Chapter 7 Solutions

Engineering and Chemical Thermodynamics 2e

Milo Koretsky
Wyatt Tenhaeff
School of Chemical, Biological, and Environmental Engineering
Oregon State University
milo.koretsky@oregonstate.edu

7.1
The fugacity in the liquid is greater. At equilibrium, the fugacities are equal. For this to be the
case, the air in the room would have to be saturated (100% relative humidity). Since the air
contains less water than saturation, water will spontaneously evaporate, and the fugacity of the
vapor is smaller.

7.2
hmix = 0. The molecular basis for the Lewis fugacity rule is that all the intermolecular
interactions are the same. Therefore, the energy of the mixture is equal to that of the sum of the
pure species.

7.3
Mixture A. The molecular basis for the Lewis fugacity rule is that all the intermolecular
interactions are the same. n-pentane and n-hexane both have dispersion interactions and they are
approximately the same size (polarizability is similar)

7.4
The van der Waals parameter b approximates repulsive interactions with a hard sphere model
that is determined by the size of the molecules. Hence it is the weighted average of the size of
each of the species in the mixture. That can be seen in the form for a binary mixture:

b y1b1 y2b2
The parameter a represents van der Waals attractive interactions and is a two-body
interactions. Thus, you must sum together all the possible pair-wise interactions. That can be
seen in the form for a binary mixture:
a y1 y1a1 y1 y2 a12 y2 y1a21 y2 y2 a2
y12 a1 2 y1 y2 a12 y22 a2

7.5
There are many ways to approach this problem. One approach is shown below. If we assume an
ideal solution, for water (species 1), we get:
y1P x1P1sat

Solving for x1 at equilibrium

x1eq

y1 P
0.9
P1sat

Since we are at 90% RH. If we calculate the mole fraction of water for 96.55 mass % water, we
get x1 = 0.99 in sweat. Since x1 x1eq , water will have a tendency to evaporate so the fugacity of
water in the liquid is greater than the fugacity of water in the vapor.

7.6
(a)
The magnitude of the Henrys Law constant is governed by the unlike (1-2) interactions. In the
case of acetone and water, strong intermolecular attraction exists due to dipole-dipole
interactions and hydrogen bonding. With methane and water, only dispersion is present.
Therefore, the interactions between methane and water are weaker, and the fugacity is greater.
There is a greater partial pressure for the methane-water system. The Henrys Law constant is
greater for this system.
(b)
The Henrys Law constant describes the unlike interactions. Since the unlike interactions result
in a fugacity that is equal to the pure fugacity of a, the unlike and like interactions are equal in
magnitude. Therefore, the solution is ideal for the entire composition range.
Activity Coefficient vs. Composition
1.2
1

ga

0.8
0.6
0.4
0.2
0
0

0.2

0.4

0.6
xa

0.8

7.7
(a)
First, we must realize that

h E hmix
Since
gE

hmix

T2
P, ni

E
we see that g

is independent of temperature when the pressure and number of moles is held

T
constant. Therefore,

gE

Ax x

a b

P, ni T P, ni

is independent of temperature, which implies

A

T P, ni

is independent of temperature at constant pressure and moles. A ~ T

(b)
Equation 7.24 provides

g E

v E vmix

T , n i

Substituting the two suffix Margules equation in for the excess Gibbs energy, we find
Ax a xb
0

T , ni

Therefore, we can see that the A parameter is independent of pressure at constant temperature
and moles.

7.9
(a) See graph below. Since the Henrys law constant which represents a-b interactions is less
than the pure species fugacity, the tendency to escape of a-b is lower and the a-b interactions
are stronger.
200

fa xa f a

150
[bar] 100

fa xa a

50

0
0

0.5

xa

(b) Both lnga and lngb go to 1 and xi goes to 0. Therefore the Henrys law reference state is being
used. Since gi> 0 the tendency to escape for some a-a or b-b interactions is greater than all a-a
interactions. Therefore the a-b interactions are stronger.

1.6

1.2

lng b
0.8

0.4

0
0

0.5

xa

7.10

7.11
200 oC and 1.56 MPa (Pisat = 1.55 MPa) ( isat 1 ) so

70 oC and 1 bar (Pisat = 31.2 kPa) ideal

fi
1
Pi sat

fi
1
Pi sat

70 oC and 1.56 MPa (Pisat = 31.2 kPa) Poynting correction

fi
1
Pi sat

7.12
Initially the system contains water and nitrogen in vapor liquid equilibrium at 1 atm. The
liquid is mostly water and the vapor contains a mole fraction of water where the fugacity of
the vapor equals the fugacity of the liquid. When the third component is added to the liquid,
the mole fraction of water in the liquid decreases, so its fugacity also decreases. To maintain
equilibrium, the fugacity of water in the vapor must also decrease to the point where it equals
the fugacity of water in the liquid. Therefore, some water will condense and the number of
moles of water in the vapor will decrease.

7.13

fi l fi v yi P Pi sat 2.34 kPa

7.14
(a)
Use Equation 7.7:
fv
g i g i RT ln i
Plow

Assume Plow 10 kPa . From the steam tables at 500 C

kJ
kJ
kJ
Plow 10 kPa : g i 3489.0 773.15K 9.8977
4163.4

kg
kg K
kg

kJ
kJ
kJ
P 2 MPa : g i 3467.6 773.15K 7.4316
2278.1

kg
kg K
kg

Therefore,

2278.1
fi v 10 kPa exp

kJ
kJ
kg 4163.4 kg 1000 J/kJ 0.0180148 kg/mol

8.314 mol K 773.15 K

f iv 1970 kPa 1.97 MPa

i 0.985
(b)
For 500 C and 50 MPa, we obtain the following from the steam tables

kJ
kJ
kJ
g i 2720.1 773.15K 5.1725
1279.0

kg
kg K
kg

Using data from Part (a), we can calculate the fugacity and fugacity coefficient:

1279.0
v
fi 10 kPa exp

v
fi 32.4 MPa
and

i 0.648

kJ
kJ
kg 4163.4 kg 1000 J/kJ 0.0180148 kg/mol

J
8.314
773.15
K

mol K

7.15
(a)
Equation 7.8 states

f iv P
v dP
RT ln
Plow i

Plow
However, the Berthelot equation is not explicit in molar volume, so the integral must be
transformed.
RT
2a
dP

dv
vi b 2 Tvi3

Substituting this result into the integral, we get

f iv vi RTvi
2a

RT ln

dv

2
2
Plow
Tv

RT i
Plow

To determine the integral of the first term above, we use decomposition by partial fractions:

v b

1
b

v b v b2

so

vi

RT
Plow

2 dv lnv i b
vi b
v i b
vi

vi

RT
Plow

and

i
f iv b
2a

ln

ln(vi b)

2
Plow vi b
RT
v
i RT

Plow

f iv 1
1

ln
ln
b

Plow vi b RT

Plow

vi b 2a

RT 2
RT
b
Plow

1 Plow

vi RT

Since

RT
b , the expression simplifies to
Plow

f iv 1
P
P v b 2a
b
ln
low ln low i

Plow vi b RT
RT

RT 2

1 Plow

vi RT

If we add ln Plow to both sides and let Plow 0 , we obtain

lnf iv

v b
b
2a
ln i

2
vi b
RT RT v i

Therefore,

f iv

b
RT
2a
exp

vi b vi b RT 2 vi

To obtain an expression for iv , we divide our expression for fugacity by total pressure:

iv

b
f iv
RT
2a

exp

P P v i b v i b RT 2v i

(b)
From Problem 4.29, we got
v c 3b

3RTc
8Pc

and

9
a v c RTc2
8

If we substitute into the definition for fugacity coefficient above, we get

iv

1
f iv
8Tr
9

exp
2
P Pr 3v i,r 1 3v i,r 1 4Tr v i,r

7.16
Equation 7.8:

f iv
vi dP RT ln Plow

Plow
P

For the Redlich-Kwong EOS

P

RT
a
1/ 2
v b T v v b

so

RT
a
a

dP

2
2 dv
1/ 2 2
v b T v v b T1/ 2v v b
Therefore,

RT
Plow

vRT

v b

f iv
a
a

dv

RT
ln

T1/ 2v v b T1/ 2 v b2
Plow

To determine the integral of the first two terms term above, we use decomposition by partial
fractions. For the first term,

v b

1
b

v b v b2

so

RT
Plow

b
v
dv lnv b

2
v b
v b

For the second term:

1
1 1
1

v v b b v v b
so

v
RT
Plow

RT
Plow

1
1 v
dv ln

v v b
b v b

v
RT
Plow

Thus, we get

fv
b
v
a
a
RT ln i RT lnv b RT
1/ 2 ln
1/ 2
v b T b v b T v b
Plow

If we note that

RT
Plow

RT
b and let Plow 0 , we obtain
Plow

a
a
RT
b
v
RT ln f iv RT ln
RT
1 / 2 ln
1/ 2
vb
vb T b vb T
v b
Therefore,

f iv

RT
a
a
v
exp
ln

vb
v b RT 3 / 2 b v b RT 3 / 2 v b

iv

v
f iv
RT
a
a

exp
ln

P P v b v b RT 3 / 2b v b RT 3 / 2 v b

and

7.17
Equation 7.8:

f iv
vi dP RT ln Plow

Plow
P

The Peng-Robinson EOS can be written

P

RT
a (T)
2
v b v 2vb b2

Thus,

2a (T)v b
RT

dP

dv
v b2 v 2 2vb b 2 2

Therefore,

RT
Plow

f iv
2a (T)v b
RT
v

dv

RT
ln

v b2 v 2 2vb b 2 2
Plow

Simplifying, we get

v
fi v
v
2a (T )
ln
dv

2
RT
RT v b
Plow
Plow

v v b

RT
Plow

2vb b

2 2

dv

(1)

To determine each of the integrals in Equation 1, we use decomposition by partial fractions. For
the first integral:

v b

1
b

v b v b2

so

RT
Plow

b
v
dv lnv b

2
v b
v b

v
RT
Plow

(2)

For the second integral, decomposition leads to:

v v b
2vb b

so

RT
Plow

1
v b
b
2
2
v 2vb b
v 2 2vb b2

v v b

2 2

2vb b 2

dv

RT
Plow

v
1
v b dv
dv b
2
2
2
2 2
v 2vb b
RT v 2vb b

(3)

Plow

We again use partial fractions. For the first term in Equation (3):
1
v 2 2vb b 2

1
1
1

2 2b v 1 2 b v 1 2 b

so
v

1
v 1 2 b
v 2 2vb b 2 dv 2 2b ln v 1 2 b RT
RT
1

(4)

Plow

Plow

For the second term in Equation (3):

v b

v 2 2vb b

2 2

v b

v 2 2vb b

2 2

2b

(5)

v 2 2vb b2

Equation (5) can be substituted into Equation (3) to give two terms. The first term gives:

RT
Plow

v b

b
dv
2
2
2
v 2 2vb b2 2v 2vb b RT

(6)

Plow

The second term is somewhat more problematic. Again decomposition gives:

1
1
1

4b v 1 2 b v 1 2 b
2
2 2
v 2vb b

2b

or
2
2

1
1
1
1
1

v 1 2 b v 1 2 b v 1 2 b
4b v 1 2 b
2
2 2

v 2vb b

(7)

2b

Intergrating the first and third term in Equation (7) gives:

2

1
1

v 1 2 b dv 4 v 1 2 b RT

4 RT

(8)

Plow

Plow

and
2

1
1

dv
v 1 2 b
4 v 1 2 b RT

4 RT

(9)

Plow

Plow

From above the second term gives:

v

1
1
1
v 1 2 b

v 1 2 b v 1 2 b 4 2b ln v 1 2 b RT

2 RT

(10)

Plow

Plow

Substituting Equations (4). (6). (8), (9) and (10) into Equation (3) gives:
vv b

1
v 1 2 b
b
dv
ln

2
2
2
2 2b v 1 2 b RT 2 v 2vb b 2 RT
RT v 2vb b 2

Plow

Plow
v

Plow

1
1
1
v 1 2 b

ln
4 v 1 2 b RT 4 v 1 2 b RT 4 2b v 1 2 b RT

Plow

Plow

Plow

Simplifying Equation (11) gives

v

RT
Plow

v 1 2 b
v
1 ln

dv

2
2
2
2
2 2

RT
4
2b
2
v

2vb

b
v

1
2
b

2vb
b

v v b

Plow

(12)

(11)

Substituting Equations (12) and (2) into Equation (1) gives

v
v

v 1 2 b
f iv
b
2a (T) 1
v

ln
ln

RT lnv b RT
2
2
RT

P
v

b
RT

4
2b
2
v

2vb
b
low
v 1 2 b

RT

Plow

Plow

If we note that

RT
b and let Plow 0 , we obtain
Plow

v 1 2 b
RT b a (T) 1
v

ln f i ln
ln

v b v b
RT 2 2b v 1 2 b v 2 2vb b 2

and

RT b a (T) 1
v 1 2 b
v

ln ln
ln
2

P
v

b
v

b
RT
2
2b
v

2vb

v 1 2 b

v
i

7.18
(a)
We can calculate the fugacity from the steam tables using the following equations

fv
g i g io RT ln i
Plow

g i hi Tsi
We can take the reference state to be 374 C and 10 kPa. Using enthalpy and entropy values
from the steam tables, interpolation gives:

kJ
g io 2934.5
kg

kJ
g i 890.9
kg

Therefore,

J
g io 52864

mol

J
g i 16049
mol

Now, the fugacity can be calculated:

16049 J 52864 J
mol
mol

f iv 10 kPa exp
9382 kPa

8.314
647 K

mol

f iv 9.38 MPa
(b)
Following the development in Example 7.2, we can use the following equation to calculate the
fugacity from the van der Waals EOS,
b
v b 2a
f iv exp
ln i

RT RTvi
vi b

The a and b parameters for water are

J m3
a 0.554

mol

b 3.05 10

m3

mol

The molar volume can be found from the van der Waals equation using the solver function on
a calculator.

m3
vi 3.80 10 4

mol
Substituting these values into the expression for fugacity, we get

f iv 9.77 MPa
(c)
The reduced temperature and pressure can be calculated from data in Table A.1.2:
Tr 1

0.344

Pr 0.52

By interpolation of the data in Tables C.7 and C.8, we obtain

log 0 0.08

log 1 0.0152

Calculate :

log log 0 log 1

0.82
Therefore,

f iv P 114 atm0.82 9.47 MPa

The agreement in values is good for the three methods. However, Part (a) likely provides the
most accurate value since it is based directly on measured data for water.

7.19
The solution method will be illustrated for parts A and F only. The answers only will be given
for the remaining parts. The generalized correlation tables can be used to answer each part,
except Part F, for which we can use the van der Waals EOS.

(a) CH4
The reduced temperature and pressure can be found using data from Appendix A:
Tr 4.06

Pr 3.26

Also from Appendix A,

0.008
Using reduced temperature and pressure, the fugacity coefficient can be found from Tables C.7
and C.8:

log iv log i0 log i1 0.0176 0.0080.0614 0.0181

iv 1.04
Calculate fugacity:

f iv 156 bar
(b) C2H6

iv 1.02
f iv 153 bar
(c) NH3

iv 0.98
f iv 147 bar
(d) (CH3)2CO

iv 0.842
f iv 126.3 bar

(e) C6H12

iv 0.803
f iv 120.5 bar
(f) CO
Following the development in Example 7.2, we can use the following equation to calculate the
fugactity from the van der Waals EOS
b
v b 2a
f iv exp
ln i

RT RTvi
vi b

The a and b parameters for CO are (see Chapter 4 for equations)

J m3
a 0.147

mol

m3
b 3.95 10 5

mol
The molar volume can be found from the van der Waals equation using the solver function on
a calculator.

m3
vi 4.48 10 4

mol
Substituting these values into the expression for fugacity, we get

f iv 156.5bar
Calculate the fugacity coefficient:

iv

f iv
1.04
P

As the strength of intermolecular forces between molecules increases, the fugacity coefficient
and fugacity decreases.

7.20
Use the virial equation expanded in pressure to express z as a function of pressure.

z 1 B' P
Calculate B:
z 0.9 1 B ' 30 105 Pa

B ' 3.33 108 Pa -1

Find an expression for v:

v

RT
1 B' P
P

Substitute into Equation 7.8 and integrate to obtain

fv
P
B' P Plow ln i
ln
Plow
Plow

Simplifying and allowing Plow to go to zero results in

f iv P exp B' P
Therefore,

f iv 27.1 bar
and

iv

27.1 bar
0.903
30 bar

7.21
(a)
Equation 7.8:
P

f
RT ln i vi dP
Plow Plow
Manipulate the fugacity expression given in the problem statement to obtain:
f
f
P
ln i ln i ln low CP
P
P
Plow

Rearrange the above equation and substitute it into Equation 7.8.

P

30
P
RT CP ln low RT 0.065 P ln Plow ln P vi dP
T
P

P

low

Differentiate both sides with respect to P:

1
30
vi RT 0.065
T
P

(b)
Substitute numerical values:

vi 8.314 10 5

m 3 bar

30
1

353.15 K 0.065

353.15 K 30 bar

mol K

m3
vi 3.93 10 4

mol

7.22
Equation 7.8:

f iv P
v dP
RT ln
Plow i

Plow
The equation from the problem statement can be rearranged to yield

1 T
0.422Tc1.6
c

vi RT
0.083
P PcT
T 1.6
Substitute the above expression into Equation 7.8 and integrate (constant T):
fv
P Tc
0.422Tc1.6

P Plow
ln i ln
0.083
1.6
Plow

P
P
T
T
low
c

or

f v T
0.422Tc1.6
ln i c 0.083
P Plow
T1.6
P PcT
Let Plow go to zero gives:

P
T P
0.422Tc1.6
0.422
c
r
f i P exp

P
exp
0.083

0.083

T1.6
Tr1.6
PcT
Tr
v

and

P
T P
0.422Tc1.6
0.422
c
r
0.083

exp 0.083 1.6

1.6
T
Tr

PcT
Tr

iv exp

From Appendix A.1:

Tc 373.2 K
Pc 89.37 bar

At 300 K and 20 bar, the expressions for fugacity and the fugacity coefficient provide

f iv 17.33 bar

iv 0.867

7.23
We are given the Schrieber volume-explicit equation of state:
RT kP 2 c
v

b
P
T

Starting with Equation 7.8, we substitute the EOS:

P
fv P
RT kP 2 c

RT ln i vi dP

b dP
P
T

Plow Plow
Plow

Carrying out the integration, we find:

P

fv
kP3 cP
RT ln i RT ln P

bP
3T T
Plow
Plow
Expand the logarithm terms, so that we can cancel the ln Plow terms.

RT ln f

v
i

RT ln Plow RT ln P RT ln Plow

kP3 cP

bP
T
3T
Plow

Collect the log terms on the left-hand side, and use the definition of the fugacity coefficient for a
pure species:
P

fi v
kP3 cP
v
RT ln
RT ln i

bP
P
3T T
P

low

Now, since we are free to choose an arbitrary pressure for Plow, we will choose a pressure
vanishingly close to 0. Thus, as Plow 0 ,
RT ln iv

kP3 cP

bP
3T
T

Rearranging this equation gives us an expression for the fugacity coefficient:

1 kP3 cP
P
b

2
RT
RT

iv exp 3

7.24
For an ideal gas reference state
fv P
gi gio RT ln i vi dP
Plow Plow

From the equation of state

RT 6.70 106 4.83 108

v
v2
v3

So
RT 13.40 106 14.49 108
dP 2

dv
v3
v4
v

And

fv
RT ln i
Plow

vi

RT
Plow

RT 13.40 106 14.29 108

v
dv
v2
v3

Integrating:

fi v
vi 13.40 106 13.40 106 7.245 108 7.245 108

RT ln

RT ln RT
RT
2
2
P
v
v

RT

i
i
low
Plow
P
low

Plow

Canceling out ln(Plow) subtracting ln(P), and letting Plow ->0, we get
fv
Pv 13.40 106 7.245 108
RT ln i RT ln i RT ln i

RT
v1
vi2
P
6.70 106 4.83 108 13.40 106 7.245 108
ln i ln 1

RTvi
RTvi2
RTv1
RTvi2

Substituting in numbers

i 0.79 and fi i P 15.2 bar

7.25
We need to pick an equation of state. We will use the virial expansion in pressure:
z

Pvi
1 B' P C ' P 2
RT

For the two states we have

v
m /mol
1.86 10-3
6.12 10-4
3

State 1
State 2

P
Pa
1.50 106
4.00 106

T
K
373.15
373.15

R
J/mol K
8.314
8.314

z
0.90
0.79

From this we can solve simultaneous equations for B and C:

0.1 B'15 C '152

0.21 B' 40 C ' 402
Solving we get,

B' 7.58 103 bar and C ' 5.76 105 bar 2

We next solve for fugacity and fugacity coefficient using this equation of state:
fi v P
RT ln
vi dP
Plow Plow

f v P 1
P
C'

2
ln i B' C ' P dP ln
B' P Plow P 2 Plow

Plow
2

Plow Plow P

Canceling out ln(Plow) subtracting ln(P), and letting Plow ->0, we get
fv
C'
ln i ln i B' P P 2
2
P
Substituting in numerical values gives:
i 0.736
and
fi v 36.8 bar

7.26
To determine the fugacity of pure methane at 220 K and 69 bar accurately, we can use the
generalized correlations. The reduced temperature and pressure can be found using data from
Appendix A:

Tr

T
220

1.15
Tc 190.6

Pr

P 69

1.5
Pc 46

Also from Appendix A,

0.008
Using reduced temperature and pressure, the fugacity coefficient can be found from Tables
C.7 and C.8:

log iv log i 0 log i1 0.16 0.008 0.034 0.16

iv 0.69
Calculate fugacity:
f1v 1P 47.7 bar

7.27
The data in the problem of the first printing are incorrect and should read
P [bar]
1.0
5.1
10.1
15.2
20.2
25.3
30.3
35.4
40.4
45.5
50.5

v [m3/mol]
2.45 x10-2
4.78 x10-3
2.32 x10-3
1.50 x10-3
1.08 x10-3
8.34 x10-4
6.66 x10-4
5.44 x10-4
4.52 x10-4
3.78 x10-4
3.17 x10-4

Equation 7.9:
ln iv

Pideal

zi 1
dP
P

The following graph has been created with data above:

0
-1

(z-1)/P x 1000 [bar]

-2
-3
-4
-5
-6
-7
-8
0.0

10.0

20.0

30.0

40.0

50.0

P (bar)

Integrate the data numerically using the Trapezoid Rule. We obtain

ln iv 0.3
Therefore,

iv 0.74

f iv iv P 37.5 bar

and

60.0

7.28
Rearrangement of Equation 7.9 yields
ln i zi 1

P
P

We can approximate the derivative at 500 bar by drawing a tangent line to the plot provided in
the problem statement and calculating the slope.

ln i
0.001 bar -1
P

Solving for the compressibility factor gives,

zi

Pvi
0.001P 1
RT

Therefore, the molar volume is:

J
-1
8.314
373.15 K 0.001 bar 500 bar 1

mol

vi
500 105 Pa

or

m3
vi 3.1 10 5

mol

7.29
If a gas obeys the Lewis fugacity rule, all the intermolecular interactions are the same. Therefore,

hmix 0
So
g mix T smix RT x1 ln x1 x2 ln x2 1, 730

J
mol

7.30
We want to calculate the fugacity coefficient of pure n-butane. The reduced temperature and
pressure can be found using data from Appendix A:

Tr

T 318.9

0.75
Tc 425.2

Pr

P 3.79

0.1
Pc 37.9

Also from Appendix A,

0.193
Using reduced temperature and pressure, the fugacity coefficient can be found from Tables
C.7 and C.8:

log iv log i 0 log i1 0.035 0.193 0.030 .041

0.91
v
i

Calculate fugacity:
f1v y11P 0.41 bar

7.31
(a)
f1v 1P
The reduced temperature and pressure can be found using data from Appendix A:
Tr

190.6
1.0
190.6

Pr

32.2
0.70
46.00

Also from Appendix A,

0.008
Using reduced temperature and pressure, the fugacity coefficient can be found from Tables C.7
and C.8:

log iv log i 0 log i1 0.113 0.008 0.022 0.113

0.77
v
i

Calculate fugacity:
fi v 24.8 bar

(b)
f1v y11P 19.8 bar

7.32
(a)
Pure Species:

fv P
RT ln 1 v1dP
Plow Plow
To acquire an expression for v1, set the mole fraction of species 1 equal to unity.

A B
1
v1 RT P
RT
P
Substituting this expression into the integral and integrating, we get
2
fv
P A B P 2 Plow

ln 1 ln

Plow
RT 2
2
Plow

By simplifying and letting Plow 0 ,

lnf1v lnP

A B P 2
RT

Therefore,

f v A B P2
ln1v ln 1

P RT 2

A B P 2
5
5 50

exp 9.0 10 3.0 10

RT 2

1v exp

1v 0.93
Species in a mixture:

f v P
RT ln 1 V1dP
yP
1 low Plow
The expression for the extensive volume is

V n1 n2 n3

RT
PAn1 n2 Bn1 n2 n3
P

Therefore,
V1

RT
PA B
P

Substituting this result into the above integral and integrating, we obtain the following after
simplifiction

P2 A
B
v

ln 1

2 RT RT
P2 A
B
v

1 exp

2 RT RT
50 atm 2

v
5 1
5 1

1 exp

9.0

10

3.0

10

atm2
atm2
2

1v 0.93

(b)
When the vapor and liquid are in equilibrium,

f1v f1l
Hence,

f1v 15 atm
We also know the value of the fugacity coefficient from part (a). This can be used to calculate
the mole fraction in the vapor.

f1v
0.93
y1 P
15 atm
y1
0.322
0.9350 atm

1v

7.33
(a)
The Lewis fugacity rule:

1v 1v
From Example 7.2
ln iv

v b P 2a
b
ln i

vi b
RT RTvi

From the van der Waals EOS,

m3
v1 1.15 10 3

mol
Now, the fugacity coefficient can be computed by substituting values.

1v 0.89
The fugacity is calculated using the fugacity coefficient.

f1v 0.2 0.89 30 bar 5.34 bar

(b)
The truncated virial form of the van der Waals equation for the mixture is
V nT

RT
1
nT bmix nT amix
P
RT

The expressions for amix and bmix are

amix y12 a1 y22 a2 y32 a3 2 y1 y2 a12 2 y1 y3a13 2 y2 y3a23

a12 a1a2 , a13 a1a3 , a23 a2 a3

bmix y1b1 y2b2 y3b3

Rewriting the volume in terms of moles, we get

n12
n22
RT
1
V n1 n2
n1b1 n2b2 n3b3
a1
a

n1 n2 n3 2
P
RT n1 n2 n3

n32
2n1n3
2n2 n3
2n1n2
a3
a12
a13
a23
n1 n2 n3 n1 n2 n3
n1 n2 n3
n1 n2 n3

To calculate fugacity, we use the following expression

f v P
RT ln 1 V1dP
yP
1 low Plow
Find V1 :
V
RT
1

2 y1a1 2 y2 a2 2 y3a13 amix

V1

b1
P
RT
dn1 T , P, n2 , n3

Substituting this expression into the integral and integrating we get,

f v
P b1
1
ln 1 ln

P Plow
2 y1a1 2 y2 a2 2 y3a13 amix P Plow

2
yP
P
RT
RT

1
low
low

By subtracting ln Plow and ln P from both sides and then letting Plow 0 , we obtain

f v b
1
ln 1v ln 1 1
2 y1a1 2 y2 a2 2 y3a13 amix P

2
y P

1 RT RT

Substitute numerical values and evaluate:

ln 1v 0.10

1v 0.906
Calculate fugacity:
f1v y11v P 0.2 0.906 30 bar

f1v 5.44 bar

7.34
(a)
Equation 7.14:
V
f v
P
RT ln a
dV

yP
nRT na T ,V , n
a low
i a
Plow

The equation of state provided in the problem statement can be rewritten as

n n n
na2 Baa nb2 Bbb nc2 Bcc 2na nb Bab 2na nc Bac 2nb nc Bbc
a
b
c

P RT

2
V

Therefore,

P
1 2n B 2nb Bab 2nc Bac

RT a aa

V2
V

na T ,V , ni a
Substitute the above equation into Equation 7.14 and integrate

f v
2n B 2nb Bab 2nc Bac
nRT 2na Baa 2nb Bab 2nc Bac Plow
ln a ln V a aa
ln

yP
V
Plow
nRT
a low
Canceling the ln Plow from both sides and then allowing Plow to go to zero, we obtain
f v
2n B 2nb Bab 2nc Bac
nRT 2na Baa 2nb Bab 2nc Bac
ln a ln V a aa
ln nRT ln

y
V
V
V

Now subtract ln P from both sides:

f v
nRT 2na Baa 2nb Bab 2nc Bac
ln a ln av ln

y P
PV
V

1 2n B 2nb Bab 2nc Bac

ln av ln a aa
V
z

2 ya Baa 2 yb Bab 2 yc Bac

av exp
z

y P
2 y B 2 yb Bab 2 yc Bac
fav a exp a aa

v
z

(b)
For this system
y a 0.2
yb 0.3
yc 0.5

Using the virial coefficient data:

Bmix 2.392 10

m3

mol

Therefore,
B
Pv
1 mix
RT
v
m3
v 1.36 10 3

mol
(Note: There are two solutions to the equation, but the other value is not sensible.)
z

Now, calculate the fugacity coefficient by substituting the appropriate values:

av 1.04
fav 0.215 bar 1.04 3.12 bar
(c)
The EOS reduces to the following expression for pure methane:
Pv a
B
1 aa
RT
va

For this expression, we can write

1 2B
dP RT 2 3aa dv a
va
va
Develop an expression for the fugacity coefficient similar to the method in Example 7.2

f av
v
dP

RT
ln

a
Plow
RT
va

Plow

Substitute the expression for dP into the above integral:

v

RT

RT
Plow

1 2 Baa
2
va
va

f av
dv

RT
ln
a

Plow

Integrating and evaluating the limits, we obtain

f av
2Baa RT 2Baa
ln
lnv a
ln

v a Plow RT
Plow

Plow

Cancel the logarithmic terms containing Plow and then let Plow go to zero:

lnf av

v
2Baa
ln a
RT
va

Therefore,

2B
RT
exp aa
va
va
2B
1
av exp aa
za
va
f av

Since we are employing the Lewis fugacity rule

2B
1
exp aa
za
va
2B
y RT
fav y a f av a exp aa
va
va

av av

To calculate the fugacity and fugacity coefficient, we will need to find the pure species molar
volume:

m3
v a 1.61103

mol
Substituting values into the above expressions, we obtain

 av 0.975

fav 2.92 bar

7.37
Calculate fugacity and fugacity coefficient of phenol in a mixture of 20 mole % phenol (1) and
80 mole % oxygen (2) at 694.2 K and 24.52 bar using the following:
(a) Ideal gas law
For an ideal gas, we assume the fugacity coefficient is 1.
Next fugacity is calculated by:

f1v y11v P 0.2 1 24.52 bar

f1v 4.904 bar

(b) The Lewis Fugacity Rule (choose the method that gives you as accurate an answer as
possible).
Options:
1) Ideal gas definitely not the most accurate!
2) E.O.S The van der Waals E.O.S is more accurate than the ideal gas assumption,
however, the van der Waals equation is not as accurate as more modern cubic equations
of state. (Text pg 310)
3) Generalized Correlations as noted in class on 2-6-08, the Lee-Kesler tables (utilized in
the generalized correlations) are more accurate than the van der Waals E.O.S.
From the above information, we can choose a more modern cubic equation of state (as will be
demonstrated with the Redlich-Kwong E.O.S. in part c) or we can choose the Generalized
Correlations. For variety, lets use the Generalized Correlations.
To use the tables in the book, we utilize the form of the generalized correlations:

log(1 ) log (0) log (1)

Pr

P
Pc

Tr

T
Tc

From Appendix A.1 we find Pc and Tc for phenol, which we can then use to get Pr and Tr.

Pc 61.3
Pr bar
0.4
Tc
Tr

694.2
K
1
0.440

Now we can use these values to find (0) & (1) .

log (0) 0.061
log (1) 0.0122
log(1 ) (0.061) 0.440 (0.0122)
We are using the Lewis Fugacity Rule, so the pure species fugacity coefficient is equal to the
mixture fugacity coefficient

1 1 0.86
f1v y11v P 0.2 0.86 24.52 bar
f1v 4.2 bar

We can check our answer for fugacity coefficient with ThermoSolver:

We can also look at results for fugacity coefficient using the Peng Robinson E.O.S. via
ThermoSolver:

Note: For the Peng Robinson E.O.S. we would use the pure species fugacity coefficient given in
the right column with the Lewis Fugacity Rule, but ThermoSolver gives both the pure species
fugacity coefficient as well as the fugacity coefficient of species i in the mixture.
(c) The Redlich-Kwong Equation of State, See Table 7.1
From Table 7.1 we get

a
1 b1a
b
RT
b
ln(1v ) ln
ln 1 b1

2 a 1 a ln 1

1.5
1.5

Pv
v
v
v b bRT (v b) bRT b
Note: In this equation a represents amix and b represents bmix.
We need to find a1, a2, a, b1, b2, b and v

a y12 a1 2 y1 y2 a1a2 y22a2

b y1b1 y2b2
y1 0.2
y2 0.8
Note: The Redlich-Kwong parameters a and b are different from those for the van der Waals
equation and cannot be interchanged
0.42748R 2Tc2.5
a
Pc
0.08664 RTc
b
Pc

Phenol (subscript 1) Oxygen (subscript 2) Mixture (no subscript)

Tc [K]
694.2
154.6
Pc [bar]
61.3
50.46
3 0.5
2
a [J m K /mol ]
61.2
1.740
6.86
3
b [m /mol]
8.16E-05
2.207E-05
3.40E-05
Next we can use the Redlich-Kwong E.O.S. to find v.
RT
a
P
1/2
v b T v v b
v can be found by using a solver function:
m3
v 0.00234
mol
Or by using an approximation as demonstrated below:
av (i) b
RT
(i1)
v

b 1/ 2 (i) (i)
P
PT v v b
Start with the ideal gas law:
RT
m3
v (0)
2.35 103
P
mol

then
RT
m3
RT
m3
: and v (2)
v (1)
2.34 103
2.34 103
P
mol
P
mol
Now use the equation from Table 7.1 to find the fugacity coefficient.
1

a
1 b1a
b
RT
b
ln(1v ) ln
ln 1 b1

2 a 1 a ln 1

1.5
1.5

Pv
v
v
v b bRT (v b) bRT b
v
0.943
1

f1v y11v P 0.2 0.94 24.52 bar

f1v 4.63 bar

7.38
(a)
f1v P
RT ln
v1dP
Plow Plow

v1

RT RT Pr ,1

P
P 8Tr ,1

f v P RT RTc ,1
RT ln 1

dP
P
P
8
P

low
c
,1

Plow

fv
P RTc ,1
RT ln 1 RT ln
P Plow

Plow
Plow 8Pc ,1
P
fv
ln 1 ln 1v r ,1
8Tr ,1
P
Tr

219
0.6
365
ln 1v

Pr

27.72
0.6
46.2

1
8

1v 1.13
f1v y11v P 7.85 bar

(b)

f v P
RT ln 1 V1dP
yP
1 low Plow
V n1 n2

RT RT n1Pr ,1 n2 Pr ,2

P
P 8Tr ,1 8Tr ,2

V
RT RTc ,1
V1

P 8Pc ,1
dn1 T , P ,n2 ,n3

 f v P RT RTc ,1
RT ln 1

dP
yP
P
8
P

1
low
c
,1

Plow
f v
P RTc ,1
RT ln 1 RT ln
P Plow

yP
P
8
P
c ,1
low
1 low
f v
P
ln 1 ln 1v r ,1
y P
8Tr ,1
1
Tr

219
0.6
365

ln 1v

1v 1.13

Pr

27.72
0.6
46.2

1
8

f1v y11v P 7.85 bar

(c)
Values are the same so all the intermolecular interactions are the same

7.39
(a)

n1 n2 RT
P

RT
n12 B11' 2n1n2 B12' n22 B22'
n1 n2

V
RT
'
V1

RT y12 B11' 2 y1 y2 B12' y22 B22

RT 2 y1B11' 2 y2 B12'

P
n1 T , P ,n2
V
RT
V1

RT B ' RT 2 y1B11' 2 y2 B12'

P
n1 T , P ,n2
P
f1v P
1

RT ln
V dP RT B ' 2 y1 B11' 2 y2 B12' dP
y P 1
P

Plow
1 low Plow
P
'
'
'
ln
2 y1 B11 2 y2 B12 B P Plow
P
low

f v
ln 1
yP
1

v
'
'
'
ln 1 2 y1B11 2 y2 B12 B P

(b)
y1 = 0.4
B11'

B12'
'
B22

- 1.9 x 10-7

[Pa-1]

- 3.6 x 10-8

[Pa-1]

- 2.0 x 10-9

[Pa-1]

So

1v 0.84
And
f1v y11v P 4.0 bar

(c)
Since B11' and B11' are very different, we do not expect the Lewis rule to be a good approximation.

7.40
Using the Lewis fugacity rule for n-pentane (1):

f1v y11P
The reduced temperature and pressure can be found using data from Appendix A:
Tr

495
1.0
469.6

Pr

18
0.70
38.74

Also from Appendix A,

0.251
Using reduced temperature and pressure, the fugacity coefficient can be found from Tables C.7
and C.8. After interpolation, we get:

log iv log i 0 log i1 0.086 0.251 0.019 0.0907

iv 0.81
Calculate fugacity:

f1v 0.137 0.8118 2.00 bar

7.41
From the definition of fugacity:
V
f v P
P
RT ln i Vi dP
dV

yP
nT RT n1 T ,V , n , n
1 low Plow
2 3
Plow

Putting the EOS in terms of T, V, n1, and, n2:

n1 n2 RT n12 a1 n22 a2 2n1n2 a12

2
V
V n1c1 n2c2

Differentiating

2c1 n12 a1 n22 a2 2n1n2 a12

P
2n1a1 2n2 a12
RT

2
3

n
V
V

n
c

n
c
1 T ,V ,n2 ,n3
1 1 2 2
V n1c1 n2c2
Into the equation above:
V
V
V
2c1 n12 a1 n22 a2 2n1n2 a12
fi v
2n1a1 2n2 a12
RT

dV
dV
RT ln

2
3
dV
y P
V

n
c

n
c
V

n
c

n
c
n
RT
n
RT
n
RT
1
low

T
T
T
1 1
2 2
1 1
2 2

Plow

Plow

Plow

Integrating we get

V
fi v
RT ln
RT ln

yP
nT RT
1 low
Plow

1
1
2n1a1 2n2 a12

V n1c1 n2c2 nT RT n c n c
1 1
2 2

Plow

1
1

2
2
c1 n1 a1 n2 a2 2n1n2 a12

2
2
V n1c1 n2 c2 nT RT n c n c

1 1
2 2

Plow

Taking and

nT RT
n1c1 n2c2
Plow


V
fi v
RT ln
RT ln

yP
nT RT
1 low
Plow

1
1
2n1a1 2n2 a12

V n1c1 n2c2 nT RT

Plow

1
1

2
2
c1 n1 a1 n2 a2 2n1n2 a12

2
2
V n1c1 n2c2 nT RT

Plow

Canceling out ln(Plow) subtracting ln(P), and letting Plow ->0, we get
f v

1
RT ln i RT ln z 2n1a1 2n2 a12

yP
V n1c1 n2 c2
1 low

c1 n12 a1 n22 a2 2n1n2 a12

2
V n1c1 n2c2

Simplifying:
RT ln 1 RT ln z 2

y1a1 y2 a12
c1a

2
vc
v c

7.42
From the definition of fugacity:
V
f v P
P
RT ln i Vi dP
dV

yP
nT RT n1 T ,V , n , n
1 low Plow
2 3
Plow

Putting the EOS in terms of T, V, n1, and, n2:

n1 n2 n3 RT n12 a1 n22 a2 n32a3 2n1n2a12 2n1n3a13 2n2n3a23

2
V n1b1 n2b2 n3b3
V n1c1 n2c2 n3c3

Differentiating

b1 n1 n2 n3 RT
P
RT

2
n1 T ,V ,n2 ,n3 V n1b1 n2b2 n3b3 V n1b1 n2b2 n3b3

2n1a1 2n2 a12 2n3a13

V n c n c
1 1

2 n3c3

2c1 n12 a1 n22 a2 n32 a3 2n1n2 a12 2n1n3a13 2n2 n3a23

V n c n c
1 1

2 2

n3c3

V
f v

RT
RT ln i
dV
yP
V

n
b

n
b

n
b

n
RT
1
low
1
1
2
2
3
3

T
Plow

b n n n RT

1
1
2
3

dV

2

nT RT V n1b1 n2b2 n3b3

P
V

low

2n a 2n a 2n a
1 1
2 12
3 13

dV
2

nT RT V n1c1 n2 c2 n3c3

P
V

low

2c1 n12 a1 n22 a2 n32 a3 2n1n2 a12 2n1n3a13 2n2 n3a23

dV

3

n
c

n
c

n
c
nT RT
1 1 2 2 3 3

P
V

low

Integrating we get

V n b n b n b
fi v
1 1
2 2
3 3

RT ln
RT ln
y P
n
RT
T
1 low
n1b1 n2b2 n3b3
Plow

1
1

RTb1 n1 n2 n3

V n1b1 n2b2 n3b3 nT RT n b n b n b

1 1
2 2
3 3

Plow

1
1

2n1a1 2n2 a12 2n3a13

V n1c1 n2c2 n3c3 nT RT n c n c n c

1 1
2 2
3 3

Plow
c1 n12 a1 n22 a2 n32 a3 2n1n2 a12 2n1n3a13 2n2 n3a23

1
1

2
2

V n1c1 n2 c2 n3c3 nT RT n c n c n c

1 1
2 2
3 3

Plow

Taking

nT RT
n RT
n1b1 n2b2 n3b3 and T
n1c1 n2c2 n3c3
Plow
Plow

V n b n b n b
fi v
1 1
2 2
3 3

RT ln
RT ln
y P
n
RT
T

1 low

Plow

1
1
RTb1 n1 n2 n3

V n1b1 n2b2 n3b3 nT RT

Plow

1
1
2n1a1 2n2 a12 2n3a13

V n1c1 n2c2 n3c3 nT RT

Plow
c1 n12 a1 n22 a2 n32 a3 2n1n2 a12 2n1n3a13 2n2 n3a23

1
1

2
2

V n1c1 n2c2 n3c3 nT RT

Plow
Canceling out ln(Plow) subtracting ln(P), and letting Plow ->0, we get

fi v
PV P n1b1 n2b2 n3b3
RT ln
RT ln

y P
nT RT

1
RTb1 n1 n2 n3

V n1b1 n2b2 n3b3

1
2n1a1 2n2 a12 2n3a13

V n1c1 n2 c2 n3c3

c1 n12 a1 n22 a2 n32 a3 2n1n2 a12 2n1n3a13 2n2 n3a23

2
V n1c1 n2c2 n3c3

Simplifying:
y a y2 a12 y3a13
c1a
bP RTb1

RT ln 1 RT ln z

2 1 1

RT v b
vc

v c

7.43
Let a refer to methane and b refer to hydrogen sulfide. From Example 7.4

2 ya aa yb aa ab
P v bmix
ba
ln av ln

RT
RTv

v bmix

In the above expression, v and bmix depend on mole fractions. First, calculate a a , ab , ba , and
bb :

27 RTc 2
a
64 Pc

RTc
8Pc

m3

mol

J m3
aa 0.230

2
mol

ba 4.31 10

J m3
ab 0.454

2
mol

m3
bb 4.34 10 5

mol

To calculate v, we need amix and bmix:

amix ya2 aa 2 ya yb aa ab yb2 ab

bmix ya ba ybbb
Using these expressions we can find the molar volume with the van der Waals EOS.
P

a
RT
mix
v bmix
v2

Once the molar volume is calculated, the molar fugacity coefficient can be found using the
expression from Example 7.4. The following table can be created:
ya
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1

yb
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

amix
0.454
0.428
0.403
0.379
0.355
0.333
0.311
0.289
0.269
0.249
0.230

bmix
4.34 x 10-5
4.34 x 10-5
4.33 x 10-5
4.33 x 10-5
4.33 x 10-5
4.33 x 10-5
4.32 x 10-5
4.32 x 10-5
4.32 x 10-5
4.31 x 10-5
4.31 x 10-5

v
0.000437
0.000447
0.000456
0.000465
0.000473
0.000481
0.000488
0.000494
0.000500
0.000506
0.000512

ln(a)
0.001
-0.007
-0.013
-0.018
-0.023
-0.026
-0.029
-0.031
-0.032
-0.033
-0.033

a
1.001
0.993
0.987
0.982
0.978
0.974
0.972
0.970
0.968
0.967
0.967

From ThermoSolver using the Peng-Robinson EOS:

ya
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1

yb
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

a
1.033
1.02
1.008
1.000
0.992
0.986
0.982
0.978
0.977
0.975
0.975

Plot the activity coefficient versus the mole fraction of methane for both methods on the same
graph:
a vs. ya From the van der Waals EOS
Compared to Thermosolver Results
1.050

1.025

1.000

van der Waals EOS

Thermosolver Results

0.975

0.950
0

0.1

0.2

0.3

0.4

0.5

0.6

ya (mole fraction)

The values agree relatively well.

0.7

0.8

0.9

7.44
Let a refer to methane and b refer to hydrogen sulfide. From Problem 7.5:

a
1 ba a
b
RT
b
ln av ln

2 aa a ln 1

ln 1 ba
1.5
1.5
Pv
v
v
v b bRT v b bRT b
(Note: a is short for amix and b is short for bmix)

In the above expression, v , amix, and bmix depend on mole fractions. First, calculate a a , ab , ba ,
and bb :

R 2Tc2.5
a 0.42748
Pc

b 0.08664

RTc
Pc

J m 3 K1/2
a a 3.22

2
mol

ba 2.99 10

J m 3 K1/2
ab 8.90

2
mol

m3
bb 3.01 10 5

mol

m3

mol

To calculate the v, we need amix and bmix:

amix ya2 aa 2 ya yb aa ab yb2 ab

bmix ya ba ybbb
Using these expressions we can find the molar volume with the Redlich-Kwong EOS:
P

amix
RT

1
/
2
v bmix T vv bmix

Once the molar volume is calculated, the fugacity coefficient can be found by substituting the
appropriate values into the expression from Problem 7.5. The following table can be created:

ya
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1

yb
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

amix
8.900
8.205
7.538
6.899
6.289
5.707
5.153
4.627
4.130
3.661
3.220

bmix
3.01 x 10-5
3.01 x 10-5
3.01 x 10-5
3.00 x 10-5
3.00 x 10-5
3.00 x 10-5
3.00 x 10-5
3.00 x 10-5
2.99 x 10-5
2.99 x 10-5
2.99 x 10-5

v
0.000437
0.000449
0.000460
0.000470
0.000479
0.000487
0.000495
0.000502
0.000508
0.000514
0.000520

We have from the Peng-Robinson EOS using ThermoSolver:

ya
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1

yb
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

a
1.033
1.02
1.008
1.000
0.992
0.986
0.982
0.978
0.977
0.975
0.975

The data plotted on the same graph reveal:

ln a
0.036
0.024
0.013
0.005
-0.002
-0.007
-0.011
-0.014
-0.016
-0.018
-0.018

a
1.037
1.024
1.013
1.005
0.998
0.993
0.989
0.986
0.984
0.982
0.982

 a vs. y a From the Redlich-Kwong EOS

Compared to Thermosolver Results
1.050

1.025

Redlich-Kwong EOS

1.000

Thermosolver

0.975

0.950
0

0.2

0.4

ya

0.6

0.8

Clearly, the results from the two solution methods agree well. The Redlich-Kwong EOS
provides a fugacity coefficient that is slightly larger over the entire composition range.

7.45
Let a refer to methane and b refer to hydrogen sulfide.
(a)
From Example 7.4,

2 xa aa xb aa ab
P v bmix
ba
ln av ln

RT
RTv

v bmix

First, calculate a a , ab , ba , and bb :

27 RTc 2
64 Pc

J m3
aa 0.230

2
mol
J m3
ab 0.454

2
mol

RTc
8Pc

m3
ba 4.31 10 5

mol
m3
bb 4.34 10 5

mol

To calculate v, we need amix and bmix:

J m3
amix ya2 aa 2 ya yb aa ab yb2 ab 0.333

2
mol

m3
bmix y a ba yb bb 4.325 10 5

mol
Using these expressions we can find the molar volume with the van der Waals EOS:
P

so

a
RT
mix
v bmix
v2

m3
v 4.81104

mol

Substituting these values into the equation for the fugacity coefficient, we get

av 0.974

(b)
From Problem 7.5:

a
1 ba a
b
RT
b
ln av ln

2 aa a ln 1

ln 1 ba
1.5
1.5
Pv
v
v
v b bRT v b bRT b
(Note: a is short for amix and b is short for bmix)

First, calculate a a , ab , ba , and bb :

a 0.42748

R 2Tc2.5
Pc

J m3
aa 3.22

2
mol
J m3
ab 8.90

2
mol

b 0.08664

RTc
Pc

m3
ba 2.99 10 5

mol
m3
bb 3.0110 4

mol

To calculate the v, we need amix and bmix:

amix ya2 aa 2 ya yb aa ab yb2 ab 5.707

m3
bmix ya ba yb bb 3.0 10 5

mol
Using these expressions we can find the molar volume with the Redlich-Kwong EOS:
P

amix
RT

1
/
2
v bmix T vv bmix

m3
v 4.871 10 4

mol
Substituting these values into the expression for the fugacity coefficient, we get

av 0.993
(c)
Using Kays mixing rules, we have the following expressions:
T pc yaTc, a ybTc, b

Ppc ya Pc, a yb Pc,b

w pc ya a ybb

Substituting values from Appendix A, we get

T pc 281.9 K

Ppc 67.69 bar

pc 0.054
Therefore,
Tr 1.58
Pr 1.03

From the generalized correlation tables

log 0 0.0336

log 1 0.0371

Therefore,
log v 0.0336 0.0540.0371
v 0.930

(d)

Using the Peng-Robinson EOS in ThermoSolver, we obtain:

av 0.986
A summary of the results for each solution method is provided in the following table. The
percent differences are based on the fugacity coefficient found using ThermoSolver.
Solution Method
(a)
(b)
(c)
(d)

van der Waals

Redlich-Kwong
Generalized Correlations Kays
ThermoSolver / Peng-Robinson

av

% Difference

0.974
0.993
0.930
0.986

1.22
0.71
5.68
0

Clearly, all of the solution methods agree reasonably well with the Peng-Robinson EOS. The
fugacity coefficient calculated with the Redlich-Kwong EOS agrees the best.

7.46
For the virial equation, we have
B P
z 1 mix
RT

where

Bmix y a2 Baa 2 y a yb Bab yb2 Bbb

At 127 oC, the second virial coefficients are

cm 3
cm 3
Baa 16
and Bbb 101

mol
mol
Solve for volume:

na nb RT na2 Baa 2na nb Bab nb2 Bbb

nT RT
V
nT Bmix

P
P
na nb
To get the partial molar volume, we differentiate with repect to na.

V
Va
na

2
2

RT 2na Baa 2nb Bab na Baa 2na nb Bab nb Bbb

P
na nb
na nb 2
T , P,nb

or
Va

RT
2 ya Baa 2 yb Bab ya2 Baa 2 ya yb Bab yb2 Bbb
P

We must now plug this into Equation 7.13 and integrate:

fav
RT

2
2

2
y
B

2
y
B

y
B

2
y
y
B

y
B
dP
=
RT
ln
a aa a b ab b bb

so
a aa
b ab
P
Plow
pa ,low
P
fav
P
2
2
RT ln
2 ya Baa 2 yb Bab ya Baa 2 ya yb Bab yb Bbb dP =RT ln

Plow Plow
ya Plow
P

Rearranging

Plow

f v
2 ya Baa 2 yb Bab ya2 Baa 2 ya yb Bab yb2 Bbb dP =RT ln a RT ln av
ya P

Integrating, we get

2y B
a

aa

2 yb Bab ya2 Baa 2 ya yb Bab yb2 Bbb P RT ln av

Setting ya=0 and yb=1:

2Bab Bbb P RT ln a
RT
ln a Bbb
Bab P
34.5
2

cm3
mol

Compare the value to the geometric average

cm 3
Bab Baa Bbb 40.2

mol
This problem can also be solved using the form of the virial equation:
z 1

Bmix
v

In that case, the solution becomes:

cm3
v vP
Bab ln a 55.9

2 RT
mol

7.47
(a)
We can start with Equation 7.14 to find the fugacity coefficient:
V
fv
P

RT ln 1
dV

n
y1 Plow
1

T ,V , n 2
nRT

Plow

Rewrite the equation of state to include extensive volume and moles:

amix
n n2 RT n1a1 n2 a2 n1 n2 1 / 2
RT

v
V
v 3 / 2T 1 / 2
V 3 / 2T 1 / 2

Differentiate:

P
RT
1
1 / 2 n a n2 a 2

a1 n1 n2 1 1

V V 3 / 2T 1 / 2
2n1 n2 1 / 2
n1 T ,V , n 2
Substitute this expression into Equation 7.14 and integrate to obtain
f1v
n1a1 n2 a2
2
1/2
VPlow
RT ln
RT ln
1/2 1/2 a1 n1 n2
1/2
nRT V T
2 n1 n2
y1 Plow
1/2
n a n a2
2
1/2
P
low
a1 n1 n2 1 1 2 1/2
1/2
nRT T
2 n1 n2
This expression can be simplified by canceling the terms containing Plow and then taking the
limit as Plow goes to zero. This results in
f1v
n1a1 n2 a2
2
1/2
nRT
RT ln RT ln
1/2 1/2 a1 n1 n2
1/2
V V T
2 n1 n2
y1

The above equation is equivalent to

f v
2
1
RT
RT ln 1 RT ln
a

y1a1 y2a2
1

2
vT
v

y1
If we subtract the natural log of pressure from both sides of the equation and rearrange, we
obtain

2
RT
ln 1v ln

Pv RT vT

a1 2 y1a1 y2 a2

Now, find the numerical value of the fugacity coefficient by substituting values for all of the
variables.

2
1

800

0.33
800

0.66
500


2
1.78 106 0.002 8.314 500 0.002 500

1v exp ln

8.314 500

1v 0.689

Note: The pressure was calculated prior to substitution using the given EOS.

8.314500 0.33800 0.66500 1.78 10 6 Pa

0.002
0.0023 500

(b)
The Lewis fugacity rule states

1v 1v
Start with Equation 7.26 to find 1v :
fv P
RT ln 1 v1dP
Plow

Plow

For the given equation of state

RT 3

a1
dv1
dP

2 T 1 / 2v5 / 2
v12
1

Substitute the above expression into Equation 7.8 and change the limits of integration:

f v v1 RT 3
a1
dv
RT ln 1

1/ 2 3 / 2 1
Plow
2

T
v
v
1

RT 1

Plow

Now perform the integration to obtain

 fv
3a
v P 3a1
RT ln 1 RT ln 1 low
1
Plow
Tv1
T
RT

Plow
RT

If we cancel the natural log terms containing Plow and then let Plow go to zero, the above equation
simplifies to

RT
ln f1v ln
v1

3a1

RT Tv1

Now subtract the natural log of P from both sides of the equation:

ln

f1v
RT
3a1

ln 1v ln

P
Pv1 RT Tv1

v1 is the molar volume of species 1 at the temperature and pressure of the mixture in Part (a) We
can calculate it from the given EOS.

1.87 10 6 Pa

8.314500
v1

800
500v13

m3
v1 0.00187

mol
Substitute values into the expression for the fugacity coefficient and evaluate:

8.314 500
3 800

exp ln

1.78 106 0.00187 8.314 500 500 0.00187

v
1

1v 0.687
The fugacity coefficient calculated using the Lewis fugacity rule is equal to the fugacity
coefficient in Part (a)

7.48
Gibbs energy can be written as
dg i si dT vi dP

Therefore,

g i
s T vi P

i
vi
P
P T
T
Equation 7.8 states

f
g i g i RT ln i g i RT ln f i RT ln Plow
Plow

Differentiate:
gi RT ln fi RT ln Plow
ln f i
gi

RT

P
P
P T
T

Hence,
ln fi
gi

RT
i

P
P T

7.49
It can be shown that

ln f i
RT
vi
P T
To solve this problem, we can assume the molar volume of liquid water at 300 C is independent
of pressure. Therefore,
fi

RT

d ln

fi

f i vil

sat

dP

P sat

fi vil
ln sat
P P sat

fi RT
We need to calculate f isat , but before we can do that, we must choose a reference. Use
T 300 C and P 10 kPa as the reference. From the steam tables
kJ
kg K
kJ
h 3076.5
kg
s 9.2812

The Gibbs energy at the reference state:

kJ
g 3076.5 573.15 K 9.2812
kg

kJ
kg K 2243.0

kJ
kg 40407.2

J
mol

For P sat 8.5810 MPa and T 300 C , the steam tables allow us the calculate the Gibbs
energy:

kJ
kJ
kJ
J
520.6 9378.5
g sat 2748.9 573.15 K 5.7044

mol
kg
kg K
kg

Now use Equation 7.7 to find f sat :

9378.5 40407.2

f sat 10 kPa exp

8.314573.15

f sat 6729 kPa

Once we find vil , we can calculate the fugacity. From the saturated steam tables,


m3
5
visat 0.001404
0.0180148 kg/mol 2.53 10

kg

m3

mol

Therefore,

2.53 105

fi 6729 kPa exp

300 105 Pa-85.18 105 Pa

8.314 573.15

f i 7542 kPa 75.4 bar

7.50
(a)
From Equation 7.35 we have the following relationship

f il iv Pisat
Since the system pressure is low (1 bar), the fugacity coefficient is unity. Calculate the
saturation pressure using Antoine Equation data in Appendix A.1:

2154.9

Pisat exp 9.0580

260 34.42

Pisat 0.610 bar

Therefore,

f il Pisat 0.610 bar

(b)
Now that the system pressure is high, we cant simplify the calculation as we did in Part (a).
Instead, we will use Equation 7.36.
P

v
f il isat Pisat exp i dP
sat RT

Pi

Since Pisat 0.610 bar , the saturation fugacity coefficient of n-butane is unity. From the
problem statement, we can obtain vi:

vi

MW i
i

0.058123 kg/mol
579 kg/m3

m3
1.00 104

mol

Since the density is constant with respect to pressure, we can substitute numerical values into
Equation 7.36 and integrate:

1.00 104 m3 /mol 200 105 Pa-6.10 104 Pa

fi l 0.610 bar exp

J
8.314 mol K 260 K

l
fi 1.53 bar

7.51
We can use Equation 7.36 to calculate the fugacity of pure liquid acetone.
f il

isat Pisat

vi

exp
dP
sat RT

Pi

Calculate the saturation pressure using Antoines Equation data in Appendix A.1:

2940.46

Pisat exp 10.0311

382 35.93

Pisat 4.64 bar

Since the saturation pressure is 4.64 bar, we cannot assume the saturation fugacity coefficient to
be unity. We can use reduced generalized correlation tables to calculate the fugacity coefficient.
From data in Appendix A.1,
Tr

382 K
0.75
508.1 K

Prsat

4.64 bar
0.099
47.01 bar

0.309

Use these values in Tables C.7 and C.8 to determine the fugacity coefficient:

log isat 0.0346 0.309 0.0297 0.0438

isat 0.904
Since the density is constant with respect to pressure, we can substitute numerical values into
Equation 7.36 and integrate:

7.34 105 m3 /mol 100 105 Pa-4.64 105 Pa

fi l 0.904 4.64 bar exp

J
8.314 mol K 382 K

l
fi 5.23 bar

7.52
We can use Equation 7.36 to calculate the fugacity of pure liquid acetone.
f il

isat Pisat

vi

exp
dP
sat RT

Pi

Calculate the saturation pressure using Antoines Equation data in Appendix A.1:

1872.46

Pi sat exp 9.1058

333 25.16

Pi sat 20.56 bar

Since the saturation pressure is 20.56 bar, we cannot assume the saturation fugacity coefficient to
be unity. We can use reduced generalized correlation tables to calculate the fugacity coefficient.
From data in Appendix A.1,
Tr

333 K
0.9
370 K

Prsat

20.53 bar
0.48
44.24 bar

0.152

Use these values in Tables C.7 and C.8 to determine the fugacity coefficient:

log isat 0.107 0.152 0.051 0.115

isat 0.767
Since the density is constant with respect to pressure, we can substitute numerical values into
Equation 7.36 and integrate:
Taking the Poynting correction to be negligible, we get

fi l isat Pi sat 15.77 bar

7.53
We can use Equation 7.36 to calculate the fugacity of pure liquid acetone.
f il

isat Pisat

vi

exp
dP
sat RT

Pi

Using values from the steam tables:

Pi sat 3.169 kPa

so

isat 1
and

vi 1.8 105

m3
mol

Taking vi to be constant
v

fi l isat Pi sat exp i P Pi sat 4557 kPa

RT

7.54
(a)
Begin by drawing a line tangent to the plot for fal as xa 0 . Then, extend the line to xa 1 .
The Henrys constant is equal to the intercept of the vertical gridline when xa 1 . Therefore,

H a 19.5 kPa
(b)
The activity coefficient is defined as

ga

fal
x f o
a a

Using a Henrys law reference state, this equation becomes

ga

fal
xaH a

From the provided graph,

fal xa 0.4 12 kPa

fal xa 0.8 31 kPa
Therefore,

g a xa 0.4
g a xa 0.8

12 kPa

0.4 19.5 kPa

1.54

0.8 19.5 kPa

1.99

31 kPa

(c)
From the Gibbs-Duhem Equation, we know
xa

d ln g a
d ln g b
xb
0
dxa
dxa

d ln g b
must be negative. Since the activity coefficient is based on a Lewis-Randall
dxa
reference state, ln g b 0 as xa 0 . Therefore, at xa 0.4 , ln g b is negative and g b 1 .

Therefore,

(d)
Since g bL / R 1 , the a-b interactions are stronger than the pure species interactions.
(e)
When a gas is in equilibrium with a liquid, the fugacities of each phase are equal. For an ideal
gas, fav ya P . Setting fugacities equal, we get

ya P fav fal
Therefore,

ya

fal 12 kPa

P 20 kPa

ya 0.6

7.55
(a)
Both species are based on the Lewis-Randall reference state because
ln g a 0 as xa 1
ln g b 0 as xb 1

(b)
The Gibbs-Duhem equation states
xa d ln g a xb d ln g b 0

This can be differentiated to provide

xa

d ln g a
d ln g b
xb
0
dxa
dxa

By drawing tangent lines to the activity coefficient lines at xa 0.6 , we obtain:

d ln g a
1.33
dxa
d ln g b
2
dxa

Therefore,

0.61.33 0.4 2 0.002 0

(c)
We cant use the two-suffix Margules equation because the lines for the activity coefficients
arent symmetric. Therefore, we will use the three-suffix Margules. Infinite dilution data from
the graph:

ln g a 2.5

ln g b 1.5
From Table 7.2:

J
RT ln g a 8.314
300 K 2.5 A B
mol K


J
RT ln g b 8.314
300 K 1.5 A B
mol K

Solve simultaneously:
A 4988.4 J mol-1

B 1247.1 J mol -1
Therefore,

gE x a x b 4988.4 1247.1x a x b J mol-1

(d)
The mixture will not separate into two phases. The system is more stable as a mixture as shown

by the activity coefficients being less than one. Furthermore, g mix is always negative because
gE is always negative. (This becomes apparent by examining the magnitude of the A and B
parameters in the three-suffix Margules equation.) Therefore, it is thermodynamically favorable
for the system to mix.

7.56
(a)
The activity coefficient for species A is based on the Lewis-Randall reference state. For the
Lewis-Randall reference state, the natural log of the activity coefficient of species A goes to zero
as the mole fraction of A goes to one since all interactions are a-a interactions.
(b)
Equation 7.84 can be used to calculate the fugacity of species a. It states
P l

v
f al asat Pasat exp a dP
sat RT

Pa

However, asat is assumed equal to one since the saturation pressure is low. The Poynting
correction can also be assumed equal to one since the system pressure is low. Therefore,

f al Pasat
f al 80 kPa
(c)
The value of H a can be calculated using Equation 7.75. It states

g a

Ha
fa

From the graph provided in the problem statement, we find

ln ya 2.5
Using the value from Part (b), we can calculate Ha:
H a 80 kPaexp 2.5
H a 975 kPa

(d)
From Table 7.1,

RT ln g a Axb2
As xb 1 , ln g a 2.5 . Therefore,

2.5RT

2.5 8.314 J mol-1 K 1 300 K

A 6235.5 J mol -1

(e)
We first calculate the mole fraction of a in the liquid mixture.
xa

na
2 mol

0.4
ntot 5 mol

Now, we can obtain the activity coefficient from the graph.

ln g a 0.875

g a 2.40

This allows us to fugacity of species a in the liquid which is equal to the fugacity of species a in
the vapor phase.

fav fal xag a f ao 0.4 2.40 80 kPa

fav 76.8 kPa

The vapor mole fraction can be determined from the definition of fugacity in the vapor phase if
we assume ideal gas behavior, which is reasonable at 1 bar.

fav ya P
ya

76.8 kPa
0.768
100 kPa

(f)
In part D, the Margules parameter was calculated for the mixture based on a Lewis-Randall
reference state. From Equation 7.56:

Ax a2 RT ln g b

6235.5 J mol-1 0.4

1.49
g b exp
8.314 J mol-1 K -1 300 K

7.57
(a)
Assume the two-suffix Margules equation represents the excess Gibbs energy data well.
Therefore, for any of the data points in the provided graph, the following relationship should be
true

g E Ax1 x2
gE A

x1 x2
R
R
When x2 0.5 :
A
32 K

128 K
R 0.50.5

To calculate the activity coefficients of cyclohexane, we can use the following equations
Ax12 RT ln g 2
A 2
R x1
g 2 exp
T

(i).

128 K 0.752
g 2 exp

343 K

g 2 1.23
(ii).

g 2

128 K 12
exp

343 K

g 2 1.45
(b)
From Equation 7.75:

g 2

H2
f2

where

f 2 P2sat
Calculate the saturation pressure of cyclohexane using data from Appendix A.1:
2766.63

P2sat exp 9.1325

343 50.50

P2sat 0.722 bar

Therefore,
H 2 1.450.722 bar
H 2 1.05 bar

(c)
Since A>0, gE is always greater than one. Therefore, like interactions are stronger.

7.58
To find the activity coefficients, we can use the following two equations:

RT ln g a GaE

RT ln g b GbE

The derivations of expressions for g a will be shown below. The method for finding g b is
analogous, and the final expressions can be found in Table 7.2.
(a)
The excess Gibbs energy:

GE

na nb
na nb

na nb

A B
n

a
b

Find GaE :

dG E
GaE
dna

xb xa xb A Bxa xb 2 Bx a xb2

T ,V , nb

Substitute xa 1 xb :

GaE A 3B xb2 4Bxb3

Therefore,
A 3B x 2 4 Bx 3
b
b
g a exp
RT

(b)
Rewrite excess Gibbs energy as
na nb
G E AB

An a Bnb

Find GaE :
dG E
GaE
dna

B 2 nb2

Ana Bnb 2
T ,V , nb

Divide the numerator and denominator of the right-hand side of the above expression by na nb
:

B 2 xb2
GaE A

Ax a Bxb 2
Therefore,
A
RT

g a exp

B 2 xb2

2
Ax a Bxb

(c)
Rewrite excess Gibbs energy as

n ab nb
n ba na
nb ln b

G E RT na ln a
na nb
na nb

Find GaE :

x 1 xa xb ab ba xb xa ba
GaE RT ln xa ab xb a

xa xb ab
xb xa ba

This can be rewritten as

xb2 ba 1

xb xa ba

1 x 1 x 1
E
b
ab b ba

Ga RT ln xa ab xb xb

xb xa ba
xa xb ab

1 xb xb 1 ab
GaE RT ln xa ab xb

xa xb ab

After some manipulation, the following is obtained

ab

ba
GaE RT ln xa ab xb xb

xa xb ab xb xa ba

ab

ba

g a exp ln xa ab xb xb

xa xb ab xb xa ba

which is consistent with the expression in Table 7.2.

(d)
Rewrite the excess Gibbs energy as

na nb
na nb
G E RT ba G ba
ab G ab
na nb G ba
nb na G ab

Find GaE :
GaE

dG E

dna

ba G 2 n 2

ab G ab nb2
ba
b

RT

2
2

n
G
n

n
G
T ,V , nb
b ba
b
a ab
a

Dividing the numerators and denominators of the above expression by na nb , we obtain

G2
ab G ab
ba ba
GaE RTxb2

xa xb G ba 2 xb xa G ab 2
Therefore,

xa xb G ba 2

g a exp xb2

ba G 2ba

2
xb xa G ab

ab G ab

7.59
Three-suffix Margules:
At infinite dilution:

RT ln g a RT ln 2 A B
RT ln g b RT ln 3 / 2 A B
Solving simultaneously,

A RT ln 3

B RT ln 3 / 2

For an equimolar solution:

3 3ln 3 /20.5 4 ln 3 /20.5

RT ln 3 3ln 3 /20.5 4 ln 3 /20.5

RT ln g a RT ln

RT ln g b

Solving, we obtain

g a 1.11
g b 1.19

Van Laar:

At infinite dilution:
RT ln g a RT ln2 A
RT ln g b RT ln3/2 B

For an equimolar solution:

ln 3 / 20.5
RT ln g a RT ln 2

ln 20.5 ln 3 / 20.5
2

ln20.5
RT ln g b RT ln3/2

ln20.5 ln3/20.5
2

Solving, we obtain

g a 1.10
g b 1.18

Wilson:
At infinite dilution:
RT ln g a RT ln2 RT ln ab ba 1
RT ln g b RT ln3/2 RT lnba ab 1
Solve simultaneously:

ab 0.407

ba 1.21

For an equimolar solution:

1.21
0.407
ln g a ln0.5 0.50.407 0.5

0.5 0.51.21 0.5 0.50.407

0.407
1.21
ln g b ln0.5 0.51.21 0.5

0.5 0.50.407 0.5 0.51.21

Solving, we obtain

g a 1.10
g b 1.17

7.60
The problem statement provides the following information:

x
a 0.9

xa 0.2

xb 0.1

xb 0.8

At equilibrium:

x
a g a xa g a

xb g b xb g b

x
ln a
x
a
x
ln b
x
b

ln g ln g
a
a

ln g ln g
b
b

Use the composition data provided in the problem statement and the expressions from Table 7.1:

1
0.9
A 3B 0.82 0.12 4 B 0.8 3 0.13
ln

0.2 8.314 493.15

1
0.1
A 3B 0.2 2 0.9 2 4 B 0.2 3 0.9 3
ln

0.8 8.314 493.15

Solve simultaneously:

A 10100 J mol -1
B 1300 J mol -1

7.61
Let the subscript a represent water and b represent ethanol. Since the activity coefficients at
infinite dilution are different for water and ethanol, the two suffix Margules equation cannot be
used. Instead, employ the three suffix Margules equation:

g E xa xb A Bxa xb
From Table 7.2, we have

RT ln g a A 3B xb2 4Bxb3

RT ln g b A 3B xa2 4Bxa3
Substituting infinite dilution data, we obtain a system of equations that can be solved for A and
B:

2
3
J
RT ln g a 8.314
343.15 K ln 2.62 A 3B 1 4 B 1

mol K

2
3
J
RT ln g b 8.314
343.15 K ln 7.24 A 3B 1 4 B 1

mol K

-1
A 4200 J mol and B 1450 J mol -1
To obtain the fugacity of liquid water, we use the following equation

fal xag a f ao

Since the activity coefficient for water as xa 0 is greater than one, the activity coefficient is
based on the Lewis-Randall reference state. Therefore, f ao is the fugacity of pure water at 70
C. The following relationship also holds since the saturation pressure at 70 C is so low that the
water vapor behaves as an ideal gas and the Poynting correction can be neglected.

f ao Pasat
From the steam tables,

Pasat 31.2 kPa

(70 C)

Using the values of A and B calculated above, we can calculate the coefficient for a mixture of
40 mole % water and 60 mole % ethanol at 70 C:

 4198 3 1450 0.6 2 4 1450 0.6 3

g a exp

8.314 J mol-1 K 1 343.15 K

g a 1.90
Now, we can calculate the fugacity.

fal 0.401.90 31.2 kPa

fal 23.7 kPa

7.62
To find expressions for ln g a and ln g b , we can use Equations 7.55 and 7.56:
GaE RT ln g a
GbE RT ln g b

The expression for the excess molar Gibbs energy can be rewritten as
gE

ABx a xb
Cxa xb xa xb 2
Ax a Bxb

By multiplying the above expression by the total number of moles and rewriting mole fractions
in terms of moles, we obtain
GE

ABn a nb
Cna nb na nb 2 na nb 3
Ana Bnb

Differentiation provides
2

GaE

Bxb

Cxb2 2 xb 16 xb 5
A
Ax

Bx
b
a

GbE

Ax a
Cxa2 2 xa 16 xa 5
B
Ax a Bxb

Substitute these expressions into Equations 7.55 and 7.56:

1
ln g a
RT

Bxb
2
A
Cxb 2 xb 16 xb 5
Ax a Bxb

1
ln g b
RT

Ax a
2
B
Cxa 2 xa 16 xa 5
Ax a Bxb

7.63
Applying Equation E6.4E to the property k = (gE/RT) gives:

gE
gE

E
m

g
RT dT RT dP Gi dx

i
T
P

ni 1 RT
RT

P ,ni

T ,ni
Substituting the following equations into the above expression

gE

hmix
RT
T RT 2

P,n i
E
g

v mix
RT
P RT

T ,n i

(Equation 7.75)

(Equation 7.74)

we obtain

m
gE hmix
v mix
d
dT

dP

ln g idxi
2
RT
RT RT
n i 1

For isobaric binary data, the pressure is constant, and the expression can be reduced to

g E hmix
hmix

d
dT ln g 1dx1 ln g 2 dx2
dT ln g 1dx1 ln g 2 d 1 x1
2
RT
RT
RT 2

g
hmix

dT ln 1 dx1
RT 2
g2

Now, integrate the above expression

gE
d RT

hmix dT ln g 1 dx1
g 2
RT 2

By the definition of excess Gibbs energy, we know g E / RT is zero when x1 0 and x1 1 .

Therefore,

T x1 1

hmix

T x1 0 RT
x1 1

dT

x1 1

g
ln 1 dx1
g
x 0 2

T x 1

1
g1
hmix

ln
dx

g 2 1 RT 2 dT
x1 0
T x1 0

We can also show the following using differentials

dT
1
d
T
T2
Hence,
x1 1

T x1 1

1
x1 1
T
hmix

g
hmix
ln 1 dx1
dT
2
g2
R
RT

1
x1 0
T x1 0
x1 0

1
d
T

7.64
(a)
Since the activity coefficients are approximately equal, we can assume the two-suffix Margules
equation sufficiently models excess Gibbs energy. Calculate the A parameter for both activity
coefficients, and use the average value for subsequent calculations:

J
J
A RT ln g a 8.314
303.15 K ln 1.27 602.4

mol K
mol

J
J
A RT ln g b 8.314
303.15 K ln 1.34 737.6

mol K
mol

J
A 670
mol
Equation 7.32:

fal xag a f al
Calculate the fugacity of pure hexane (a) at 30 C and 1 bar assuming the saturated hexane vapor
acts ideally since its saturation pressure is low at 30 C:

f al Pasat
f al 0.25 bar

(Used Antoines equation and data from Appendix A.)

Calculate g a when xa 0.2, xb 0.8 :

6700.82
1.19
8.314303.15

g a exp
Therefore,

fal 0.2 1.19 0.25 bar

fal 0.06 bar
(b)
Calculate g a when xa 0.5, xb 0.5 :

6700.52
1.07
8.314303.15

g a exp

Therefore,

fal 0.51.07 0.25 bar

fal 0.134 bar
(c)
Calculate g a when xa 0.9, xb 0.1 :

6700.12
1.00
8.314303.15

g a exp
Therefore,

fal 0.9 1.00 0.25 bar

fal 0.23 bar

7.65
We are given the density and the Henrys law constant for 1-propanol in water:

1l 0.80

g
, and H a 0.61 bar
cm 3

(a)
Noting that the system pressure is high (100 bar), we begin with Equation 7.85 from the text:
v1l

P P1sat

sat sat RT

1
1

f1l P e

The specific molar volume of 1-propanol is found from the given density:

v1l

MW1

1l

60.1 g/mol
cm 3

75
.
1
0.80 g/cm 3
mol

The saturation pressure is found using the Antoine equation, and the appropriate constants given
in Appendix A:
B
3166.38
10.9237
T C
298 80.15
sat
P1 0.027 bar

ln P1sat A

Since the saturation pressure is very low, we can assume that 1-propanol acts ideally. Thus,

1sat 1 (ideal)
And we can now find the fugacity of 1-propanol in the liquid:
3

6 m
75.1

10

5
5 J
mol
0.027 bar exp
100

10

0.027

10

m3
8.314 J 298K

mol K

v1l

P P1sat

sat RT

f1l P e

Cranking the arithmetic, we get the pure-species fugacity for 1-propanol:

f1l 0.037 bar

Now, we can calculate the activity coefficient from the pure-species fugacity and the given
Henrys law constant.

Recall that (Equation 7.75):

g 1

H1 0.61 bar

16.70
f1l 0.037 bar

Now we can use a model for the free Gibbs energy to determine the solution fugacity. Since the
two species are similar in size and polarity, we can expect the two-suffix Margules (2SM) model
to fit it adequately. From Table 7.1, we know that:

RT ln g 1 Ax 22
Since at infinite dilution, x2 = 1, we can easily determine the 2SM parameter, A :
A
ln g 1 2.81
RT

Now, use the same model to determine the activity coefficient in the given mixture (i.e. x2 = 0.6):
A 2
2
x2 2.810.6 1.01
RT
g 1 2.75
ln g 1

And finally, we can find the solution fugacity of 1-isopropanol in the given mixture:

f1l x1g 1 f1 0.4 2.75 0.037 bar

f1l 0.040 bar

7.66
You have the parameters for this system from the van Laar (vL) equation:
AvL 3000

J
,
mol

BvL 5040

and

J
mol

(a)
Find the 3SM parameters A and B :
From Table 7.2, the van Laar parameters are related to the activity coefficients by:
2

Bx b

RT ln g a A
, and
Ax a Bx b

Ax a
RT ln g b B

Ax a Bx b

From these values, we can calculate the infinite-dilution activity coefficients for the two species,
and calculate the 3SM parameters from these. Note that for species a at infinite dilution, species
b is pure (i.e. xa = 0, and xb = 1). The bracketed terms in the expressions above then equal one.
RT ln g a A 3000

J
, and
mol

RT ln g a B 5040

J
mol

Applying this same reasoning to the 3SM model,

RT ln g a A B 3000

J
, and
mol

RT ln g b A B 5040

J
.
mol

Solving the two equations with two unknowns, we find:

A 4020

J
, and
mol

B 1020

J
mol

(b)
Calculate the fugacity of liquid benzene (a) in a 30 mole% mixture in 1-propanol at 81kPa.
Start with Equation 7.77 from the text:
fal xag a f a xag a Pasat

(Note: the system pressure is low, so f al Pasat )

Calculate the activity coefficient using either the vL or 3SM model. We will use the 3SM model,
the results are slightly different if you choose the vL model (can you explain why?)
From Table 7.2, we find the expression for the activity coefficient of a in the 3SM model:

RT ln g a ( A 3B) xb2 4 Bx b3 2070

J
mol

Solving for the activity coefficient of benzene in the mixture,

g a 2.04
Now, we need to find the saturation pressure of benzene. Turning to the Antoine equation and
the tables in Appendix A, we calculate:
ln Pasat A

B
0.147
T C

Pasat 0.86 bar

Substituting these values into the original equation, we find the fugacity of liquid benzene in the
mixture:
fal xa g a Pasat 0.32.040.86 bar
fal 0.53 bar

(c)
Determine the mole fraction of vapor in the mixture, assuming the system is in equilibrium.
Since the system is in equilibrium, we know that
y a av P xa g a f fav fal 0.53 bar

We can assume again that the vapor phase is ideal, so that

y a P 0.53 bar

Solving for ya, and substituting the system pressure (0.81 bar) :
ya

0.53 bar
0.65
0.81 bar

7.67
We are asked to determine the fugacity of a, and the Henrys Law constant Ha in a mixture of a
and b at 30 kPa and 20C. The saturation pressure of a and an equation for the excess Gibbs
energy of the mixture is given:
Pasat 50 kPa , and

gE
0.25 xa 0.5 xb xa xb
RT

(a)
Looking in Table 7.1, we find that the given equation for gE is a variant of the Margules 3-suffix
equation. If we rewrite the given equation and compare it to the Margules equation, the values
for the two coefficients are given by:
g E xa xb Aba xa Aab xb 0.25RTxa 0.5RTxb xa xb

Aab 0.5RT and

Aba 0.25RT
Reading from the same table (or explicitly evaluating the derivative), we find an expression for
the activity coefficient of a in the mixture:
RT ln g a xb2 Aab 2 Aba Aab xa

Substitute the values for Aab and Aba, and the mole fraction of each species (xa = 0.2, xb = 0.8):
RT ln g a xb2 0.5RT 20.25 0.5RTxa

ln g a xb2 0.5 0.5xa 0.256

g a 1.29
Now use the relation for fugacity of a condensed phase to find the fugacity fal :
fal xa g a Pasat 12.9 kPa

(b)
Now calculate the Henrys law constant. First, find the activity of a at infinite dilution:
ln g a xb2 0.5 0.5 xa

xa 0

0.5

g a 1.68
Now multiply the infinite-dilution activity coefficient by the saturation pressure:
H a g a Pasat 84 kPa

7.68
From the expressions in Table 7.4, we have:
Acetone Water

xi ri
*i
x1r1 x2 r2
xi qi
i
x1q1 x2 q2

i'
li

xi qi'
x1q1' x2 q2'

0.545

0.455

0.417

0.583

0.501

0.499

-0.42

-2.32

For the combinatorial part of the activity coefficients, we get:

ln g 1, combinatorial ln

1* z

r
q1 ln 1* *2 l1 l2 1 0.236
x1 2
1
r2

and
ln g 2, combinatorial

*2 z

r
ln
q2 ln 2* 1* l2 l1 2 0.116
x2 2
2
r1

For the residual part of the activity coefficients, we calculate the energy parameters
a
a
12 exp 12 0.204
21 exp 21 1.35
and
T
T
With these values, we get:

ln g 1,residual q1' ln 1' 2' 21 2' q1' ' 21' ' 12 ' 0.568
1 2 21 1 12 2
and

ln g 2, residual q2' ln 1'12 2' 1'q2' ' 12 ' ' 21' 0.102
112 2 1 2 21
Summing the combinatorial and residual parts and taking the exponential gives

g1 = 2.23 and g2 = 1.24.

These values are 3 6% lower than the experimentally measured values of g 1exp 2.30 and

g 2exp 1.32 .

7.69
From the expressions in Table 7.4, we have:
Ethanol Benzene

xi ri
*i
x1r1 x2 r2
xi qi
i
x1q1 x2 q2

i'
li

xi qi'
x1q1' x2 q2'

0.319

0.681

0.368

0.632

0.214

0.786

-0.41

1.76

For the combinatorial part of the activity coefficients, we get:

ln g 1,combinatorial ln

1* z

r
q1 ln 1* *2 l1 l2 1 0.063
x1 2
1
r2

and
ln g 2,combinatorial

*2 z

r
ln
q2 ln 2* 1* l2 l1 2 0.022
x2 2
2
r1

For the residual part of the activity coefficients, we calculate the energy parameters
a
a
12 exp 12 1.266
21 exp 21 0.467
and
T
T
With these values, we get:

ln g 1,residual q1' ln 1' 2' 21 2' q1' ' 21' ' 12 ' 0.215
1 2 21 1 12 2
and

ln g 2,residual q2' ln 1'12 2' 1' q2' ' 12 ' ' 21' 0.070
1 12 2 1 2 21
Summing the combinatorial and residual parts and taking the exponential gives

g1 =1.32 and g2 =1.09.

g 1exp

y1 P
1.66
x1P1sat

7.70
From the expressions in Table 7.4, we have:
Acetone Chloroform

xi ri
*i
x1r1 x2 r2
xi qi
i
x1q1 x2 q2

i'
li

xi qi'
x1q1' x2 q2'

0.192

0.808

0.200

0.800

0.200

0.800

-0.42

0.1

For the combinatorial part of the activity coefficients, we get:

ln g 1,combinatorial ln

1* z

r
q1 ln 1* *2 l1 l2 1 0.008
x1 2
1
r2

and
ln g 2,combinatorial

*2 z

r
ln
q2 ln 2* 1* l2 l1 2 0.001
x2 2
2
r1

For the residual part of the activity coefficients, we calculate the energy parameters
a
a
12 exp 12 1.745
21 exp 21 0.737
and
T
T
With these values, we get:

ln g 1,residual q1' ln 1' 2' 21 2' q1' ' 21' ' 12 ' 0.544
1 2 21 1 12 2
and

ln g 2,residual q2' ln 1' 12 2' 1' q2' ' 12 ' ' 21' 0.051
112 2 1 2 21
Summing the combinatorial and residual parts and taking the exponential gives

g1 =0.585 and g2 =0.951.

g 1exp

y1 P
0.536
x1P1sat

7.71
The fugacity of ethanol in solution is calculated with the following equation:

f1l x1g 1P1sat

To find the activity coefficient, we can use Equation 7.73:
x111
x2 21

x x x x x x
1 11
2 12
3 13
1 21
2 22
3 23
ln g 1 1 ln x111 x2 12 x313

x3 31
x x x

3 33
1 31 2 32

Substituting the values given in the problem statement, we obtain

ln g 1 0.192
g 1 1.21

Now calculate the saturation pressure of ethanol at 60 C using Antoines Equation data in
Appendix A.1.

3803.98
bar 0.468 bar
P1sat exp 12.2917
333.15 41.68

Therefore, the fugacity of the ethanol in the liquid is

f1l 0.31.21 0.468 bar 0.17 bar

7.72
First, we need to find the Wilson parameters at 8 C. We can use the following equations:
v

ab b exp ab
va
RT

v

ba a exp ba
vb
RT

Find the energetic parameters (lowercase lambdas) at 60 C, and use them to calculate the
uppercase lambdas at 8 C. The molar volumes for ethanol and 1-propanol can be calculated
using the Rackett EOS. The saturated steam tables provide an estimate for waters molar
volume. Using the above equations with the 60 C data, we obtain:
Pairing
12
21
13
31
23
32

(J/mol)
1.13 x 102
6.83 x 102
1.39 x 103
3.52 x 103
4.73 x 103
5.04 x 103

Now, we can calculate the Wilson parameters at 8 C since the energetic parameters are less
sensitive to changes in temperature. We obtain
Pairing
12
21
13
31
23
32

1.214
0.586
0.204
0.602
0.038
0.400

We will find the fugacity of the ethanol with the following equation

f1l x1g 1P1sat

To find the activity coefficient, with the Wilson parameters at 8 C:

x111
x2 21

x x x x x x
1 11
2 12
3 13
1 21
2 22
3 23
ln g 1 1 ln x111 x2 12 x313

x3 31
x x x

3 33
1 31 2 32

g 1 1.32
We can find the saturation pressure from Antoines Equation data in Appendix A.1.

3803.98
bar 0.028 bar
P1sat exp 12.2917
281.15 41.68

Therefore,

f1l 0.21.32 0.028 bar 7.39 103 bar

7.73
Equation 7.81 provides

H i hi
ln g i

RT 2
T P , x
Equation 6.26 states that

H
mix

H i hi

Therefore,

H mix
ln g i

RT 2
T P , x

For the expression given in the problem statement

H mix

2
3
3802 n2 n1 1200 n2 n1 1554 n2 n1
n1n2

447.8

2
3
n1 n2
n1 n2
n1 n2
n1 n2

Thus, we find

H x
mix

2
2

28731.8x13 4156.6 x12 x2 13131.4 x1 x22 3708.2 x23

For an equimolar solution

H
mix

J
1062.5
1
mol

Now calculate the activity coefficient at 100 C by integrating Equation 7.81:

1
g 1062.5 1
ln 1

1.65 8.314 373.15 333.15

g 1 1.58

7.74
Since we are assuming that the tin and cadmium form a regular solution,

g E hmix
Find the activity coefficient by using the following equation:
E
GCd
RT ln g Cd

E
To find GCd
, start with

G E H mix

13000nCd nSn
nCd nSn

Differentiating provides

E
2
GCd
13000 X Sn

Therefore,

2
130000.6

g Cd exp

J
8.314

773
.
15
K

mol K

g Cd 2.07

7.75
Select the isothermal ethanol/water experimental data set in the Models for gE Parameter
Fitting menu. The temperature, 74.79 C, is automatically selected. We have the capability of
determining the activity coefficients with three different objective functions, but only the
coefficients found using the pressure objective function, OFP, are shown below.
Part (a)
Two
Suffix
Margules
A
3652.3

Part (b)

Part (c)

Part (d)

Part (e)

Three Suffix
Margules

van Laar

Wilson

NRTL

A
3521.0

B
-1102.3

A
B
Gab
Gba
ab
ba
ab
ba
5001.0 2692.8 0.167 0.869 0.979 0.523 0.055 1.683

ThermoSolver provides the following plot

We can look at the value of each objective function to determine which model fits the data best.
We want the objective function with the smallest value. The values are tabulated below for each
model.
Pressure Objective Function Values (bar2)
Two
Three
van
Suffix
Suffix
Wilson
NRTL
Laar
Margules Margules

1.34E-02

2.77E-04

5.45E05

1.40E04

5.39E05

The NRTL model best represents the data.

7.76
Select the isothermal pentane/acetone experimental data set in the Models for gE Parameter
Fitting menu. The temperature, 25 C, is automatically selected. We have the capability of
determining the activity coefficients with three different objective functions, but only the
coefficients found using the pressure objective function, OFP, are shown below.
Part (a)
2 Suffix
Margules
A
4371.1

Part (b)
Three Suffix
Margules
A
B
4365.8
208.7

Part (c)

Part (d)

Part (e)

van Laar

Wilson

NRTL

A
B
ab
ba
Gab
Gba
ab
ba
4150.2 4600.6 0.366 0.226 1.963 2.280 0.573 0.700

ThermoSolver provides the following plot

We can look at the value of each objective function to determine which model fits the data best.
We want the objective function with the smallest value. The values are tabulated below for each
model.
Pressure Objective Function Values (bar2)

Two
Suffix
Margules

Three
Suffix
Margules

1.69E-03

1.11E-03

van
Laar

Wilson

NRTL

1.08E03

1.73E04

1.00E04

The NRTL model best represents the data.

7.77
Select the isothermal chloroform/heptane experimental data set in the Models for gE
Parameter Fitting menu. The temperature, 25 C, is automatically selected. We have the
capability of determining the activity coefficients with three different objective functions, but
only the coefficients found using the pressure objective function, OFP, are shown below.
Part (a)
2 Suffix
Margules
A
1329.8

Part (b)
Three Suffix
Margules
A
B
1235.5
261.6

Part (c)

Part (d)

Part (e)

van Laar

Wilson

NRTL

A
B
ab
ba
Gab
Gba
ab
ba
1028.7 1548.1 1.109 0.478 0.559 0.856 0.519 0.138

ThermoSolver provides the following plot

We can look at the value of each objective function to determine which model fits the data best.
We want the objective function with the smallest value. The values are tabulated below for each
model.
Pressure Objective Function Values (bar2)
Two
Three
van
Suffix
Suffix
Wilson
NRTL
Laar
Margules Margules
2.66E1.64E9.12E4.39E-05 1.33E-06
07
07
08

The NRTL model best represents the data.

7.78
We are given a plot of oxygen content vs. partial pressure of oxygen for an emulsion of 24%
(w/v) perflubron (C8F17Br) in water. Estimate the oxygen capacity of the emulsion, which might
be used as a blood substitute, in units of moles of oxygen per liter of emulsion. Compare this
result with the solubility of oxygen in pure water at the same conditions (25C, atmospheric
pressure). Use these results to determine the value of the Henrys Law constant for oxygen in
pure perflubron (not the emulsion).
a) First, estimate [O2] in the emulsion, as
moles O2/L solution.
We are given a graph showing the
concentration of oxygen in the emulsion at
25C. We are given ambient pressure is 1.0
atm.

O2 1.4 mL/100 cm3

PO = 160 mmHg
2

The standard atmosphere contains 21% O2,

and 79% N2 and other gases. Assuming air
acts as an ideal gas at 1 atm, the partial pressure of oxygen is:
PO2 yO2 P 159.6 mmHg

At this partial pressure, the oxygen concentration of the emulsion is 1.4 mL/100 cm3. Since the
air acts as an ideal gas, the number of moles of oxygen in the emulsion is:

-6 m3

5 J
1.013 10 3 1.4 mL 10

PO2V
m
mL

nO2

5.726 105 moles O2

J
RT

8.314
298K
mol

If we assume that the gas dissolves completely (i.e. there is no volume change when the 1.4 mL
of oxygen is absorbed into the 100 cm3 of emlusion), then

O2

moles O2 5.73 104 moles

L solution
L solution

(where 1 L = 10 x 100 cm3)

b) Compare the result from part A with the oxygen capacity of pure water:
From Table 8.1, we can get the Henrys Law constant H O2 44, 253.9 bar for oxygen in water
at 25C. Since pressure is low and the gas solution is dilute, we can assume ideal behavior, so
Equation 8.30 holds:

xO2

Since xO2

yO2 P
H O2

0.21 bar
4.75 106
44, 253.9 bar

nO2

nO2 nH 2O

nO2
nH 2O

, we can write nO2 xO2 nH2O . Assuming the solution volume is

approximately equal to the volume of pure water, we can define the molality of oxygen to be:

O2

nO2

Vsolution

nO2
VH 2O

Substituting the above relation for nO2 , and noting that vH 2O

O2

VH 2O
nH 2O

xO2
vH 2 O

The molar volume of water can be found from the density at 25C and molecular weight:
vH 2O

M H 2O

H O

18 g/mole
L
0.018
1000 g/L
mole

Substituting this value, we calculate:

O2

Since VO2

xO2
vH 2 O

mole O2
4.75 106
2.64 104
liter H 2O
liter H 2 O
0.018
mole H 2O

VH 2O , the volume of solution is essentially the same as that of the water:

O2 2.64 104

mole O2
.
liter

Thus, the perflubron emulsion can carry approximately 2.2 times as much oxygen as pure
water.
c) Find the value of the Henrys Law constant for oxygen in pure perflubron (PFB).
Previously, we found the mole fraction of oxygen in the emulsion
and in water at the given partial pressure of oxygen. Using the
definition of the Henrys Law constant, we can write (for each of
the two phases in the emulsion):

Xa, yaP

yaP
Ha

xa

Ha

ya P
xa

(see the figure at right)

To find xa, we will first find the number of moles of PFB and water in 100 cm3 of the emulsion.
The emulsion contains 24g of PFB per 100cm3 of solution. This is equivalent to:
1 mole PFB
24g PFB
0.0481 mole PFB , and
498.96 g PFB
1 cm3 PFB
3
24g PFB
12.435 cm PFB .
1.93 g PFB

Since 12.435 cm3 of the total 100 cm3 is taken up by the PFB, the remaining 87.565 cm3 must be
water (since this is an emulsion, we can assume that Vmix 0 ). Therefore, we have
1.00 g H 2O 1 mole H 2O
87.565 cm3 H 2O
4.865 moles H 2O .

cm3

18 g H 2O

Oxygen must be dissolved in either the water or PFB. A simple mole balance on the total oxygen
taken up by the emulsion nO2 ,emulsion allows us to determine the amount of O2 in the PFB phase:
nO2 , PFB nO2 ,emulsion nO2 , H2O

We determined the molar uptake of the emulsion and pure water in Parts (a) and (b), above.
However, recall that we calculated nO2 , H 2O as the moles of O2 taken up by 100 cm3 of water.
Since we have less than 100 cm3 of water, we must scale nO2 , H 2O appropriately:
86.565 cm3
5
nO2 , PFB 5.726 105 moles
2.64 10 moles
3
100
cm

-5
nO2 , PFB 2.64 10 moles O2

Now find the mole fraction of O2 dissolved in the PFB in the 100 cm3 of PFB/H2O emulsion:
xO2 , PFB

nO2

nO2 nPFB

nO2
nPFB

3.44 105 moles O2

0.0481 moles PFB

xO2 , PFB 7.153 10

Applying the definition of the Henrys Law constant above, we can compute H O2 , PFB :

H O2 , PFB
H O2 , PFB 300 bar

yO2 P
xO2 , PFB

0.211.01325 bar
297.5 bar
7.153 104

(Note that a smaller Ha implies a larger xa for a given Pa)