Phase Equilibrium

Phase Diagrams
 Definitions
• F: the number of degrees of freedom, i.e.
the number of independent variables needed
to describe the state of the system.
• C: the number of independent substances in
the system.
• P: the number of phases in the system,
where a phase is a form of matter that is
uniform throughout in composition and
state.
 The Phase Rule
• Each phase needs C-1 composition
variables plus T and p to describe its state.
Therefore, the total number of state
variables is P(C-1) + 2
• For each substance, there are P-1 equil.
constraints of the form (
• Therefore F = P(C-1) + 2 - C(P-1)
or F = C - P + 2
 Phase Diagram
critical point
p

liquid
1 atm

solid gas
triple point

Tb T
Cooling Curve: Pure Substance
T

liquid cooling

arrest
Tf solid cooling

liquid freezing

time
 Boiling Pt./Composition Diagram
Tb
vapor TA*
Tb for the liquid
with composition xA

boiling pt. of pure B boiling

pt. of
TB* liquid pure A
composition of the
vapor that boils off yA xA
at Tb
xA
 Lever Rule
T
• Let z be the total mole
fraction of A, both phase 
phases combined.
• Let n and n be the phase 
moles in phases  and .
• nz = nx+ nyA l l
= nz+ nzA
• n(z-x) = n(y-z)
• nl = nl
yA zA xA
 Azeotropes
Tb

azeotropic
boiling pt. vapor TA*

TB* liquid

xA azeotropic
composition
Ideal Boiling Pt./Composition
*
pA xA p
yA   * A
p pB  ( p A  pB ) x A
* *

where from the Clausius - Clapeyron eq' n,

  H vap ( A)  1 1 
p  p exp 
*
A
0
  
 R  T Tb ( A) 
 Immiscible Liquids
T
1 liquid phase
upper
critical
temperature
T
2 liquid phases

x xA x
composition of composition of
phase  at T phase  at T
Boiling of Immiscible Liquids

vapor phase
l+v
l+v

T
1 liquid phase

2 liquid phases

xA zA
Boiling of Immiscible Liquids

vapor phase

l+v
T l+v

l
l
2 liquid phases

xA zA
 Melting of Solid Mixtures
liquid phase

s+l
T s+l

Eutectic point

2 solid phases

xA zA
 Intermediate Compound
liquid phase
liquid phase

s+l s+l

s+l
T s+l

solid AB + solid A
solid B + solid AB

B AB A
xA
Spinel
liquid phase

T liquid + solid 

Solid
liquid + Sol’n.
solid 
Solid 2 solid phases
Sol’n.  and 

B A
xA
 Immiscible Melts: Ex 8.17
94
liquid phase

91 Two phase liquid

89
T
s+ l
86
solid B+ liquid s+l

84
solid B + solid A

CH4 CF4
mole fraction CF4 
 Incongruent Melting

liquid phase
A(s) + l

T
B(s) + l AB(s) + l

solid AB + solid A
solid B + solid AB

B AB A
xA
 Triangular Coordinates
• Each vertex corresponds
A
to a pure substance.
• The side opposite a xC=0.20
vertex corresponds to a
mixture of the other two xA=0.65
substances.
• The mole fraction of A
is proportional to the
distance from the
opposite side.
C xB=0.15 B
 Triangular Phase Diagrams
fixed T and P A

composition of
composition of
C-rich phase
B-rich phase
P=1

P=2

C B
tie line
 “Salting Out” H2O

P=2
K2CO3(s) + sol’n P=1 P=2
liquid immiscible liquids

P=3
K2CO3(s) and
2 immiscible liquids

K2CO3 CH3OH
P=2
K2CO3(s) + sol’n
 Double Solubility Diagram
H2O

P=2
NH4Cl(s) & sat’d. sol’n. P=1
sol’n P=2
(NH4)2SO4(s) &
sat’d. sol’n.

P=3
both solids &
sat’d. sol’n.

NH4Cl (NH4)2SO4