CH2105 – The Chemistry of Phases

Defining a Phase
A system is said to be homogenous when it is uniform throughout its whole extent and possesses, in
every part, identical physical properties and chemical composition.
A system is said to be heterogeneous if it consists of parts having different physical and/or chemical
properties or composition.

The ice, water and vapour are

The system as a
separated by bounding surfaces
whole is Water vapour
which are called interfaces.
heterogeneous.
The homogenous, physically distinct
Ice Ice parts of a heterogeneous system
are called phases.

Water

The Co-existence of Phases

a) Gases are miscible in all proportions
-no boundaries, always end up as 1 phase no matter how they are mixed

b) Liquids may or may not be miscible

e.g. water and ethanol are miscible – 1 phase
ether and water are immiscible and form 2 separate layers – 2 phases
ether, water and mercury form 3 separate layers – 3 phases
The number of phases depends on the miscibility relationship of the liquids under the particular
pressure and temperature conditions.

c)Solids give rise to a similar criteria as for liquids

-a mechanical mixture of n solids contains n phases, each individual solid and each allotropic form is
considered a different phase
-one solid dissolved in another must be regarded as 1 phase (as a solid solution) e.g. Copper/Nickel
alloys

The equilibria between phases is independent of the amount of a particular phase – a saturated
solution of aqueous sodium chloride at constant pressure and temperature (water and solid NaCl
present) will exhibit the same equilibrium irrespective of how much solid NaCl is present (as long as
some remains)
Components of a Phase
-the number of components (C) is defined as the minimum number of species required to define the
composition of a system

There are 4 factors to consider; -the number of species/constituents (S)

-the number of reversible equilibria (R)
-the number of electrical neutrality constraints (E)
-the material balance (M)

C=S-R-E-M

There is, however, a grey area. Considering the following reaction;

1
H2(g) + O2(g)⇋ H2O(g)
2

This reaction has very slow kinetics; as such the mixture is stable indefinitely – 3 components.
Add a spark and the reaction occurs instantaneously, the H2O formed is thermodynamically stable –
1 component.

Whether or not the equilibrium can be taken into account is a question of time and common sense.

The Phase Rule

The phase rule is a method of relating the variables of a system in equilibrium.
For a phase containing ‘C’ components the sum of their mole fractions must equal 1, i.e. ;

Moles of A
Where XA= , X1+X2+X3...+XC=1
Total no .of Moles
For X1+X2+X3+X4=1, and if X1, X2 and X3 are known then X4= 1-(X1+X2+X3)
Therefore if there are C components, only (C-1) mole fractions are required to define the
composition.

If there are P phases present there must be a total of P(C-1) compositional variables. The total
number of variables that can be changes is therefore P(C-1)+2, where the 2 refers to temperature
and pressure.

When two phases are in equilibrium their chemical potentials (µ) are equal. The chemical potential is
the contribution to the total Gibbs free energy of a system of each component of phase. It is a
measure of the direction of spontaneous change in that all systems achieve equilibrium by
minimising their Gibbs free energy.

If a component, ‘i’, is distributed among a number of different phases, each at equilibrium then;

µi (phase 1)= µi (phase 2)

µi (phase 2)= µi (phase 3)
µi (phase 3)= µi (phase 4)

Three different equations define for four separate phases in equilibrium; therefore there are (P-1)
equations for each component. There are C(P-1) equations that must be satisfied. Since µ is a
function of pressure and temperature each of these C(P-1) equations reduces the freedom to vary
 independently to the [C(P-1)+2] found earlier.
The total number of variables (the variance, F) that may be changed for a given system (while
maintaining equilibrium – the same number of phases) must be;

F={P(C-1)+2} – C(P-1)
[The total no. of variables – the no. of variables to be satisfied for phase equilibria]

The phase rule can therefore be defined as;

F=C-P+2

The Implications of Variance Upon A Given System

The variance of a system defines the number of parameters or variables that may be changed while
maintaining equilibrium, to explain this the following scenarios can be considered.

e.g. 1 – a container containing only steam, C=1 and P=1

F=1-1+2=2 – this is therefore a bivariant system

e.g. 2 – steam in equilibrium with water, C=1 and P=2

F=1-2+2=1 – this is therefore a univariant system, in order to maintain equilibrium it is impossible to
vary the temperature without also altering the pressure, this can be shown in a P-T graph;

At a set pressure the liquid and the vapour will only

P
Liquid come into equilibrium at a certain temperature, i.e. the
boiling point of water occurs at a single value of pressure
Pb and temperature.

Pa The line defines when the liquid and vapour are in

Vapour equilibrium and so if at pressure Pa the corresponding
temperature to achieve equilibrium is Tba, a change in
pressure to Pb will require a change in temperature to Tbb
if equilibrium is to be maintained.
Tba Tbb T

e.g. 3 – steam, water and ice in equilibrium, C=1 and P=3

F=1-3+2=0 – this is an invariant system, it is not possible to vary any of the parameters, again this
can be shown on a P-T graph, this time as a single point.

There is a single point on the graph which gives all three

P phases in equilibrium. At this point the slightest change of
pressure or temperature will change the number of phases.
This is called the triple point.
Liquid
Ice

Pt
Vapour

Tt T
e.g. 4 – is C=1 and P=4 possible?
F=1-4+2=-1 – this is impossible, one component cannot simultaneously exist as four phases in
equilibrium

Uses of the Phase Rule

a) Widely different physical and chemical systems may be classified and their behaviour predicted
b) It is not necessary to take into account the molecular complexity of substances
c) It is independent of any theory of matter
d) Although the phase rule may be used to discover the value of F it can alternatively be used to
predict the number of phases given the number of components and the variance. It can be used to
determine if a body is a single homogeneous substance or a heterogeneous mixture.

Gibbs Free Energy – G

Gibbs free energy can be thought of as the energy available in a system to perform ‘useful’ work, it
can be used to define the equilibrium state of a system and is a consideration of the properties of
the system only and not their surroundings.

G is defined by;
G=H-TS=U+PV-TS

For a small change in G;

dG=dH-TdS-SdT
or dG=(dV+PdV+VdP)-TdS-SdT
dG=dq-PdV+PdV+VdP-TdS-SdT
∴ dG=VdP-SdT+(dq-TdS)
Since dq-TdS=0 (using the Second Law of Thermodynamics at a phase transition)

dG=VdP-SdT - The Master Equation (true at equilibrium)

Using the relationship between Gibbs free energy and chemical potential it is possible to determine
an equation linked to a phase transition;

dG
= dµ
n

And dGm=VmdP – SmdT (where m=molar quantity)

Where α and β are phases, consider α⇋β ⟹ dµ (α, P, T)=dµ (β, P, T)
∴ Vm(α)dP – Sm(α)dT = Vm(β)dP – Sm(β)dT then rearranged to gather like terms;
{Vm(α)dP – Vm(β)dP} = {Sm(α)dT – Sm(β)dT} which can easily be rearranged as a differential
equation.
dP Sm α − Sm(β) ∆Sm
= = at the phase transition
dT Vm α − Vm(β) ∆Vm

∆Hm dP ∆Hm
Since = ∆Sm then =
T dT T∆Vm
(dP/dT=the gradient of a phase diagram, ∆Hm=the molar enthalpy change of a phase transition,
T=absolute temperature (K) and ∆Vm=molar volume change of a phase transition)
This can be re-arranged to predict the freezing or boiling temperature with a change in pressure;
T∆Vm × ∆P
∆T =
∆Hm
 The Phase Diagram of Water

P Liquid Critical Point

(P=218.3
Normal freezing and T=647.3) Water is special, particularly when regarding the
boiling points
change between water and ice. The slope is
Ice
1 negative, due to the strong hydrogen bonds
0.006 formed in water.

Vapour
T
273.16 373.15
Triple Point

Critical Pressure and Temperature-The Critical Point

In a container containing water and steam which is subjected to a temperature increase, the vapour
pressure increases as the density of the liquid decreases. Provided the temperature doesn’t rise high
enough to boil off all of the liquid the vapour pressure (which in essence is the density of the vapour)
and the density of the liquid will, at temperature T c, become identical. The system will cease to be
heterogeneous, now containing only 1 phase, the liquid and vapour cannot be distinguished from
each other.

This temperature, Tc, is called the critical temperature, the corresponding pressure, Pc, is called the
critical pressure.

For T>Tc no amount of pressure, no matter how large, can liquefy the vapour.

The Phase Diagram of Carbon Dioxide

P
The critical point of CO2 is particularly useful due to the
Solid low temperature and, for industry, low pressures
involved. As a supercritical solvent carbon dioxide is;
72.9
-non-toxic, non-flammable and inexpensive
Liquid -non-polar
5.11 -a good solvent for a range of organic components (non-
1 water soluble glycerides, esters, fatty acids)
Vapour
-useful for dissolving some inorganic compounds which
T
194.17 216.8 304.2 have organic functionalities
-a fine-tuneable solvent, density changes with variations
in pressure and temperature (low density is used for decolourisation, high densities for extraction of
oil seed, spice extracts etc)
-not very useful when there are hydrogen bonds within the solute, polar supercritical fluids such as
ammonia are better used in these situations

Supercritical carbon dioxide is commonly used for the extraction of;

-essential oils from plants
-flavours from fruits and vegetables
-oils from oilseeds
-caffeine from tea, coffee and cocoa
-odours from oils/fats

The biggest advantage of supercritical extractions is the easy separation of the solvent from the
solute, the temperature can simply be brought back below the critical temperature, releasing the
liquid solvent saturated with the desired solute. The low extraction temperature also minimises the
degradation of thermally labile compounds.
The Clausius-Clapeyron Equation
Supposing that one of the phases associated with a phase transition is an ideal gas;

PV=nRT ∴ P∆Vm=RT (since V/n = ∆Vm)

Substitution for ∆Vm in the Clapeyron equation gives;

d lnP ∆Hvap
= which can then be integrated to give
dT RT 2

−∆Hvap 1 1
lnP2 − lnP1 = − The Clausius − Clapeyron Equation
R T2 T1
(Note; this equation takes the form y=mx+c)
Two Component Systems (Liquid-Vapour)
Any liquid substance will be somewhat volatile, with a vapour formed above the liquid surface
forming a vapour pressure. If two miscible liquids are mixed together the vapour pressure of each
component above the surface of the formed solution is lowered compared to that of the pure liquid
component.
Quantitatively this is expressed using Raoult’s Law which states that the relative lowering of the
vapour pressure of a given component is equal to its molar fraction in the liquid mixture. For an ideal
two component system (with components A and B) which is in thermodynamic equilibrium at a
constant temperature Raoult’s law can be expressed as;

PA=xAPA* and PB=xBPB*

where PA= the vapour pressure of A
PA*=the vapour pressure of the pure liquid
xA=the molar fraction of A (where xA+xB=1)

T T
Boiling point of B Vapour
TB

Liquidus TA

Boiling point of A
Liquid

0% Liquid Composition of A 100%

In order to then work out the vapour composition of A Dalton’s law of partial pressures can be used;

PA PB
+ =1
P P

T T
Boiling point of B Vapour
TB

Vaporus
TA

Boiling point of A
Liquid

0% Vapour Composition of A 100%

These two graphs are then combined to give the following for miscible liquids;

T T

Vapour
TB D Vaporus

B C
Liquid + Vapour β
∆ α σ G
E
Liquidus TA
H
∆
A
F I

Liquid

X Y Z
0% Overall Composition of A 100%

From A-D, F-C, I-G are called isopleths and represent the result of an increase in temperature.
From α-β is called a tie-line.

The ratio of;

σβ
ασ
gives the ratio of liquid to vapour in the condensate at σ.

A zeotropic mixture is one that obeys Raoult’s law and can be separated by distillation.

Fractional Distillation
Most Volatile The column is filled with thousands of small
Compounds glass beads; these define the number of
Column theoretical plates.
Temperature A theoretical plate is the surface on which
Gradient Theoretical equilibrium is established between the
(Hot to Cold) Plates
condensed liquid on the bead and the
vapour passing over.
Least Volatile
Compounds
The wider the gap in the two-phase region
of the phase diagram, the fewer theoretical
plates are needed.
Vapour Still Pot

Liquid
Mixture

Heat
Azeotropic Mixtures
These are mixtures which do not obey Raoult’s law due to either positive or negative deviations.
a)Negative Deviations
Negative deviations are due to strong interactions between A and B

T T

TB

TA

Xaz

0% Composition of A 100%

At the point Xaz the vapour composition becomes equal to the liquid composition, there is no
separation between the two and they form a constant boiling mixture (i.e. upon boiling there is no
change in the composition).
An example of an azeotropic mixture which undergoes a negative deviation is H2O/HCl which is
azeotropic at 108oC.

b)Positive Deviations
These are instead caused by weak interactions and repulsive interactions
T T

TB

TA

Xaz

0% Composition of A 100%

An example of an azeotropic mixture which undergoes a positive deviation could be H2O/95%

CH3COOH which forms a constant boiling mixture at 78.1oC.
 Immiscible Liquids
T The boiling temperature for an immiscible
T
mixture is independent of the mixture since
Vapour P=PA*+PB* and the mixture boils when P=1 atm.

This is the basis of steam distillation. The water

TB
vapour contributes to the pressure, P, lowering
the boiling point of the pure organic
Two Liquid Layers component. This is useful due to the fragility of
organic molecules as it allows a lower
temperature for extraction, preventing the
breakdown of thermally labile compounds.
0% Composition of A 100%

The Lever Principle

Suppose the following behaviour;

T T
ω1 – A ω2 – B
If the overall composition in the two-phase
dissolved in B dissolved in A region is X, the proportion of phase ω1 to phase
ω2 is given by;

BC
A B C AB

2-phase

X1 X X2
0% Composition of A 100%

For a bi-liquid system (C=2, partially miscible), i.e. nitro-benzene (NB)/n-hexane (NH)

T At ‘A’ the NH can no longer dissolve in NB,

T
phase separation occurs. Eventually by adding
more NB all of the NH is dissolved.
B’
TUC290K
At TUC (the upper consulate temperature), or
A B A’ critical solution temperature, and above no
T’273K
phase separation occurs. This is due to the
violence of the molecular collisions at these
2-phase temperatures.

Y X Z
0% NB Composition of NB NH 100%
dissolved in NH dissolved in NB
 T The Lever diagram, in essence, is a visual
T
representation of the interactions of
molecules. In the above example two phases
2-phase
are formed at low temperatures due to
repulsive interactions, which are overcome
with increased temperature.
In this example of water and trimethylamine
attractive forces at lower temperatures are
TLC
overcome to form 2 phases at higher
temperatures as the complex breaks apart.
The temperature at which 2 phases begin to
0% Composition of Me3N 100% form is known as the lower consulate
temperature.

Nicotine and water is a special case in

T T
that it displays both upper and lower
consulate temperatures. TUC 210 C
o

2-phase

o
TLC61 C
1-phase

0% 100%

Two-Component Systems (Liquid-Solid)

Eutectics – two components, A and B,
T T
Liquid Only which do not combine to form a
compound or solid solution. The melting
A liquidus points of the pure components are
lowered by the presence of the other.
liquidus B
A=melting temperature of pure A
B= melting temperature of pure B
A (Solid/Liquid) B (Solid/Liquid) C=the eutectic point, at which solid
C E -solidus
D A/solid B/solid eutectic are all in
A Solid Only B equilibrium

0% Composition of B 100% At point C, F=C-P+2

100% Composition of A 0% F=2-3+2=1 (P=1atm) so F=0 (invariant)
 A eutectic mixture possesses attributes of definite composition and melting point. It is not a
chemical compound because it seldom corresponds to a simple formula. Separate crystals of A and B
can be seen under a microscope, it is best described as a mechanical mixture of crystalline
conglomerates of A and B.

Gold/Thallium – Eutectic at 73% Tl/27% Au

T At m there is liquid Au, at n pure gold

T m begins to precipitate out of the liquid. At o
there will be pure gold, liquid thallium and
1064oC A
n eutectic mixture.
In comparison, from X to C, since there is
X B 303oC no 2-phase area a single melting
Au (Solid/Liquid) temperature is displayed, lower than both
of those of the pure component solids.
Tl (Solid/Liquid)
o C E
D
Au (Solid+Eutectic) Tl (Solid+Eutectic)

0% 73% 100%
100% 27% 0%

The Uses of Eutectics

-Solder, i.e. for joining copper pipes together to form waterproof seals

 For many years a lead-tin alloy has been used due to its low melting point
 A ‘near eutectic’ composition is used to produce a small range of melting temperatures
(essentially introducing a small 2-phase stage) to allow for some movement once the solder
is applied to leave room for slight error

-in electronics a Cu-T alloy is used due to it being less toxic

Completely Miscible Solid Solutions

There are four main conditions required for the formation of ionic solid solutions (which can also be
extended to metals);

1. Their formulae must be analogous

2. The substances must have similar unit cells containing the same number of positive and
negative ions in geometrically similar arrangements
3. The difference in size between the ions must be no greater than 10%
4. The polarisations of the ions must be similar

Garrelli’s Rule; the miscibility of solids increases as their chemical relationship becomes closer
i.e. Pb2+/Sr2+ or Mg2+/CO2+ form solid solutions as they are similar in size
Mg2+/Ca2+ or K+/Na+ cannot due to the differences in ion size

Some examples of organic solid solutions are anthracine (in its various formations) and 1-4
dibromobenzene/1-4 dichlorobenzene.
Copper/Nickel
o T T
-different to eutectics since the solid 1455 C
Liquidus
solution of Cu/Ni cannot melt of solidify
Liquid (l)
at a constant temperature

l+α

Solid
Solution (α)
Solidus
o
1085 C

0% Composition of Nickel 100%

Congruent and Incongruent Melting

Sometimes two compounds, A and B, can react to form a compound C.
Suppose that A+B2→AB2 and that A+AB2forms a eutectic mixture, and B+AB2 also forms a eutectic
mixture, this would form one of the following behaviours;

Congruent melting- T T
Liquid
X marks the point
X
at which
AB2(s)⇋AB2(l) of
the same
composition. In
AB2(s)+Liquid B+Liquid other words, AB2
undergoes
A+Liquid congruent melting

A(s)+AB2(s) B(s)+AB2(s)

0% Composition of B 100%
100% Composition of A 0%

Incongruent
melting- T T
Liquid
Z is the peritectic
point, the point of
incongruent melting.
XY2(s)→Y+Liquid, a
AB2(s)+Liquid B+Liquid different
composition.
Z This is due to AB2 not
A+Liquid being stable as a
liquid, decomposing
after melting.
A(s)+AB2(s) B(s)+AB2(s)

0% Composition of B 100%
100% Composition of A 0%