CHEM 212: Phase Equilibria

CHEM 212
Chapter 6
PHASE EQUILIBRIA
Dr. A. Al-Saadi
1
About Chapter 6
Chapter 6 gives additional examples of and more details about
equilibrium between phases.
• Implementing the “phase rule”.

• Applying the phase rule to:
• One-component systems.
• Binary systems.
• Liquid-vapor equilibrium.
• Temperature-composition diagrams.
• Azeotropes.
• Immiscible liquids.
• Condensed binary systems:
• Liquid-liquid systems.
• Solid-liquid systems (Eutectic phase diagram).
• Ternary systems.
2
The Phase Rule
 It was first presented by Gibbs in 1875.

 It is very useful to understand the effect of intensive
variables, such as temperature, pressure, or
concentration, on the equilibrium between phases as well
as between chemical constituents.
 It is used to deduce the number of degrees of freedom
(f) for a system.
The number of degrees of freedom (f) is:
The number of intensive variables that can be
independently varied without changing the number
of phases.
Sometimes called: “the variance of the system”.
3
The Phase Rule
The phase rule is stated as:
f=c–p+2
(f) The number of degrees of freedom is the number of intensive

variables that can be independently varied without changing the
number of phases.
(c) The number of components is the minimum number of
independent chemical components needed to form the system
or, in other words, to define all the phases.
(p) The number of phases is the number of homogeneous and
distinct parts of the system separated by definite boundaries.
The number (2) is for the two intensive variables temperature
and pressure.
4
Example: Phase Diagram of Water
How many components do

you have?
We have only one
component which is H2O.
In the one-phase regions, one

can vary either the
temperature, or the pressure,
or both (within limits) without
crossing a phase line.
We say that in these regions:
f=c–p+2
=1–1+2
= 2 degrees of freedom.
5
Along a phase line we have

two phases in equilibrium with
each other, so on a phase line
the number of phases is 2.
If we want to stay on a phase
line, we can't change the
temperature and pressure
independently.
We say that along a phase

line:
f=c–p+2
=1–2+2
= 1 degree of freedom.
6
At the triple point there are

three phases in equilibrium,
but there is only one point on
the diagram where we can
have three phases in
equilibrium with each other.
We say that at the triple point:

f=c–p+2
=1–3+2
= 0 degrees of freedom.
7
Phase Rule in One-Component Systems
 Notice that in one-component systems, the number of

degrees of freedom seems to be related to the number of
phases.
8
Phase Rule in One-Component Systems
 The phase rule should be applicable for any single-
component systems in general.
9
Number of Components (c)
f=c–p+2
 The number of components (c) is the minimum number of
independent chemical components needed to form the system
or, in other words, to define all the phases.
 "Independent" means:
 If you have equilibrium balance between reactants and
products, the number of components will be reduced by
one.
 If you have equal amounts (concentrations) of products
formed, the number of components will also be reduced by
one.
10
f=c–p+2
Examples (Chemical reactions):
products, the number of components will be reduced by one.
formed, the number of components will also be reduced by one.
Example 1:
NaCl(s) dissolved in H2O.
+ –
Available chemical constituents are: Na , Cl , NaCl and H2O.
Is it correct to say c = 4 ?
+ –
Because Na and Cl have the same amount “equal neutrality” as
NaCl, then c = 2 and not 4.
11
f=c–p+2
Example 2:
CaCO3(s) CaO(s) + CO2(g)
Available chemical constituents are three.
Is it correct to say c = 3 ?
Because of the equilibrium condition the number of independent
components is reduced by one. Thus, c = 2 instead of 3.
12
f=c–p+2
Example 2:
Can you specify the number of phases for the reaction?
We have here three homogeneous, distinct parts of the system
separated by definite boundaries.
p=3
13
f=c–p+2
Example 2:
So, what’s the number of degrees of freedom the system
would have?
f=c–p+2
= 2 – 3 + 2 = 1 degree of freedom.
14
Phase Diagram of Hydrogen
15
Phase Diagram of Sulfur
 Sulfur solid exists in two crystalline forms.
 Orthorhombic. S8 or S(rh)
 Monoclinic. S4 or S(mo)
Yellow sulfur of the

orthorhombic (or rhombic)
crystalline form. It is the
form that commonly exists
under normal conditions.
16
Phase Diagram of Sulfur
17
A More Comprehensive Phase Diagram
of Sulfur
18
Liquid-Vapor Binary Systems
We need to introduce an Vapor

approach that enables us
to describe: the purely
liquid, purely vapor, and
liquid-vapor regions, as
well as the boundaries y1 , y2
between them.
Liquid
x1 , x2
19
Liquid
+
Vapor
20
21
Lever Rule, nl/nv
When the point
xtot
corresponding to xtot is
closer to the liquid curve,
the amount of the liquid is Liquid
expected to predominate +
as compared to that in the Vapor
vapor phase.
When the point

corresponding to xtot is
closer to the vapor curve,
the amount of the vapor is
expected to predominate
as compared to that in the
liquid phase.
22
Lever Rule
xtot
nl y1  xtot

nv xtot  x1 Liquid
+
Vapor
bxtot

axtot
23
24
Isothermal Distillation
 This process takes
place at constant
temperature.
 The vapor is
continuously removed.
As a result, the
composition of the
liquid phase will
change. As the process
is repeated more times,
the concentration of the
less volatile component
in the liquid will
increase.
25
Liquid-Vapor Equilibrium Deviating from
Raoult’s Law
When Raoult’s law holds,

then:
Ptot = PA + PB Liquid
+
Vapor
The total vapor pressure
value will be somewhere
between the vapor
pressures of the pure
components.
P*B < Ptot < P*A
26
Raoult’s Law
When we have positive

deviation from Raoult’s
law, Ptot could be in some
parts greater than both
P*A and P*B .
As a result, a maximum in
the pressure-composition
curve is observed.
27
Raoult’s Law
When we have positive

parts greater than both
P*A and P*B .
As a result, a maximum in
curve is observed.
28
Raoult’s Law
When we have negative

parts less than P*A and
P*B .
As a result, a minimum in
curve is observed.
29
Raoult’s Law
When we have negative

parts less than P*A and
P*B .
As a result, a minimum in
curve is observed.
30
Binary-System Phase Diagram with Three
Variables: P, T and x
 The solid part of the

surface represents the
“liquid + vapor” region.
 Above it we have the
liquid phase and below
it we have the vapor
phase.
 On the T-P planes we
have pure liquid curves
where the boiling point
curves can be seen.
31
Binary-System Phase Diagram with Three
Variables: P, T and x
 On the P-x plane we
have the normal
pressure-composition
phase diagram. It can
be viewed at different
temperatures.
 On the T-x plane we
have the temperature-
composition phase
diagram, which is more
commonly used in
experimental work
since it is more
convenient to fix P
rather than T.
32
Temperature-Composition Phase
Diagram
 The T-x (isobaric) phase Vapor
diagram is represented by a compositions
double curve or a lens, above
which the vapor phase exists
and below which the liquid
phase exists, unlike the case in
the P-x phase diagram. Boiling
point of
 The lowest part of the lens liquid
corresponds to the pure liquid
with the highest vapor pressure
“the one that vaporizes more
easily”.
 The opposite is true for the
highest part end of the diagram.
33
Distillation
 More commonly than
using the isothermal
processes, distillation
process makes use of
the change in the
compositions in the
liquid and vapor phases
with the respect to
temperature at constant
pressure.
34
Fractional Distillation
35
Raoult’s Law
If the P-x plot shows

maximum (positive
law), the T-x plot will
show a minimum.
36
Raoult’s Law
If the P-x plot shows

minimum (negative
law), the T-x plot will
show a maximum.
37
Azeotropes
Azeotropes
or
azeotropic
mixtures
An azeotropic mixture “boiling without changing” is the mixture

whose liquid and vapor phases have identical compositions of
38
the two components.
Distillation of Azeotropes
You can not separate an azeotropic

mixture into two pure components at
the azeotropic composition.
But you can distill one pure

component from the azeotropic
system.
For example, boiling a mixture with a
composition corresponding to p’
would produce a vapor richer with
component 2 that can be condensed
and re-boiled until you get pure
component 2 (distillate) and a
mixture (residue).
39
Distillation of Azeotropes
The same situation is applied for the

minimum boiling temperature
azeotrope. However, the pure
component will be collected at the
bottom of the fractional column
(higher boiling point than the
mixture).
40
Examples of Azeotropes
41
Effect of Pressure Change on
Azeotropic Mixtures
With the change in pressure,

not only the azeotropic boiling
temperature would change (like
the case for pure compounds),
but also the azeotropic
composition would change.
42
Immiscible Liquids
Immiscible liquids are
those whose solubility Vapor
within each other is so
small.
At temperature T, The
Mixing
total pressure above
such a system is simply P *A Ptot =
the sum of the vapor P *A + P *B

P *
pressures of individual A
B
components. B
Immiscible
liquids
43
Steam Distillation of Immiscible
Liquids
Since:
Ptot = P *A + P *B
then the mixture is expected to boil at a temperature
that is lower than the boiling point of either
component.
If you want to do “steam distillation” for the system, Ptot =
then the relative amounts of components A and B in P *A + P *B
the vapor can be given by:
nA/nB = P *A / P *B
Because the ratio P *A / P *B is always constant at
given T, then the relative amounts of A and B in the
distillate at that T should be also constant. Immiscible
liquids
44
Immiscible Liquids
45
Partially Miscible Liquids
46
Condensed Binary Systems
 In many cases, the
liquid-liquid interactions
are more important to be
understood than the
condition of liquid-vapor
equilibrium.
 This can be
represented by having a
fixed external pressure
“such as a vessel open
to the atmosphere”, and
the solubility of the two
liquids is studied as a
function of temperature.
47
 Aniline dissolves in
water (layer L1) as it is
added in small amounts
at any temperature
below 441K.
 As more aniline is
added, another layer
(layer L2) which is rich L2
with aniline is formed.
 The lever rule can be
used to determine the L1
compositions of the two
layers.
48
 As more aniline is
added the amount of L2
increases on the
expense of L1.
 These are known as
conjugate solutions.
 Just right after
passing point e, L1
disappears and only the
aniline-rich layer exists.
49
50
 The solubility of
aniline in water and of
water in aniline
increases as the
temperature increases
for a constant
composition system
“Isopleths”.
 The “upper consolute”
temperature, Tuc, is the
highest possible
temperature at which
the two layers can
coexist or a separation
can occur.
51
The “upper consolute”
temperature, Tuc,
existence can be
explained in terms of
intermolecular forces.
Above Tuc the forces
holding the molecules
close together are
counteracted by the
thermal motions or by
the kinetic energy.
52
 For other systems, a
lower consolute
temperature (Tlc) exists.
 Above Tlc, two
immiscible layers exists.
 Below Tlc the two
liquids are miscible
because they can form
weak complexes
(internal forces). As T
increases, these weak
complexes break up and
immiscible systems is
being formed.
53
 Other systems show
both an upper and lower
consolute temperatures.
 Such systems are
known as closed
miscibility loops.
54
Zinc-Lead System
 The Zn-Pb system has
important metallurgical
applications.
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CHEM 212: Phase Equilibria

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CHEM 212

• Implementing the “phase rule”.

 It was first presented by Gibbs in 1875.

The phase rule is stated as:

(f) The number of degrees of freedom is the number of intensive

How many components do

In the one-phase regions, one

Along a phase line we have

We say that along a phase

At the triple point there are

We say that at the triple point:

 Notice that in one-component systems, the number of

Yellow sulfur of the

We need to introduce an Vapor

When the point

When Raoult’s law holds,

When we have positive

When we have positive

When we have negative

When we have negative

 The solid part of the

If the P-x plot shows

If the P-x plot shows

An azeotropic mixture “boiling without changing” is the mixture

You can not separate an azeotropic

But you can distill one pure

The same situation is applied for the

With the change in pressure,

the sum of the vapor P *A + P *B

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the sum of the vapor P A + P B