1 component Phase Equilibria

Degrees-of-freedom (variance), F the number of independent intensive

variables that can be modified to achieve a specific intensive state

Gibbs Phase Rule

For C independent components and P phases
- There will be (C-1) independent concentration variables
- If every component is present in each phase, this amounts to P(C-1)
- Therefore, there would be a total of P(C-1) + 2 intensive variables including
pressure and temperature that can be modified
Not all of these are necessary to specify the state of the system

P(C-1) + 2 independent variables

- There should be an equivalent number of equations to provide a complete
solution
- At equilibrium, the chemical potential of each component must be equal in
all phases it is present
- Total of (P-1) chemical potential for each component in each phase
- For C components, a total of C(P-1) equations
F = number of variables number of equations
F = 0 if the state of the system is completely known
F = [P(C-1) + 2] [C(P-1)] = C P + 2

P(C-1) + 2 independent variables

- There should be an equivalent number of equations to provide a complete
solution
- At equilibrium, the chemical potential of each component must be equal in
all phases it is present
- Total of (P-1) chemical potential for each component in each phase
- For C components, a total of C(P-1) equations
F = number of variables number of equations
F = 0 if the state of the system is completely known
F = [P(C-1) + 2] [C(P-1)] = C P + 2
For r independent chemical reactions
F=CP+2r
For additional constraints, a, (e.g. electroneutrality)
F=CP+2ra
F = Cind P + 2
where Cind = C r a

Ex. Aqueous solution of HCN

HCN H+ + CNH2O H+ + OH[H+] = [CN-] + [OH-]

5 components
1 phase
2 independent chemical reactions
1 electroneutrality condition
Cind = 5 2 1 = 2
F=21+2=3
These are T, P and [HCN]

1 component Phase Equilibria

For water
Cind = 3 1 1 = 1
F=1+2P=3P

When P = 1, F = 2
When P = 2, F = 1
When P = 3, F = 0

F=2

F=1
F=2

F=1

F=0
F=1

F=2

1 component Phase Equilibria

For water
Cind = 3 1 1 = 1
F=1+2P=3P

When P = 1, F = 2
When P = 2, F = 1
When P = 3, F = 0

Liquid

Solid

Vapor

The term normal refers to an equilibrium between two phases at a pressure

of 1 atm (e.g. normal boiling point)

1 component Phase Equilibria

Hvap measures the strength of
IMFA
Troutons Rule
Sm,vap = Hm,vap /Tb= 10.5R
The molar entropies of
vaporization for non-associated
liquids are the same when
evaporated to the same molar
volume in the gas phase.

Liquid

Solid

Vapor

Slope of equilibrium lines

For any two phases and , Gm = Gm
so

dGm dGm
S m dT Vm dP S m dT Vm dP

Vm dP S m S m dT

dP S m

dT Vm
S m H m T

Vm
Vm

Clapeyron equation

Liquid-vapor and solid-vapor

equilibrium
Vm Vmgas Vmliquid Vmgas

RT
P

Assuming ideal gas behavior

dP PH m

dT
RT 2
dP H m

dT
2
P
RT
H m
H m
d ln P
dT

d (1 / T )
2
R
RT
Clausius-Clapeyron equation
P2 H m 1 1

ln

P1
R T2 T1
Assuming that the molar enthalpy of vaporization is constant
in the temperature range

Ex. The normal boiling point of ethanol is 78.3oC, and at this temperature, Hm,vap
= 38.9 kJ/mol. To what value must the pressure be reduced to boil ethanol at
25.0oC?

Ex. The normal boiling point of ethanol is 78.3oC, and at this temperature, Hm,vap
= 38.9 kJ/mol. To what value must the pressure be reduced to boil ethanol at
25.0oC?

1 1

T2 T1
P2
38.9 x10 3 1
1
ln

2.40
760
8.314 298 351.3
P1 68torr
P2 H m
ln

P1
R

Solid-liquid equilibrium
H m, fus
dP S m, fus
P

dT Vm, fus T fus Vm, fus T

P2 P1

S m, fus
Vm, fus

P2 P1

T2 T1

H m, fus
Vm, fus

H m, fus
T1Vm, fus

T2
ln
T1

Thermodynamic properties are almost

immune to pressure variations (low
change in T for large changes in P)
this is why the solid-liquid curve is
steep!

T2 T1

constant

constant H m, fus
Vm , fus

S m , fus
Vm , fus

At the normal melting point of NaCl, 801oC, its enthalpy of fusion is 28.8 kJ/mol.
The density of the solid is 2.165 g/cm3, and the liquid, 1.733 g/cm3. What pressure
increase is needed to raise the melting point by 1.00oC?

28800
82.06
(1)
39atm
1
1
8.314
801 273

1.733 2.165