ERT 108 :

PHYSICAL
CHEMISTRY
Phase Diagrams
By; Mrs Hafiza Binti Shuko

ERT 108/3 PHYSICAL CHEMISTRY

SEM 2 (2010/2011)
Definitions
The Phase Rule
Two-component Systems:

a) Vapour pressure Diagrams

b) Temperature-composition
Diagrams
c) Liquid-liquid Phase Diagrams
d) Liquid-solid Phase Diagrams
ERT 108/3 PHYSICAL CHEMISTRY
SEM 2 (2010/2011)
 A phase of a substance is a form of matter that is
uniform throughout in chemical composition & physical
state (solid, liquid, gas).
 The number of phases in a system is denoted P.

 A solution of NaCl in water is a single phase (P=1).

 A slurry of ice & water is two-phase system (P=2).
 A calcium carbonate system undergoes thermal
deposition – two solid phase (CaCO3 & CaO)
one gaseous phase (CO2) so, Total: (P=3)
 An alloy of two metals is a two-phase system (P=2) if
they are immiscible but a single-phase system (P=1) if
they are miscible.
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SEM 2 (2010/2011)
 A phase transition is the spontaneous conversion of one phase into another phase occurs at a
characteristics temperature for a given pressure.

 Constituent – a chemical species (an ion or a molecule) that is present.

 A mixture of ethanol & water – Two constituents.
 A solution of sodium chloride – Three constituents
(water, Na+ ions & Cl- ions).

 Component – a chemically independent constituent of a system. Each phase in the system

may be considered to be composed of one or more components. The number of components in
the system must be the minimum required to define all of the phases.
 For example, in our system salt and water, we might have the components Na, Cl, H, and O
(four components), NaCl, H, and O (three components), NaCl and HO (two components), or
NaCl-H2O (one component). However, the possible phases in the system can only consist of
crystals of halite (NaCl), H2O either liquid or vapor, and NaCl-H 2O solution. Thus only two
components (NaCl and H2O) are required to define the system, because the third phase (NaCl -
H2O solution) can be obtained by mixing the other two components

Phase Diagram – one of the most ways of presenting the physical

ERT 108/3 PHYSICAL CHEMISTRY
changes of state that a substance can undergo. 4 SEM 2 (2010/2011)
 Phase rule – relation between the degree of freedom or
variance (F), the number of component (C) & the
number of phases at equilibrium (P) for a system of
any composition: F  C  P  2

 In a system of solid sucrose in equilibrium with an

aqueous solution of sucrose:
 the system has two components (C) – water &
sucrose.
 the system has two phases (P) – solution & solid
sucrose
 the degree of freedom (F) = 2 – 2 + 2 = 2

ERT 108/3 PHYSICAL CHEMISTRY

SEM 2 (2010/2011)
 Variance (F) – the number of intensive variables (P, T
& mole fractions in each of the phases) that can be
changed independently without disturbing the number
of phases in equilibrium.
 In a single-component, single phase system (C=1, P=1),
the P & T may be changed independently without the
number of phases – F = C-P+2=1-1+2=2.
 Such system is has two degrees of freedom.
 If two phases are in equilibrium (a liquid & its vapor) in a
single component system (C=1, P=2), the change of T &
P can demands an accompanying change in P (or T) to
preserve the number of phases in equilibrium ,F=C-
P+2=1-2+2=1.

ERT 108/3 PHYSICAL CHEMISTRY

SEM 2 (2010/2011)
 When two components are present in a system:
 C = 2, ……….F=C-P+2= 2-P+2=4-P.
 If the temperature is constant, F = 3-P (which max value
of 2).
 One of these two remaining F – P & composition
(mole fraction of one
component).
 One form of the phase diagram is a map of P &
compositions at which each phase is stable.
 Alternatively, the pressure could be held constant & the
phase diagram depicted in terms of T & composition.

ERT 108/3 PHYSICAL CHEMISTRY

SEM 2 (2010/2011)
 CaCO3 ( s )  CaO
 ( s )  CO2 ( g )
   Phase 2

Phase 1 Phase 3

 There are Three phases ( 2solid phase + 1 gaseous

phase) & Three constituents.
 To specify the composition of Phase 3 – need CO2

 To specify the composition of Phase 2 – need CaO

 To specify the composition of Phase 1 – do not need
an additional species (stoichiometry).
 The system has only Two components (C=2).

ERT 108/3 PHYSICAL CHEMISTRY

8 SEM 2 (2010/2011)
 In a system in which ammonium chloride undergoes
thermal decompositaion:
NH 4Cl ( s )  NH 3 ( g )  HCl  g 
 How many phases & constituents in the system?
 How many components are present in the system?

 There are Three constituents & Two phases (one solid &
one gas).
 NH3 & HCl are formed in fixed stoichiometric proportions by
the reaction.
 The compositions of both phases can be expressed in terms of
the single species NH4Cl.
 It follows that there is only one component in the system
(C=1). ERT 108/3 PHYSICAL CHEMISTRY
SEM 2 (2010/2011)
Raoult’s law:
 Used to calculate the total vapour pressure of a binary
system of 2 volatile liquids.
Dalton’s law:
Used to calculate the composition of the vapour in
equilibrium with a binary system

Lever Rule
Used to deduce the relative abundances of each phase in
equilibrium

The compositions of the vapour and the liquid phase in

equilibrium are located at each end of a tie line
ERT 108/3 PHYSICAL CHEMISTRY
SEM 2 (2010/2011)
 The partial pressure of the components of an ideal
solution of two volatile liquids are related to the
composition of the liquid mixture ( by Roult’s Law)

PA  x A p *A p *A  vapour _ pressure _ of _ pure _ A

PB  x B p *
B p  vapour _ pressure _ of _ pure _ B
*
B

 So, total vapour pressure,P of the mixture is:

P  PA  PB
P  x A PA*  x B PB*
P  PB*  ( PA*  PB* ) X A
 It shows that the total vapour pressure change linearly
with the composition from P*B to P*A as XA change from
0 to 1 ERT 108/3 PHYSICAL CHEMISTRY
SEM 2 (2010/2011)
 The composition of the liquid & vapour that are in
mutual equilibrium are not necessarily the same.
 The vapour should be richer in the more volatile
component.
pA pB
 The mole fraction in the gas: y A  yB 
P P
 Provided the mixture is ideal:
* PA  x A p *A
xA p
yA  * A

pB  p A  pB x A
* *
 PB  x B p B*

P  PB*  ( PA*  PB* ) X A

yB  1  y A
ERT 108/3 PHYSICAL CHEMISTRY
SEM 2 (2010/2011)
 In all cases, yA>xA, the vapour is
richer than the liquid in the more
volatile component.
 If B is non-volatile, so that at the
p *A
temperature of interest, then it *
1
pB
makes no contribution to the
vapour (yB=0).

x A p *A
yA  *
p B   p *A  p B*  x A
ERT 108/3 PHYSICAL CHEMISTRY
SEM 2 (2010/2011)
 The relation of the total
vapor pressure to the p *A
composition of the vapour: *
1
pB

* *
p p
p * A B
p A   p  p *A  y A
*
B

ERT 108/3 PHYSICAL CHEMISTRY

SEM 2 (2010/2011)
 In distillation, both vapour & the liquid compositions are
of equal interest – combine graph of pressure vs mole
fraction of A & graph total vapour pressure vs mole
fraction of A the graphs into one.

ERT 108/3 PHYSICAL CHEMISTRY

SEM 2 (2010/2011)
‘ a’ indicates the vapour
pressure of a mixture
of composition, xA
z A  xA

‘b’ indicates the

composition of the zA  yA
vapour that is in
equilibrium with the
liquid at that pressure

2 phases present (liq & vapour)

ERT 108/3 PHYSICAL CHEMISTRY
SEM 2 (2010/2011)
 Effect of lowering the pressure on a liquid
mixture of overall composition ‘a’
(a) A liquid in a container exist in
equilibrium with its vapour.

(b) Drawing out piston – P change.

The composition of the phase
adjust as shown by the tie line in
Vapour phase

phase diagram.(> vapour than liq)

Liq phase

(c) Piston is pulled so far out – all

liquid has vaporized and only
vapour is present. (P falls as the
Lowering P – piston is withdrawn and the point
by drawing out a piston on the phase diagram moves into
the one-phase region.
ERT 108/3 PHYSICAL CHEMISTRY 17
SEM 2 (2010/2011)
Changes to the system do not affect the overall Tie line
composition, so the state of the system moves
down the verticle line (isopleth / equal
abundance) that pass through ‘a’.
Until ‘a1’ is reached (P reduced to P1) –the sample
consist of a single liquid phase.
At ‘a1’, the liq can exist in eq with its vapour
(composition of the vapour phase is ‘a’1’.
The composition of liq is the same as initially (a1
lies on the isopleth through a) – conclude that at
this P, no vapour present , however the tiny
amount of vapour that is present has the
composition
Effect lowering‘a’
P-1’p to p
1 2

Composition of such liq is a2.

Composition of the vapour in eq with that liq
is a’2
A further decrease in P- take system to a4
(only vapour is present) where composition
of vapour is the same as the initial overall
composition of the original liq. ERT 108/3 PHYSICAL CHEMISTRY 18
SEM 2 (2010/2011)
 A point in the two-phase region of a
phase diagram indicates not only
qualitatively that both liquid & vapour
are present, but represents quantitatively
the relative amount of each.
 to find the relative amounts of two
phases α & β that are in equilibrium –
measure the distances l α & lβ along the
horizontal line & then use lever rule.
 Lever rule:
n l  n l
Amount of phase α
Amount of phase β

ERT 108/3 PHYSICAL CHEMISTRY

SEM 2 (2010/2011)
 Temperature-composition diagram (to discuss
distillation) :
 a phase diagram – the boundaries show the
composition of the phases that are in equilibrium
at various temperatures (at a given P [1atm]).

 The distillation of mixtures:

 When liq composition a1 is heated, its boils
when reach T2 (so, Liq has comp a2 same as
a1 & vapour has comp a’2) – vapour is
reacher at in the > volatile comp A (at lower
boiling point)

 We can state the vapour comp at the boiling

point and from the location of tie line joining
a2 to a’2 we can read off the boiling temp, T2 of
the original liq mixture.

ERT 108/3 PHYSICAL CHEMISTRY

SEM 2 (2010/2011)
 Simple Distillation:
 The vapour is withdrawn and condensed.
 it is used to separate a volatile liquid from a non-
volatile solute or solid.
 Fractional Distillation:
 The boiling & condensation cycle is repeated
successively.
 It is used to separate volatile liquids.
 Theoretical plates – expressed the efficiency of a
fractionating column.
 The number of effective vaporization &
condensation steps that are required to achieve a
condensate of given composition from a given
distillate.
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SEM 2 (2010/2011)
ERT 108/3 PHYSICAL CHEMISTRY
SEM 2 (2010/2011)
 Azeotropes
 is a mixture of two or more liquids in such a ratio
that its composition cannot be changed by simple
distillation.

 This occurs because, when an azeotrope is boiled, the

resulting vapor has the same ratio of constituents
as the original mixture.

ERT 108/3 PHYSICAL CHEMISTRY

SEM 2 (2010/2011)
 Vapour at a’2 at a2 is richer in A. Composition vapour=composition liquid
If that vapour is removed (condensed), (azeotrope)
remaining liq will move to a
composition that is richer in B.
(vapour is eq in a3 at a’3) condensed

As evaporation proceeds- composition

of remaining liq shifts towards B as
A is drawn off.
Boiling point of liq rises, vapour
becomes richer in B.
When so much A has been evaporated,
the liq reached comp b(vapour has
same comp as liq)
Evaporation occurs without change of
composition(azeotrope)
A high boiling azeotrope. When the liq
Eg; of composition a is distilled, the
composition of the remaining liq
HCl/water: azeotropic at 80% mass of changes towards b but not further
water & boils unchanged at 108.60C.
ERT 108/3 PHYSICAL CHEMISTRY
SEM 2 (2010/2011)
 Start from mixture of composition
a1, and follow the changes in
the comp of the vapour rises
through a fractionating column.
Mixture boils at a2 (give vapour
comp of a’2)
Vapour condensed in the column
to a liq of the same comp of
a’2 (a3)
Liq reach eq with its vapour at a’3
(same liq comp as a4)
Fractionation shifts the vapour
towards the azeotropeic
comp at b but not beyond.
Eg;
Ethanol/water: Azeotropic at 4% mass water content & boils
A low boiling azeotrope. When the liq unchanged at 780C (below normal boiling point of water n
of composition a is fractionally ethanol..
distilled, vapour in eq in the  100% ethanol cannot be prepared by distillation at 1atm of a
fractioning column moves towards b dilute aqueous solution of ethanol
and then remain unchange

ERT 108/3 PHYSICAL CHEMISTRY

SEM 2 (2010/2011)
 Temperature-composition
diagrams
1 phase
 for partially miscible liquids
systems
(occur when the temp is below
the upper critical solution temp 2 phases
or lower critical solution temp).
 Liquids that do not mix in all
proportions at all temperatures.
 E.g. hexane/nitrobenzene

Upper critical solution temp – highest temp at which

phase separation occurs
Lower critical solution temp – temp below which
ERT 108/3 PHYSICAL CHEMISTRY
component not mix in all proportions (form 2 phase) SEM 2 (2010/2011)
 The composition of the former

Small amount of a liq B is added to a sample of

another liq A at T’. Liq B dissolved completely
& binary system remains a single phase. As >
B is added, a stage comes at which no >
dissolves. (2 phases in eqm- A saturated with B.

The relative abundances amount of the 2 phases

in equilibrium are given by the LEVER RULE.

B added, A dissolves in it slightly.(the

compositions of the 2 phases in eq remain a’ and
a’’)-B dilutes the solution and from then on a
single phase remains.

The composition of the 2 phases at eqm

varies with the temp

ERT 108/3 PHYSICAL CHEMISTRY

SEM 2 (2010/2011)
 A mixture of 50 g of hexane (0.59
mol C6H14) & 50 g of nitrobenzene
(0.41 mol C6H5NO2) was prepared at
290K.
a) What are the compositions of the
phases?
b) In what proportions /ratio do they
occur?
c) To what temperature must the
sample be heated in order to obtain a
single phase?

Lets denote hexane by H and

nitrobenzene by N

ERT 108/3 PHYSICAL CHEMISTRY

SEM 2 (2010/2011)
(a) The composition of phases in eqm is given by the 0.83
points where the tie line representing intersects the 0.35
phase boundry.
XN = 0.41, T=290K (occur in 2 phases region)
XN=0.35 & XN=0.83
 Those are the composition of the two phases.
(b) The proportion s are given by the Lever rule (ratio
amount of each phase=ratio of distance I α & Iβ:
n l  n l
n l 0.83  0.41 0.42
   7
n l 0.41  0.35 0.06
 The temp at which the components are completely
miscible is found by following isopleth upwards
and noting the temp at which it enters the 1 phase
region of the phase diagram
 There is about 7 times more hexane rich phase than
nitrobenzene rich phase.
(c) Heating the sample to 292K takes it into the single-
phase region.
ERT 108/3 PHYSICAL CHEMISTRY
SEM 2 (2010/2011)
 The upper critical solution
temperature (TUC):
 the highest temperature at which
phase separation occurs.
 Above the upper critical temperature
the two components are fully miscible.
 E.g. palladium/hydrogen system.
2 phases:
1)Solid solution of H2 in
palladium
2)Palladium hydride
(up to 300oC, but form a
single phase at highest temp)

ERT 108/3 PHYSICAL CHEMISTRY

SEM 2 (2010/2011)
 The lower critical solution temperature
(TLC):
 the lowest temperature at which phase
separation occurs.
 Below TLC, they mix in all proportions.
 Above TLC, they form two phases.
 E.g. Water/triethylamine
At low temp, the 2 components
are > miscible bcz they form a
weak complex

At higher temp, the complexes

break up and the 2 components are
< miscible.

ERT 108/3 PHYSICAL CHEMISTRY

SEM 2 (2010/2011)
 By combining figure 6,21 & 6.24.
 Some systems have both upper &
lower critical solution
temperatures.
 Occur because after the week
complexes have been disrupted,
leading to partial miscibility, the
normal motion at higher temp
homogenizes the mixture again,
just as in the case of ordinary
partially miscible liquids
 E.g. nicotine/water

Partially miscible between

61oC and 210oC
ERT 108/3 PHYSICAL CHEMISTRY
SEM 2 (2010/2011)
  Summarizes the temp-
composition properties of a
binary system with solid n
liquid phases
 Immiscible solid in phase +
miscible in liq phase
 Temperature-composition
diagrams for solid mixtures
guides the design of
important industrial
processes: liquid crystal
displays (LCD) &
semiconductors.
Figure: The temperature-composition phase
diagram for two almost immiscible solids &
their completely miscible liquids.
ERT 108/3 PHYSICAL CHEMISTRY
SEM 2 (2010/2011)
 Eutectic composition:
 Consider the 2 component liq (liq solution
of A & B)of composition a1. (the changes
that occur as the system is cooled)
 a1 to a2: system enters 2-phase region (Liq
+solid B). Pure solid B begins to come out of
solution and the remaining liq becomes
richer in A)
 a2 to a3 : > of solid B forms and the relative
amounts of the solid & liq (in eqm) are given
by lever rule (equal amount of each).the liq Eutetic composition –
phase is richer in A than before (b3) because the mixture with the
some B has been deposited. lowest melting point.
 a3 to a4 : less liq than at a3 (composition e).
This liq now freezes to give a 2-phase
system of pure solid B and pure solid A.
ERT 108/3 PHYSICAL CHEMISTRY
SEM 2 (2010/2011)
 Eutectic composition:
 the mixture with the lowest melting point
(point e).
 A liquid with the eutectic composition
freezes at a single temperature, without
previously depositing solid A or B.
 A solid with the eutectic composition
melts, without change of composition, at
the lowest temperature of any mixture.
 E.g. Plumbum/ antimony, tin/plumbum,
Silicon/ aluminium, benzene/napthalene,
chloroform/aniline

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