7.

PHASE EQUILIBRIA IN ONE COMPONENT SYSTEMS

7.1 Phase Equilibria in a One Component System under Constant Pressure

At 1 atm total pressure and 273 K, ice and water are in equilibrium with one
another at 0C.

) ( 2 ) ( 2 l s
O H O H

Hence, for these values of temperature and pressure, the Gibbs free energy,
G, of the system is a minimum.

G = G
H
2
O
l
( )
G
H
2
O
s
( )
= 0
or
( ) ( ) solid O H liquid O H
G G
2 2
=

Thus, at equilibrium
G
H
2
O
l
( )
= G
H
2
O
s
( )


If the ice + water system is at 1 atm pressure and some temperature greater or less
than 0C, then the system becomes unstable and the ice spontaneously melts or
the water freezes.

This process decreases the free energy of the system, and equilibrium is
attained again when all the ice has melted or when all the water has frozen.

That is, for the reaction
) ( 2 ) ( 2 l s
O H O H at T>273K, P = 1 atm

G = G
H
2
O
l
( )
G
H
2
O
s
( )
< 0
i.e.,
G
H
2
O
l
( )
< G
H
2
O
s
( )


Conversely, if the temperature is less than 0C, then

G
H
2
O
l
( )
> G
H
2
O
s
( )


2
The variations of G
H
2
O
l
( )
and G
H
2
O
s
( )
with temperature, at unit pressure, can be
graphically represented as in the following figure.



The slopes of the lines are

G
T




P
= S


G
T




P
= S

and the curvatures are obtained as

2
G
T
2






P
=
S
T




P
=
c
p
T


Similarly, also the variation of G
sl ( )
with temperature at unit pressure can be
easily drawn and then the slope of the line is given as

where S is the entropy change for the reaction.

3

The slope is negative, indicating that at all temperatures

S
H
2
O
l
( )
> S
H
2
O
s
( )


as is to be expected in view of the fact that at any temperature the liquid phase is
more disordered than is the solid phase.

The state in which the solid and liquid phases of a one-component system are in
equilibrium with one another can be determined from a consideration of the
enthalpy H and the entropy S of the system.

G = H TS

This can be written for both the solid and liquid phases,

G
l ( )
= H
l ( )
TS
l ( )

and
G
s ( )
= H
s ( )
TS
s ( )


and for the reaction solid liquid , subtraction gives

G
sl ( )
= H
sl ( )
TS
sl ( )



4
where H
sl ( )
and S
sl ( )
are respectively the molar enthalpy and molar entropy
changes accompanying melting at the temperature T.

Equilibrium between the two phases thus occurs as the result of a
compromise between enthalpy considerations and entropy considerations.
This figure shows that G
sl ( )
= 0 at T = T
m
= 273K , which is thus the
temperature at which solid and liquid water coexist at equilibrium at 1 atm pressure.




7.2 Phase Equilibria in a One Component System Under Constant
Temperature

Consider an ice + water system at 0C and one atm pressure.
If the pressure acting on the ice + water system is increased above 1 atm at 0C
the state of the system will shift in that direction which tends to nullify the effect of
the pressure increase; i.e., the state of the system will move in that direction which
results in a decrease in the volume of the system.
As ice at 0C has a larger molar volume than has water at 0C, then the change
of state produced by an increase in pressure is the melting process.


5
The effect (on the free energy of the phases) of an increase in pressure at
constant temperature is given as

G
s ( )
P






T
= V
s ( )
and
G
l ( )
P






T
= V
l ( )


i.e., the rate of increase of G with increase in pressure at the constant temperature T
equals the molar volume of the phase at the temperature T and the pressure P.


For the reaction solid liquid

G
sl ( )
P






T
= V
sl ( )


and as V
sl ( )
is a negative quantity for H
2
O at 0C, then the ice melts as the
result of the pressure increase.






6
7.3 Phase Diagram of One Component System

Next figure is a one-component phase diagram which uses T and P as the
coordinate axes.


Line AO A is a graphical
representation of Clapeyron
equation, which expresses the P-T
relationship for solid-liquid
equilibrium. The slope of the line
dP dT , is given as H
melt
TV
melt
.
The line BO B is the liquid-vapor
equilibrium line where H
T
is
H
evap, T
. The triple point, O, is the
state represented by the invariant
values of P and T at which the
solid, liquid, and vapor phases are
in equilibrium with each other.

The lines OA, OB, and OC divide the figure into three distinct areas within each of
which only one phase is stable. Within these areas the pressure exerted on the
phase and the temperature of the phase can be independently varied without
upsetting the one-phase equilibrium. The system is thus said to have two degrees
of freedom, where the number of degrees of freedom that an equilibrium has is the
maximum number of variables which may be independently varied without upsetting
the equilibrium. Along the lines OA, OB, and OC, two phases coexist in equilibrium,
and for continued maintenance of any of these equilibria only one variable (either P
or T) can be independently varied. Two-phase equilibrium thus has only one degree
of freedom. As solid, liquid, and vapor coexist in equilibrium only at the invariant
point, i.e., at unique values of T and P, then three-phase equilibrium has no degrees
of freedom. This expression is known as the Gibbs phase rule that the number of
degrees of freedom, F, that a system containing C components can have, when P
phases are in equilibrium, is given as

F = C P + 2 .


7
.






In the rule, the phase is defined as being a finite region in the physical system
across which the properties are uniformly constant, i.e., do not experience any
abrupt change in passing from one point in the region to another. Within any of

8
the one-phase areas in the phase diagram, the system is said to be homogeneous.
The system is heterogeneous when it contains two or more phases, e.g., coexisting
ice and liquid water is a heterogeneous system comprising two phases,


7.4 Phase Equilibria in a One Component System as a Function
of Temperature and Pressure

For equilibrium to be maintained,

G
s ( )
= G
l ( )


or, for any infinitesimal change in T and P,

dG
s ( )
= dG
l ( )


dG
s ( )
= S
s ( )
dT + V
s ( )
dP
and
dG
l ( )
= S
l ( )
dT + V
l ( )
dP

Thus, for equilibrium to be maintained between the two phases,

S
s ( )
dT + V
s ( )
dP = S
l ( )
dT + V
l ( )
dP
or
dP
dT




eq
=
S
l ( )
S
s ( )
V
l ( )
V
s ( )
=
S
sl ( )
V
sl ( )


At equilibrium G = 0 , and hence H = TS, substitution of which into the above
equation gives,

dP
dT




eq
=
H
TV


This equation is known as the Clapeyron equation, and this equation gives the
required relationship between variations of temperature and pressure which
are necessary for the maintenance of equilibrium between the two phases.


9
In the case of the ice-water system, V
sl ( )
is negative, and in any system,
H
sl ( )
is positive. Thus, dP dT ( )
eq
is a negative quantity; i.e., an increase in
pressure decreases the equilibrium melting temperature. It is for this reason that
ice-skating is possible.

The states of the solid and liquid phases can be represented on a three-dimensional
diagram with G,T, and P as the coordinates in the following figure.




7.5 Equilibrium Between the Vapor Phase and a Condensed
Phase

If Clapeyron equation in the previous section is applied to vapor-condensed phase
equilibria, then V is the molar volume change accompanying the evaporation or
sublimation, and H is the molar latent heat of evaporation or sublimation,
depending on whether the condensed phase is, respectively, the liquid or the solid.


10
V = V
vapor
V
condensed phase


and as V
vapor
>> V
condensed phase


V V
vapor


Thus for condensed phase-vapor equilibria, it can be written as

dP
dT




eq
=
H
TV
v ( )


If it is further assumed that the vapor in equilibrium with the condensed phase
behaves ideally, that is, PV = RT , then

dP
dT




eq
=
PH
RT
2


rearrangement of which gives

dP
P
=
H
RT
2
dT

or,
d ln P =
H
RT
2
dT

This equation is known as the Clausius-Clapeyron equation.

Based on the Clausius-Clapeyron equation the vapor pressures of the elements is
normally expressed in the form since ) 298 (
298
+ = T c H H
p T


ln P =
A
T
+ BlnT + C

For example, curve fitting of experimentally measured vapor pressures of liquid
water to an equation of the form gives

ln p atm ( ) =
2900
T
4. 65logT +19. 732.


11
The vapor pressures of several of the more common elements are presented in the
following figure.





Ex. 1 The vapor pressures of solid zinc and liquid zinc are as follows, respectively:

ln p(atm) =
15775
T
0. 755lnT +19.25 for solid zinc

ln p(atm) =
15246
T
1. 255lnT + 21. 79 for liquid zinc.
Calculate a) normal boiling temperature of liquid zinc, b) triple point temperature,
and c) heat of evaporation of zinc at the normal boiling temperature.
Ans.: a) 1181 K, b) 708K, c) 114,440 J/mole