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Physical Chemistry I

Physical transformations of pure

Chapter 4
Dr. Mohammed Suleiman

Phase Transformations

Chemical potentials are equivalent to molar Gibbs energies

for pure substances, so the phase with the lowest chemical
potential will be the most stable phase

Phases, Components and Degrees of Freedom
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 it is 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

A chemical species that is present in a system. For example, a mixture of water and
ethanol has 2 constituents
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 (or:
smallest number of independently variable chemical species to describe the
composition of each phase)

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
dependent change in pressure (or temperature) to preserve the phases in

F = 1, system has one degree of freedom

If three phases are in equilibrium (C=1, P=3) (e.g., s, l and g), neither the
T nor p can be changed, otherwise the equilibrium is not preserved.

F = 0, system has no degrees 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:

4.1 Stabilities of Phases
Phase: A form of matter that is uniform throughout in both
chemical composition and physical state

Phase Transition: Spontaneous conversion of one phase into

another, occurring at a characteristic temperature for
a given pressure
Consider water at p = 1 atm:

Rates of Phase Transitions
Distinguish between:
Spontaneity of transition Rate of transition

Consider the phase transition from diamond to graphite:

For change to take place, C atoms must exchange positions, which is an

incredibly slow process for solids (except at high temperatures)
In gases and liquids, these changes can take place rapidly, but in solids,
thermodynamic instability may be inherent in the system

Metastable phases:
Thermodynamically unstable phases that persist due to kinetic hindrance

Phase Boundaries
Phase Diagram: Shows regions of pressure and temperature where
phases are thermodynamically stable

Vapour Pressure
Pressure of a gas in
Sublimation Vapour equilibrium with the liquid
Pressure phase
Pressure of gas in
equilibrium with solid
Phase Boundaries
separate regions and
show p and T where
two phases exist in
equilibrium Triple Point
Critical Temperature

Vapour pressures increase with increasing T, as the

Boltzmann distribution populates the higher energy
states with increasing temperature
Critical Points and Boiling Points
In an open vessel, at the temperature where the vapour pressure is equal to the
external pressure, free vapourization occurs throughout the liquid, and vapour can
expand freely into the surroundings. Free vapourization is known as boiling

The normal boiling point, Tb, is the temperature of free vapourization at

a pressure of 1.0 atm
The standard boiling point is the temperature of free vapourization at a
pressure of 1.0 bar (0.987 atm) (e.g., water: 99.6oC for Tb = 100oC)

In a closed vessel, boiling does not occur - rather

the vapour pressure and density of the vapour
increase with increasing temperature
(a) equilibrium, (b) increasing density & (c) two
densities equal, surface btw. phases disappears
Critical temperature, Tc and critical
pressure, pc:
where interphase surface disappears
Supercritical fluid: fills container and
interface no longer exists (figure c)
Melting Points and Triple Points
The temperature at a specified pressure where the liquid and solid
phases coexist in equilibrium is called the melting temperature (or freezing
temperature or fusion temperature)
The normal freezing point, Tf, is the temperature of freezing at a
pressure of 1.0 atm (for water, Tf = 0 oC)

The standard freezing point is the temperature of freezing at a pressure

of 1.0 bar (0.987 atm) (negligibly different from Tf)
The point where all three phases exist in equilibrium is called the triple
point, T3 (three phase boundaries meet)

T3 occurs at a specific temperature and pressure which are

characteristic of a substance
T3 marks lowest pressure in which a liquid phase of a substance
can exist