Phase Rule

It help us to predicts quantitatively equilibrium existing between different phases of a heterogeneous

systems
This rule was first put forward by J. Willard Gibbs, an American Chemist, in the year 1876 The full
implications of this rule was understood by chemists only when Roozeboom, Ostwald and van’t Hoff applied it to
some well-known physical and chemical equilibria.
Dynamic equilibria: When the reactants in a closed vessel at a particular temperature react to give products, the
concentrations of the reactants keep on decreasing, while those of products keep on increasing for some time after
which there is no change in the concentrations of either of the reactants or products. This stage of the system is
the dynamic equilibrium and the rates of the forward and reverse reactions become equal. Also called equilibrium
EQUILIBRIUM IN PHYSICAL PROCESSES :If we examine some physical processes. The most familiar examples are
phase transformation processes, e.g.,Solid – liquid, l iquid – gas, solid – gas, solid1 –solid2
S-L: Melting /fusion, L-G: Vaporization/condensation, S-G: Condensation/Deposition S1-S2: Transition

Phase reactions: Any physical/chemical change associated with appearance/disapperance of phases is

termed as phase reaction
• Equilibrium conditions:
• The system is said to be under thermal/Mechanical/Chemical equilibrium if
• 1.Thermal: All phases exist in equilibrium are at same temperature (Temp not changes)
• 2. Mechanical: All phases exist in equilibrium are at same pressure(No exchange of particles into surrounding)
• 3.Chemical: all phases exist in equilibrium are at same Chemical potential. (Composition not changes)
• Statement of Phase rule
• In heterogeneous system at equilibrium sum of degree of freedom & phases greater than component by two
i.e F + P = C + 2
• F=C-P+2
• Where
• P = Phases of system
• C = Component &
• F = Degree of freedom
• 2 stands for the intensive variables pressure, P and temperature
• Terms in phase rules
• Phase: (P):A phase is defined as number of any homogeneous and physically distinct part of a system which is
separated from other parts of the system by interfaces/ boundary surface.
• A phase may be gas, liquid or solid.
• A gas or a gaseous mixture is a single phase.
• Totally miscible liquids constitute a single phase.
• In an immiscible liquid system, each layer is counted as a separate phase.
• Every solid constitutes a single phase except when a solid solution is formed
• A solid solution is considered as a single phase.
• Each polymorphic form constitutes a separate phase.
• The number of phases does not depend on the actual quantities of the phases present. It also does not depend on
the state of subdivision of the phase
• Examples of phases
• Counting the number of phases
• a) Liquid water, pieces of ice and water vapour are present together.
• The number of phases is 3 as each form is a separate phase. Ice in the system is a single phase even if it is
present as a number of pieces.
• b) Calcium carbonate undergoes thermal decomposition.
• The chemical reaction is: CaCO3(s) ↔CaO(s) + CO2 (g)
• Number of phases = 3
• This system consists of 2 solid phases, CaCO3 and CaO and one gaseous phase, that of CO2
• c) Ammonium chloride undergoes thermal decomposition. The chemical reaction is: NH4Cl(s) → NH3 (g) + HCl (g)
Number of phases = 2
• This system has two phases, one solid, NH4Cl and one gaseous, a mixture of NH3andHCl.
• d) A solution of NaCl in water Number of phases = 1
• e) A system consisting of monoclinic sulphur, rhombic sulphur , liquid sulphur and sulphur Number of phases = 4
This system has 2 solid phases and one liquid and vapour phase. Monoclinic and rhombic sulphur, polymorphic
forms, constitute separate phases.
• Component (C):Def: Minimum number of molecular species involved by means of which chemical composition of
every phase in a system is expressed OR
• It should be noted that the term “constituents” is different from “components”,
• which has a special definition. When no reaction is taking place in a system, the number of components is the same
as the number of constituents. For example, pure water is a one component system because all the different
phases can be expressed in terms of the single constituent water. In order to find out minimum number of C zero
&/or –ve quantity of composition be consider.
• Examples of Component
• a) The sulphur system is a one component system. All the phases, monoclinic, rhombic,liquid and vapour – can be
expressed in terms of the single constituent – sulphur.
• b) A mixture of ethanol and water is an example of a two component system. We need both ethanol and water to
express its composition.
• c) An example of a system in which a reaction occurs and an equilibrium is established is the thermal
decomposition of solid CaCO3. In this system, there are three distinct phases: solid CaCO3, solid CaO and gaseous
CO2. Though there are 3 species present, the number of components is only two, because of the equilibrium
• CaCO3 (s) →CaO(s) + CO2(g)
• Any two of the three constituents may be chosen as the components. If CaO and CO2 are chosen, then the
composition of the phase CaCO3 is expressed as one mole of component CO2 plus one mole of component CaO. If,
on the other hand, CaCO3 and CO2 were chosen, then the composition of the phase CaO would be described as one
mole of CaCO3 minus one mole of CO2
• A system in which ammonium chloride undergoes thermal composition. NH4Cl (s) →NH3(g) + HCl (g)
• There are two phases, one solid-NH4Cl and the other gas – a mixture of NH3 and HCl. There are three constituents.
Since NH3 and HCl can be prepared in the correct stoichiometric proportions by the reaction: NH4Cl → NH3+HCl
• The composition of both the solid and gaseous phase can be expressed in terms of NH4Cl alone. Hence the number
of components is one.
• If additional HCl (or NH3) were added to the system, then the decomposition of NH4Cl would not give the correct
composition of the gas phase. A second component, HCl (or NH3) would be needed to describe the gas phase it
become two component system
• Degrees of freedom (F) (or variance)
• The degrees of freedom or variance of a system is defined as the minimum number of variables such as
temperature, pressure, concentration, which must be arbitrarily fixed in order to define the system completely
• Examples of Degree of freedom
• a) A system having only liquid water has two degrees of freedom or is bivariant. Both temperature and pressure
need to be mentioned in order to define the system.
• b) In water system containing liquid water, pieces of ice are added and this system with 2 phases is allowed to
come to equilibrium, then it is anunivariant system. Only one variable, either temperature or pressure need to be
specified in order to define the system. If the pressure on the system is maintained at 1 atm, then the temperature
of the system gets automatically fixed at 0oC, the normal melting point of ice.
• c) In water system mentioned above, a small quantity of water is allowed to evaporate and then the system is
allowed to come to equilibrium, then the number of phases in equilibrium will be three. This system has no degrees
of freedom or it is invariant. Three phases, ice, water, vapour can coexist in equilibrium at 0.0098oC and 4.6mm of
Hg pressure only. A change in temperature or pressure will result in one or two phases disappearing.
• Hence the degree of freedom of a system may also be defined as the number of variables, such as temperature,
pressure and concentration that can be varied independently without altering the number of phases
• True and metastable equilibrium
• True equilibrium is obtained when the free energy content of a system is at a minimum for the given set of
variables
• A state of true equilibrium is said to exist in a system when the same state can be obtained by approaching from
either direction.
• An example of such an equilibrium is ice and liquid water at 1 atm pressure and 0oC.At the given pressure, the
temperature at which the two phases are in equilibrium is the same whether the state is attained by partial
freezing of liquid water or by partial melting of ice
• Liquid water at – 4 0C is said to be in a state of metastable equilibrium because this state of water can be obtained
by only careful cooling of the liquid and not by fusion of ice. If an ice crystal is added to this system, then
immediately solidification starts rapidly and the temperature rises to 0oC.
• A state of metastable equilibrium is one that is obtained only by careful approach from one direction and may be
preserved by taking care not to subject the system to sudden shock, stirring or “seeding” by solid phase.
• Phase equlibria of one component systems – water, and S systems
• Applying the phase rule to a one component system, we write F = C-P+2 = 1-P+2 = 3-P Three different cases are
possible with P taking values 1, 2 and 3.
• a) System having only one phase, i.e., P=1 F=3-P=3-1=2
• This is a bivariant system. We need to state the values of 2 variables in order to define the system completely.
These are temperature and pressure. The given component may exist in any of the three phases, solid, liquid or
vapour.
• b) System having 2 phases, i.e. P=2 F=3-P=3-2=1 This is a univariant system and hence the value of either of the 2
variables, temperature or pressure, would define the system completely. The two phases in equilibrium with each
other may be solid-solid, solid-liquid, liquid-vapour and solid-vapour.
• c) System having 3 phases, i.e. P=3. F=3-P=3-3=0 The system is invariant and three phases can exist in equilibrium
only at definite values of temperature and pressure. The three phases in equilibrium with each other may be solid-
liquid-vapour, solid-solid-liquid, and solid-solid-vapour.
• Thus, we see that the maximum number of phases existing in equilibrium in a one component system is three.
• For a one component system, as the maximum number of degrees of freedom is two,
• The equilibrium conditions can be represented by a phase diagram in two dimensions choosing pressure and
temperature variables.
• Water system
• The simplest case of a one component system is one in which there is only one solid phase.
• In a system having more than one solid phase, there are a number of possible equilibria and the phase diagram
gets quite complicated.
• In the case of “water” system, above –20oC and below 2000 atm pressure, there is only one solid phase, namely,
ordinary ice

•
• Water system is one component system since all three phases are represented with same chemical formula H2O
• There are three phases
• Water Ice –Solid, Water liquid – liquid, Water Vapour – Gas
• It is one component system Hence Phase diagram of one component system will be Shown by Temperature &
Pressure Variable which is as shown in above figure
• Phase diagram of water system consist of
• A)Curves: There are three stable curves namely BO,AO,OC & one metastable curve OD’
• Curve BO : It is sublimation curve It starts B( at -2730C) and ends at O (at 0.0098 OC) The two phase Solid & Vapour
are in equilibrium along this curve each point gives Vaporization temperature of Ice w.r.t pressure Hence system
along curve is uni variant.
• Curve AO : it is Vaporisation curve It starts A( at 3740C) and ends at O (at 0.0098 OC) The two phase Liquid & Vapour
are in equilibrium along this curve each point gives Vapour pressure temperature above 374 it exist in vapour
phase Hence system along curve is univariant
• Curve CO : it is Freezing curve It starts O(at 0.0098 OC) and ends at A The two phase Solid & Liquids negative slope
means Melting temperature falls as the pressure is raised Hence system along curve is uni variant
• Metastable Curve: OD’: By sudden cooling of water below 0OC allows existence of liquid water up to D’ i.e. -4OC
Here at temperature below that of triple point liquid water has a vapour pressure higher than sublimation pressure
of ice & hence the supercooled liquid unsable at these temperature w.r.t. ice. System is uni variant.
• B) Area: These three curves split phase diagram in 3 areas Each area shows existence of single phase
• BOC- ICE(S), AOC-Water(L), AOB- Water Vapour(G)
• To define any point in area both Temperature & Pressure must be known i.e system is bivariant
• i.e T&P may be changed independently without changing no, of phases
 • C) Triple point: (In heterogeneous system a point at which three phases of system are in equilibrium/ point in
phase diagram where three phases are in equilibrium)There is only one triple point since no of phases of system is
three
At this point phase S,L,V are in equilibrium, corresponding temperature is 0.0098OC & pressure is 4.568mm, It occurs at
single definite variable, which is characteristic of substance Hence system is non variant
Application of water system
• We have seen in the water system, the fusion curve OC is almost vertical with a slight tilt (bend) towards the
pressure axis. This indicates that an increase in pressure decreases the melting point of ice
• A property that contributes to making skating on ice a possibility. The pressure exerted by the weight of the skater
through the knife edge of the skate blade lowers the melting point of ice. This effect along with the heat developed
by friction produces a lubricating layer of liquid water between the ice and the blade. It is of interest to note that
the skating is not good if the temperature of ice is too low.
• In boiler industry demands dry vapour which possible above critical level (Temp: 374 & Pressure 218atm)
The phase diagram for sulphur
• Sulphur exists in two solid modifications, the rhombic form stable at ordinary temperatures and the monoclinic
form at higher temperatures. Substances that can exist in more than one crystalline form, each form having its own
characteristics vapour pressure curve, are said to exhibit the phenomenon of polymorphism. Two types of
polymorphism are observed, enantiotropy (Greek: opposite change) and monotropy (Greek: one change).
• Enantiotropy
• Two crystalline modifications of a substance are said to be enantiotropic (or to exhibit enantiotropy) when each
has a definite range of stability and conversion from one modification to the other takes place at a definite
temperature in either direction. This temperature is the transition point and it is the only temperature at which the
two modifications can coexist in equilibrium at a given pressure. A change in this temperature results in the
complete transformation of one modification into the other, one being stable above the transition point and the
other below it.
• Monotropy
• If one crystalline form is stable and the other form metastable over the entire range of their existence, the
substance is said to exhibit Monotropy. The transformation from one form into another takes place in one
direction only, that is, from metastable to stable form.

• Sulphur system is one component system since all four phases are represented with same chemical formula S
• Four are three phasesSr(S),SM(S),SL(L),SV(G)
• It is one component system Hence Phase diagram of one component system will be Shown by Temperature &
Pressure Variable which is as shown in above figure
• Phase diagram of sulphur system consist of
• A)Curves: There are Six stable curves namely AB,BC,CD,BE,CE & FE & three metastable curve BF,CF,EF
Curve AB : it is sublimation curve for SR. It starts at A and ends at B . above which SR does not exist. The two phase
SR& SV are in equilibrium along this curve. Each point on curve gives Vaporization temperature of SR w.r.t pressure
Hence applying phase rule system along curve is uni variant
• Curve BC : it is sublimation curve for SM. It starts at B the transition temperature of SR and ends at C The melting
point for SM. The two phase SM& SV are in equilibrium along this curve. Each point on curve gives Vaporization
temperature of SM w.r.t pressure Hence applying phase rule system along curve is uni variant.
• Curve BE : it is Transition curve for SR. It starts at B and ends at E(Fusion/Melting temp. of SR at corresponding P)
The curve depicts effect of pressure on transition temperature. An increase in pressure increases transition
temperature The two phase SR & SV are in equilibrium. Hence system along curve is uni variant
• Curve CE: It is melting point curve for SM. Starts at C(M.P.of SM) ends at E. gives effect of pressure on melting
point. Two phases SM&SL are in equilibrium along the curve system is univariant
Curve EG: It is melting point curve for SR at 1290atm transition temp. equals melting temperature hence SM is not
formed beyond point E. The two phases SR&SL are in equilibrium along the curve. System is univarient
• Metastable Curve: There are three metastable curves BF,CF, EF By sudden heating SR above 96 OC SR is retained up
to point F giving curve BF. Similarly rapid cooling of SL allow existence of SL up to F giving Curve CF, It metastable SR
&supercooled SL are formed it gives cuve FE wher SR&SL are in equilibrium no SM is present. But it needs careful
heating of SR & careful cooling of SL. The system along three curves is also uni variant.
• B) Area: Six curves split phase diagram in 4 areas Each area shows existence of single phase
• ABCD- SV ABEF- SR, BCE- SM, DCEF- SL
• To define any point in area both Temperature & Pressure must be known i.e system is bivariant
• i.e T&P may be changed independently without changing no, of phases
• C) Triple point: There are three stable triple point and one metastable triple point since no of phases of system is
four 1. point B: At this point phases SR,SM,SV are in equilibrium. The corresponding temp. is 96 &Pis 0.006mm.
changing this the system may follow any curve or area hence nonvarient2. point C: At this point phases SL,SM,SV
are in equilibrium. The corresponding temp. is 120 &Pis 0.04mm. changing this the system may follow any curve or
area hence nonvarient3. point E: At this point phases SR,SM,SL are in equilibrium. The corresponding temp. is
160&Pis 1290 atm. changing this the system may follow any curve or area hence nonvarient
• Rapid cooling of SR allows existence of SR upto 114OC without forming SM & giving metastable curves BF. Similarly
when SL is cooled suddenly, liquid phase exists up to 114OC without forming SM. It gives metastable curve CF.
When curve BF & CF are obtained then existence of SM is totally vanished & point F will emerge as metastable
triple point where SR,SL,SV are in equilibrium slight disturbance will vanishes point F & SR & SL converted to SM.
• Phase equilibria of two component systems
• Applying the phase rule to two component systems we have the degrees of freedom, F=C– P+2=4–P. when a single
phase is present in a two component system, the number of degrees of freedom, F=3, means that three variables
must be specified to describe the phase and these are temperature, pressure and composition of the phase. When
two phases are present, the number of degrees of freedom, 4–P, is reduced to 2, temperature and composition of
the liquid phase. The values of the other variables get automatically fixed. If there are three phases present, then
F=4– 3=1 which means the value of only one variable needs to be stated to describe the phases
• The maximum number of degrees of freedom for a two component system we see from the preceding discussion is
three.
• In order to represent the variation in three variables graphically, we require a three dimensional diagram, a space
model, which is difficult to construct on paper.
• To overcome this difficulty, a common practice that is adopted is to keep one of the variables constant.
• There are various types of equilibria, that are generally studied at constant external pressure.
• Thus, out of the three variables (F=3), one is already stated and the variation in the other two can be represented
on a two dimensional diagram.
• Equilibria such as solid-liquid equilibria are such systems in which the gas phase is absent and hence are hardly
affected by small changes in pressure.
• Systems in which the gas phase is absent are called condensed systems. Measurements in these systems are
generally carried out at atmospheric pressure.
• As these systems are relatively insensitive to small variation in pressure, the pressure may be considered constant.
Reduced Phase rule
• The phase rule takes the form
• P+F=C+1 One independent variable remain constant
• For such systems and in this form it is known as the reduced phase rule. For a two component simple eutectic
system, this equation becomes F=3-P where the only remaining variables are temperature and composition. Hence
solid-liquid equilibriumsare represented on temperature – composition diagrams.
• Determination of solid-liquid equilibria
• Many experimental methods are used for the determination of equilibrium conditions between solid and liquid
phases. The two most widely used are the thermal analysis and saturation or solubility methods. Whenever
required additional data are obtained by investigating the nature of the solid phases occurring in a system.
Simple Eutectic & Solid Solution
• Simple Eutectic: If two substances are completely miscible in the liquid state, but completely immiscible in the solid
state, form a simple eutectic. Of the various mixture, one mixture has the lowest melting point such a mixture is
known as a eutectic mixture (eutectic means easy melting).
 • Solid Solution: When two substances, especially metals, are completely miscible in both the solid and liquid states,
they form solid solutions, where mixing takes place in the atomic levels. A condition for the formation of solid
solution is, the two metals should not differ in atomic radius by more than 15%.
Cooling curve of a pure component
A pure component, say A, is taken and heated to get a melt. The liquid A is allowed to cool on its own and the temperature
of the melt is noted at, say, every half a minute. A cooling curve is obtained by plotting temperature versus time

Cooling of liquid A takes place along ac, when at c solidification starts and the system has two phases in equilibrium
becoming an invariant system (F=C+1-P=1+1-2=0). The temperature remains constant till the entire liquid A solidifies along
cd. The system is cooling, losing heat to the surroundings, yet the temperature remains constant during solidification. This
is due to the fact that heat is released during solidification compensate for cooling. Cooling of solid A takes place along
de. The system represented by any point on either ac or de has only one phase and hence is univariant
Cooling curve of a mixture of two components with only pure components crystallizing on cooling the system.
Solid B is added to solid A to get a mixture of known composition. This mixture is heated to get it in the liquid phase.

• The liquid cools along ab and at b solid A starts solidifying. Temperature and composition of liquid phase have to be
stated to define the liquid phase completely (P=1, F=3-P, F=2) when A starts solidifying, the system becomes
univariant (P=2, F=3-P=1). Thus, the temperature at which solid A starts solidifying from the liquid mixture of
known composition will have a definitevalue given by the point b. This temperature is expected to be a little lower
than the freezing point of pure A as the addition of B to A lowers the freezing point of A. Solidification of a small
quantity of A changes the composition of the liquid phase and hence the temperature at which A solidifies from
this liquid will take place at another fixed value but lower than the previous temperature as the molality of B in the
liquid increases with the solidification of A. Thus as moreand more of A separates from the liquid, the temperature
of the system falls along bc. The rate of cooling is affected by the heat evolved due to the solidification of A and
hence a break is observed in the curve at b. The break point indicates the temperature at which A just starts
solidifying. Along the curve bc, there are two phases, liquid and solid A, hence the system is univariant (P=2, F=3-
P=1). As cooling continues along bc, more and more of solid A separatesand the liquid gets richer in B. At the point
C, the liquid becomes saturated in B and hence B starts separating along with A. Along cd both the solids A and B
separate and the system becomes invariant (P=3, F=3-P=0). Solidification from a solution of fixed composition, one
corresponding to the saturation solubility of B in A takes place at constant temperature. This results in a halt or
complete arrest of the cooling curve (cd). As the saturation solubility of B in A has to be maintained at this
temperature, the composition of the solid phase that separates will be the same as that of the liquid phase. The
temperature of the systems will remain unchanged till the whole of the liquid phase solidifies. The cooling of the
solid phase is represented by de and the system is univariant (P=2, F=3-P=1).
• Eutectic system: System in which definite proportion of component involved are simultaneously crystallized from
melt at minimum possible temp.
• Eutectic Mixture: Definite composition of components from eutectic system, that solidifies at lowest possible temp.
 • Eutectic point: Binary alloy system in which component involved are freezes/ crystallized simultaneously from melt
at minimum possible temp
• Eutectic Temperature: Lowest possible temp. for eutectic mixure at which component involved are simultaneously
crystallized or melt.
The Lead-Silver system \The metals lead and silver are completely miscible in the liquid state and do not form any
compound. Hence the phase diagram of this system is

• Simple Eutectic (Pb-Ag system)

• It is a two-component system. The phase diagram of the Pb-Ag system is shown in the above fig
• Curve AO
• Point A is the melting point of pure Silver. Curve AO shows melting point depression of silver by the addition of
lead. At any point in this curve there is equilibrium between solid Ag and liquids part. Hence curve AO called
Freezing curve of pure Silver
• According to reduced phase rule equation. The system is univarient.
• F’=C-P+1; F’=2-2+1; F’=1
• Curve BO
• Point B is the melting point of pure lead, (327oC), curve BO shows the melting point depression of lead on gradual
addition of silver to it. Along this curve solid lead and solution co – exist and hence curve is called Freezing curve of
Pure Pb& the system is univariant.
• Point O: The two curves AO & BO meet at point O, where three phases solid pb, solid Ag and their
• solution co-exist, according to condensed phase rule the system is invariant.
• F’=C-P+1; F’=2-1+1; F’=2
• The point ‘O’ is known as eutectic point, its composition (Ag=2.6%; Pb=97.4%) and temperature (303 0C) is known as
eutectic composition and eutectic temperature respectively. Further cooling below the eutectic temperature
respectively. Further cooling below the eutectic temperature will cause simultaneous crystallization of a mixture of
lead and silver
• Area AOB: Consists of only one phases namely pb-Ag solution. According to reduced phase rule equation. F’=C-P+1;
F’=2-1+1; F’=2
• The system is bivarient i.e., both T & composition has to be specified to define the system.
 • Below the eutectic point (O), area COEF consists of solid and eutectic compound, where
• crystalline silver and eutectic compounds are stable. Similarly the area ODFG consists of solid Pb and eutectic
compound, where crystalline lead eutectic compounds are stable.
Phase diagram General Description
• Graphical representation of heterogeneous system and possible equilibrium states is phase diagram . It predicts
effect of change in Temperature, pressure, composition on various possible equilibrium of system under study.
• Generally it is in the form of P-T,T-C,P-C diagram & the variables of least significance is neglected / kept constant
where ever necessary
• In general as phase digram will consist Curves, Areas & points
• A)Curves: Region in phase diagram where two phases are in equilibrium along this region. The point on curves is
defined by only one variable (univariant). Depending upon actual phase reaction curved are named like Liquid –
vapour (vaporization curve ) Solid – vapour (sublimation curve) Solid – liquid (fusion/ freezing curve) Solid 1 –
solid 2 (transition curves ) Metastable curves- extended stability of certain phase
• B) Area: Area is region of phase diagram where single phase exist. The point in area is defined with two variables
(Bivarant)
• c) Points: There are various points in phase diagram like Freezing point, Boiling point, Critical Temp. Critical
pressure Triple point: This point where 3 curves meets. 3 phases are in equilibrium with definite sets of variables.
Hence nonvariant.
• Eutectic point: Binary alloy system in which component involved are freezes/ crystallized simultaneously from melt
at minimum possible temp. Hence nonvariant
• It also help to show of polymorphism enantiotropy (Greek: opposite change) and monotropy (Greek: one change).
• E.g Water system
Applications of Eutectic system
• A mixture of 23.3% NaCl& ice by mass providing -21.2 0C eutectic temp. hence freezing mix is prepared by adding
common salt to ice
• Eutectic alloy of Na& K (NaK) are liquid at RTP are acts as coolant in nuclear reactors
• Eutectic alloy of Pb&Sn and Ag & Au are used for soldering purpose
• Eutectic mixture are used as inks in inkjet printers which can operate at low temp.
• Eutectic alloy of low Melting point are used to prepare safety valve in pressure cookers, automobiles, boilers etc
• In semiconductor industry gold silver Eutectic is used.
• In brazing process one of the element from an alloy can be removed by diffusion of another element forming an
eutectic that melts at a lower temp.
• In a rock, the mineral portion always contains both miscible (solid soln) &immisible (binery eutectic) phase & on
heating it splite into two separate fractions
Temperature response i.e wood metal & field metals used for fire sprinklers
Uses (or) merits of phase rule
• 1. Applicable to both physical and chemical equilibria.
• 2.A convenient method to classify the equilibrium systems in terms of phases, components and degree of freedom.
• 3.Indicates that different systems having the same degrees of freedom behave similarly.
• 4. Decides whether the given number of substances remains in equilibrium or not.
• 5. Applicable to macroscopic systems without considering their molecular structures.
6. Does not consider the nature (or) amount of substances in the system
Limitations of phase rule
• 1. Phase rule can be applied only for the heterogeneous systems in equilibrium.
• 2. Only three variables like P, T & C are considered, but not electrical, magnetic and gravitational forces.
• 3. All the phases of the system must be present under the same conditions of pressure and temperature.
• 4. Solid and liquid phases must not be in finely divided state, otherwise deviations occur
Modified Adv/Disadv
Advantages/ Merits Phase rule

1 Simple approach to study equilibrium state of heterogeneous system

2 It confirmed that different system with same degree of freedom, behave similarly

3 It predicts behaviour of system towards change in T,P, Composition

4. Applicable to physical/chemical phase equilibria

5. Neglect nature of reactant and product

6. It predicts number of phases remains or not remaining in equilibrium after phase reaction

Disadvantages/Demerits Phase rule

1. Not applicable for system attain equilibrium slowly

2 Do not consider effect of electric charges, Magnetic forces, surface tension, gravitational forces

3. applicable to single equilibrium state at a time and not for other possible equilibriums

4. Phase in equilibrium must at same T,P and they should contain same chemical potential of component

5. Two phase should not finely divided state.