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5.60 Thermodynamics & Kinetics

Spring 2008

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5.60 Spring 2008

Lecture #22

Two-Component Phase Equilibria III

Ideal and Non-Ideal Solutions
Free energy change Gmix in ideal solutions
G
A (liq)

B (liq)

G1 (l) = nAxAA* (l) + nBxBB* (l)

A + B (liq)

G2 (l) = nAxAAmix (l) + nBxBBmix (l

)

Gmix = G2 (l) G1 (l)

= nxA A (l) + RTln xA + nxB B (l) + RTln xB nxAA (l) nxBB (l)
Gmix = nRT ( xA ln xA + xB ln xB )

Purely entropic, as in gas mixture

G = Vdp SdT
Gmix
Smix =
= nR ( xA ln xA + xB ln xB )
T

Hmix = Gmix + TSmix = 0

No enthalpy change, all of G is due to entropy of mixing
Change in volume Vmix
Gmix
= 0
p T

Vmix =

No volume change, just like ideal gas.

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5.60 Spring 2008

Lecture #22

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Non-Ideal Solutions:
In reality, molecules interact:
A

uAA < 0

PURE

uBB < 0

uAB

MIXED

uAB

u = 2uAB- (uAA + uBB)

This difference determines how solutions depart from ideality.
I.

Positive Deviations: u > 0 (most common)

Mixing is energetically not favorable in liquid phase.

H = U + (PV) U
Gmix =

n
u + nRT ( xA ln xA + xB ln xB ) > Gmix (ideal)
4

e.g. acetone & carbon disulphide

CH3
CH3

C=O
A

S=C=S
B

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Lecture #22

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p = pA + pB

Real
*
pCS
= pB*
2

*
pacetone
= pA*

Raoult

pB
xCS2 = xB

pA
*
pCS > xCS pCS
2

*
pacetone > xacetonepacetone

ptot (real) > ptot (Raoult )

vapor pressure is higher than expected by Raoults Law

II.

Negative Deviations: u < 0

e.g. acetone & chloroform

CH3
CH3

Cl
C=O

H - C - Cl
Cl

B
H-bonding
attraction

Mixing is energetically favorable in liquid phase.

5.60 Spring 2008

Lecture #22

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p = pA + pB

Real
*
pCHCl
= pB*
3

*
pacetone
= pA
*

Raoult

pB
xCHCl3 = xB

pA

*
pCS < xCS pCS
2

*
pCHCl < xCHCl pCHCl
3

ptot (real) < ptot (Raoult )

Ideal Dilute Solutions and Henrys Law:

Non-ideal solutions are difficult to describe completely

Describe limits xB 1 and xB 0 Ideal Dilute Solution

I. xCS2 = xB 1

(B is the solvent)

Then Raoults Law applies for CS2

CS2 molecules see mostly other CS2 molecules
*
pCS = xCS pCS
2

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Lecture #22

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II. xB 0 (B is the solute)

Then Henrys Law applies:

pCS = xCS KCS

2

pB = xBKB

Henrys Law constant

KB Henrys Law constant, depends on the solvent/solute mixture

and the temperature.

Labeled just KB, even though it depends on A also.

KCS2 = KB
Real

Positive deviation KB > pB*

Henry

*
*
pCS
=
p
B
2

(Negative deviation would

have KB < pB* )

Raoult

xCS2 = xB

Ideal dilute solution:

Solvent, e.g. A:

Solute, e.g. B:

xA ~ 1

xB ~ 0

Raoults Law

Henrys Law

pA = xA pA*
p B = x B KB

5.60 Spring 2008

Lecture #22

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Total phase diagram:

Ideal
p

Real

Liquid
phase

pA*

pB*

pA*

gas
phase
xB,yB

Liquid
phase

pB*

gas
phase
xB,yB

Stronger non-ideality: Azeotropes

Liquid
phase

pB*
*
pA

At this point
xB = yB

gas

phase

xB,yB

Cannot distill
past azeotrope
xB = yB

Similar for constant p phase diagram

Can have positive or negative azeotropes
T

gas
phase

TA*

TA*

TB*

Liquid
phase
0

gas
phase

xB,yB

TB*

Liquid
phase
0

xB,yB