5.

60 Spring 2008 Lecture #23 page 1

Colligative Properties
These are properties of solutions in the dilute limit, where there is a
solvent A and a solute B where n
A
>> n
B
.
These properties are a direct result of
A
mix
(, T, p) <
A
pure
(, T, p)
Use two measures of concentration:
a. Mole Fraction: x
B
= n
B
/(n
A
+n
B
) ~ n
B
/n
A
b. Molalility: m
B
= (moles solute)/(kg solvent) = n
B
/(n
A
M
A
)
Where M
A
is the mass in kg of one mole of solvent.
There are FOUR Colligative Properties:
1. Vapor pressure lowering: Ap
A
= p
A
p
A
*
= x
B
p
A
*
2. Boiling point elevation: AT
b
= T
b
T
b
*
= K
b
m
B
*
M R(T )
2
K
b
=
A b
AH
vap
3. Freezing point depression: AT
f
= T
f
T
f
*
= K
f
m
B
*
M
A
R(T
f
)
2
K
f
=
AH
f
4. Osmotic pressure: t = RTc
~
where c
~
=
n
B
is concentration of solute
V
5.60 Spring 2008 Lecture #23 page 2
Lets go through these one at a time:
1. Vapor pressure lowering: This is just Raoults Law.
p
A
= x
A
p
A
*
= (1 x
B
)p
A
*
So Ap
A
= p
A
p
A
*
= x
B
p
A
*
(<0)
2. Boiling point elevation:
Lets derive this. Start with
A
(, T, p) =
A
(g, T, p)
So,
A
*
(, T, p) + RTln x
A
=
A
(g, T, p)
And ln x
A
=
1
[
A
(g, T, p)
A
*
(, T, p)] =
AG
vap
RT RT
But lnx
A
= ln(1-x
B
) ~ -x
B
= -n
B
/(n
A
+n
B
) ~ -n
B
/n
A
= -(Mn
B
)/(Mn
A
)
Where M is the total mass of A,
So, lnx
A
~ m
B
M
A,
where M
A
is the molar mass of A.
AG
Putting it all together then, m
B
=
vap
M
A
RT
But we need AT in there!
|
cm
B
| 1
|
c(AG
vap
T)|
|
AH
vap
| =

=
\
cT
.
p
M
A
R

\
cT
|
.
p
M
A
RT
2
M
A
RT
2
which gives us oT = om
B
AH
vap
5.60 Spring 2008 Lecture #23 page 3
If om
B
= m
B
0 (mixed pure) and m
B
is very small
oT = T
b
T
b
*
=
M
A
R(T
b
*
)
2
m
B
= K
b
m
B
AH
vap
Then
3. Freezing point depression:
Same arguments as above, replacing AG
vap
with AG
f
AH
vap
with AH
f
T
b
with T
f
K
b
with K
f
4. Osmotic Pressure:
A
A+B
p
ext
o - | -
The pressures at points:
h |: p = p
ext
+ g

o: p + t = p
ext
+ g + h g
At equilibrium:
A
(, p + t, T) =
A
*
(, p, T)
Using Raoults Law: RTln x
A
+
A
*
(, p + t, T)
A
*
(, p, T) = 0
At constant T: dG = Vdp, or d
A
*
= V
A
*
dp
5.60 Spring 2008 Lecture #23 page 4
p+t
Integrating
A
*
(, p + t, T)
A
*
(, p, T) =
}
V
A
*
dp = V
A
*
t
p
(this assumed an incompressible liquid, where volume does not depend
on p)
So then RTln x
A
+ V
A
*
t = 0
Again using lnx
A
~ -n
B
/n
A
Then RT(-n
B
/n
A
) + (V
A
/n
A
)t = 0
But V
A
~ V
A
+ V
B
= V (V
B
<<V
A
)
So finally, tV = RTn
B
This is the Vant Hoff Equation. It looks like the ideal gas law!
If we replace c
~
= n
B
/V in the Vant Hoff Eq., then we get the osmotic
pressure relation:
t = RTc
~