5.

60 Spring 2008 Lecture #22 page 1

Two-Component Phase Equilibria III
Ideal and Non-Ideal Solutions
Free energy change AG
mix
in ideal solutions
A (liq)
B (liq)
A + B (liq)
AG

*
( )
*
G ( )
mix
( )
mix
G ( ) = n x + n x ( ) = n x + n x ( )
1 A A A B B B 2 A A A B B B
AG = G ( ) G ( )
mix 2 1
A

-
A
( )
A
(
B

B
-
( )
B
nx
A

A
-
nx
B

B
-
= nx + RTlnx + nx + RTlnx
(
( ) ( )
AG = nRT x lnx + x lnx
mix
(
A A B B
)
Purely entropic, as in gas mixture
G = Vdp SdT
| cAG |
mix

\
cT
mix
|
|
.
p
(
A A B B
)
AS = = nR x lnx + x lnx
AH
mix
= A G
mix
A
mix
+ T S = 0
No enthalpy change, all of AG is due to entropy of mixing
Change in volume AV
mix
AV
mix
=
|

cA
c
G
p
mix
|
|
|
= 0
\ .
T
No volume change, just like ideal gas.
5.60 Spring 2008 Lecture #22 page 2
Non-Ideal Solutions:
In reality, molecules interact:
A A A
A
B
B B B
u
AA
< 0 u
BB
< 0 u
AB
u
AB
PURE MIXED
Au = 2u
AB
- (u
AA
+ u
BB
)
This difference determines how solutions depart from ideality.
I. Positive Deviations: Au > 0 (most common)
Mixing is energetically not favorable in liquid phase.
AH = AU + A(PV) AU
AG = Au + nRT x lnx + x lnx > AG
(
ideal
)
mix
n
4
(
A A B B
)
mix
e.g. acetone & carbon disulphide
CH
3
C = O + S = C = S
CH
3
B
A
*
5.60 Spring 2008 Lecture #22 page 3
=
* *
acetone A
p p
=
2
*
B CS
p p
p = p
A
+ p
B
p
B
p
A
1
x
CS2
= x
B
0
p
Real
Raoult
*
p
CS
2
> x
CS
2
p
CS
2
*
p
acetone
> x
acetone
p
acetone
p
tot
(
real
)
> p
tot
(
Raoult
)
vapor pressure is higher than expected by Raoults Law
II. Negative Deviations: Au < 0
e.g. acetone & chloroform
CH
3
CH
3
C = O +
B
A
Cl
Cl
H - C - Cl
H-bonding
attraction
Mixing is energetically favorable in liquid phase.

3
*
CHCl
p
B
A B
5.60 Spring 2008 Lecture #22 page 4
Real
p
0 x
CHCl3
= x
=
p = p + p
p
B
p
A
*
p
B
* *
p
acetone
= p
A
Raoult
1
*
p
CS
2
< x
CS
2
p
CS
2
*
p
CHCl
3
< x
CHCl
3
p
CHCl
3
p
(
real
)
< p
(
Raoult
)
tot tot
Ideal Dilute Solutions and Henrys Law:
Non-ideal solutions are difficult to describe completely
Describe limits x
B
1 and x
B
0 Ideal Dilute Solution
I. x
CS2
= x
B
1 (B is the solvent)
Then Raoults Law applies for CS
2
CS
2
molecules see mostly other CS
2
molecules
*
p
CS
2
= x
CS
2
p
CS
2



0
5.60 Spring 2008 Lecture #22 page 5
II. x
B
0 (B is the solute)
Then Henrys Law applies: p
CS
2
= x
CS
2
K
CS
2
p
B
= x
B
K
B
Henrys Law constant
K
B
Henrys Law constant, depends on the solvent/solute mixture
and the temperature.
Labeled just K
B
, even though it depends on A also.
2
K
CS
=
B
K
Positive deviation
B
K
*
B
p >
Henry
* *
(Negative deviation would
2
p
CS
=
B
p
have
B
K
*
B
p < )
1 x
CS2
= x
B
p
Raoult
Real
Ideal dilute solution:
Solvent, e.g. A: x
A
~ 1 Raoults Law
A
p
*
A A
x p =
Solute, e.g. B: x
B
~ 0 Henrys Law p
B
= x
B
K
B
*
5.60 Spring 2008 Lecture #22 page 6
Total phase diagram:
Ideal
Real
p
Liquid
p
Liquid
* *
phase
p
B
phase
p
B
* *
p
A
p
A
gas
gas
phase
phase
0 x
B
,y
B
1
0 x
B
,y
B
1
Stronger non-ideality: Azeotropes
Liquid
p
phase
At this point
p
B
x
B
= y
B
*
p
A
gas
phase
0 x
B
,y
B
1
Similar for constant p phase diagram
Can have positive or negative azeotropes
T T
phase
gas
T
A
*
T
A
*
T
B
*
Liquid
Liquid
phase
phase
0 x
B
,y
B
1
0 x
B
,y
B
1
Cannot distill
past azeotrope
x
B
= y
B
gas
phase
T
B
*