Solution thermodynamics

theory—Part IV
Chapter 11
 When we deal with mixtures of liquids or
solids
• We define the ideal solution model

• Compare it to the ideal gas mixture, analyze

its similarities and differences
i  i (T )  RT ln( yi P)
ig Component i in a mixture
of ideal gases

This eqn. is obtained by combining

Gi  i (T )  RT ln P
ig

  Gi (T , P)  RT ln yi
ig
i
ig

Now we define

  Gi (T , P)  RT ln xi
id
i Ideal solution model
 Other thermodynamic properties
for the ideal solution: partial molar volume

Gi  Gi (T , P)  RT ln xi
id

 Gi id
  Gi 
Vi id
       Vi
 P T , x  P T
V id
  xiVi   xiVi
id

i i
 partial molar entropy in the ideal solution

Gi  Gi (T , P)  RT ln xi
id

 Gi id
  Gi 
S id
       R ln xi  Si  R ln xi
 T  T
i
 P, x P
S   xi S
id
i
id
  xi Si  R xi ln xi
i i i
 partial molar enthalpy in the ideal solution

Gi  Gi (T , P)  RT ln xi
id

H iid  Gi id  TSiid  Gi  RT ln xi  TSi  RT ln xi  H i

H id   xi H iid   xi H i
i i
 Chemical potential ideal solution

i  i (T )  RT ln fˆi
Chemical potential component i
in a Real solution

Gi  i (T )  RT ln f i Chemical potential
Pure component i

fˆi
Subtracting:
i  Gi  RT ln
fi
For the ideal solution ˆf id
i id
 Gi  RT ln i
fi
 Lewis-Randall rule

i  Gi  RT ln xi
id

ˆf id
i id
 Gi  RT ln i
fi
ˆf id  x f
i i i Lewis-Randall rule

ˆ
i  i
id
(Dividing by Pxi each side of the equation)
 When is the ideal solution valid?
• Mixtures of molecules of similar size and
similar chemical nature
• Mixtures of isomers
• Adjacent members of homologous series
Virial EOS applied to mixtures
BP
Z 1 
RT
B   yi y j Bij
i j
How to obtain the cross coefficients
Bij

ˆ
Bij  B  ij B
0 1

Bij Pcij
Bˆ ij 
Tcij

Mixing rules for Pcij, Tcij, ij, 11-70 to 11.73

 
Fugacity coefficient iˆ
from virial EOS

ˆ
ln 1 
P
B11  y2 12 
2

RT
 12  2 B12  B11  B22

For a multicomponent mixture, see eqn. 11.64

 problem
• For the system methane (1)/ethane (2)/propane (3)
as a gas, estimate
fˆ , fˆ , fˆ and ˆ , ˆ , ˆ
1 2 3 1 2 3

at T = 100oC, P = 35 bar, y1 =0.21, and y2 =0.43

Assume that the mixture is an ideal solution
Obtain reduced pressures, reduced temperatures, and calculate

 Prk 0 1 
k id
 exp  ( Bkk  Bkk )
 Trk 
ˆf id   id y P
k k k
Results: methane (1) ethane (2) propane (3)

ˆ1  1.02;ˆ2  0.88;ˆ3  0.78 Virial model

fˆ1  7.49; fˆ2  13.25; fˆ3  9.76bar

1  0.98;2  0.88;3  0.76 Ideal solution

ˆf id  7.18; fˆ id  13.25; fˆ id  9.57bar

1 2 3
 Now we want to define a new type of
residual properties
• Instead of using the ideal gas as the reference,
we use the ideal solution
 Excess properties

M  M M
E id

The most important excess function is

the excess Gibbs free energy GE

Excess entropy can be calculated

from the derivative of GE wrt T

Excess volume can be calculated

from the derivative of GE wrt P

And we also define partial molar excess properties

 ˆ
Gi  i (T )  RT ln f i
Gi  i (T )  RT ln xi f i
id

subtracting :

ˆf
i  i
Definition of activity coefficient
xi f i
 Summary

Gi  RT ln  i
E

G  RT ln 
R ˆ
i i
 Summary

  G  RT ln yi
ig
i i
ig

  Gi  RT ln xi
id
i

i  Gi  RT ln  i xi
 Note that:
  G  RT ln yi  i (T )  RT ln yi P
ig
i i
ig

  Gi  RT ln xi  i (T )  RT ln xi f i 
id
i

ˆ
 i (T )  RT ln f i id

i  Gi  RT ln  i xi  i (T )  RT ln  i xi f i 
 i (T )  RT ln fˆi
 problem
• The excess Gibbs energy of a binary liquid mixture
at T and P is given by

G / RT  (2.6 x1  1.8x2 ) x1 x2
E

a) Find expressions for ln 1 and ln 2 at T and P

Using x2 =1 – x1
GE/RT= x12 -1.8 x1 +0.8 x13
 Since i comes from

Gi  RT ln  i
E

We can use eqns 11.15 and 11.16

E
dG
G  G  x2
1
E E
 RT ln  1
dx1
E
dG
G  G  x1
2
E E
 RT ln  2
dx1
 then
E
dG / RT
 1.8  2 x1  2.4 x1
2

dx1

And we obtain

ln  1  1.8  2 x1  1.4 x  1.6 x

2
1
3
1

ln  2   x  1.6 x
2
1
3
1
 If we apply the additivity rule and the
Gibbs-Duhem equation
E
G
  xi ln  i
RT i
At T and P

 x d ln 
i
i i 0
(b and c) Show that the ln i expressions satisfy
these equations Note: to apply Gibbs-
Duhem, divide the equation
by dx1 first
 Plot the functions and show their
values
0
0 0.2 0.4 0.6 0.8 1

-0.5
GE/RT

-1
ln 1
-1.5
ln 2
-2 GE/RT
ln g2
ln g1
-2.5

-3
x1