PHASE RULE
Phase Rule was given by J. W. Gibbs in 1870 and it states that the equilibrium between
different phases is influenced by temperature, pressure and concentration only and not by
gravity, electrical or magnetic forces. The number of degrees of freedom (F) is related to
the number of components (C) and number of phases (P) by the following phase rule
equation.
F = C-P+2
(Gibbs Phase Rule)
• C = Number of chemical components
• P = Number of phases
• F = Degree of Freedom
PHASE RULE
The phase rule describes the possible number of degrees of freedom in an enclosed
system at equilibrium, in terms of the number of separate phases and the number of
chemical constituents in the system. It was deduced by J.W Gibbs in the 1870s.
Gibbs Phase Rule provides the theoretical foundation, based in thermodynamics, for
characterizing the chemical state of a system, and predicting the equilibrium relations of the
phases (minerals, melts, liquids, vapors) present as a function of physical conditions such as
pressure and temperature.
Gibbs Phase Rule also allows us to construct phase diagrams to represent and interpret
phase equilibria in heterogeneous systems.
Explanation of Terms
Phase A phase is a homogenous, physically distinct and mechanically separable portion of a system which is
separated from other parts of the system by a definite boundary.
Examples:
1. A gaseous mixture, being thoroughly miscible in all proportions constitutes one phase only.
2. If two liquids are immiscible (e.g., oil and water), they will constitute two separate phases till solution is
concerned. But the system as a whole will have three phases- two phases of liquid and third one being vapours
containing vapours of both the liquid.
3. Two miscible liquids (e.g., water and alcohol) constitute one phase only till solution is concerned. But the
system as a whole will have two phases - one phase will be solution (liquid) and the other one being vapours
above it.
4. A solute completely dissolved in a solvent constitutes a single phase, for example, a solution of glucose in
water, salt in water, etc.
5. Saturated solution of water and sugar will have two phases (solution of water+sugar and solid sugar settled at
the bottom.
Explanation of Terms
6. At freezing point, water consists of three phases: Ice (s) Water (l) Water vapour (g)
7. Each solid constitutes a separate phase. A mixture of rhombic and monoclinic sulphur is a two phase system.
8. A homogenous solution of Mohr’s salt [FeSO4.(NH4)2SO4.6H2O] constitutes a single phase.
Components The number of components of a system at equilibrium is the smallest number of independently
variable constituents by means of which the composition of each phase present can be expressed either
directly or in the form of a chemical equation. While expressing the composition of a phase in terms of its
components, zero and negative quantities are permissible. The components of a system do not represent the
number of constituents or chemical individuals present in the system.
Examples:
1. The sulphur system consists of four phases – rhombic, monoclinic, liquid and vapour.
The composition of each phase can be expressed in terms of sulphur alone. Hence, it is a one-component
system.
Explanation of Terms
2. Water system has three phases.
Each of these phases is a different physical form of the same chemical compound represented by H2O. Hence,
it is a one-component system.
3. The thermal decomposition of calcium carbonate involves three phases.
However, the composition of each of these three phases can be expressed in terms of at least two constituents.
Hence it is a two-component system.
i. By using CaCO3 & CaO :-
CaCO3(s) = CaCO3(s) + 0 CaO(s)
iii. By using CaCO3 & CO2 :-
CaO(s) = 0 CaCO3(s) + CaO(s)
CaCO3(s) = CaCO3(s) + 0 CO2(g)
CO2(g) = CaCO3(s) - CaO(s)
CaO(s) = CaCO3(s) - CO2(g)
CO2(g) = 0 CaCO3(s) + CO2(g)
ii. By using CaO & CO2 :-
CaCO3(s) = CaO(s) + CO2(g)
CaO(s) = 0 CO2(g) + CaO(s)
CO2(g) = 0 CaO(s) + CO2(g)
Component
Explanation of Terms
Degrees of freedom :The number of degrees of freedom of a system is the minimum number of independent
variables of a system, such as temperature, pressure and concentration which can define a system in equilibrium
completely.
Examples:
Problems On Number of Phases
Problems On Number of Phases
Problems based on Number of Component
Problems based on Degree of Freedom
Problems based on Degree of Freedom
Phase Diagram
A diagram which shows the conditions of equilibrium between phases of a heterogeneous system is
called a phase diagram. Phase diagrams are also called equilibrium diagrams. The phase diagram is a
graphical representation obtained by plotting one degree of freedom against another.
If the temperature (T) is plotted against pressure (P), the diagram is called a T–P diagram. If the
temperature (T) is plotted against composition (C), the diagram is called a T–C diagram.
Important properties of a substance like its melting point, boiling point, transition temperature
and triple point can be found with the help of a phase diagram. A phase diagram is usually studied under
three heads:
1. Areas or regions
2. Curves or lines
3. Points
True and Metastable Equilibrium
True equilibrium It is obtained when the free energy content of a system is minimum for a given set of
variables. A true equilibrium exists when the same state can be approached from either direction. For
example, an equilibrium between ice and water at 0 °C and at 1 atmospheric pressure is an example of a
true equilibrium because this state can be achieved both by partial freezing of liquid water or by partial
melting of ice.
Metastable equilibrium A state of metastable equilibrium is one that is obtained by careful
approach from one direction only and can be preserved by taking care not to subject the system to shock,
stirring or ‘seeding’ by the solid phase. For example, liquid water at –4 °C is said to be in a state of
metastable equilibrium because this state can be achieved only by carefully cooling water below 0 °C. This
state cannot be achieved by the fusion of ice. Moreover, if an ice crystal is added to the system, then
immediate solidification occurs and the temperature rises to 0 °C.
Water System
Phase Diagram of Water
Supercool water
Liquid water cooled below its normal freezing point normally remains liquid (in a metastable
state) for a few degrees below 0 °C and then forms solid hexagonal ice if shaken or after
seemingly random periods of time . If it is very pure and cooled quickly or carefully without
vibration, the liquid water may supercool further and occasionally to a minimum temperature
of about -42 °C, or even lower temperatures at higher pressures or shorter times. Supercooled
water occurs naturally in high altitude clouds.
Phase Diagram of Water System
Phase Diagram of Sulphur System
Phase Diagram of Sulphur System
Phase Diagram of Sulphur System
Triple Points
Triple Point B
Triple Point C
Triple Point E
At any Triple Point, phase rule becomes:
F = 3-P = 3-3 = 0 (nonvariant)
Area ABEG (Rhombic Sulphur)
Area BCEB (Monoclinic Sulphur)
Area DCEG (Sulphur Liquid)
Area ABCD (Sulphur Vapors)
In an area, Phase Rule becomes:
F = 3-P= 3-1 = 2 (bivariant)
Metastable Equilibrium
curve BF (sublimation curve of metastable SR)
curve CF (vapour press. Curve of supercooled liquid
sulphur)
curve FE (fusion curve of metastable SR)
Two Component system
F=C–P+2
F=2–P+2=4–P Three variables—temperature,
When P = 1, the D.O.F. has the highest value. pressure and composition—
F=C–P+2 are required to explain the
F=2–1+2=3 system completely.
Such a three-dimensional diagram cannot be expressed conveniently on paper. In order to have a single-phase
diagram for a two-component system, the usual practice is to choose any two of the three variables for graphic
representation, assuming the third to be constant. Hence, we can have
(i) Pressure–temperature diagram ( P–T ) when composition is constant
(ii) Temperature–composition diagram (T–C) when pressure is constant
(iii) Pressure–composition diagram (P–C) when temperature is constant
A solid liquid equilibrium of an alloy has practically no gas phase and the effect of pressure on these equilibria is
negligible. Experiments are generally conducted at room temperature. Hence in most cases, pressure is kept
constant at 1 atmosphere and the phase diagram is constructed using the variables, temperature and concentration.
Such a solid–liquid equilibrium, with the gas phase absent is termed as the condensed system and the
degree of freedom for such a system will be one and the phase rule becomes:
F=C–P+1 Reduced or condensed phase rule
It is widely applicable to solid–liquid two-component systems. The solid–liquid equilibria are represented on
temperature–composition diagrams.
Thermal analysis (cooling curve for pure substance)
Thermal analysis is the study of the cooling curves of various compositions of a system during solidification.
In this method, solids of different compositions are taken at a temperature above their melting points. The
resulting mixture is cooled slowly and cooling curves are constructed by plotting temperature against time.
For a mixture of definite composition, cooling curves help us to determine
1. Freezing point
2. Eutectic point
Pure substance
Figure shows cooling curve of a pure substance.
During the initial stage (part AB ), the liquid cools and the fall in temperature is continuous. After this, there is
a flat portion in the cooling curve from B to C. This is known as thermal arrest or temperature halt, where the
temperature remains constant; the value corresponding to this is called the freezing point (Tf).
The constancy of temperature continues from B, which marks the beginning of solidification, to C, which
marks the end point of solidification.
Sometimes, the liquid may cool to a temperature below its freezing point before crystallisation occurs-this is
called super cooling.
After the liquid has completely solidified at
point C, the fall in temperature again becomes
continuous (part CD of the curve) which
indicates that the solid cools down further till
its temperature is equal to the room
temperature.
Mixture of two solids
When a mixture of two solids is cooled, a continuous cooling curve is obtained initially (part AB).
Point B marks the beginning of freezing or appearance of solid. However, the temperature does not remain
constant. It decreases continuously in part BC but at a different rate.
At point B, one of the components begins to solidify. During this solidification, heat is liberated and
temperature falls slowly.
From B to C, the composition of the mixture changes continuously.
At point C, which is the eutectic point TE, the remaining
liquid solidifies as a whole, that is, both the components
crystallise out separately and the temperature remains constant
from C to D.
After the solidification is completed, the temperature falls
uniformly as represented by part DE of the cooling curve.
Eutectic Mixture
A eutectic system is a binary system consisting of two substances which are miscible in all proportions in the liquid
phase and which do not react chemically. e.g. a mixture of lead–silver comprises such a system.
The two substances have the tendency to lower each other’s freezing point. A solid solution of two or more
substances having the lowest freezing point of all the possible mixtures of the components is called the eutectic
mixture. The eutectic mixture has a definite composition and a sharp melting point, that is, it melts to a liquid of the
same composition. Hence, it resembles a compound. However, it is not a compound as the components are not
present in stoichiometric proportions.
The minimum freezing point attainable corresponding to the eutectic mixture is termed as the eutectic point (lowest
melting point).
The system at eutectic point is invariant, the degree of
freedom
F = 0.
For a two-component system, at eutectic point:
C = 2, P = 3
F=C–P+1
F=2–3+1=0
Characteristics of Eutectic point
1. The system at eutectic point is invariant, the degree of freedom F = 0. For a two-component system, at eutectic point, C =
2, P = 3 (both the solids and their solution)
2. It is the lowest freezing point of the system, that is, below this temperature, the liquid phase does not exist.
3. If the liquid is cooled below the eutectic point, both the components will solidify without change in composition.
4. Eutectics are mixtures and not compounds. When they were examined under an electron microscope, both the
constituents are seen to lie as separate crystals. Moreover, physical properties such as density and heat of solution of
eutectic solids were almost equal to the mean values of the constituents; hence, it is a mixture and not a compound.
5. The alloys of eutectic composition have greater strength than their individual components because of their crystal
characteristics.
Phase Diagram of Lead-Silver System (Simple Eutectic)
Points, Curves and Areas
Eutectic Point
Phase Diagram of Lead-Silver System (Simple Eutectic)
Application of Ag–Pb system
Pattinson’s process for desilverisation of argentiferous lead
The process of heating argentiferous lead containing a very small quantity of Ag (0.1% by mass) and cooling it
to get pure lead and liquid rich in silver is called Pattinson's process.
Argentiferous lead is first heated to a temperature above its melting point. The system consists of only the liquid
phase represented by point x in phase diagram of Ag-Pb system. It is then allowed to cool. The temperature of
the melt will fall along the perpendicular line xy without change in composition. As the point y is reached, lead
will begin to crystallise and the percentage of silver will increase in the solution. The system moves along the
curve yo. The melt continues to be richer and richer in silver until the point O is reached. At point O, the
percentage of silver is 2.6% by mass. After removing the lead that separates out, the liquid is cooled further to
give a mixture of eutectic composition (97.4% Pb + 2.6% Ag). Pure silver is obtained from this alloy by other
processes.
Phase Diagram of Zn-Mg System (Congruent Melting Point)
Two-component system which forms a stable compound with congruent melting point.
If the two-components of a system at a certain stage enter into chemical combination with
one another forming stable compounds, the compound formed may have congruent melting
point.
A compound is said to have congruent melting point when it melts sharply at a constant
temperature into a liquid of the same composition as that of the solid from which it is
derived, for example, zinc–magnesium system.
Phase Diagram of Zn-Mg System (Congruent Melting Point)
Congruent melting occurs during melting of a compound when the composition of the
liquid that forms is the same as the composition of the solid from which it is derived. For
Example Zn-Mg system
It is an example of a two-component system in which two metals form a compound
having congruent melting point. The compound is an alloy having the formula Mg (Zn)2
with a melting point of 590 °C, which lies between the melting point of the two metals.
The melting point of zinc is 420 °C and that of magnesium is 651 °C. Mg (Zn)2 is stable
and melts without change in composition. As the experiment is carried out at constant
pressure and the vapour phase is not considered, the condensed phase rule will be applied.
F=C–P+1
Phase Diagram of Zn-Mg System (Congruent Melting Point)
Phase Diagram of Zn-Mg System (Congruent Melting Point)
Phase Diagram of Zn-Mg System (Congruent Melting Point)
Phase Diagram of Zn-Mg System (Congruent Melting Point)
Application
phase diagram gives a lot of information like the triple point, sublimation temperature,
boiling point and freezing point and metastable state .
Phase rule is applicable to both chemical and physical equilibria.