Definitions and Basic Concepts
System – some portion of the universe that you wish to study
Surroundings – the adjacent part of the universe outside the
system
Closed system – only exchange of mechanical and thermal
energy, no mass exchange.
Open system – exchange of energies and mass
Degrees of freedom – the number of variables to define a
system in a phase diagram
Intensive properties – P, T, pH, Eh (materials variables)
Extensive properties – v, m, partial pressure
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Definitions and Basic Concepts
Homogeneous System – a system in which every property of the
system is constant irrespective of the coordinates of the system.
Phase – a portion of a system that has uniform physical and chemical
characteristics
A single phase system is called homogenous system
Systems with two or more phases are called mixtures or
heterogeneous systems. At least one property is a discontinuous
function with the coordinates
Solvent and Solute – a solvent is the host or major component in
solution and the solute is the minor component.
A phase of a thermodynamic system and the states of matter have
uniform physical properties.
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Definitions and Basic Concepts
A eutectic transformation, is one in which a two component
single phase liquid is cooled and transforms into two solid
phases. The same process but beginning with a solid instead of
a liquid is called a eutectoid transformation.
Liquid crystals (LCs) are a state of matter which has properties
between those of conventional liquids and those of solid
crystals
A diffusionless transformation is a phase change that occurs
without the long-range diffusion of atoms but rather by some
form of cooperative, homogeneous movement of many atoms
that results in a change in crystal structure.
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Definitions and Basic Concepts
Component: The elements or compounds which are present in the
alloy (e.g., Al and Cu)
Solubility limit of a component in a phase is the maximum amount
of the component that can be dissolved in it. Example, alcohol has
unlimited solubility in water, sugar has limited solubility, and oil is
insoluble
(lighter phase)
Phase
The physically and chemically (darker phase)
distinct material regions that
form (e.g. and )
A material may undergo various
phase changes during processing.
Figure 1. Aluminum – copper alloy
A phase change may include
melting, vaporization, sublimation, transformation, crystallization, or the
chemical formation of a compound
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Phase Diagrams
“A phase diagram is the sum of the description of the behaviour of
the phases present in equilibrium”
The number of phases that exist in equilibrium depends on the
conditions of temperature and pressure or temperature and
composition, pressure being constant.
These conditions are determined experimentally and the values of
the variables can be expressed graphically by using appropriate
coordinates.
These diagrams are called phase diagram.
It is very easy to describe the phase behaviour of a system by such
diagrams and to investigate the conditions in which various phases
will constitute the system .
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Phase Diagrams
A phase is a state of matter with the following characteristics:
It has the same structure or atomic arrangement throughout
It has roughly the same composition and properties throughout
There exists a definite interface between it and its surroundings or
adjoining phases
A phase diagram is a graphical representation of the phases that are
present in a material at various temperatures, pressures and
compositions
It usually describes the equilibrium conditions
Sometimes non-equilibrium conditions are also shown when well
known.
It indicates the melting/solidification temperatures of the constituents
It indicates the compositions of alloys where solidification begins and
the temperature range over which it occurs
Phase transformation – is an alteration in the number and/or
character of the phases in the system 22
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Gibb’s Phase Rule
Gibb’s phase rule describes the thermodynamic state of a
material.
It also states the degree of freedom available to describe a
particular system with various phases and substances
F=C–P+v
F = number of degrees of freedom
The number of variables to define a system in a phase diagram
P = number of phases
Phases are mechanically separable constituents
C = number of components
chemical constituents that must be specified in order to define all phases
v = intensive properties or materials variables
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P/T and pH/Eh diagrams = 2 www.knust.edu.gh
Gibb’s Phase Rule
Gibbs phase rule works best in (constructing) a phase diagram. And
those are usually 2-dimensional - with pressure along one axis and
temperature the other. So the "2" simply reflects that 2
dimensionality.
At 2 degrees of freedom, there are no constraints and the system can
change either pressure or temperature and be stable without a phase
transition.
If you have 1 degree of freedom, then you are likely to have a
constraint. These are not really constants.
If the degree of freedom is 0, then they are ... "fixed‘' – or better yet
"constrained".
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Merits of the Phase Rule
1. It is applicable to both physical and chemical equilibria.
2. It requires no information regarding molecular/microstructure, since
it is applicable to macroscopic systems.
3. It is a convenient method of classifying equilibrium states in terms
of phases, components and degrees of freedom.
4. It helps us to predict the behaviour of a system, under different sets
of variables.
5. It indicates that different systems with same degree of freedom
behave similarly.
6. It helps in deciding whether under a given set of conditions:
a) various substances would exist together in equilibrium, or
b) some of the substances present would be interconverted, or
c) some of the substances present would be eliminated.
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Limitations of Phase Rule
1. It can only be applied to systems in equilibrium. Consequently, it is of
little value in case of very slow equilibrium state attaining system.
2. It applies only to a single equilibrium system; and provide no
information regarding any other possible equilibria in the system.
3. Phases existing in the equilibrium state must be carefully stated, since
it considers only the number of phases, rather than their amounts.
Thus even if a trace of phase is present, it accounts towards the total
number of phases.
4. All phases of the system must be present simultaneously under the
identical conditions of temperature and pressure.
5. Solid and liquid phases must not be in finely-divided state; otherwise
deviations will occur.
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Unary Phase Diagrams
Phase Diagrams: The diagram representing conditions of
temperature, pressure and composition at which one or more phases
exit together.
Phase Diagram of Water System:
Fusion Curve
2 phases Critical
Point
Pc
Solid Liquid
(1 phase)
Pressure
(1 phase)
Vapor Pressure
Curve (2 phases)
Triple Point Vapor (1 phase)
(3 phases)
Sublimation Curve (2 phases)
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Tc
Temperature www.knust.edu.gh
Unary Phase Diagrams
Phase Diagram of Water System:
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Unary Phase Diagrams
Some important features of Water System:
Possible phases : Ice (s), Water (l), Vapour (g)
Curves: three stable curves throughout
OA ( Vapour pressure curve, Water Vapour)
OB ( Sublimation Curve, Ice Vapour)
OC ( Melting point curve, Ice Water)
One metastable curve OA’
OA’ (Vapour pressure curve of super cooled water)
Areas : Three areas representing ice, water and vapour.
Triple point (O): Where all the three phases are in equilibrium
(0.0098 oC and 4.58 mm pressure).
The melting point curve OC has a negative slope, showing that
the melting point of ice decreases with increase of pressure
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Unary Phase Diagrams
Phase Diagram of Sulphur System:
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Unary Phase Diagrams
Some important features of Sulphur System:
Possible phases : Rhombic sulphur (SR), monoclinic sulphur (SR),
sulphur vapour (SV) and sulphur liquid (SL).
Maximum phases: If P = 4, then F = C – P + 2 = 1 – 4 + 2 = –1
Which is meaningless. Hence all the four phases cannot coexist.
Areas : Four areas containing one phase each
Curves: there are six stable curves
Sublimation curve of SR
Sublimation curve of SM
Vapour pressure curve of SL
Transition curve of SR
Melting curve of SM
Melting curve of SR
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Unary Phase Diagrams
Some important features of Sulphur System:
Metastable curves : There are four metastable curves
Sublimation curve of SR
Sublimation curve of SM
Vapour pressure curve of SL
Melting curve of SR
Triple point (O): There are three stable triple points SR-SM-SV, SM-SL-
SV, SR-SM-SL and one metastable triple point SR-SL-SV.
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Unary Phase Diagrams
Polymorphism or Allotropy
Metals exist in more than one crystalline form
Change of these forms is called Allotropic Transformation
Example, iron exists in both BCC and FCC form depending on the
temperature
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Unary Phase Diagrams
Phase diagram of pure Fe
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