October 24, 2001

Reading: Chapter IX
Homework: none
Theory of Solutions:

PA 0

A(s or l)

Pure A

Equilibrium between a condensed phase (an element or compound or a multi-component

solutions) and the gas phase implies that the chemical potential of every component is
uniform. That is,
Gi ( s or l ) = Gi ( g ) [i.e., i ( s or l ) = i ( g )]
If the condensed phase is pure A, then
G A ( s or l ) = G A ( g ) only one component
If the condensed phase is considered to be in its standard state, then
G A ( s or l ) is G A0 ( s or l )

G A ( s or l ) = G A0 ( s or l ) = G A ( g )
Notice that now the gas is not in its standard state because the vapor pressure, p A0 << 1.0
So,

G A ( g ) = G A0 ( g ) + RT ln p A0
G A ( s or l ) = G 0 ( s or l ) = G A0 ( g ) + RT ln p 0A

Now, lets consider a solution of A and B. The vapor phase contains both A and B.

pA, pB

A, B solution

In the vapor phase, now p A p 0A and p B p B0 .

Also, we expect p A < p 0A and p B < p B0 .
If the solution is pure A, p A = p A0 ,

pB = 0

If the solution is pure B, p B = p ,

pA = 0

0
B

Clearly, both p A and p B must be functions of composition. Since we are considering a

binary solution only, i.e., xA=1-xB, then
p A = pB (x A ) = p A (xB )
pB = pB (xB ) = pB (x A )
Now, G A ( s, l ) = A ( s, l ) is the partial molar free energy of A or the chemical potential of
A in the condensed phase.
In the gas phase, G A ( g ) = A ( g ) = G A0 ( g ) + RT ln p A
Once again, equilibrium requires that
G A ( s, l ) = G A ( g ) = G A0 ( g ) + RT ln p A
We also know that G A0 ( s, l ) = G A0 ( g ) + RT ln p A0 , from a single component system.
Eliminating G A0 ( g ) from these two equations, we get
p
G A ( s, l ) = G A0 ( s, l ) + RT ln A0
pA
Similarly for B,

G B ( s, l ) = G B0 ( s, l ) + RT ln

pB
p B0

We define the activity of A, aA, as the ratio of partial pressure.

p
p
a A = 0A , a B = B0
pA
pB
Clearly, both aA and aB are functions of composition. When the solution is pure A,
p A = p 0A , a A = 1
In general, G A ( s, l ) = A ( s, l ) = G A0 ( s, l ) + RT ln a A
And G B ( s, l ) = B ( s, l ) = G B0 ( s, l ) + RT ln a B

Now, a A = a A ( x A )
Let us expand aA as a function of xA about xA =0 in Taylors series.
da
1 d 2aA
a A = a A ( 0) + A
xA +
x A2 + ...
dx A x =0
2 dx A2 x =0
A

Clearly, aA (0), i.e., aA (xA =0)=0, because pA=0, when no A is present.

So, a A =

da A
dx A

xA +
x A =0

1 d 2aA

2 dx A2

x A2 + ...
x A =0

And similarly for B

Thus, a A = 1 x A + 2 x A2 + 3 x 3A + ...
When x A = 0, a A = 0
Also when x A = 1, a A = 1.0
n

Therefore,

i =1

= 1 , where aA is expanded to an nth order polynomial.

When 1 = 1 , all other s must equal to zero. Then, aA=xA and similarly, aB=xB, and the
corresponding partial molar free energies (chemical potentials) are given by
G A ( s, l ) = G A0 ( s, l ) + RT ln x A

G B ( s, l ) = G B0 ( s, l ) + RT ln x B
The above are for Ideal Solutions (Raoults Law)
When, a A x A , a B x B , the solution is said to be non-ideal.
In such a case, when x A 0, a A = 1 x A

or

a A = HA x A

Where HA = Henrian activity coefficient (Dilute Solution)

When x B 0, a B = HB x B , HB =Herian activity coefficient
When x A 1.0, a A 1.0 ; so, when x A 1.0, a A x A

Positive and negative deviation from ideality:

If bond AB is stronger than AA and BB bonds,

pA
p
< x A , a B = B0 < x B
0
pA
pB
This is called a negative deviation from ideality.
aA =

If bond AB is weaker than AA and BB bonds,

p
p
a A = A0 > x A , a B = B0 > x B
pB
pA
This is referred to as a positive deviation from ideality.
Positive

Negative

1.0

1.0

aA

aB

aB

xB

aA

xB

The proceeding shows that when the solution is dilute, the solute behaves Henrian, while
the solvent behaves ideal (Raoultian).

Gibbs-Duhen equation and graphical construction:

We have seen that for a multi-component system.
dG ' = S ' dT + V ' dP + Gi dni
i

dG' = Gi dni

At fixed P and T,

But, we also know, G' = Gi ni , which gives

i

dG' = Gi dni + ni d Gi
i

For the two equations to be identical, we must have

ni d Gi = 0 : Gibbs-Duhen equation
i

On a per mole basis, G = Gi xi . And

i

x dG
i

=0

For a two-component system,

G = x A G A + x B GB
And x A d G A + x B d G B = 0
Thus, differentiating G,
dG = G A dx A + G B dx B + x A d G A + x B d G B
1442443
0

So, dG = G A dx A + G B dx B = (G B G A )dx B
Since, dx A + dx B = 0, ( x A + x B = 1)
So, G B G A =

dG
dx B

Multiply by xA, x A G B x A G A = x A

dG
dx B

Add to G = x A G A + x B G B
Then, x A G A + x B G B + x A G B x A G A = G + x A

GB = G + x A

dG
dx B

dG
dx B

Similarly, G A = G + x B

dG
dG
= G xB
dx A
dx B

GB 0
GA 0

xB

dG
dx B

dG
dxB

G A = G xB

xA

G
dG
dx B

xB
A

GB = G + x A
xA

xB

dG
dx B

G A and G B depend on xB(xA), which are given by the intercepts on the vertical (G) axis
at A and B, respectively.