Peter Atkins • Julio de Paula

Atkins’ Physical Chemistry

Eighth Edition

Chapter 6 – Lecture 1
Phase diagrams

1
 Contents
Phases, components, and degrees of freedom
6.1 Definitions
6.2 The phase rule
Two-component systems
6.3 Vapor pressure diagrams
6.4 Temperature-composition diagrams
6.5 Liquid-liquid phase diagrams
6.6 Liquid-solid phase diagrams
6.7 Ultrapurity and controlled impurity
2
 In Chapter 5 (Simple Mixtures), we discussed the
phase diagrams for pure substances. We shall
develop their use systematically and show how they
are rich summaries of empirical information about a
wide range of systems. To set the stage, we
introduce the famous phase rule of Gibbs, which
shows the extent to which various parameters can
be varied yet the equilibrium between phases
preserved. With the rule established, we see how it
can be used to discuss the phase diagrams that we
met in the two preceding chapters.
3
 8.1 Definitions
• Phase (P) -“State matter which is uniform throughout not only in
chemical composition but also in physical state” J. Willard Gibbs
– Solid
 Various phases [e.g. crystal structures (diamond; graphite) or
compositions (UC;UC2)]
 Alloys (sometimes its difficult to tell this - microscopic examination may
be necessary {dispersions uniform on macroscopic scale})
 Miscible one phase (P = 1)
 Immiscible multiple phases (P > 1)
– Liquid
 Miscible liquids are one phase
 Immiscible liquids are multiple phases (P > 1)
– Gas
 Systems consisting of gases can have only one phase
– Shape or degree of subdivision irrelevant 4
 8.1 Definitions

A phase of a substance is a form of matter that is uniform

throughout in chemical composition and physical state.

(a) a single-phase solution, in

which the composition is
uniform on a microscopic scale.

(b) a dispersion, in which regions

of one component are embedded
in a matrix of a second
component.

5
 8.1 Definitions The phase

The number of phases in a system is denoted P.

A gas, or a gaseous mixture, is a single phase.

A crystal is a single phase.
P=1
Two totally miscible liquids form a single phase.
Ice is a single phase even though it might be chipped
into small fragments.

Any sample cut from the sample, however small, is

representative of the composition of the whole.
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 The phase
A slurry of ice and water is a two-phase system.
An alloy of two metals is a two-phase system
if the metals are immiscible. P=2

A dispersion of clays in water is uniform on a

macroscopic scale but not on a microscopic
scale.

A small sample comes entirely from one of the minute

grains of pure A and would not be representative of the
whole.

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 Components

A constituent is a chemical species that is present in a

system.
A component is a chemically independent constituent
of a system.
The number of components, C, in a system is the
minimum number of independent species necessary to
define the composition of all the phases present in the
system.

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The number of components, C

 No chemical reactions

When no reaction takes place, the

number of components is equal to the
number of constituents.

The pure water is a one-component system, C = 1,

because we need only the species H2O to specify its
composition.
Similarly, a mixture of ethanol and water is a two-
component system, C = 2: we need the species H2O and
C2H5OH to specify its composition.
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The number of components, C

 With chemical reactions

When a reaction can occur in the system, we need to

decide the minimum number of species that can be used
to specify the composition of all the phases.

In general: C  K R
Where K is the number of constituents and R is the
number of independent reactions.

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 Example

Method:
There are three phases in the system. To specify the
composition of the gas phase 3 we need the species CO2; and
to specify the composition of phase 2 we need the species
CaO. However, we do not need an additional species to specify
the composition of the phase 1 because its identity (CaCO3)
can be expressed in terms of the other two constituents by
making use of the stoichiometry of the reaction. 11
Answer:

12
 Remember you must count reactions which actually occur
not those which could occur
 Consider a system in which we has the following : O2(g),
H2(g), H2O(g)
 If conditions are such O2(g) + H2(g) → H2O(g) does not occur, C = 3
 If conditions are such (T, catalyst) O2(g) + H2(g) → H2O(g) occurs, then C
= 3 components − 1 reaction = 2
 If conditions are such (T, catalyst) O2(g), H2(g) → H2O(g) occurs and you
impose the condition that all the hydrogen and oxygen come from
dissociation of water, then C = 3 constituents − 1 condition − 1 reaction = 1
 Identity of components is a matter of some choice, number isn’t
 Chose components that cannot be converted into one
another by reactions
 E.g. CaCO3(s) → CaO(s) + CO2(g)
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 Degrees of freedom, F

Degrees of freedom, or the variance of a system, F, is

the number of intensive variables that can be changed
independently without disturbing the number of phases
in equilibrium.

In a single-component, single-phase system (C = 1, P =

1), p and T may be changed independently without
changing the number of phases, so F = 2.
We say that such a system is bivariant, or that it has two
degrees of freedom.
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 If two phases are in equilibrium in a single-
component system (C = 1, P = 2), T(or p) can be
changed at will, but the change in T (or p)
demands an accompanying change in p (or T) to
preserve the number of phases in equilibrium.
That is, the variance of the system has fallen to F = 1.

15
 8.2 The phase rule
• In discussing phase equilbria, you need only consider intensity factors (temperature,
pressure, and concentration)
– Only certain of these can be varied independently
– Some are fixed by the values chosen for the independent variables and by the
requirements of thermodynamic equilibrium
 e.g. if you chose ρ and T for a system, p is fixed
– Number of variables which can be varied independently without changing the
number of phases is called the degrees of freedom of the system

The phase rule is a general relation between the variance, F, the

number of components, C, and the number of phases at
equilibrium, P, for a system of any composition:

F CP2
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 Proof F CP2
• In any system the number of intensive variables are: pressure,
temperature plus the mole fractions of each component of each
phase.
• Only C − 1 mole fractions are needed since the ∑xJ = 1
» Thus for P phase, the number of intensive variables = P(C − 1) + 2
• At equilibrium the chemical potential of phase must be equal,
i.e. µJP1= µJP2= µJP3= µJP4= µJP5….{there are P − 1 such equations}
– Since there are C components, equilibrium requires that there are C(P − 1)
equations linking the chemical potentials in all the phases of all the
components
– F = total required variables - total restraining conditions
F = P(C − 1) + 2 − C(P − 1) = PC − P + 2 − CP + C = C − P + 2

17
 One Component Systems
• Phase rule says that you can have at most 3 phases
F = C − P + 2; C = 1 so F = 3 − P
 If P = 3, F = 0 system is invariant
Specified by temperature and pressure and occurs at 1 point (called
the triple point)
• If one phase is present, F = 2 that is p and T can be varied
independently
–This defines an area in a p, T diagram which only one
phase is present
• If two phases are present, F = 1 so only p or T can be varied
independently.
–This defines a line in a p, T diagram
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Fig.6.2 The typical regions
of a one-component phase
diagram. The lines represent
conditions under which the
two adjoining phases are in
equilibrium. A point
represents the unique set of
conditions under which
three phases coexist in
equilibrium. Four phases
cannot mutually coexist in
equilibrium.

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F CP2 For a one-component system:

If only one phase is present,

F=1–1+2=2

Both p and T can be varied

independently without changing
the number of phases. In other
words, a single phase is
represented by an area on a phase
diagram.

20
F CP2 For a one-component system:

If two phases are in equilibrium,

F=1–2+2=1

Which implies that p is not

freely variable if T is set. The
equilibrium of two phases is
represented by a line in the phase
diagram. Therefore, freezing (or
any other phase transition) occurs
at a definite T at a given p.

21
F CP2 For a one-component system:

If three phases are in equilibrium,

F=1–3+2=0

The system is invariant. The

special condition can be
established only at the definite T
and p that is characteristic of the
substance and outside our control.
The equilibrium of three phases is
therefore represented by a point,
the triple point, on the phase
diagram.
22
Single Component Phase Diagram

• Point a: only vapor present

• Point b: Liquid boils - 1 atm= Tb but
vapor and liquid co-exist along
line(vapor pressure curve)
• Point C : Liquid freezes
• Point D: Only solid
• Triple point: 3 phases in equilibrium
• Line Below triple point: Vapor pressure
above solid
Note: You don’t necessarily have to have
3 phases and they don’t have to be
solid liquid and gas

23
 Cooling Curve
A Gas Cooling
Gas Condensing
• You can generate a cooling
100癈
B
curve @ constant pressure
Temp.
Liquid Cooling
(isobar) from previous
Solid freezing phase diagram
• Halts occur during 1st
C
0癈
D
Solid Cooling
order phase transitions
(e.g. freezing)
Time

24
 Experimental Measurements
• Phase changes can be measured by performing
DTA (differential thermal analysis) on samples
– In DTA sample is heated vs. a reference
– 1st order transitions can be measured even when they
can’t be observed
 They will occur as peaks in DTA
• High Pressures can be achieved with diamond
anvil cells
– See text descriptions (Further reading)
25
Summary

F CP2
For a one-component system
 Only one phase, an area:
C = 1, P = 1 → F = 1 – 1 + 2 = 2
 Two phases, the lines:
C = 1, P = 2 → F = 1 - 2 + 2 = 1
 Three phases, a point:
C = 1, P = 3 → F = 1 – 3 + 2 = 0

Four phases cannot mutually coexist in equilibrium

26
 Contents
Phases, components, and degrees of freedom
6.1 Definitions
6.2 The phase rule
Two-component systems
6.3 Vapor pressure diagrams
6.4 Temperature-composition diagrams
6.5 Liquid-liquid phase diagrams
6.6 Liquid-solid phase diagrams
6.7 Ultrapurity and controlled impurity
27
Two-component systems

F CP2
If two components are present in a system

C2
F CP2
 4P

The degree of freedom has a maximum value of 3.

The properties of the system depend on T, p and
composition.

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For two components are present in a system

If T or p is constant, the remaining variance is

F  3 P
'

The remaining degrees of freedom has a maximum value of

2. One is the p (or T) and the other is the Composition (C).

At constant T, the phase diagram is a map of p and C at

which each phase is stable;

At constant p, the phase diagram depicts in terms of T

and C.
29
8.3 Vapor pressure diagrams

1). The composition of the vapour

The partial vapor pressures of the components of an

ideal solution of two volatile liquids are related to the
composition of the liquid mixture by Raoult's law:

pA  xA p *
A
p B  xB p *
B

where p*Ais the vapor pressure of pure A and p*B is that

of pure B.

30
The total vapour pressure of the mixture:

The total vapour pressure

changes linearly with the
composition from p*B to p*A
as xA changes from 0 to 1.

p  p A  pB
 x A p  xB p
*
A
*
B

 p  ( p  p ) xA
*
B
*
A
*
B
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 The compositions of the liquid and vapor that are in
mutual equilibrium are not necessarily the same. From
Dalton's law that the mole fractions in the gas, yA and
yB, are:
pA pB
yA  yB 
p p
Provided the mixture is ideal, the partial pressure pi and
the total pressure p may be expressed in terms of the
mole fractions in the liquid:
x A p *A
yA  *
pB  ( p A  pB ) x A
* *

yB 1  y A
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 *
xA p
yA  * A
pB  ( p A  pB ) x A
* *

It shows that the composition

of the vapor plotted against the
composition of the liquid for
various values of p*A/p*B > 1.
In all cases yA > xA, so the
Figure 6.7. The mole fraction of A vapour is richer than the liquid
in the vapor of a binary ideal in the more volatile
solution expressed in terms of its
mole fraction in the liquid for
component.
various values of p*A/p*B with A
more volatile than B. In all cases the
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vapor is richer than the liquid in A.
 From the relation of the total
vapor pressure of the mixture that
varies with the composition of the
liquid, we can relate the
composition of the liquid to the
composition of the vapor and
relate the total vapor pressure to
the composition of the vapor:
* *
Figure 6.8. The dependence of p p
the vapor pressure of the same p * A B
system expressed in terms of the
mole fraction of A in the vapor.
pA  ( p  pA ) yA
**
B
Individual curves are labelled with
the value of p*A/p*B.
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According to Raoult's law: A short summary
pA  p A* xA pA*

p→
pB  pB* xB  pB* (1  xA )
Then yA represents the mole fraction of A
in gas phase，according Dalton's law: pB*
pA p*A x A
yA   *
p p A x A  pB* (1  x A )
pB pB* x B
yB   B xA→ A
p p
y A  yB  1
From above equations, we can get：
pA*

p→
yA p*A x A
 * 
yB p B xB
Ammuse substance A is more volatile,
yA x pB*
p ＞p
* * ＞ A
A B yB xB
Finally, we can get:
y A＞x A xA yA
B xA→ A
From 17强化 张胜寒
 The horizontal axis as shows the overall
composition, zA, of the system. all the points
up to the solid diagonal line (blue) in the
graph correspond to a system which is under
such high pressure that it contains only a
liquid phase, so zA= xA, the composition of
the liquid.

• Assume the composition on the x

axis is the overall composition, zA
(as mole fraction)
– In Liquid region zA = xA
– In vapor Region region zA = yA
Figure 6.9. The dependence of – In between two phases present
the total vapor pressure of an F′ = 1 so at given pressure
ideal solution on the mole compositions are fixed by tie lines
fraction of A in the entire
system.
36
 Points that lie between the two
lines correspond to a system in
which there are two phases
present, one a liquidand the
other a vapor.

The point a indicates the vapor

pressure of a mixture of
composition xA, and the point b
Figure 6.9. The dependence of indicates the composition of the
the total vapor pressure of an
ideal solution on the mole
vapor that is in equilibrium with
fraction of A in the entire the liquid at that pressure.
system.
37
 F  3 P
'

When two phases are in

equilibrium, P = 2 so F' = l.
That is, if the composition is
specified, the pressure at
which the two phases are in
equilibrium is fixed.
Figure 6.9. The dependence of
the total vapor pressure of an
ideal solution on the mole
fraction of A in the entire
system.
38
 Points that lie
between the two lines
correspond to a system
in which there are two
phases present, one a
liquid and the other a
vapor.

The vertical line is called an isopleth. Until point a1

is reached (produced to p1), the sample consists of a
single liquid phase. 39
Isopleth Compositions in Each Phase
• A vertical line represents a line of
constant composition or isopleth
– Until pressure = p1 sample is liquid
vapor phase composition is a1
– At p1, vapor composition is given by
tie line to vapor curve
– At p2 vapor composition is a'2, liquid
composition is a2 and overall
composition is a
– At p3 virtually all the liquid is vapor
and trace of liquid has composition
given by tie line to liquid

40
 For all points between the
two lines, two phases are in
equilibrium, so F' = 1. For
a given pressure the
variance is zero, and the
vapor and liquid phases
have fixed compositions.

41
The lever rule

The lever rule is so called because a similar rule relates

the masses at two ends of a lever to their distances from
a pivot (mαlα= mβlβ for balance).

nl = nl or n= nl/l

42
 Homework Set 8

Atkins & de Paula, 7e

Chapter 8
Exercises: 8.2, 8.3, 8.6, 8.13, and 8.17,

43