October 25, 2001

Reading: Chapter IX
Homework: 9.1, 9.3, 9.5, 9.7, 9.9, 9.10, 9.11
Theory of Solutions:
Our discussion will be confined to binary solutions. There can be either solid solutions or
liquid solutions.
Ideal Solutions: a A = x A , a B = x B
G A = A = G A0 + RT ln x A
G B = B = G B0 + RT ln x B : Partial molar free energy or chemical potential
Non-ideal Solutions:
G A = A = G A0 + RT ln a A = G A0 + RT ln( A x A ) = G A0 + RT ln x A + RT ln A
G B = B = G B0 + RT ln a B = G B0 + RT ln( B x B ) = G B0 + RT ln x B + RT ln B
The A and B are activity coefficients. Remember that A and B are always functions of
compositions (or equal to 1 over the entire range of compositions when the solution is
ideal)
Free energy of Solution (per mole):
G = x A G A + x B G B at constant P and T
Free energy of pure components (per mole) before mixing:
G 0 = x A G A0 + x B G B0 at constant P and T
Change in free energy when xA moles of A and xB moles of B are mixed to form a
solution.
G M = G G0 = x A (G A G A0 ) + x B (G B G B0 )
M

= x A G A + x B G B

= x A RT ln a A + x B RT ln a B
If the solution is ideal,
G Mid = x A RT ln x A + x B RT ln x B
G AM and G BM are referred to as partial molar free energies of mixing A and B,
respectively.

Molar Entropy of Solution:

S = x A S A + xB S B
Entropy before missing:
S 0 = x A S A0 + x B S B0
Entropy of mixing:
S M = S S 0 = x A ( S A S A0 ) + x B ( S B S B0 )
M

= x AS A + xB S B
M

S A and S B are referred to as partial molar entropies of mixing A and B, respectively.

G A0
G B0
0

Now, S =
, S B = T

0
A

G
G
S A = A
, S B = B
T P ,comp
T

P ,comp

For an ideal solution:

G A0

0
R ln x A = S A0 R ln x A
SA =
G A + RT ln x A =
T
T P
G B0

0
R ln x B = S B0 R ln x B
SB =
G B + RT ln x B =
T
T P

G M
= x A ( S A S A0 ) + x B ( S B S B0 )
S M =

T P ,comp

So,

= R{x A ln x A + x B ln x B }
Enthalpy (molar) of Solution:
H = x A H A + xB H B
Enthalpy before mixing:
H 0 = x A H A0 + x B H B0
Entropy of mixing:
H M = H H 0 = x A ( H A H A0 ) + x B ( H B H B0 )
M

= x A H A + xB H B
M

H A and H B are referred to as partial molar enthalpies of mixing A and B,

respectively.

0
G A0 / T
0
2 GB / T
,
H A0 = T 2
H
=

B
T P
T P

GA / T
H A = T 2

T P ,comp

= T 2
T

G A0

+ R ln x A
T
P ,comp

= H A0
Similarly, for ideal solution,
M

H A = H A H A0 = 0 and H B = H B H B0 = 0
Thus, H Mid = 0
Non-ideal Solutions:
G A = G A0 + RT ln a A = G A0 + RT ln x A + RT ln A
G B = G B0 + RT ln a B = G B0 + RT ln x B + RT ln B

G M = x A (G A G A0 ) + x B (G B G B0 )
= x A RT ln x A + x B RT ln x B + RT {x A ln A + x B ln B )
G M = G Mid + G MXS
Where, G MXS = RT {x A ln A + x B ln B )
Partial Molar Entropies in a Non-ideal Solutions:
G
G 0
RT ln A
RT ln x A
S A = A
= A

T
T
P ,comp
xA
T P
T P ,comp

ln A
= S A0 R ln x A R ln A RT

T P ,comp

ln B
S B = S B0 R ln x B R ln B RT

T P ,comp
The above may be written as
Similarly,

id

XS

id

XS

S A = S A + S A , SB = S B + S B

Entropy of mixing:
S M = x A ( S A S A0 ) + x B ( S B S B0 )
ln B
ln A
= R{x A ln x A + x B ln x B } R{x A ln A + x B ln B ) RT x A
+ xB

T
T

= S Mid + S MXS
Partial Molar Enthalpies in a Non-ideal Solution:

GA / T
GB / T
H A = T 2
, H B = T 2

T P ,comp
T P ,comp
Since,
G A = G A0 + RT ln x A + RT ln A

H A = T 2
T

G A0

+ R ln x A + R ln A
T
P ,comp

G A0 / T
2 ln A
= T 2

RT
T P ,comp
T P
ln A
= H A0 RT 2

T P ,comp
Similarly,

ln B
H B = H B0 RT 2

T P ,comp
Thus, the enthalpy of mixing per mole is
H M = H H 0 = x A ( H A H A0 ) + x B ( H B H B0 )

ln A

ln B
= RT 2 x A
+ xB

T P ,comp
T P ,comp
Molar Volume of a Solution:
V = x A V A + x B VB
Before mixing:
V 0 = x AV A0 + x BV B0

Relationship between a partial molar quantity and molar quantity:

If Q = x A Q A + x B Q B
Then,

QA = Q xB

dQ
dQ
= Q + xB
dx A
dx B

QB = Q + x A

dQ
dQ
= Q xA
dx A
dx B

Determination of the activity of B as a function of composition when the activity of A as

a function of composition is known Gibbs-Duhem Integration: Often it is possible to
experimentally measure the activity of one of the components in a solution. It is then
possible to determine the activity of the second component using Gibbs-Duhem equation.
Suppose we know aA as a function of composition, the object is to determine aB as a
function of composition.
According to the Gibbs-Duhem equation,
x A d G A + xB d GB = 0

x A d {G A0 + RT ln A + RT ln x A } + x B d {G B0 + RT ln B + RT ln x B } = 0

x A RTd ln A + x B RTd ln B + RT {x A d ln x A + x B d ln x B } = 0
RT {x A d ln A + x B d ln B } + RT {x A

dx A
dx
+ xB B } = 0
xA
xB

RT {x A d ln A + x B d ln B } + RT {dx A + dx B } = 0
Since, x A + x B = 1.0, dx A + dx B = 0
Thus, the Gibbs-Duhem equation reduces to
x A d ln A + x B d ln B = 0
x
d ln B = A d ln A
Or,
xB
Lets integrate the above equation from x B = 1 to x B = x B
For x B = 1, ln B = 0,
For, x B = x B , ln B = ln B
So,

ln B

ln B =

d ln B =

ln A for x A = x A

ln A for x B =1, x A = 0

xA
d ln A
xB

xA
d ln A
xB

ln A for x A = 0

xA/xB

( Henrian )

xA=0
xB=0

ln A

lnA

for x B = x B

The above schematic is for positive deviation from ideality

A > 1.0, ln A > 0
Note that

ln A for x A = x A

ln

xA
d ln A < 0
xB
involves moving

for x B =1, x A = 0

Because integration
ln A axis. (ln A < 0)
x
Since ln B = A d ln A , and
xB
If

the solution exhibits

A < 1.0, ln A < 0

xA

along

negative

direction

on

the

d ln A < 0 , we see that ln B > 0, B > 1.0

negative

deviation

from

Graphically,

ideality,

we

will

xA/xB

ln A for x A = 0
( Henrian )

lnA

Note that one moves along the positive direction on the ln A axis.
x
x
Thus, A d ln A > 0 , Since, ln B = A d ln A , and ln B < 0, B < 1.0 .
xB
xB

have