Phase Transformations

Chapter 8 of Atkins: Sections 8.1-8.3

Phases, Components and Degrees of Freedom
Definitions
The Phase Rule
Two-Component Systems
Vapour Pressure Diagrams
Composition of the Vapour
Interpretation of the Diagrams
The Lever Rule
Last updated: Nov. 28, 2003

Phases, Components and Degrees of Freedom

Phase diagrams are extremely useful for systems with multiple
components, and serve to describe physical and chemical equilibria over
a range of different compositions, as well as points where substances
are mutually miscible, or even when a system has to be brought to a
specific set of conditions for equilbrium to exist (e.g., pressure,
temperature and composition)
Phase diagrams are very important in the development of:
# alloys
# ceramic materials
# steels
# semiconductors
# plastics
# superconductors
# cosmetics
# petroleum product separations
# food products
# glasses
All phase diagrams are developed around one relationship, the phase
rule, which was derived by J.W. Gibbs - it can be applied to a wide
variety of systems
Phase diagrams: pictorial way of understanding the properties of a
system

Some Definitions
Phase: Signifies a form of matter that is uniform throughout, not only in
chemical composition but also in physical state
Number of phases is denoted by P:
P = 1 for gas, gaseous mixture, crystal, two miscible liquids, ice
P = 2 for slurry of ice and water, immiscible metal alloys
Sometimes not easy to decide how many phases there are - for
example, a solution of solid A in solid B - homogeneous on molecular
scale - A atoms are surrounded by B atoms, representative of
composition on the whole (example a)

A dispersion (example b) is uniform macroscopically,

but not on the microscopic molecular level - for
examples, regions of A are embedded withing a matrix
of B, still uniform composition - very important in
materials synthesis, especially production of steels,
tailoring materials mechanical and electrical properties

Some Definitions, 2
Constituent: A chemical species that is present in a system. For
example, a mixture of water and ethanol has 2 consituents
Component: A chemically independent component of the system. The
number of components in a system, C, is the minimum
number of independent species needed to define the
composition of all of the phases present in the system
# When no reaction takes place, Constituents = Components
# When a reaction can occur, the number of components is the
minimum number of species which specifies the composition
of all of the phases
CaCO3(s)
W CaO(s)
+ CO2(g)
Phase 1
Phase 2
Gas Phase
Number of Phases, P = 3
Number of Constituents = 3
Number of Components, C = 2*
*CaCO3 can be expressed in terms of 2 components in two different
phases from the stoichiometry of the reaction

Components Example
Consider the thermal decomposition of ammonium chloride:
NH4Cl (s)
W NH3 (g)
+ HCl (g)
Number of Phases, P = 2
Number of Constituents = 3
Number of Components, C = 1*
*NH3 and HCl are fixed in stoichoimetric proportions by the reaction, and
compositions of both phases can be specified by NH4Cl
N.B., if additional HCl or NH3 were added to the system, decomposition
of the NH4Cl would not give the correct gas phase compositions, and
either HCl or NH3 would be invoked as a 2nd component
H2O (l) 6
O2 (g)
+ H2 (g) (at room temp)
Number of Phases, P = 2
Number of Constituents = 3
Number of Components, C = 3*
*At room temperature, O2 (g) and H2 (g) do not react to form water, so
they are not in equilibrium: regarded as independent constituents

Variance and Degrees of Freedom

The variance, F, is the number of intensive variables in a system 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 pressure
and temperature may be changed independently without disturbing the
number of phases in equilibrium:
F = 2, system is bivariant, or has two degrees of freedom
If two phases are in equilibrium in a single-component system (C=1,
P=2) (e.g., a liquid and its vapour), the temperature (or pressure) can be
changed, but there must be an accompanying change in pressure (or
temperature) to preserve the phases in equilibrium
F = 1, system has one degree of freedom

Phase Rule
J.W. Gibbs, regarded as Americas first theoretical scientist and the
father of chemical thermodynamics, wrote that the number of
components, C, and the number of phases at equilibrium, P, for a
system of any composition:
F = C - P + 2
1.
2.
3.
4.

5.

Count the number of intensive variables (p and T count as 2)

Specifcy composition of the phase by mole fractions of C - 1
components (need C - 1, not C, since sum of all mole fractions = 1)
Since there are P phases, total number of composition variables is
P(C - 1), and total number of intensive variables is P(C - 1) + 2
At equilibrium, chemical potential of J must be same in every phase
J,"
= J,$
= ....
for P phases
There are P - 1 equations of this kind for each component J. If there
are C components, total equations is C(P - 1)
Each equation reduces our freedom to vary P(C - 1) + 2 intensive
variables, so the number of degress of freedom is
F

P(C - 1) + 2 - C(P - 1) = C - P + 2

One Component Systems

Phase diagrams are extremely useful for systems with multiple
components, and serve to describe physical and chemical equilibria over
a range of different compositions, as well as points where substances
are mutually miscible, or even when a system has to be brought to a
specific set of conditions for equilbrium to exist (e.g., p, T and
composition). For a one-component system, F = 3 - P :
If 1 phase present, F = 2, and p and T
can be varied without changing the
number of phases (single phase is an
area on the phase diagram)
If 2 phases in eqb, F = 1, implying the
pressure in not freely variable if the
temperature is set
If 3 phases in eqb, F = 0, and the
system is invariant - this condition can
only be established at a definite p and T
4 phases cannot exist in a one
component system, since F cannot be
negative

Phases, Components and Degrees of Freedom

Consider pure water:

In gas phase, cooled at constant p, F = 2

Liquid appears at the phase transition (the

boiling temperature), and F = 1. We have
specified constant p (single degree of
freedom), so equilibrium T is not under our
control

Lowering T takes liquid to single phase

liquid region, F = 2, T can be varied at will

Liquid-solid phase transition at Tf, with F =

1, and at constant p, T is not under our
control

Lowering T further results in single solid

phase with F = 2, where p and T can be
varied

Experimental Procedures
Detecting phase transitions is tricky, requiring special techniques
Thermal analysis: technique which takes advantage of the enthalpy
change during a first order phase transition:
- sample is allowed to cool and the temperature is monitored
- at a 1st-order transition, heat is evolved and cooling stops until the
transition is complete
- cooling curve for the isobar cde in the water phase diagram is:
High pressure phase transitions can be
observed in the diamond-anvil cell, in which
pressure can be exerted by turning a screw (1
Mbar pressures) and the phase transition is
monitored spectroscopically by shift in lines
from small ruby pieces added to the sample

Two Component Systems

When there are two components in a system, C = 2, and F = 4 - P, so if
the temperature is held constant, remaining variance is F & = 3 - P, which
has a maximum value of 2 for a single phase. The remaining degrees of
freedom are assigned normally to p and the composition (mole fraction).
#
#

Phase diagrams of pressures & compositions for stable phases

Phase diagrams of temperatures & compositions for stable phases

Vapour pressure diagrams:

Partial pressures of components of an

ideal solution of two volatile liquids are
related to the composition of the mixture by
Raoults Law
(
(
pA ' xA pA
pB ' xB pB
where * signifies the vapour pressures of
pure A and B. Total vapour pressure is
p = pA + pB = xApA* + xBpB* = pB* + (pA*-pB*)xA
linear variation of vapour pressure at fixed
temperature with changed composition

Composition of the Vapour

Compositions of liquid and vapour in equilibrium are
not necessarily the same, vapour should be richer in
the more volatile component
For mole fractions of a gas yA and yB
pA
pB
yA '
yB '
p
p
For an ideal mixture, partial pressures may be
expressed in terms of mole fractions in the liquid
(see equations on previous page)

pA*/pB*

yA '

xApA
(

yB ' 1 & y A

pB % (pA & pB ) xA

In all cases, yA > xA (vapour richer in more volatile

component). If B is non-volatile, pB* = 0, yB = 0. The
total vapour pressure as composition of the vapour:
( (

pA '

pA pB
(

pA % (pB & pA ) yA

pA*/pB*

Interpretations of the Diagrams

For distillations, both vapour and liquid contributions are of interest, so
we combine the two previous diagrams into one
liquid & vapour
present

Point a: vapour pressure of mixture of composition xA

Point b: composition of vapour in equilibrium with liquid at that pressure
At equilibrium, P = 2, F& = 1, so if composition specified, pressure at
which equilibrium exists is fixed

Interpretations of the Diagrams, 2

The horizontal axis shows the overall composition, zA, of the system:
All points down the solid diagonal
correspond to a system under high
pressure where there is only a liquid
phase (zA = xA, composition of liquid)
All points on lower curve correspond to a
system with low pressure where only the
vapour phase exists (applied pressure is
less than the vapour pressure, so zA = yA)
Points between lines are systems where
two phases exist: 1 liquid & 1 vapour
Lowering the pressure on a liquid by drawing out a piston: start at
point a: Here, F & = 2 and P = 1; only the liquid phase exists; changes to
system do not effect overall composition, so system moves down vertical
line that passes through a (vertical line called an isopleth), until point a1
is reached (pressure reduced to p1)

Interpretations of the Diagrams, 3

a1: Liquid is in equilibrium with its vapour
(composition of vapour phase given by a1&,
horizontal line is called a tie line)
Composition same at the lower pressure, at
this pressure, virtually no vapour pressure
a2": Pressure is lowered to p2, new pressure
is below the vapour pressure of the liquid, so
it vapourizes until the vapour pressure of the
remaining liquid falls to p2
Two phases are at equilibrium here, so F &
=1 for a given pressure p2, variance is zero
and vapour and liquid phases have fixed
compositions, at a2 and a2&
a3&: Pressure is further dropped to p3, and now the composition of the
vapour is the same as the overall composition, so the amount of liquid
present must be negligible, with tiny composition a3 (still in equilibrium)
a4: Pressure drops to p4, and now only the vapour phase exists, same
composition as the overall composition of the system

Interpretations of the Diagrams, 4

The previous diagram can be viewed more generally below, considering
pressure reduction via a piston
Isopleth

In (a), the liquid and

vapour phase are in
equilibrium, the
compositions and
abundances of the
two phases can be
predicted.
In (b) compositions
of phases are
determined from the
tie lines.
In (c), the applied pressure is much less than the vapour pressure, so
all of the liquid has vapourized, and we are in a one phase region

The Lever Rule

The point in a two-phase region of a phase diagram indicates not only
qualitatively if both liquid and vapour are present, but also quantitatively
tells us the relative amounts of each.
To find the relative amounts of phases
" and $ in equilibrium, measure
distances l" and l$ along the tie lines,
and use the lever rule:
n"l" ' n$l$

Proof: If n = n" + n$ and the overall

amount of A is nzA, then the overall
amount of A is the sum of its two
phases: nz ' n x % n y
A
" A
$ A
nzA ' n" zA % n$ zA
Then equating the sides:
Above, l$ . 2l", the amount of
phase " is 2x that of phase $

n" (xA & zA) ' n$ (zA & yA)

Phase Transformations
Chapter 8 of Atkins: Sections 8.4-8.6
Temperature-Composition Diagrams
Distillation of Mixtures
Azeotropes
Immiscible Liquids
Liquid-Liquid Phase Diagrams
Phase Separations
Critical Solution Temperatures
Distillation of Partially Miscible Liquids
Liquid-Solid Phase Diagrams
Eutectics
Reacting Systems
Incongruent Melting
Last updated: Dec. 1, 2003, Dec. 4, 2003: slight modification to slides 2, 6, 11, 14!

Temperature Composition Diagrams

Temperature compositions diagrams show the boundaries of
compositions of phases at equilibrium at different temperatures at a
given pressure (typically 1 atm) - liquid phase in lower part of diagram
Region between lines: F & = 1, compositions of
AB system, A more
phases are fixed at given temperature
volatile (lower b.p.)
&
Region outside lines, F = 2, temperature and
phase composition are variable
a1: pure phase liquid is heated and boils at
T2, with composition a2 = a1, vapour has
minuscule component a2& (location of the
tie line gives us the b.p. T2)
a3: first bit of condensation drawn off from
a distillation (collect a2N), richer in the more
volatile component, with composition a3&
a4: Vapour is drawn off, liquid condenses
to this composition, very rich in volatile
component, and almost pure A is obtained
Boiling and condensation cycle is known as fractional distillation

High-Boiling Azeotropes
Sometimes favourable interactions between molecules reduce vapour
pressure of the mixture below the ideal value: i.e., A-B interactions
stabilize the liquid phase - here GE = -ve, more favourable for mixing
Examples: propanone/ trichloromethane and
nitric acid/water mixtures
Composition a heated to boiling (a2& > a2)
Vapour (rich in A) is removed, and liquid left
is richer in B, composition a3, vapour with a3&
Vapour removed, composition shifts to a4,
vapour composition at a4&
Composition of remaing liquid shifts to b as
more A is drawn off, and b.p. of liquid,
vapour becomes richer in B
Finally, at composition b the vapour of A
has the same composition as the liquid
Evaporation occurs without change in
composition, and the mixture is an
azeotrope (boiling without changing), &
distillation cannot separate the components

Low Boiling Azeotropes

The diagram below also shows azeotropic behaviour, except that the
mixture is destabilized relative to the ideal solution (A-B interactions are
unfavourable, GE is +ve, less favourable to mixing)
Examples: dioxane/H2O & ethanol/H2O
Start at a1, boil at point a2, with vapour
composition a2&
Vapour condenses to a3, vapour at a3&
composition, condensing higher up the
fractional condensation tube to give
composition a4
Azeotropic vapour comes out of the
column at b, but not beyond

Immiscible Liquids
Distillation of two immiscible liquids A and B (example, octane and water)
and at equilibrium, there is a tiny amount of A dissolved in B, and a tiny
amount of B dissolved in A - liquids are saturated with the other
component (in figure a)
The total vapour pressure is close to
p = pA* + pB*
If p = atmospheric pressure, then boiling
commences, and the dissolved substances are
purged from solution
Mixture is agitated, each component is kept
saturated in the other component, purging
continues until very dilute solutions are
replenished
Mixing is essential, as separated components
(figure b) would not boil at the same
temperature
Presence of saturated solution means that components boil at a lower
temperature than they would alone - basis of steam distillation

Liquid-Liquid Phase Diagrams

Partially miscible liquids are liquids that do not mix in all proportions at
all temperatures
When P = 2, F & = 1 (prime denotes constant pressure), the selection of
temperature makes the compositions of the immiscible phases fixed
When P = 1 (two liquids are fully mixed) both temperature and
composition can be changed
1 Add small amt. of B to A at 290 K, it
dissolves completely, single phase, P=1
2 Add more B to the point where B no
longer dissolves, P = 2, major phase is A
1
2
3
4
saturated with B, minor phase is B
saturated with A (relative abundances
are given by the lever rule)
3 Add enough B to dissolve all of the A,
and system has single phase, P=1
4 Addition of more B dilutes the solution
Compositions of two phases vary with
changing temperature

Hexane and Nitrobenzene

Mixture of 50 g hexane (0.59 mol C6H14) and 50 g nitrobenzene (0.41 mol
C6H5NO2) was prepared at 290 K.
What are the compositions of the phases? To what temperature must
the sample be heated to obtain a single phase?
At 290 K, point xN = 0.41 occurs in a two phase region of the diagram,
with the tie line cutting the boundary at xN = 0.35 and xN = 0.83 (these are
the compositions of the two phases)
Ratio of amount of each phase:
N
H
n"
l$
0.83-0.41
0.42
=
=
=
=7
l"
0.41-0.35
0.06
n$
There is 7 times as much nitrobenzene rich
phase as there is hexane-rich phase.
If the sample is heated to 292 K, we go into
a single phase region

Critical Solution Temperatures

The upper critical solution temperature, Tuc, is the highest temperature
at which phase separation occurs
This temperature exists since the thermal motion finally overcomes the
potential energy advantage of certain molecules being close together
The Pd/H solid solution
system has a solution of
H2 in Pd and palladium
hydride up to 300oC,
single phase at higher
temperatures
Gibbs energy of mixing
varies with T - double
minima indicate partially
miscible phases, and as
the temperature rises,
single minimum occurs at
the upper critical
temperature

Critical Solution Temperatures, 2

The lower critical solution temperature, Tlc, is the lowest temperature
at which phase separation occurs
For triethylamine and
water, the system is
partially miscible
above Tlc, and single
phase below
Some systems have
both Tuc and Tlc, with
a famous example
being nicotine in
water, where Tuc =
210oC and Tlc = 61oC

Liquid-Solid Phase Diagrams

Solid and liquid phases can be present below the boiling point (e.g.,
immiscible pair of metals right up to their melting points (As and Bi)
2-component liquid at temperature a1:
(1) a1 6 a2

(2) a2 6 a3
(3) a3 6 a4

System enters Liquid+B

pure solid B comes out of
solution, remaining liquid
richer in A
More solid B forms, equal
amounts from lever rule,
liquid even richer in A
Less liquid than at a3,
composition given by e,
liquid now freezes into a
two component system of
A and B

Composition at e is known as the eutectic composition (easily melted),

and the horizontal line at e is known as Te, the eutectic temperature.

Eutectics
Liquid with eutectic composition freezes at a single temperature, Te,
without depositing A or B in advance of the freezing point
Solid with eutectic composition melts, without any composition change, at
the lowest temperature of any mixture
Solutions to the left of e deposit A as
they cool.
Solutions to the right of e deposit B as
they cool.
Only the eutectic solidifies at a single
temperature (FN = 0 when C = 2 and P =
3), no other components unloaded
Liquid + A

Liquid + B

Examples:
Solder, 67% tin and 33% lead,
m.p. 183oC
23% NaCl, 77% H2O m.p. -21.1oC; salt
added to ice on a road (isothermal)
mixture melts at T > -21.1oC

Eutectic formation and thermal analysis

Eutectic formation happens in many binary alloy systems, important in
alloy microstructure - eutectic solids have two phases, but crystallizes in a
homogeneous mixture of microcrystals (microscopy, X-rays, NMR)
Thermal analysis useful for detecting eutectics (this is done in the
engineering department at the University of Windsor)
This type of analysis is conducted by
cooling down an isopleth like the a
isopleth from liquid to complete solid.
The place where the temperature remains
constant over time is the eutectic halt
The cooling curves assist in making a
phase diagram of the material for various
temperatures and compositions.

Reacting Systems
Many binary systems react to produce different compounds - one
important example is the formation of GaAs (gallium arsenide) which is
very important for the manufacturing of III/V semiconductors:
Ga + As W GaAs
System prepared with A (i.e., Ga) and
excess of B (i.e., As) consists of C (i.e.,
GaAs) and unreacted B (i.e., As).
The binary B,C system forms a eutectic
The important part of the phase diagram
are the compositions of equal amounts of
A and B (x = 0.5), pure A and pure B
Solid deposited along the cooling isopleth
a is compound C
Below a4 there are two solid phases, with
some C and some B

Incongruent Melting
Sometimes component C is not stable as a liquid (e.g., alloy Na2K)

Peritectic point

(1) a1 6 a2 Some Na deposited, liquid

richer in K
(2) a2 6 a3 Just below a3, solid sample,
with solid Na and solid Na2K

(1) b1 6 b2 No change until Na begins to

deposit at b2
(2) b2 6 b3 Solid Na deposits, but reaction
happens to make Na2K (K
atoms diffuse into solid Na)
Here, liquid Na/K in eqb. with Na2K solid
(3) b3 6 b4 Amount of solid increases until
b4, liquid hits eutectic point,
now two phase solid is formed
Incongruent melting: The temperature at which one solid phase
transforms into another solid phase plus a liquid phase both of different
chemical compositions than the original substance (i.e., the peritectic
temperature, Tp).

Final Exam Outline

Material: Exam is comprehensive, but about 65-75% of the focus is upon
chapters 6 through 8 (combines all of your general knowledge of
thermodynamics
Question 1:
Mandatory (8 marks)
Question 2-9:
Choose seven of eight (6 marks)
Bonus Question: Give this a shot!

8
42
2-3 marks

How to prepare:
# Nerd notes - summarize each set of notes on one page in an
organized form that helps to isolate all key points
# Try the A list problems with your solutions manual
# Attempt the corresponding B list problems
# Review assignments and in-class problems
# Download all available handouts, including equation sheets
# Attend tutorials, book consultation times

Physical Chemistry @ U of Windsor

Physical Chemistry (where to go from here?):

U59-240: Thermodynamics: Physical & Chemical Properties of Materials

9
9 59-241: Kinetics, Statistical Thermodynamics & Reactions
9 59-340: Quantum Chemistry - Properties of Molecules
9 59-341: Symmetry & Spectroscopy - Interaction of Light and Matter
9 59-351: Materials Chemistry - Physical Inorganic Chemistry
Honours/Graduate Level
9 59-440: Photochemistry & Kinetics
9 59-441/541: Statistical Mechanics
9 59-445/542: Nuclear Magnetic Resonance (NMR) Spectroscopy
9 59-470/570: Computational Chemistry & Molecular Orbital Theory
9 59-636: Mesomorphic Materials