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5.60 Thermodynamics & Kinetics

Spring 2008

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5.60 Spring 2008 Lecture #22 page 1

Two-Component Phase Equilibria III

Ideal and Non-Ideal Solutions

Free energy change ∆Gmix in ideal solutions

∆G
A (liq) B (liq) A + B (liq)

G1 (l) = nAxAµA* (l) + nBxBµB* (l) G2 (l) = nAxAµAmix (l) + nBxBµBmix (l

)

∆Gmix = G2 (l) − G1 (l)

= nxA ⎡⎣µA∗ (l) + RTln xA ⎤⎦ + nxB ⎡⎣µB∗ (l) + RTln xB ⎤⎦ − nxAµA∗ (l) − nxBµB∗ (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 ⎠p
∆Hmix = ∆Gmix + T∆Smix = 0

No enthalpy change, all of ∆G is due to entropy of mixing

Change in volume ∆Vmix

⎛ ∂∆Gmix ⎞
∆Vmix = ⎜⎜ ⎟⎟ = 0
⎝ ∂p ⎠T

No volume change, just like ideal gas.

5.60 Spring 2008 Lecture #22 page 2

Non-Ideal Solutions:

In reality, molecules interact:

A B A A

A B B B

uAA < 0 uBB < 0 uAB uAB

PURE MIXED

∆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

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

e.g. acetone & carbon disulphide

CH3
C=O + S=C=S
CH3

A B
5.60 Spring 2008 Lecture #22 page 3

p p = pA + pB
Real

pCS
*
2
= pB*

pacetone
*
= pA*
Raoult

pB
0 xCS2 = xB 1
pA

pCS > xCS pCS

*
2 2 2

pacetone > xacetonepacetone

*

⇒ ptot (real) > ptot (Raoult )

⇒ vapor pressure is higher than expected by Raoult’s Law

II. Negative Deviations: ∆u < 0

e.g. acetone & chloroform

Cl
CH3
C=O + H - C - Cl
CH3
Cl
A B
H-bonding
attraction

Mixing is energetically favorable in liquid phase.

5.60 Spring 2008 Lecture #22 page 4

p p = pA + pB Real
pCHCl
*
3
= pB*

pacetone
*
= pA
*

Raoult

pB
0 xCHCl3 = xB 1
pA
pCS < xCS pCS
*
2 2 2

pCHCl < xCHCl pCHCl

*
3 3 3

⇒ ptot (real) < ptot (Raoult )

Ideal Dilute Solutions and Henry’s 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 Raoult’s Law applies for CS2

CS2 molecules see mostly other CS2 molecules

pCS = xCS pCS

*
2 2 2
5.60 Spring 2008 Lecture #22 page 5

II. xB → 0 (B is the “solute”)

Then Henry’s Law applies: pCS = xCS KCS pB = xBKB

2 2 2

Henry’s Law constant

KB ≡ Henry’s Law constant, depends on the solvent/solute mixture

and the temperature.

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

KCS2 = KB

Positive deviation ⇒ KB > pB* p Real

Henry
pCS
*
2
= pB
*

(Negative deviation would

have KB < pB* )

Raoult 0 xCS2 = xB 1

Ideal dilute solution:

Solvent, e.g. A: xA ~ 1 ⇒ Raoult’s Law pA = xA pA*

Solute, e.g. B: xB ~ 0 ⇒ Henry’s Law p B = x B KB

5.60 Spring 2008 Lecture #22 page 6

Total phase diagram:

Ideal Real

p
p
Liquid Liquid
phase pB* pB*
phase

pA* pA*
gas gas
phase phase

0 xB,yB 1 0 xB,yB 1

Stronger non-ideality: Azeotropes

Liquid
p phase
At this point
pB*
xB = yB
*
pA gas

phase

0 xB,yB 1
Cannot distill
Similar for constant p phase diagram past azeotrope
Can have positive or negative azeotropes xB = yB

T gas T
gas
phase
TA* TA* phase

Liquid TB* TB*

phase Liquid
phase
0 xB,yB 1 0 xB,yB 1