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
