Beruflich Dokumente
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Reading: Chapter IX
Homework: none
Theory of Solutions:
PA 0
A(s or l)
Pure A
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
pB = 0
pA = 0
0
B
G B ( s, l ) = G B0 ( s, l ) + RT ln
pB
p B0
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
da A
dx A
xA +
x A =0
1 d 2aA
2 dx A2
x A2 + ...
x A =0
Therefore,
i =1
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
pA
p
< x A , a B = B0 < x B
0
pA
pB
This is called a negative deviation from ideality.
aA =
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).
dG' = Gi dni
At fixed P and T,
dG' = Gi dni + ni d Gi
i
x dG
i
=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.