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SS Lecture - 7 1
DALTON’S LAW
PtotalV ni RT
i
SS Lecture - 7 2
If we divide the expression for each constituent by the
expression for the mixture we obtain:
P1 n1 P2 n2
X1 X2
P ni P ni etc.
i i
or
P1 = X1·Ptotal
P2 = X2·Ptotal
etc.
Ptotal = P1 + P2 + P3 + …
P1, P2, etc. are called the partial pressures.
SS Lecture - 7 3
RAOULT’S LAW
8 Pt
otal
6
P PB
o
0
0.0 0.2 0.4 0.6 0.8 1.0
A XB B
SS Lecture - 7 5
The only way that such a simple relationship as Raoult’s
law can hold is if the intermolecular forces between
A-A, B-B, and A-B are identical. Solutions in which
this is the case are called ideal solutions.
The most general way of expressing Raoult’s Law is:
Pi = Xi·Piº
SS Lecture - 7 7
Non Ideal – Positive deviation
SS Lecture - 7 8
PARTIAL AND APPARENT
MOLAR PROPERTIES
SS Lecture - 7 9
MOLAR VS. PARTIAL MOLAR QUANTITIES
SS Lecture - 7 11
SUMMING PARTIAL MOLAR QUANTITIES
ni
Xi n
n
i 1
i
SS Lecture - 7 13
CHE154: Physical Chemistry for Honors
B. Sc. Biotech. Chemistry Course, Term: II, Session: February 2009 – May 2009
Solutions
SS Lecture - 8 14
In the case of the volume of a two-component system, e.g., NaCl-H2O, we
can write:
V X NaClVNaCl X H2OVH2O
y
V
A
Vsolution
XH O
2
B
x
XNaCl
i - i° = RT ln Xi
where i is the chemical potential of some component i in a solution
and i° is the chemical potential of that component in the pure
form.
Partial Molar free energy
G X i i
i
substituting we get
i
These equations tell us that the free energy of an ideal
solution is the sum of two terms: the free energy of a
pure component, and a free energy of ideal mixing.
SS Lecture - 7 18
ENTHALPY AND VOLUME
OF AN IDEAL SOLUTION
Gideal mix RT X i ln X i
i
Sideal mix R X i ln X i
i
SS Lecture - 7 20
B
o
o
Molar Gibbs Free Energy
o
+ X B B
= XA A
ix
G mech m
A
o
G ideal sol'n
SS Lecture - 7 21
o
Molar Volume
VB
o
o
+ X BV B
= X AV A
V sol'n
sol ution
ideal
o
VA
SS Lecture - 7 22
PARTIAL MOLAR FREE ENERGY -
THE CHEMICAL POTENTIAL
G
Gi i Chemical potential
ni T ,P ,n j
The previous relationships also apply:
n
G ni i
n
G X i i
i 1
i 1
SS Lecture - 7 23
GIBBS-DUHEM EQUATION
At equilibrium
dG AdnA B dnB n Ad A nB dB 0
Substituting the previous expression
dG AdnA B dnB 0
we obtain
n Ad A nB d B 0
n d
i 1
i i 0
SS Lecture - 7 25
GIBBS-DUHEM EQUATION
- CONTINUED
SS Lecture - 7 26 26
THE GIBBS-DUHEM EQUATION
REVISITED
SS Lecture - 7 27 27
This equation shows that the slopes of tangents to curves of
chemical potential vs. mole fraction for binary solutions are not
independent of one another.
For example, if XB = 0, and A has a finite value,
X B T ,P ,n A
then .
B
X B T ,P ,n A
If XA = 0.5, then etc.
A B
X B T ,P ,n A X B T ,P ,n A
SS Lecture - 7 28 28
Chemical potentials in
solutions of carbon disulfide
and acetone.
Gibbs-Duhem Equation
A
X B T ,P ,n A XB
B 1 X B
X B T ,P ,n
A
SS Lecture - 7 29 29
THE DUHEM-MARGULES
EQUATION
Realizing that dXB = -dXA, and that d ln P = d P/P we can rewrite this as:
PA
PA
A T , P ,n B
X XA
PB PB
XB
B T , P ,n
X
A
SS Lecture - 7 31
APPLICATION OF THE
GIBBS-DUHEM EQUATION
dX B
d ln PB d ln X B d ln PB
XB
Now we integrate from XB = 1 to XB = XB
XB P
ln ln Bo
1 PB
where PB° is the partial pressure of B when XB = 1, i.e.,
the partial pressure of pure B.
P PB
ln X B ln Bo XB o
PB PB
PB X B PBo Raoult’s Law!
SS Lecture - 7 34
SS Lecture - 7 35
SS Lecture - 7 36