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

y1 P
x1eq   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 Henry’s 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 Henry’s Law constant is
greater for this system.

(b)
The Henry’s 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

0.8

0.6
ga

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1

xa
7.7
(a)
First, we must realize that

h E  hmix

Since

 gE 
   hmix
 T   0
 T  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 
 T 
  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
 P 
 T , n i

Substituting the two suffix Margules equation in for the excess Gibbs energy, we find

 Ax a xb 
  0
 P 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 Henry’s 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
fˆa  xa f a
150

[bar] 100
fˆa  xa  a
50

0
0 0.5 xa 1

(b) Both lnga and lngb go to 1 and xi goes to 0. Therefore the Henry’s 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 1
xa
7.10
7.11
fi
200 oC and 1.56 MPa (Pisat = 1.55 MPa) ( isat  1 ) so 1
Pi sat

fi
70 oC and 1 bar (Pisat = 31.2 kPa) ideal 1
Pi sat

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

fˆi l  fˆi v  yi P  Pi sat  2.34 kPa

7.14
(a)
Use Equation 7.7:

 fv 
g i  g i¼  RT ln  i 
 Plow 
 

Assume Plow  10 kPa . From the steam tables at 500 ºC

 kJ    kJ    kJ 
Plow  10 kPa : gˆ iº  3489.0     773.15K   9.8977     4163.4  
 kg    kg  K    kg 
 kJ    kJ    kJ 
P  2 MPa : gˆ i  3467.6     773.15K   7.4316     2278.1  
 kg    kg  K    kg 

Therefore,

  kJ   kJ   
  2278.1  kg      4163.4  kg   1000 J/kJ  0.0180148 kg/mol  
   
fi v  10 kPa  exp   
   J   

  8.314  mol  K    773.15 K  

    
f iv  1970 kPa  1.97 MPa
 i  0.985

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

 kJ    kJ    kJ 
gˆ 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:

  kJ   kJ   
  1279.0  kg      4163.4  kg   1000 J/kJ  0.0180148 kg/mol  
   
fi  10 kPa  exp  
v 
   J  

  8.314  mol  K    773.15 K  

   
fi  32.4  MPa 
v

and
 i  0.648
 7.15
(a)
Equation 7.8 states

 f iv  P
RT ln    v dP
 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
 Plow     2 2
  RT  iv b Tvi 
Plow

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

v 1 b
 
v  b v  b v  b2
2

so
 vi
vi
vi  b 
  2 dv  lnv i  b   
RT v i  b  vi  b RT
Plow Plow

and
v
  f iv   b 2a 
i

ln     ln(vi  b)  
 Plow   vi  b 2
   RT vi  RT
Plow
   
 f iv   1   
vi  b  2a  1 Plow 
  ln 
  1
ln  b     
 Plow   vi  b RT   RT 2
b
RT  vi RT 
   b 
 Plow 
  Plow 
 RT
Since  b , the expression simplifies to
Plow

 f iv   1 P   P v  b  2a  1 Plow 
ln  b
  low   ln  low i    
 Plow   vi  b RT   RT  RT 2  vi RT 
 

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

b v  b 2a
lnf iv   ln i 
vi  b 2
 RT  RT v i

Therefore,

RT  b 2a 
f iv  exp   
vi  b  vi  b RT 2 vi 


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

f iv RT  b 2a 
 iv   exp   
P P v i  b  v i  b RT 2v i 

(b)
 From Problem 4.29, we got

3RTc
v c  3b 
8Pc
and

 9
a  v c RTc2
8

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



f iv 8Tr  1 9 
 iv   exp   2 
P Pr 3v i,r 1  3v i,r 1 4Tr v i,r 


 7.16
Equation 7.8:

P  f iv 
 vi dP  RT ln Plow 
Plow  

For the Redlich-Kwong EOS

RT a
P  1/ 2
v  b T v v  b

so
  
RT a a
dP     
2 dv
 v  b T v v  b T1/ 2v v  b 
2 1/ 2 2

Therefore,
 v    f iv 
vRT a a
    
T1/ 2v v  b T1/ 2 v  b2 
dv  RT ln 
 v  b
2
RT  Plow 
Plow

To determine the integral of the first two terms term above, we use decomposition by partial
fractions. For the first term,

v 1 b
 
v  b v  b v  b2
2

so
 v
v
v  b 
  dv  lnv  b   
v  b  v  b
2
RT RT
Plow Plow

For the second term:

 1 1 1 1 
  
v v  b b v v  b

so

 v
v
1 1  v 
 v v  b
dv  ln 
b  v  b RT
RT
Plow Plow

Thus, we get
 v
 fv   b  a  v  a
RT ln i   RT lnv  b  RT    1/ 2 ln   1/ 2
 Plow   v  b  T b  v  b  T v  b RT
Plow

RT
If we note that  b and let Plow  0 , we obtain
 Plow

 RT   b  a  v  a
RT ln f iv  RT ln    RT    1 / 2 ln    1/ 2
vb vb T b vb T v  b
Therefore,

RT  b  a  v  a 
f iv  exp   ln    
vb  v  b  RT 3 / 2 b  v  b  RT 3 / 2 v  b 
and
f iv RT  b  a  v  a 
 iv   exp   ln   
P P v  b  v  b  RT 3 / 2b  v  b  RT 3 / 2 v  b


 7.17
Equation 7.8:

P  f iv 
 vi dP  RT ln Plow 
Plow  

The Peng-Robinson EOS can be written

RT a (T)
P  2
v  b v  2vb b2 

Thus,
  
 RT 2a (T)v  b 
dP    dv
 v  b2 v 2  2vb  b 2 2 
 

Therefore,
  
v
RT 2a (T)v  b   f iv 
 v 
 v  b2 v 2  2vb b 2 2 
dv  RT ln 
 Plow 
RT
Plow
 

Simplifying, we get

 fi v  v
v 2a (T )
v
v v  b
ln    dv   dv (1)
RT  v  b  v 
2 2 2
 Plow  RT RT
2
 2vb  b
Plow Plow

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

v 1 b
 
v  b v  b v  b2
2

so
 v
v
v  b 
  dv  lnv  b    (2)
v  b  v  b
2
RT RT
Plow Plow


 For the second integral, decomposition leads to:

v v  b 1 v  b
 b
v 
2 2 v  2vb  b v 2  2vb b2 
2 2 2
2
 2vb b

so
v
v v  b v
1 v
v  b dv
  dv   dv  b  (3)
v  2vb b 2  v  2vb  b RT v  2vb  b 
2 2 2 2 2 2 2
RT RT
Plow Plow Plow

We again use partial fractions. For the first term in Equation (3):

1 1  1 1 
 
v 2  2vb  b 2

 
2 2b  v  1  2 b v  1  2 b    
so

v
1
1 v  1 2 b   v

 v 2  2vb  b 2 dv  2 2b ln v  1  2 b RT   (4)
RT
Plow
Plow

For the second term in Equation (3):

v  b 
v  b 
2b
(5)
v 2  2vb b 
2 2
v 2  2vb b 2 2
 v 2  2vb b2 
2

Equation (5) can be substituted into Equation (3) to give two terms. The first term gives:
 v
v
v  b b
b  dv  (6)
v 2  2vb b2  2v  2vb  b  RT
2 2 2
RT
Plow Plow

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

 2
1 
 2b 1   1 
    
2
v  2vb  b 2 2

4b  v  1  2 b   v  1  2 b     
 or

 2
 
2
 2b 1  1   1  1   1
    2     
 v  1  2 b  v  1  2 b    v  1  2 b  
       
 2
v  2vb  b 2 2
 
4b  v  1  2 b       
(7)

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

v 2 v
1  1  1

4 RT

 

 v  1  2 b  dv   4 v  1  2 b RT
     (8)
Plow
Plow
and
v 2 v
1  1  1

4 RT


 dv  
 v  1 2 b 
  
4 v  1  2 b RT    (9)
Plow
Plow

From above the second term gives:

1
v
 1  1  1 v  1 2 b   v
 
2 RT





 v  1  2 b  v  1  2 b    4 2b ln v  1  2 b RT
       (10)
Plow
Plow

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

v
vv  b 
1 v  1 2 b b   v v

 2 dv  
   
 
ln
RT v  2vb  b 2
2 2 2b v  1  2 b RT 2 v  2vb  b 2 RT
2
Plow Plow
Plow (11)
1 1
v
1 v  1 2 b
v
  v

  
  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
 v  1 2 b 
v
v v  b  1 ln v
 dv    (12)
RT
Plow
v 2
 2vb b  
2 2  4 2b 2
v  1 2 b 2v 2
 2vb  b 2
 RT
 
Plow


 Substituting Equations (12) and (2) into Equation (1) gives
 
v
 f iv   v  v  1 2 b 
 b  2a (T)  1 v 
ln   RT lnv  b  RT    ln 
P
 low    v  b  RT
Plow
RT 
 4 2b 
v  1 2 b 2v 2
 2vb b 2
 RT
Plow

RT
If we note that  b and let Plow  0 , we obtain
 Plow

ln f i  ln
v
 

 RT   b  a (T)  1
ln
v  1 2 b
v 

 v  b  v  b
  
RT 2 2b v  1 2 b v 2  2vb b 2 


and

 RT   b  a (T)  1
ln   ln
v
   ln

v  1 2 b
 2
v


i
 P v  b  v  b  RT 
 2 2b 
v  1 2 b  v  
2vb  b 2



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 ºC and 10 kPa. Using enthalpy and entropy values
from the steam tables, interpolation gives:

 kJ   kJ 
gˆ io  2934.5   gˆ i  890.9  
 kg   kg 

Therefore,

 J   J 
g io  52864   g i  16049 
 mol   mol 

Now, the fugacity can be calculated:

 
  16049  J    52864  J  
  mol   mol  
f iv  10 kPa exp    9382 kPa 
   
 647 K  
 J 
  8.314 
   mol  K   
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  
 vi  b  RT  RTvi 

The “a” and “b” parameters for water are

 J  m3 
a  0.554  
 mol 
 5
 m3 
b  3.05  10  
 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 Pr  0.52   0.344

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 atm0.82 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  i0   log  i1  0.0176  0.0080.0614 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  
 vi  b  RT  RTvi 

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  156.5bar 

Calculate the fugacity coefficient:

f iv
 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 108 Pa -1 

Find an expression for v:

v
RT
1 B' P 
P

Substitute into Equation 7.8 and integrate to obtain

 P   fv 
ln    B' P  Plow   ln  i 
 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
27.1 bar
 iv   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  Plow   P 

Rearrange the above equation and substitute it into Equation 7.8.

P
  P    30  
RT  CP  ln  low   RT    0.065   P  ln Plow  ln P    vi dP
  P    T   P
low

Differentiate both sides with respect to P:

1  30 
vi  RT     0.065  
P  T 

(b)
Substitute numerical values:

  m 3  bar      1 
vi   8.314  10  5  353.15 K    0.065 
30
 
 
 mol  K     353.15 K  30 bar 


 m3 
vi  3.93  10  4  
 mol 
 7.22
Equation 7.8:

 f iv  P
RT ln    v dP
 Plow   i
  Plow

The equation from the problem statement can be rearranged to yield

1 T  0.422Tc1.6 
vi  RT   c  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 
ln  i   ln 
 Plow 
 

0.083 
1.6 
P  Plow 
   Plow  Pc T  T 
or

 f v T  0.422Tc1.6 
ln i   c 0.083  P  Plow 
 P  PcT  T1.6 

Let Plow go to zero gives:

 P 
T P  0.422Tc1.6  0.422 
f i  P exp 
v c
0.083    P exp  r
 0.083  
 PcT  T1.6   Tr  Tr1.6 
and
T P  0.422Tc1.6  P  0.422 
 iv  exp  c
 0.083  1.6   exp  0.083  1.6 
r

  PcT  T   Tr  Tr 

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:

 fv  P P
 RT kP 2  c 
RT ln  i    vi dP      b  dP
 Plow  Plow Plow  
P T

Carrying out the integration, we find:

P
 fv  kP3 cP
RT ln  i   RT ln P    bP
 Plow  3T T Plow

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

P
 kP3 cP 
 RT ln f i
v
 
 RT ln Plow  RT ln P  RT ln Plow     bP 
 3T T  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
RT ln  RT ln i 
v
  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 ,

kP3 cP
RT ln iv    bP
3T T

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

 1 kP3  cP P 
iv  exp  3 2
b 
 RT RT 
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

P  
v v2 v3

So

 RT 13.40 106 14.49 108 

dP    2    dv
 v v3 v4 

And

 fv   RT 13.40 106 14.29 108 

vi

RT ln  i  
 Plow 

RT
 v 
 v2

v3  dv

Plow

Integrating:

 
 fi v  vi 13.40 106 13.40 106   7.245 108 7.245 108 
RT ln     RT ln RT      
 
RT 2 2
 low 
P Plow 
vi P   vi  RT  
 Plow  
low


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  
P RT v1 vi2

 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:

Pvi
z  1  B' P  C ' P 2
RT

For the two states we have

v P T R z
3
m /mol Pa K J/mol K
State 1 1.86 10-3 1.50 106 373.15 8.314 0.90
State 2 6.12 10-4 4.00 106 373.15 8.314 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 103 bar and C '  5.76 105 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  C'
 B'  P  Plow    P 2  Plow 
P
ln  i      B'  C ' P  dP  ln 2

 Plow  Plow  P  Plow 2

Canceling out ln(Plow) subtracting ln(P), and letting Plow ->0, we get
fv C'
ln  i   ln i  B' P  P 2
P 2

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:

T 220 P 69
Tr    1.15 Pr    1.5
Tc 190.6 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 i1  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] v [m3/mol]
1.0 2.45 x10-2
5.1 4.78 x10-3
10.1 2.32 x10-3
15.2 1.50 x10-3
20.2 1.08 x10-3
25.3 8.34 x10-4
30.3 6.66 x10-4
35.4 5.44 x10-4
40.4 4.52 x10-4
45.5 3.78 x10-4
50.5 3.17 x10-4
Equation 7.9:

P
zi  1
ln  iv   P
dP
Pideal

The following graph has been created with data above:

0

-1

-2
(z-1)/P x 1000 [bar]

-3

-4

-5

-6

-7

-8
0.0 10.0 20.0 30.0 40.0 50.0 60.0

P (bar)

Integrate the data numerically using the Trapezoid Rule. We obtain

ln  iv  0.3

Therefore,
  iv  0.74 and f iv   iv P  37.5 bar 

 
 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,

 Pvi
zi   0.001P  1
RT

Therefore, the molar volume is:

  J 
8.314 
  mol  K 
 
373.15 K 0.001 bar 500 bar   1
-1

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
J
g mix  T smix   RT  x1 ln x1  x2 ln x2   1, 730
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:

T 318.9 P 3.79
Tr    0.75 Pr    0.1
Tc 425.2 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 i1  0.035  0.193  0.030   .041
  0.91
i
v

Calculate fugacity:
fˆ1v  y11P  0.41  bar 
7.31
(a)
f1v  1P

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

190.6 32.2
Tr   1.0 Pr   0.70
190.6 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 i1  0.113  0.008  0.022   0.113
  0.77
i
v

Calculate fugacity:

fi v  24.8  bar 
(b)

f1v  y11P  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.

1
v1  RT   P
A  B 
P RT 

Substituting this expression into the integral and integrating, we get

 fv   P  A  B  P 2 Plow 
2
ln  1   ln    
 Plow   Plow  RT  2 2 
   

By simplifying and letting Plow  0 ,

lnf1v  lnP  
A  B P 2 
 
RT  2

Therefore,
  f v   A  B P2
ln1v  ln 1    
 P   RT  2

 
 5 50
 A  B  P 2  2
5
1v  exp     exp   9.0 10  3.0 10 
 RT  2   2 

1v  0.93

Species in a mixture:

 fˆ v  P
RT ln  1    V1dP
yP 
 1 low  Plow

The expression for the extensive volume is

 V  n1  n2  n3   PAn1  n2  Bn1  n2  n3 
RT
P

Therefore,

 PA  B
RT
V1 
P

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

 ˆ
ln 1  v P2  A

B 
2  RT RT 


ˆ  P2  A B 
1  exp  
v
 
 2  RT RT  
  50 atm 2  5  1  5  1  

ˆ
1  exp       atm2   
v
 9.0 10  atm2  3.0 10
 2   
ˆ1v  0.93

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

fˆ1v  fˆ1l

Hence,

fˆ1v  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.

fˆ1v
ˆ1v   0.93
y1 P
15 atm
y1   0.322
0.9350 atm
7.33
(a)
The Lewis fugacity rule:

ˆ1v  1v

From Example 7.2

  v  b  P  2a
ln iv  
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.

fˆ1v  0.2  0.89   30  bar   5.34  bar 

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

RT 1
V  nT  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

 1  n12 n22
V  n1  n2   n1b1  n2b2  n3b3 
RT
 a1  a
P RT  n1  n2  n3  n1  n2  n3  2
n32 2n1n2 2n1n3 2n2 n3 
 a3  a12  a13  a23 
n1  n2  n3  n1  n2  n3  n1  n2  n3  n1  n2  n3  

To calculate fugacity, we use the following expression

 fˆ v  P
RT ln  1    V1dP
yP 
 1 low  Plow

Find V1 :

 V 
V1    
RT
 b1 
1
2 y1a1  2 y2 a2  2 y3a13  amix 
 dn1 T , P, n2 , n3 P RT

Substituting this expression into the integral and integrating we get,

 fˆ v   P  b1 1
2 
ln  1   ln     P  Plow   2 y1a1  2 y2 a2  2 y3a13  amix   P  Plow 
yP   
 1 low   Plow  RT RT
By subtracting ln Plow  and ln P  from both sides and then letting Plow  0 , we obtain

 fˆ v   b 
 
ln ˆ1v  ln  1    1 
 y P
1
 2 y1a1  2 y2 a2  2 y3a13  amix  P
 1   RT  RT 
2


Substitute numerical values and evaluate:

 
ln ˆ1v  0.10
ˆ1v  0.906

Calculate fugacity:

fˆ1v  y1ˆ1v P  0.2  0.906  30  bar 

fˆ1v  5.44  bar 
7.34
(a)
Equation 7.14:

 fˆ v  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 
P  RT  a b c
 
 V V 2 
 
Therefore,

 P   1 2n B  2nb Bab  2nc Bac 

   RT   a aa 
 na T ,V , ni  a V V2 

Substitute the above equation into Equation 7.14 and integrate

 fˆ 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

 fˆ 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
  a

Now subtract ln P from both sides:

 fˆ v   nRT  2na Baa  2nb Bab  2nc Bac

 y P  
ln  a   ln ˆav  ln 
 PV

 V
 a 

 1  2n B  2nb Bab  2nc Bac

 
ln ˆav  ln    a aa
z V

1  2 ya Baa  2 yb Bab  2 yc Bac 

ˆav    exp  
z  v 

 y P  2 y B  2 yb Bab  2 yc Bac 
fˆav   a  exp  a aa 
 z   v 
 (b)
For this system

y a  0.2
yb  0.3
yc  0.5

Using the virial coefficient data:

4
 m3 
Bmix  2.392  10  
 mol 
Therefore,

Pv B
z  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.)

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

ˆav  1.04

fˆav   0.215 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
 va
 f av 
 a
v dP  RT ln 
 Plow 
RT
Plow


 Substitute the expression for dP into the above integral:

v
 1 2 Baa   f av 
 RT 
RT
  2
 va va
 a

dv  RT ln  
 Plow 
Plow

Integrating and evaluating the limits, we obtain

  
  
 f av   2Baa    RT  2Baa 
ln    lnv a    ln 
 Plow   v a    Plow   RT  
    
   Plow  

Cancel the logarithmic terms containing Plow and then let Plow go to zero:
 2Baa v 
lnf av   ln a 
va  RT 

Therefore,
  2B 
RT
f av  exp  aa 
va  va 
1  2B 
 av  exp  aa 
za  va 

Since we are employing the Lewis fugacity rule
  2B 
1
ˆ av   av  exp  aa 
za  va 
y RT  2B 
fˆav  y a f av  a exp  aa 
va  va 

To calculate the fugacity and fugacity coefficient, we will need to find the pure species molar
volume:

 m3 
v a  1.61103  
mol

Substituting values into the above expressions, we obtain


 ˆ av  0.975
fˆav  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:

fˆ1v  y1ˆ1v P  0.2 1  24.52  bar 

fˆ1v  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, let’s 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)

P
Pr 
Pc

T
Tr 
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 694.2
Tr K
1
ω 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

ˆ1  1  0.86

fˆ1v  y11v P  0.2  0.86   24.52  bar 

fˆ1v  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

 RT   b  1 a  1  b1a   b
ln(ˆ1v )  ln    ln 1    b1     1.5 
 2 a 1 a  ln 1  
 Pv   v  v  b bRT (v  b)  bRT  b   v
1.5

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:
RT av (i)  b
v (i1)
  b  1/ 2 (i) (i)
P PT v v  b
Start with the ideal gas law:
RT m3
v (0)   2.35 103
 P mol
then
RT m3 RT m3
v (1)   2.34 103 : and v (2)   2.34 103
P mol P mol

Now use the equation from Table 7.1 to find the fugacity coefficient.
 RT   b  1 a  1  b1a   b
ln(ˆ1v )  ln    ln 1    b1     1.5 
 2 a 1 a  ln 1  
 Pv   v  v  b bRT (v  b)  bRT  b   v
1.5

ˆ  0.943
v
1

fˆ1v  y1ˆ1v P  0.2  0.94   24.52  bar 

fˆ1v  4.63 bar
7.38
(a)

 f1v  P
RT ln     v1dP
 Plow  Plow

RT RT  Pr ,1 
v1    
P P  8Tr ,1 

 f v  P  RT RTc ,1 
RT ln  1      dP
 Plow 
 Plow  P 8 Pc ,1 

 fv   P  RTc ,1
RT ln  1   RT ln    P  Plow 
 Plow   Plow  8Pc ,1

 fv
ln  1   ln 1v   r ,1
P
 P  8Tr ,1

219 27.72
Tr   0.6 Pr   0.6
365 46.2

ln 1v  
1
8
1v  1.13
fˆ1v  y11v P  7.85  bar 

(b)

 fˆ v  P
RT ln  1    V1dP
yP 
 1 low  Plow

RT RT  n1Pr ,1 n2 Pr ,2 
V   n1  n2     
P P  8Tr ,1 8Tr ,2 

 V  RT RTc ,1
V1     
 dn1 T , P ,n2 ,n3 P 8Pc ,1
  fˆ v  P  RT RTc ,1 
RT ln  1      dP
yP   P 8 P 
 1 low  Plow  c ,1

 fˆ v   P  RTc ,1
RT ln  1   RT ln 
yP    P  Plow 
 1 low   low 
P 8 Pc ,1

 fˆ v 
ln  1   ln ˆ1v   r ,1
P
 y P 8Tr ,1
 1 

219 27.72
Tr   0.6 Pr   0.6
365 46.2

ln ˆ1v  
1
8
ˆ1v  1.13
fˆ1v  y1ˆ1v P  7.85  bar 
(c)

Values are the same so all the intermolecular interactions are the same
7.39
(a)

V
 n1  n2  RT  RT
 n12 B11'  2n1n2 B12'  n22 B22' 
P  n1  n2 
 V 
 RT  y12 B11'  2 y1 y2 B12'  y22 B22   RT  2 y1B11'  2 y2 B12' 
RT
V1     '

 n1 T , P ,n2 P
 V 
 RT  B '   RT  2 y1B11'  2 y2 B12' 
RT
V1    
 n1 T , P ,n2 P
 fˆ1v  P P
1 
 V dP RT     B '    2 y1 B11'  2 y2 B12'   dP
 y P   1
RT ln 
Plow  
 1 low  Plow P
 P 
 ln     2 y1 B11  2 y2 B12  B   P  Plow 
' ' '

 low 
P

 fˆ v 
ln  1   ln ˆ1    2 y1B11  2 y2 B12  B  P
v ' ' '
yP
 1 

(b)
y1 = 0.4
B11' - 1.9 x 10-7 [Pa-1]
B12' - 3.6 x 10-8 [Pa-1]
'
B22 - 2.0 x 10-9 [Pa-1]

So

ˆ1v  0.84

And

fˆ1v  y1ˆ1v 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):

fˆ1v  y11P

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

495 18
Tr   1.0 Pr   0.70
469.6 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 i1  0.086  0.251 0.019   0.0907
iv  0.81

Calculate fugacity:
fˆ1v  0.137  0.8118  2.00 bar
7.41
From the definition of fugacity:

 fˆ v  P V
 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:

P
 n1  n2  RT  n12 a1  n22 a2  2n1n2 a12
V   n1c1  n2c2  
2
V

Differentiating

 P  RT 2n1a1  2n2 a12  2c1  n12 a1  n22 a2  2n1n2 a12 

    
   1 1 2 2  V   n1c1  n2c2  
2 3
 1 T ,V ,n2 ,n3
n V V  n c  n c

Into the equation above:

 fˆi v  V
 RT 
V 
2n1a1  2n2 a12 
V 
2c1  n12 a1  n22 a2  2n1n2 a12  
RT ln      dV   
  dV     dV
 y P             
2 3
 1 low  nT RT V nT RT
 V  n c
1 1  n c
2 2  nT RT
 V  n c
1 1  n c
2 2 
Plow Plow Plow

Integrating we get

   
 fˆi v   V   1 1 
RT ln     RT ln     2n1a1  2n2 a12    
yP   nT RT  V   n1c1  n2c2  nT RT   n c  n c  
 1 low 
 Plow   Plow
1 1 2 2

 
 
 
c1  n1 a1  n2 a2  2n1n2 a12  
1 1
2 2
 2
 V   n1c1  n2 c2    nT RT   n c  n c   
2

  2 2 
 
1 1
 Plow

nT RT
Taking and   n1c1  n2c2 
Plow
    
 fˆi v   V   1 1 
RT ln     RT ln     2n1a1  2n2 a12    
yP   nT RT  V   n1c1  n2c2  nT RT 
 1 low 
 Plow   Plow 
 
 
 
c1  n1 a1  n2 a2  2n1n2 a12  
1 1
2 2
 2
 V   n1c1  n2c2    nT RT  
2

  
 Plow  

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

 fˆ v   1 
RT ln  i    RT ln  z    2n1a1  2n2 a12   
yP 
 1 low  V   n1c1  n2 c2  
 
c1  n12 a1  n22 a2  2n1n2 a12  
1

 V   n1c1  n2c2   
2
 

Simplifying:

y1a1  y2 a12 c1a

RT ln ˆ1    RT ln  z   2 
vc v  c
2
7.42
From the definition of fugacity:

 fˆ v  P V
 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:

P
 n1  n2  n3  RT  n12 a1  n22 a2  n32a3  2n1n2a12  2n1n3a13  2n2n3a23
V   n1b1  n2b2  n3b3  V   n1c1  n2c2  n3c3  
2

Differentiating

 P  RT b1  n1  n2  n3  RT
   
 n1 T ,V ,n2 ,n3 V   n1b1  n2b2  n3b3  V   n1b1  n2b2  n3b3  
2

2n1a1  2n2 a12  2n3a13 2c1  n12 a1  n22 a2  n32 a3  2n1n2 a12  2n1n3a13  2n2 n3a23 
 
V   n c  n c 2  n3c3   V   n c  n c  n3c3  
2 3
1 1 2 1 1 2 2

 fˆ v  V
 RT 
RT ln  i       dV
yP  V   n b  n b  n b 
 1 low  nT RT  1 1 2 2 3 3 
Plow

V b  n  n  n  RT 
   1 1 2 3
 dV
nT RT V   n1b1  n2b2  n3b3   

2

P
  
low

V  2n a  2n a  2n a 
   1 1 2 12 3 13 

nT RT  V   n1c1  n2 c2  n3c3   
2
dV
P
 
low

V  2c1  n12 a1  n22 a2  n32 a3  2n1n2 a12  2n1n3a13  2n2 n3a23  

    dV
nT RT    1 1 2 2 3 3  
3
 V  n c  n c  n c 
P low

Integrating we get
  
 fˆi v   V  n b  n b  n b  
RT ln    RT ln  
 y P 
1 1 2 2 3 3

 1 low   T
n RT
  n1b1  n2b2  n3b3  
 Plow 
 
 1 1 
 RTb1  n1  n2  n3    
V   n1b1  n2b2  n3b3  nT RT   n b  n b  n b  
 Plow
1 1 2 2 3 3

 
 1 1 
  2n1a1  2n2 a12  2n3a13    
V   n1c1  n2c2  n3c3  nT RT   n c  n c  n c  
 Plow
1 1 2 2 3 3

c1  n12 a1  n22 a2  n32 a3  2n1n2 a12  2n1n3a13  2n2 n3a23  
 
 
 1 1 
  2
 V   n1c1  n2 c2  n3c3    nT RT   n c  n c  n c   
2

  3 3 
 
1 1 2 2
 Plow

nT RT n RT
Taking   n1b1  n2b2  n3b3  and T   n1c1  n2c2  n3c3 
Plow Plow
  
 fˆi v  V   n b  n b  n b  
RT ln    RT ln  
 y P 
1 1 2 2 3 3

 1 low   n T RT 
 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
 V   n1c1  n2c2  n3c3    nT RT  
2

  
 Plow  

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

 fˆi v   PV  P  n1b1  n2b2  n3b3  

RT ln     RT ln  
 y P
 1   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  
1

 V   n1c1  n2c2  n3c3   
2
 

Simplifying:

 bP  RTb1 y a  y2 a12  y3a13 c1a

RT ln ˆ1    RT ln  z    2 1 1 
 RT  v  b vc v  c
2
7.43
Let “a” refer to methane and “b” refer to hydrogen sulfide. From Example 7.4

 P  v  bmix   
2 ya aa  yb aa ab 
 
ln ˆav   ln 
 RT

ba
 v  bmix

RTv

In the above expression, v and bmix depend on mole fractions. First, calculate a a , ab , ba , and
bb :
27 RTc 2 RTc
a b
64 Pc 8Pc
 J  m3  5
 m3 
aa  0.230   ba  4.31  10  
2
 mol   mol 
 J  m3   m3 
ab  0.454   bb  4.34  10  5  
2
 mol   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.

RT a
P  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 yb amix bmix v ln(a) a

0 1 0.454 4.34 x 10-5 0.000437 0.001 1.001
0.1 0.9 0.428 4.34 x 10-5 0.000447 -0.007 0.993
0.2 0.8 0.403 4.33 x 10-5 0.000456 -0.013 0.987
0.3 0.7 0.379 4.33 x 10-5 0.000465 -0.018 0.982
0.4 0.6 0.355 4.33 x 10-5 0.000473 -0.023 0.978
0.5 0.5 0.333 4.33 x 10-5 0.000481 -0.026 0.974
0.6 0.4 0.311 4.32 x 10-5 0.000488 -0.029 0.972
0.7 0.3 0.289 4.32 x 10-5 0.000494 -0.031 0.970
0.8 0.2 0.269 4.32 x 10-5 0.000500 -0.032 0.968
0.9 0.1 0.249 4.31 x 10-5 0.000506 -0.033 0.967
1 0 0.230 4.31 x 10-5 0.000512 -0.033 0.967
From ThermoSolver using the Peng-Robinson EOS:

ya yb öa
0 1 1.033
0.1 0.9 1.02
0.2 0.8 1.008
0.3 0.7 1.000
0.4 0.6 0.992
0.5 0.5 0.986
0.6 0.4 0.982
0.7 0.3 0.978
0.8 0.2 0.977
0.9 0.1 0.975
1 0 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
a

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 0.7 0.8 0.9 1
ya (mole fraction)

The values agree relatively well.

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

 1 
   RT 
ln ˆav  ln 
 b
  ln 1    ba  
a

1  ba a
1.5 
  b
 2 aa a  ln 1  
 Pv   v  v  b bRT  v  b   bRT  b   v
1.5

(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 RTc
a  0.42748 b  0.08664
Pc Pc
 J  m 3  K1/2  5
 m3 
a a  3.22   ba  2.99  10  
2
 mol   mol 
 J  m 3  K1/2   m3 
ab  8.90   bb  3.01  10  5  
2
 mol   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:

RT amix
P 
v  bmix T vv  bmix 
1 / 2

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 yb amix bmix v ln öa öa
0 1 8.900 3.01 x 10-5 0.000437 0.036 1.037
0.1 0.9 8.205 3.01 x 10-5 0.000449 0.024 1.024
0.2 0.8 7.538 3.01 x 10-5 0.000460 0.013 1.013
0.3 0.7 6.899 3.00 x 10-5 0.000470 0.005 1.005
0.4 0.6 6.289 3.00 x 10-5 0.000479 -0.002 0.998
0.5 0.5 5.707 3.00 x 10-5 0.000487 -0.007 0.993
0.6 0.4 5.153 3.00 x 10-5 0.000495 -0.011 0.989
0.7 0.3 4.627 3.00 x 10-5 0.000502 -0.014 0.986
0.8 0.2 4.130 2.99 x 10-5 0.000508 -0.016 0.984
0.9 0.1 3.661 2.99 x 10-5 0.000514 -0.018 0.982
1 0 3.220 2.99 x 10-5 0.000520 -0.018 0.982

We have from the Peng-Robinson EOS using ThermoSolver:

ya yb öa
0 1 1.033
0.1 0.9 1.02
0.2 0.8 1.008
0.3 0.7 1.000
0.4 0.6 0.992
0.5 0.5 0.986
0.6 0.4 0.982
0.7 0.3 0.978
0.8 0.2 0.977
0.9 0.1 0.975
1 0 0.975

The data plotted on the same graph reveal:

  a vs. y a From the Redlich-Kwong EOS
Compared to Thermosolver Results
1.050

1.025

Redlich-Kwong EOS
a

1.000


Thermosolver

0.975

0.950
0 0.2 0.4 ya 0.6 0.8 1

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,

 P  v  bmix   
2 xa aa  xb aa ab 
 
ln ˆav   ln 
 RT
 
ba
 v  bmix

RTv

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

27 RTc 2 RTc
a b
64 Pc 8Pc
 J  m3   m3 
aa  0.230   ba  4.31  10  5  
2
 mol   mol 
 J  m3   m3 
ab  0.454   bb  4.34  10  5  
2
 mol   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:

RT a
P  mix
v  bmix v2
so
 m3 
v  4.81104  
mol

Substituting these values into the equation for the fugacity coefficient, we get

ˆav  0.974
(b)
From Problem 7.5:

 1 
   RT 
ln ˆav  ln 
 b
  ln 1    ba  
a

1  ba a
1.5 
  b
 2 aa a  ln 1  
 Pv   v  v  b bRT  v  b   bRT  b   v
1.5

(Note: a is short for amix and b is short for bmix)

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

R 2Tc2.5 RTc
a  0.42748 b  0.08664
Pc Pc
 J  m3   m3 
aa  3.22   ba  2.99  10  5  
2
 mol   mol 
 J  m3   m3 
ab  8.90   bb  3.0110  4  
2
 mol   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:

RT amix
P 
v  bmix T vv  bmix 
1 / 2

 m3 
v  4.871 10  4  
 mol 

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

ˆav  0.993

(c)
Using Kay’s mixing rules, we have the following expressions:

T pc  yaTc, a  ybTc, b
 Ppc  ya Pc, a  yb Pc,b
w pc  ya a  ybb

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  0.0540.0371

 v  0.930

(d)

Using the Peng-Robinson EOS in ThermoSolver, we obtain:

ˆav  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 öav % Difference

(a) van der Waals 0.974 1.22
(b) Redlich-Kwong 0.993 0.71
(c) Generalized Correlations – Kay’s 0.930 5.68
(d) ThermoSolver / Peng-Robinson 0.986 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:

nT RT na  nb RT na2 Baa  2na nb Bab  nb2 Bbb

V  nT Bmix  
P P na  nb

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

2 2
 V  RT 2na Baa  2nb Bab na Baa  2na nb Bab  nb Bbb
Va      
 na T , P,nb P na  nb na  nb 2
or
 2 ya Baa  2 yb Bab   ya2 Baa  2 ya yb Bab  yb2 Bbb 
RT
Va 
P

We must now plug this into Equation 7.13 and integrate:

P
 RT   fˆav 
P  2 y B
a aa  2 y B
b ab   a aa a b ab b bb 
y 2
B  2 y y B  y 2
B dP =RT ln   so
Plow   pa ,low 
 fˆav 
 
P
  2 ya Baa  2 yb Bab   ya Baa  2 ya yb Bab  yb Bbb  dP =RT ln 
P 2 2
RT ln 
Plow Plow  ya Plow 
Rearranging

 fˆ v 
 
P
2 ya Baa  2 yb Bab   ya2 Baa  2 ya yb Bab  yb2 Bbb  dP =RT ln  a   RT ln ˆav
Plow  ya P 
Integrating, we get
 2y Ba aa 
 2 yb Bab   ya2 Baa  2 ya yb Bab  yb2 Bbb  P  RT ln ˆav

Setting ya=0 and yb=1:

 2Bab  Bbb  P  RT ln ˆa

RT
ln ˆa  Bbb  cm3 
Bab  P  34.5  mol 
2  

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:

Bmix
z  1
v

In that case, the solution becomes:


v  ˆ vP  cm3 
Bab  ln a   55.9  
2  RT   mol 


7.47

(a)
We can start with Equation 7.14 to find the fugacity coefficient:

 föv  V
 P 
RT ln  1       dV
 y1 Plow   n 
  nRT 1 T ,V , n 2
Plow

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

RT amix n  n2 RT n1a1  n2 a2 n1  n2 1 / 2

P   1 
v v 3 / 2T 1 / 2 V V 3 / 2T 1 / 2

Differentiate:

1 / 2 n a  n2 a 2 
 P   
a1 n1  n2   1 1
RT 1
    
 n1 T ,V , n 2 V V 3 / 2T 1 / 2  2n1  n2 1 / 2 

Substitute this expression into Equation 7.14 and integrate to obtain

 fˆ1v   VPlow  2   n1a1  n2 a2  
   RT ln    1/2 1/2  a1  n1  n2  
1/2
RT ln 
 nRT  V T  2  n1  n2  
1/2
 y1 Plow 

 P 
  low 
1/2
2   n a  n a2  
 a1  n1  n2   1 1 2 1/2
1/2

 nRT  T  2  n1  n2  
1/2

This expression can be simplified by canceling the terms containing Plow and then taking the
limit as Plow goes to zero. This results in

 fˆ1v   nRT  2   n1a1  n2 a2  

RT ln    RT ln    1/2 1/2  a1  n1  n2  
1/2

 V  V T  2  n1  n2  
1/2
 y1 

The above equation is equivalent to

 fˆ v   RT  2 
 y1a1  y2a2 
1
RT ln  1   RT ln    a1 
 y1   v  vT  2 

If we subtract the natural log of pressure from both sides of the equation and rearrange, we
obtain
  RT  2  1 
ln ˆ1v  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.

  8.314  500     
ˆ1v  exp ln   
2
800 
1
  
0.33 800  0.66   
500
  1.78 106   0.002   8.314  500   0.002  500   2  

ˆ1v  0.689

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

P
8.314500  0.33800 0.66500  1.78  10 6 Pa
0.002 0.0023 500
(b)
The Lewis fugacity rule states

ˆ1v  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 
dP     dv1
 v12 2 T 1 / 2v5 / 2 
 1 

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

 f v  v1   RT 3 
RT ln  1    
a1
  dv
 Plow   v 2 T 1/ 2 3 / 2  1
v
  RT  1 1 
Plow

Now perform the integration to obtain

  fv   v P  3a1
RT ln  1    RT ln  1 low  
3a Plow
 1
 Plow   RT  Tv1 T RT
 

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

 RT  3a1
ln f1v  ln   
 v1  RT Tv1

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

 f1v   RT 
ln 
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 
8.314500  800
v1 500v13
 m3 
v1  0.00187  
 mol 

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

   8.314  500   3  800  

v

  exp ln    
  1.78 106   0.00187    8.314  500   500  0.00187  
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 T  P T

Equation 7.8 states

 f 
g i  g i¼ RT ln  i   g i¼ RT ln f i  RT ln Plow
 Plow 
 

Differentiate:

 gi     giº  RT ln fi  RT ln Plow      ln f i  

      RT 
 P T  P  P 
T  T

Hence,

 gi     ln fi  
   v  RT 
 P T
i
 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 ºC is independent
of pressure. Therefore,

fi P
RT  d ln
sat
f i   vil  dP
fi 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 ºC and P  10 kPa as the reference. From the steam tables

kJ
s º  9.2812
kg  K
kJ
h º  3076.5
kg

The Gibbs energy at the reference state:

 kJ    kJ    kJ   J 
g º  3076.5     573.15 K   9.2812  kg  K    2243.0  kg   40407.2  mol 
 kg      
For P sat  8.5810 MPa and T  300 ¼C , the steam tables allow us the calculate the Gibbs
energy:

 kJ    kJ    kJ 
  520.6    9378.5 
J 
g sat  2748.9    573.15 K  5.7044   
 kg  

 kg  K    kg   mol 
Now use Equation 7.7 to find f sat :

  9378.5  40407.2 
f sat  10 kPa exp  
 8.314573.15 
f sat  6729 kPa

Once we find vil , we can calculate the fugacity. From the saturated steam tables,
   m3    m3 
visat   0.001404   0.0180148 kg/mol   2.53  10
5
 
  kg 
   mol 


Therefore,

 2.53 105 
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 can’t 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:

 MW i 0.058123  kg/mol  m3 
vi    1.00 104  
i 579  kg/m3   mol 

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

 

fi l   0.610 bar  exp 

   
 1.00 104  m3 /mol   200 105 Pa-6.10 104 Pa  

   J  
  8.314  mol  K    260 K  
    
fi  1.53  bar 
l
7.51
We can use Equation 7.36 to calculate the fugacity of pure liquid acetone.

P 
 vi
f il   isat Pisat exp  dP 
 sat RT 
 Pi 

Calculate the saturation pressure using Antoine’s 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,

382 K 4.64 bar

Tr   0.75 Prsat   0.099   0.309
508.1 K 47.01 bar

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:

 

fi l   0.904  4.64 bar  exp 

   
 7.34 105  m3 /mol  100 105 Pa-4.64 105 Pa  

   J  
  8.314  mol  K    382 K  
    
fi  5.23  bar 
l
7.52
We can use Equation 7.36 to calculate the fugacity of pure liquid acetone.

P 
 vi
f il   isat Pisat exp  dP 
 sat RT 
 Pi 

Calculate the saturation pressure using Antoine’s 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,

333 K 20.53 bar

Tr   0.9 Prsat   0.48   0.152
370 K 44.24 bar

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.

P 
 vi
f il   isat Pisat exp  dP 
 sat RT 
 Pi 

Using values from the steam tables:

Pi sat  3.169 kPa

so
isat  1

and

m3
vi  1.8 105
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 fˆal as xa  0 . Then, extend the line to xa  1 .
The Henry’s 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

fˆal
ga 
x fˆ o
a a

Using a Henry’s law reference state, this equation becomes

fˆal
ga 
xaH a

From the provided graph,

fˆal  xa  0.4   12  kPa 

fˆal  xa  0.8  31  kPa 

Therefore,

12  kPa 
g a  xa  0.4    1.54
0.4 19.5  kPa 
31  kPa 
g a  xa  0.8   1.99
0.8 19.5  kPa 

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

d ln g a  d ln g b 
xa  xb 0
dxa dxa

d ln g b 
Therefore, 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 .
(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, fˆav  ya P . Setting fugacities equal, we get

ya P  fˆav  fˆal

Therefore,

fˆal 12  kPa 
ya  
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

d ln g a  d ln g b 
xa  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,

0.61.33 0.4 2  0.002  0

(c)
We can’t use the two-suffix Margules equation because the lines for the activity coefficients
aren’t 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 1247.1x 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

Ha
g a 
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 kPaexp 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,
 A
2.5RT
1
  
 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.

na 2 mol
xa    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.

fˆav  fˆal  xag a f ao   0.4 2.40 80  kPa 

fˆav  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.

fˆav  ya P
76.8 kPa 
ya   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

g b  exp


 
6235.5  J  mol-1   0.4 
2

  1.49
   
 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 :

32 K 
 128 K 
A

R 0.50.5

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 0.752 
g 2  exp  
 343 K  
g 2  1.23

(ii).
 128 K 12 
g 2  exp  
 343 K  
g 2  1.45

(b)
From Equation 7.75:
 H2
g 2 
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  1.450.722 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:

na nb   na  nb 
GE   A  B 
na  nb   n a  nb 

Find GaE :

 dG E 
GaE     xb  xa xb A  Bxa  xb  2 Bx a xb2
 dna 
 T ,V , nb

Substitute xa  1  xb :

GaE  A  3B xb2  4Bxb3

Therefore,

 A  3B x 2  4 Bx 3 
g a  exp  b b
 RT 
 

(b)
Rewrite excess Gibbs energy as

 na nb 
G E  AB  
 An a  Bnb 

Find GaE :

 dG E   B 2 nb2 
GaE     A 
 dna   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  B 2 xb2 
g a  exp   
 RT 2 
 Ax a  Bxb   


(c)
Rewrite excess Gibbs energy as

  n   ab nb   n   ba na 
G E   RT na ln  a   nb ln  b 
  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
1  xb xb 1   ab 
GaE   RT ln xa   ab xb   
 xa  xb  ab xb  xa  ba 
 
  1  x 1    x   1 
Ga   RT ln xa   ab xb  xb 
E  b ab  b ba 
  xa  xb  ab xb  xa  ba  
  

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 :

 dG E    ba G 2 n 2  ab G ab nb2 
GaE    RT  ba b  
 dna     2
  2
 T ,V , nb  an n G
b ba nb n G
a ab 

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

  G2  ab G ab 
GaE  RTxb2  ba ba  
 xa  xb G ba 2 xb  xa G ab 2 

Therefore,

   ba G 2ba  ab G ab 
g a  exp  xb2   
  xa  xb G ba 2 2 
xb  xa 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:

RT ln g a  RT ln  3 3ln 3 /20.5  4 ln 3 /20.5 

2 3

 RT ln 3 3ln 3 /20.5  4 ln 3 /20.5 

2 3
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 ln2  A
RT ln g b  RT ln3/2  B

For an equimolar solution:



ln 3 / 20.5
2
 
RT ln g a  RT ln 2 
 ln 20.5 ln 3 / 20.5
2
 ln20.5 
RT ln g b  RT ln3/2 
ln20.5  ln3/20.5

Solving, we obtain

g a 1.10
g b 1.18



 Wilson:

At infinite dilution:

RT ln g a  RT ln2  RT ln ab    ba 1

RT ln g b  RT ln3/2  RT lnba    ab 1

 Solve simultaneously:

 ab  0.407
 ba  1.21

For an equimolar solution:

  1.21 0.407 
ln g a  ln0.5  0.50.407 0.5  
 0.5  0.51.21 0.5  0.50.407
  0.407 1.21 
ln g b  ln0.5  0.51.21 0.5  
 0.5  0.50.407 0.5  0.51.21

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 
x   
a g a  xa g a  ln  a   ln g   ln g 
 x  a a
 a 
 x 
xb g b  xb g b  ln  b   ln g   ln g 

 x b b
 b 

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

 0.9 
ln  
1
  
 A  3B   0.82   0.12  4 B  0.8 3   0.13
 0.2   8.314  493.15 

 0.1 
ln  
1
 0.8  8.314  493.15 
  
 A  3B   0.2 2   0.9 2  4 B  0.2 3   0.9 3 
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  Bxa  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:

  J 
RT ln g a    8.314   343.15  K  ln  2.62    A  3B 1  4 B 1
2 3
 
  mol  K  
  J 
RT ln g b    8.314   343.15  K  ln  7.24    A  3B 1  4 B 1
2 3
 
  mol  K  
A  4200 J  mol  and B  1450 J  mol -1 
-1

To obtain the fugacity of liquid water, we use the following equation

 
fˆal  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
ºC. The following relationship also holds since the saturation pressure at 70 ºC 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 ºC)

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 ºC:
   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.

fˆal   0.401.90  31.2  kPa 

fˆal  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

ABx a xb
gE   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

ABn a nb
GE   Cna nb na  nb 2 na  nb  3
Ana  Bnb

Differentiation provides

2
 Bxb 
GaE  A   Cxb2 2 xb  16 xb  5
 a
Ax  Bx b
2
 
  Cxa2 2 xa  16 xa  5
Ax a
GbE  B
 Ax a  Bxb 

Substitute these expressions into Equations 7.55 and 7.56:

  
2 
ln g a 
Bxb
  Cxb 2 xb  16 xb  5
1  A 2
RT   Ax a  Bxb  
 
  Ax a 
2 
ln g b     Cxa 2 xa  16 xa  5
1  B 2
RT   Ax a  Bxb  
 
 7.63
Applying Equation E6.4E to the property k = (gE/RT) gives:

  gE    gE 
        
g 
E
 RT   dT    RT   dP  Gi dx
m E
d   
T P
 i
 RT      ni 1 RT
   
  P ,ni  T ,ni

Substituting the following equations into the above expression

 gE 
  RT  hmix
 T   RT 2 (Equation 7.75)
 P,n i
 g E 
  RT  v mix
 P   RT (Equation 7.74)
  T ,n i

we obtain
  gE  hmix m
v mix
d  
 RT  RT
2
dT 
RT
dP  ln g idxi
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 
 RT  2
RT 2
  RT
 hmix g 
 dT  ln  1 dx1
RT 2 g2 

Now, integrate the above expression

 gE 
   hmix dT  ln  g 1 dx1
 d  RT   RT 2   g 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 x1 1
 hmix g 
0  2
dT   ln  1 dx1
g
T x1 0  RT x 0  2 
1

x1 1 T x 1
 g1  1
hmix
  g 2  1  RT 2 dT
ln   dx 
x1 0 T x1 0 

We can also show the following using differentials

1 dT
d   
T  T2

Hence,

x1 1 T x1 1
1
x1 1
g  hmix T hmix 1
 ln  1 dx1  
 g2  2
dT   
R
d 
T 
x1 0 T x1 0  RT 1
x1 0 
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:

fˆal  xag a f al

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

f al  Pasat
f al  0.25 bar (Used Antoine’s equation and data from Appendix A.)

Calculate g a when xa  0.2, xb  0.8 :

 6700.82 
g a  exp    1.19
 8.314303.15
 

Therefore,

fˆal   0.2 1.19  0.25 bar 

fˆal  0.06 bar

(b)
Calculate g a when xa  0.5, xb  0.5 :

 6700.52 
g a  exp    1.07
 8.314303.15
 
Therefore,

fˆal   0.51.07  0.25 bar 

fˆal  0.134 bar

(c)
Calculate g a when xa  0.9, xb  0.1 :

 6700.12 
g a  exp    1.00
 8.314303.15
 

Therefore,

fˆal  0.9 1.00  0.25 bar 

fˆal  0.23 bar
7.65
We are given the density and the Henry’s law constant for 1-propanol in water:

g
1l  0.80 , 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 
f1l   P e
1
sat sat  RT
1


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

MW1 60.1 g/mol cm 3

v1l    75.1
1l 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
ln P1sat  A   10.9237 
T C 298  80.15
P1  0.027 bar
sat

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:

 6 m
3 
 v1l



P  P1sat   75.1  10 

 5 J 
sat  RT
f1l  P e 
  0.027 bar  exp  mol
 100  105
 0.027  10 
  8.314 J  298K 
1
m3  
   
 mol  K  

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
Henry’s law constant.
Recall that (Equation 7.75):

H1 0.61 bar
g 1    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):

x2  2.810.6  1.01
A 2
ln g 1 
2

RT
g 1  2.75

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

fˆ1l  x1g 1 f1   0.4 2.75 0.037 bar 

fˆ1l  0.040 bar

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

J J
AvL  3000 , and BvL  5040
mol 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 2
 Bx b   Ax a 
RT ln g a  A  , and RT ln g b  B  
 Ax a  Bx 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.

J J
RT ln g a  A  3000 , and RT ln g a  B  5040
mol mol

Applying this same reasoning to the 3SM model,

J J
RT ln g a  A  B  3000 , and RT ln g b  A  B  5040 .
mol mol

Solving the two equations with two unknowns, we find:

J J
A  4020 , and B  1020
mol 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:

fˆal  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:
 J
RT ln g a  ( A  3B) xb2  4 Bx b3  2070
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:

B
ln Pasat  A   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:

fˆal  xa g a Pasat  0.32.040.86 bar 

fˆal  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  fˆav  fˆal  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) :

0.53 bar
ya   0.65
0.81 bar
7.67
We are asked to determine the fugacity of a, and the Henry’s Law constant Ha in a mixture of a
and b at 30 kPa and 20°C. 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  20.25  0.5RTxa 

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 fˆal :

fˆal  xa g a Pasat  12.9 kPa

(b)
Now calculate the Henry’s law constant. First, find the activity of a at infinite dilution:

ln g a  xb2 0.5  0.5 xa   0.5

xa 0

 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  0.545 0.455
x1r1  x2 r2
xi qi
i  0.417 0.583
x1q1  x2 q2
xi qi'
i'  0.501 0.499
x1q1'  x2 q2'
li -0.42 -2.32

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

1* z   r 
ln g 1, combinatorial  ln  q1 ln 1*  *2  l1  l2 1   0.236
x1 2 1  r2 

and

*2 z   r 
ln g 2, combinatorial  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 and  21  exp   21   1.35
 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
 112   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  0.319 0.681
x1r1  x2 r2
xi qi
i  0.368 0.632
x1q1  x2 q2
xi qi'
i'  0.214 0.786
x1q1'  x2 q2'
li -0.41 1.76

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

1* z   r 
ln g 1,combinatorial  ln  q1 ln 1*  *2  l1  l2 1   0.063
x1 2 1  r2 

and

*2 z   r 
ln g 2,combinatorial  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 and  21  exp   21   0.467
 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.

y1 P
g 1exp   1.66
x1P1sat
7.70
From the expressions in Table 7.4, we have:

Acetone Chloroform
xi ri
*i  0.192 0.808
x1r1  x2 r2
xi qi
i  0.200 0.800
x1q1  x2 q2
xi qi'
i'  0.200 0.800
x1q1'  x2 q2'
li -0.42 0.1

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

1* z   r 
ln g 1,combinatorial  ln  q1 ln 1*  *2  l1  l2 1   0.008
x1 2 1  r2 

and

*2 z   r 
ln g 2,combinatorial  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 and  21  exp   21   0.737
 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
 112   2 1   2 21 
Summing the combinatorial and residual parts and taking the exponential gives

g1 =0.585 and g2 =0.951.

y1 P
g 1exp   0.536
x1P1sat
7.71
The fugacity of ethanol in solution is calculated with the following equation:

fˆ1l  x1g 1P1sat

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

 x111 x2  21 
x   x   x   x   x   x  
ln g 1  1  ln x111  x2 12  x313  
1 11 2 12 3 13 1 21 2 22 3 23 
 x3 31 
 x   x   x  
 1 31 2 32 3 33 

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 ºC using Antoine’s Equation data in
Appendix A.1.

 3803.98 
P1sat  exp 12.2917   bar  0.468 bar
 333.15  41.68 

Therefore, the fugacity of the ethanol in the liquid is

fˆ1l   0.31.21 0.468 bar   0.17 bar

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

v    v   
 ab  b exp  ab   ba  a exp  ba 
va  RT  vb  RT 

Find the energetic parameters (lowercase lambdas) at 60 ºC, and use them to calculate the
uppercase lambdas at 8 ºC. The molar volumes for ethanol and 1-propanol can be calculated
using the Rackett EOS. The saturated steam tables provide an estimate for water’s molar
volume. Using the above equations with the 60 ºC data, we obtain:

Pairing  (J/mol)
12 1.13 x 102
21 6.83 x 102
13 1.39 x 103
31 3.52 x 103
23 4.73 x 103
32 5.04 x 103

Now, we can calculate the Wilson parameters at 8 ºC since the energetic parameters are less
sensitive to changes in temperature. We obtain

Pairing 
12 1.214
21 0.586
13 0.204
31 0.602
23 0.038
32 0.400

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

fˆ1l  x1g 1P1sat

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

 x111 x2  21 
x   x   x   x   x   x  
ln g 1  1  ln x111  x2 12  x313  
1 11 2 12 3 13 1 21 2 22 3 23 
 x3 31 
 x   x   x  
 1 31 2 32 3 33 
g 1  1.32

We can find the saturation pressure from Antoine’s Equation data in Appendix A.1.
  3803.98 
P1sat  exp 12.2917   bar  0.028 bar
 281.15   41.68 

Therefore,

fˆ1l   0.21.32  0.028 bar   7.39 103  bar 

7.73
Equation 7.81 provides

  ln g i    H i  hi 
  
 T  P , x RT 2

Equation 6.26 states that

 H mix
i
 H i  hi

Therefore,

  ln g i 

 H mix   i
 
 T  P , x RT 2

For the expression given in the problem statement

n1n2  3802  n2  n1  1200  n2  n1  1554  n2  n1  

2 3

H mix   447.8    
n1  n2  n1  n2  n1  n2   n1  n2  
2 3

Thus, we find

 H   x
mix
1
2
2
28731.8x13  4156.6 x12 x2  13131.4 x1 x22  3708.2 x23 

For an equimolar solution

 H mix
1
 J 
 1062.5 
 mol 

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

 g  1062.5  1 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

13000nCd nSn
G E  H mix 
nCd  nSn

Differentiating provides

E 2
GCd  13000 X Sn

Therefore,

 
 
 130000.6 2

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 ºC, 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) Part (b) Part (c) Part (d) Part (e)
Two
Three Suffix
Suffix van Laar Wilson NRTL
Margules
Margules
A A B A B ab ba Gab Gba ab ba
3652.3 3521.0 -1102.3 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
 5.45E- 1.40E- 5.39E-
1.34E-02 2.77E-04 05 04 05

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 ºC, 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) Part (b) Part (c) Part (d) Part (e)
2 Suffix Three Suffix
van Laar Wilson NRTL
Margules Margules
A A B A B ab ba Gab Gba ab ba
4371.1 4365.8 208.7 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 Three
van
Suffix Suffix Wilson NRTL
Laar
Margules Margules
1.08E- 1.73E- 1.00E-
1.69E-03 1.11E-03 03 04 04

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 ºC, 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) Part (b) Part (c) Part (d) Part (e)
2 Suffix Three Suffix
van Laar Wilson NRTL
Margules Margules
A A B A B ab ba Gab Gba ab ba
1329.8 1235.5 261.6 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
2.66E- 1.64E- 9.12E-
4.39E-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 (25°C, atmospheric
pressure). Use these results to determine the value of the Henry’s 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
25°C. We are given ambient pressure is 1.0 O2 ≈ 1.4 mL/100 cm3

atm.
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:

 5 J   -6 m3  
1.013 10 3  1.4 mL 10 
PO2V  m   mL  
nO2    5.726 105 moles O2
 J 
  298K 
RT
 8.314
 mol  K 

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

moles O2 5.73 104 moles

O2    (where 1 L = 10 x 100 cm3)
L solution L solution

b) Compare the result from part A with the oxygen capacity of pure water:

From Table 8.1, we can get the Henry’s Law constant H O2  44, 253.9 bar for oxygen in water
at 25°C. Since pressure is low and the gas solution is dilute, we can assume ideal behavior, so
Equation 8.30 holds:
 yO2 P 0.21 bar
xO2    4.75 106
H O2 44, 253.9 bar
nO2 nO2
Since xO2   , we can write nO2  xO2 nH2O . Assuming the solution volume is
nO2  nH 2O nH 2O
approximately equal to the volume of pure water, we can define the molality of oxygen to be:

nO2 nO2
O2   
Vsolution VH 2O

VH 2O
Substituting the above relation for nO2 , and noting that vH 2O  ,
nH 2O
xO2
O2  
vH 2 O

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

M H 2O 18 g/mole L
vH 2O    0.018
H O2
1000 g/L mole

Substituting this value, we calculate:

xO2 4.75 106 mole O2

O2   
liter H 2O
 2.64 104
vH 2 O 0.018 liter H 2 O
mole H 2O

Since VO2 VH 2O , the volume of solution is essentially the same as that of the water:

mole O2
O2   2.64 104 .
liter

Thus, the perflubron emulsion can carry approximately 2.2 times as much oxygen as pure
water.

c) Find the value of the Henry’s 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 Henry’s Law constant, we can write (for each of Xa, yaP

the two phases in the emulsion): yaP

Ha

xa
 ya P
Ha  (see the figure at right)
xa

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 
  12.435 cm PFB .
3
24g 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 
nO2 , PFB  5.726 105 moles   3
5
 2.64 10 moles
 100 cm 
nO2 , PFB  2.64 10 moles O2
-5

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

nO2 nO2 3.44 105 moles O2

xO2 , PFB   
nO2  nPFB nPFB 0.0481 moles PFB
4
xO2 , PFB  7.153 10

Applying the definition of the Henry’s Law constant above, we can compute H O2 , PFB :
 yO2 P 0.211.01325 bar 
H O2 , PFB    297.5 bar
xO2 , PFB 7.153 104

H O2 , PFB  300 bar (Note that a smaller Ha implies a larger xa for a given Pa)