 ∂ ln ϕ2 dv
= + +
dx2 ∂x2 ∂x1 dx2 ∂v dx2
It is understood here that all differentials are at constant P and T so that

f2 = γ2∗ x2 H2,1 = ϕ2 x2 P

51
or
P
γ2∗ = ϕ2
H2,1
ln γ2∗ = ln(ϕ2 P) − lnH2,1

For small values of x2 we may expand

(P s )
f2 = f2 (x2 = 0)a2 = H2,11 γ2∗ x2
f2 (P s )
∴ = H2,11 γ2∗
x2
f2 (P s ) (P s ) 2A A 2
ln = ln H2,11 + ln γ2∗ = ln H2,11 − x2 + x (9.4)
x2 RT RT 2

If we consider ln xf22 as function of x2 and expand around x2 = 0 at constant P and T , we get

(P1s )
 
 ∂ ln xf2 
 
f2 

 H 2,1 2 x 
2 
ln = ln  +   x2 + ...
x2  x2  ∂x2 
P,T,x2 =0 P,T,x2 =0
(P1s )
 
 ∂ ln H 
(P s ) 2,1 
= ln H2,11 +   x2 + ... (9.5)
∂x2 
P,T,x2 =0

Comparing Eq. 42 with and using Eq. 39, we find

(P1s )
 
2A  ∂ ln H2,1 
" # !
∂ ∂ ln ϕ2
− =  = (ln ϕ2 + ln P) =
RT  ∂x2  ∂x2 P,T,x2 =0 ∂x2 x2 =0
P,T,x2 =0

Note that the differentiation with respect to x2 represents the effect of variation in compo-
sition only, and that P and T are held constant (P = P1s ). We must consider both x1 and x2
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 = v̄∞ ∞ ∞ ∞ ∞
1 x1 + v̄2 x2 = v̄1 + (v̄2 − v̄1 )x2

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
dµ1 (l) = −s1 (l)dT + RT d ln x1
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
dµ1 (s) = −s1 (s)dT
If equilibrium is established after the change, the two changes in chemical potential must
be equal:
−s1 (l)dT + RT d ln x1 = −s1 (s)dT
or
∆fus h1
RT d ln x1 = [s1 (l) − s1 (s)] dT = ∆fus s1 dT = dT (44)
T
Equation 44 is the basic equation for freezing-point depression. Integration from pure
solvent to an actual mixture composition of x1 gives
" #T
x1 ∆fus h1 1
[ln x1 ]1 = −
R T T∗
!
∆fus h1 1 1
ln x1 = − −
R T T∗
where T ∗ is the melting point of pure solvent. This equation can be solved for T :
1 1 R
= ∗− ln x1
T T ∆fus h1
Since the mixture is rich in benzene, and the melting points of the two components are not
very different, we may assume that benzene freezes out first, and consider it as the solvent
(component 1):
1 1 8.3145 J mol-1 K-1
= − ln 0.95 = 0.003631
T 278.7 K 9843 J mol-1
∴ T = 275.4 K

The phase diagram for the system is shown in Figure 20.

53
 360

340

320

T, K
300

280

260
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x1

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 coefficients is available, we may assume
a nonideal mixture in this case. The expression for T is, by analogy to problem 11.1:

1 1 R 1 R
= ∗− ln a1 = ∗ − (ln γ1 + ln x1 )
T T ∆fus h1 T ∆fus h1

In this case, it is not clear which of the components will freeze out first 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 first. 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 coefficients:

A′
ln γ1 =  ′
2
1 + AB′ xx12
B′
ln γ2 =  ′
2
1 + BA′ xx21
v1
A′ = (δ1 − δ2 )2
RT
v2
B′ = A′
v1
A′ v1
=
B′ v2

The phase diagram for this system is shown in Figure 21. We see from the figure that
x1 = 0.1 is at the benzene-rich side of the eutectic point. We therefore consider benzene as

54
 300

280

260

240

T, K
220

200

180

160
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x1

Figure 21: Liquidus curve for the n-heptane-benzene system. Benzene is component 1.

the solvent (component 1) and find:

89 cm3 mol-1 146.54 K

A′ = -1 -1
(18.8 − 15.1)2 J cm-3 =
8.3145 J mol K T T
3 -1
148 cm mol 243.69 K
B′ = A′ -1
=
3
89 cm mol T
3 -1
A′ 89 cm mol
= = 0.6014
B′ 148 cm3 mol-1
A′ 146.54 K 128.76 K
ln γ1 =  2
=  2
=
T
′
 
1 + A x1 B′ x2
T 1 + 0.6014 0.1 0.9
′
B 243.69 K 0.9559 K
ln γ2 =  2 =  =
0.9 2 T
B′ x2

1+ A′ x1
T 1 + 1.6629 0.1

This gives the following expression for the freezing temperature:

8.3145 J mol-1 K-1 128.76 K

!
1 1
= − + ln 0.1
T 278.7 K 9843 J mol-1 T
!
8.3145 × 128.76 1 1 8.3145
1+ = − ln 0.1
9843 T 278.7 K 9843 K
1 + 8.3145×128.76
9843
∴T = 1 8.3145
= 200.39 K
278.7 K
− 9843 K ln 0.1

Problem 11.9
The condition for equilibrium is
f2 (g) = f2 (l)
that is, the fugacity of the CO2 (component 2) is the same in gas and liquid phases. At
194.3 K and x2 = 0.05, the solution is undersaturated with respect to CO2 . If the mole

55
fraction x2 were equal to 0.25, the fugacity of the liquid would have been equal to that of
the solid, i.e.
f2 (g) = f2 (l) = f2 (s) (45)
and the saturation pressure would in that case have been P2s = 0.99 bar. In the actual case
with x2 = 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

P2 = f2 (g) = f2 (l) (46)

The fugacity in the liquid phase is the activity times the fugacity of a standard state,

f2 (l) = a2 f2L = γ2 x2 f2L (47)

where f2L is the fugacity of (the hypothetical state) pure liquid CO2 at T = 194.3 K. This
implies that the standard state corresponding to the activity coefficient γ2 is pure liquid
CO2 . In order to use the information provided by Eq. 45, it is convenient, however, to use
pure solid CO2 at T = 194.3 K as the standard state. This gives
f2L
f2 (l) = γ2 x2 f2L = γ2 x2 f2S = f2 (s) = f2S = P2s
f2S
where f2S is the fugacity of (pure) solid CO2 at T = 194.3 K. Combining Eqs. 45–47 gives
f2L
P2 = γ2 x2 f2S f2S
for x2 = 0.05
f L
P2s = γ2 x2 P2s f2S for x2 = 0.25
2

We first determine the activity coefficient from the data at x2 = 0.25:

1 f2S 0.56
γ2 (x2 = 0.25) = L
= = 2.24
x2 f2 0.25
The activity coefficient at x2 = 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-suffix Margules
equation:
A 2
ln γ2 =x
RT 1
A ln γ2 ln 2.24
∴ = 2 = = 1.4337
RT x1 0.752
Hence,
A
ln γ2 (x2 = 0.05) = 0.952 = 1.4337 × 0.952 = 1.2939
RT
∴ γ2 (x2 = 0.05) = 3.6471

The partial pressure of CO2 at x2 = 0.05 is therefore

1
P2 = 3.6471 × 0.05 × 0.99 bar × = 0.322 bar
0.56

56
Chapter 12

Problem 12.3
The thermodynamic condition for equilibrium is

µ′A = µ′′A (48)

where µA 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

µA = µoA + RT ln xA + RT ln γA (49)

where µoA is the chemical potential in a reference state, xA is the mole fraction of the alcohol,
and γA is the activity coefficient of the alcohol. We note that the excess Gibbs energy is of
the form
gE = AxA xB
where A is a constant and xB is the mole fraction of the solvent (hexane or DMSO). This
leads to the following form for the activity coefficient:

RT ln γA = Ax2B (50)

Combining Eqs. 48–50 gives

RT ln x′A + A′ x′B 2 = RT ln x′′A + A′′ x′′B 2

x′A
!
RT ln ′′ = A′′ 1 − x′′A 2 − A′ 1 − x′A 2



(51)
xA
 
 ′ !

 xA  A′′ − A′
ln K = ln  lim =
 x′A →0 x′′A  RT
′′
xA →0

The problem is now to find 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 find

dgE = vE dP − sE dT (52)

57
This can be used to compute the difference 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 sE available. Instead we use the Gibbs-
Helmholtz equation for the temperature variation:

d(gE /T ) = hE d(1/T )

The effect of the pressure change is (assuming constant excess volumes over the pressure
range in question):
∆gE = vE ∆P
The effect of the temperature change is (assuming constant excess enthalpies over the tem-
perature range in question):
gE
! !
E 1
∆ =h ∆
T T
Inserting the given numbers leads to for the hexane phase and the DMSO phase at the actual
pressure:

gE = 2400x′A x′H J mol-1 + 16x′A x′H cm3 mol-1 × 990 N cm-2 = 2558.4x′A x′H J mol-1
gE = 320x′′A x′′D J mol-1 − 10x′′A x′′D cm3 mol-1 × 990 N cm-2 = 221.0x′′A x′′D J mol-1

Similarly at the actual temperature:

!
-1 303 K 303 K
g E
= 2558.4x′A x′HJ mol × + 4800x′A x′H J mol-1 × 1 −
273 K 273 K
′ ′ -1
= 2312.1xA xH J mol
∴ A′ = 2312.1 J mol-1 !
-1 303 K -1 303 K
gE = ′′ ′′
221.0xA xD J mol × ′′ ′′
+ 600xA xD J mol × 1 −
273 K 273 K
′′ ′′ -1
= 179.4xA xD J mol
∴A ′′
= 179.4 J mol-1

Used in Eq. 51, we then find:

(179.4 − 2312.1) J mol-1

ln K = = −0.8465
8.3145 J mol-1 K-1 × 303 K
∴ 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,

µl (P, T ) = µs (P, T )

58
 200.000
150.000
100.000
50.000

P, bar
0.008

0.006

0.004
265 270 275 280 285 290 295 300
T, K

Figure 22: P − T diagram for benzene.

the equilibrium at P + dP and T + dT will be given by

µl (P + dP, T + dT ) = µs (P + dP, T + dT )

The corresponding changes in the chemical potentials must be the same in the two phases,

dµl = µl (P + dP, T + dT ) − µl (P, T ) = dµs

The change in chemical potential is given by

dµl = vl dP − sl dT

and similarly for the solid phase. This gives the following differential equation for the
liquidus curve:
   
vl − vs dP = sl − s s dT (53)

The molar volumes at 278.7 K may be found from the given densities:

M 78.1 g mol-1
vl
= l
= -3
= 87.65 cm3 mol-1
ρ 0.891 g cm
M 78.1 g mol-1
vs = = = 77.33 cm3 mol-1
ρ s 1.010 g cm-3
vl − vs = (87.65 − 77.33) cm3 mol-1 = 10.32 cm3 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:
!
o∆vap h 1 1
ln P = ln P − − o
R T T

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 find
∆vap h
= 1785 K
R
∆sub h
= 2310 K
R
Enthalpy is a state function, and at the triple point we must have

∆fus h = ∆sub h−∆vap h = (2310−1785) K×83.145 bar cm3 mol-1 K-1 = 43651 bar cm3 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 h 43651 bar cm3 mol-1
∆fus s = = (56)
T T
The resukts 54 and 56 inserted into Eq. 53 gives:

dT
10.32 cm3 mol-1 dP = 43651 bar cm3 mol-1
T
43651 bar cm3 mol-1 T T
∴ P = Po + ln = P o
+ 4230 bar × ln
10.32 cm3 mol-1 To To
The fixed points Po and T o are given by the normal melting point: Po = 1.013 bar and
T o = 278.7 K, leading to

T
P = 1.013 bar + 4230 bar × ln
278.7 K
At 200 bar, we then find:
T
200 bar = 1.013 bar + 4230 bar × ln
278.7! K
(200 − 1.013) bar
∴ T = 278.7 Kexp = 292.1 K
4230 bar

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 (x1 ln x1 + x2 ln x2 ) + gE (P, T ) (57)
At 1 atm and 273 K, the excess Gibbs energy of the mixture is given as

gE (1 atm, 273 K) = RT × 1.877 × x1 x2

60
At a pressure P and 273 K, the excess Gibbs energy is
ZP
gE (P, 273 K) = gE (1 atm, 273 K) + vE dP
1 atm
ZP
= RT × 1.877 × x1 x2 + x1 x2 (4.026 − 0.233 ln P)dP
1 atm
3 -1 -1
= 82.0578 atm cm mol K × 1.877 × 273 K × x1 x2
h i
+ 4.026 cm3 mol-1 (P − 1 atm) − 0.233 cm3 mol-1 (P ln P − P + 1 atm) x1 x2
= (42048 − 4.026 − 0.233) atm cm3 mol-1 × x1 x2
+ (4.026 + 0.233 − 0.233 ln P) cm3 mol-1 × P × x1 x2
= (42044 atm + 4.259P − 0.233P ln P) × x1 x2 cm3 mol-1 (58)
Eq. 58 in 57 gives at 273 K:
∆mix g = 22402 atm cm3 mol-1 (x1 ln x1 + x2 ln x2 )
+ (42044 atm + 4.259P − 0.233P ln P) × x1 x2 cm3 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 x1 = x2 = 0.5. To find the minimum

0
-200 ∆mixg, P=2000 atm
-400
∆mixg, J mol-1

-600
∆mixg, P=10 atm
-800
-1000
-1200
-1400
∆mixg
id

-1600
-1800
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x1

Figure 23: Gibbs energy of (regular) mixing.

pressure at which the mixture separates, we have to find the solution to

∂2 ∆mix g
= 0 at x1 = 0.5
∂x21
With gE (P, 273 K) of the form
gE (P, 273 K) = A(P)x1 x2
where
A(P) = (42044 atm + 4.259P − 0.233P ln P) cm3 mol-1

61
we first find
∂∆mix g
= RT [ln x1 − ln(1 − x1 )] + A(1 − 2x1 )
∂x1
and then
∂2 ∆mix g RT
2
= − 2A
∂x1 x1 (1 − x1 )
Setting this expression equal to 0 at x1 = 0.5 gives

RT 82.0578 atm cm3 mol-1 K-1 × 273 K

A= 2
= 2
= 44804 atm cm3 mol-1
2 × 0.5 2 × 0.5
This corresponds to a pressure given by the equation

(42044 atm + 4.259P − 0.233P ln P) cm3 mol-1 = 44804 atm cm3 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 x1 = 0.5), given by
∂∆mix g
= RT [ln x1 − ln(1 − x1 )] + A(P = 1500 atm)(1 − 2x1 ) = 0
∂x1
This gives the following solution for x1 :

A(P) = (42044 atm + 4.259 × 1500 atm − 0.233 × 1500atm ln 1500)cm3 mol-1
= 45877 atm cm3 mol-1

which makes

82.0578 atm cm3 mol-1 K-1 × 273 K [ln x1 − ln(1 − x1 )]

+45877 atm cm3 mol-1 (1 − 2x1 ) = 0

and finally
x′1 = 0.37, x′′1 = 0.63

62