Conditions for different equilibria :

➢ The following conditions must be satisfied for the existence of equilibrium between various phases .
1. Thermal Equilibrium:
All phases must be in same temperature otherwise there will be a flow of heat from one phase from another phase
T = T 
2. Mechanical Equilibrium:
All the phases must be having same pressure otherwise volume of one phase will increase at the expense of other
P = P 
3. Chemical equilibrium:
The chemical potential () of a component should be same in all phases
 = 

The chemical potential tells how the Gibbs (Gibbs free energy) function will change as the composition of the
mixture changes
Phase Diagrams
A phase diagram is a graph
❖ For a one component system, the conditions of Pressure and Temperature under which two or more physical
states can exist together in a state of dynamic equilibrium (P-T diagram, generally for C = 1).

❖ For two component system, the conditions of Temperature and Composition under which two or more physical
states can exist together in a state of dynamic equilibrium (T-C diagram for C = 2).
How to construct a Phase diagram for one component system?
➢ For liquid–vapour and solid-vapour equilibrium:
➢ variation in vapour pressure can be measured by varying temperature
➢ For solid-solid and solid-liquid system:
➢ Cooling curves are recorded.
➢ Cooling curves (T of material vs time) are used to determine phase transition
temperature at various pressures
➢ Record Temperature of material as it cools from its molten state through
solidification and finally to RT (at a constant pressure w.r.to time)

➢ When cooled from its molten state, temperature decreases

➢ At freezing point temperature remines steady for a while or until the freezing
(exothermic) process is complete
➢ Get the cooling curve for various pressures
➢ Plot transition temperature as a function of pressure
Phase Diagrams
The phase rule equation F = 1 – P + 2, F = 3 – P
The phase diagram consists of Regions (Areas), Lines (Boundaries), and Points (Junction between lines)
(a) The Regions or Areas; A single phase is represented by an area (P = 1) F = 3 – 1 = 2, Bivariant
The system can be completely defined by specifying the two variables, temperature and pressure.
(b) The Lines or Curves; Two phases are in equilibrium, (P = 2)
F = 3 – 2 = 1, Monovariant
The pressure cannot be changed independently (change the temperature)
Represent conditions of equilibrium between any two phases
solid ⇄ liquid ; Melting curve or Fusion curve.
liquid ⇄ vapour: Vapour Pressure or Vaporisation curve
solid ⇄ vapour: Sublimation curve
solid ⇄ solid: phase transition curve

(c) The Triple point; Three phases (solid, liquid, vapour) can coexist in equilibrium.
(P = 3 ) F = 3 – 3 =0, F = 0, Invariant
➢ This special condition can be attained at a definite temperature and pressure.
➢ The system is, defined completely and no further statement of external conditions is necessary.
H2O (s) ⇄ H2O(l)⇄ H2O(g)
 P-T diagram
Water System (ice, liquid and water vapour)
Water Liquid
• Hence there will be three different equilibria
H2O (s) ⇄ H2O(l) H2O(l) ⇄ H2O(g) H2O (s) ⇄ H2O(g) Solid ice

• Each equilibria involve two phases.

The salient features of the phase diagram are
➢ The Curves OA, OB, OC
➢ The Triple Point O
➢ The Areas, AOC, AOB, BOC
Water Vapour
Curve OA (Vapour pressure curve): monovariant with dynamic equilibrium
• Represents the H2O(l) ⇄ H2O(g) at different Temperature
• Or the variation of vapour pressure with Temperature
• Curve OA follows Clapeyron equation
𝑑𝑃 Hvp
= ∆𝐻𝑣𝑝 = Heat of vaporisation
𝑑𝑇 𝑇 (Vg − Vl )

= Hvp
𝑃2 𝑇 −𝑇
⇒ 𝑙𝑛 [ 2 1]
𝑃1 𝑅 𝑇𝑇 2 1

• Boiling point of water lies at 100 0C, where vapour pressure of water meets 1 atm on curve OA
• Point A is the critical temp. of water is 374 0C above which liquid water does not exist
Problem 1 :At 1000C, the specific volumes of water and steam are, respectively, 1 c.c. and 1673 c.c. Calculate the change in
vapour pressure of the system by 1 oC change in temperature. The molar heat of vaporization of water in this range may be taken
as 40584.8 J mol-1.

𝑑𝑃 HVp dT = 1 oC = 1K,
=
𝑑𝑇 𝑇 (Vg − Vl ) T = 373 K
∆𝐻𝑣𝑝 = 40584.8 J mol-1
𝑑𝑇. HVp Vl = 18 cm3 mol-1 = 18x10-6 m3 mol-1
𝑑𝑃 =
𝑇 (Vg − Vl ) Vg = 18x1673 cm3 mol-1 = 302114x10-6 m3 mol-1
𝑑𝑃 = 0.003561x106 Nm-2 = 0.03561 atm

Problem 2 : The vapour pressure of water at 950C, is found to be 634 mm. what would be the vapour pressure at a temperature
of 100 0C. The molar heat of vaporization of water in this range may be taken as 40584.8 J mol -1.

= HVp
𝑃2 𝑇 −𝑇
𝑙𝑛 𝑃 𝑅
[ 2 1]
𝑇𝑇
1 2 1

P2 = 759.8 mm
Water System
Curve OC (Fusion curve): Ice and water co-exist; monovariant Water Liquid
• Represents the H2O(s) ⇄ H2O(l) at different Temperature
• Slope of OC is negative: Melting point of ice is lowered by Solid ice
increasing pressure
Pressure M. P. of ice
• Slope of OC is steep: Enormous
pressure is needed to bring about 1 atm 0 0C
significant changes 128.3 atm -1 0C

▪ Curve OC is represented by Clapeyron equation Water Vapour

𝑃2 ∆Hf 𝑇2−𝑇1
𝑙𝑛 = [ ]∆𝐻𝑓 = Heat of fusion
𝑃1 𝑅 𝑇2𝑇1

Curve OB (sublimation curve): Monovariant

• Represents the H2O(s) ⇄ H2O(g) Triple point: Nonvariant
• Its lower end extends to absolute zero ➢Curve OA, OC and OB meets at point O where three phase
co-exist
Curve OB can be represented by
➢Point O is at T = 0.0075 0C and 4.58 mm Hg
𝑃2 Hsub 𝑇2−𝑇1 ➢ If we supply heat at O more ice will melt keeping same
𝑙𝑛 = [ ]
𝑃1 𝑅 𝑇2𝑇1 T and pressure, finally T will move in OA
Hsub = Heat of sublimation ➢ If apply pressure, vapor will condense to ice or liquid
Metastable liquid state, Curve OA’
Water Liquid
➢ Very slow cooling of the liquid water results in no ice formation ⇒ the
curve AO can be extended to OA’ (a metastable equilibrium or a
Solid ice
Supercooled Liquid Vapour).
➢ The liquid can be supercooled far below the freezing point without the
separation of the crystals (Unstable Excited state with shorter life).
➢ A slight disturbance or the introduction of a seed crystal, the entire liquid
solidifies rapidly, or This system reverts to the true stable system Water Vapour
➢ The dashed curve OA' of the metastable liquid lies above the normal
sublimation curve (BO).
➢ The vapour pressure of the metastable phase is always higher
than that of the stable phase at the same temperature.

❖ Solid system approaches equilibrium very slowly

❖ Free energy considerations do not provide information about
the rate for attaining equilibrium characteristics of a particular
system”
❖ Often, metastable structures are of more practical significance
than normal (Diamond, Metal alloys)
Water System
x a
The Areas Water Liquid

c d
➢ Area AOC, BOC , AOB represents water, ice and
vapour respectively. Solid ice
b
➢ C = 1 and P = 1 for areas, F = 1 – 1 +2 ; F = 2

➢ In order to define the system at any point in the

areas, it is essential to specify both temperature and
pressure.

➢ The degree of freedom of the system is two. i.e.,

Bivariant. Water Vapour

➢ This is predicted by the phase rule

Phase Diagram of CO2 System

Dry CO2 or dry ice?

➢ The triple point (-56.4 oC, 5.11 bar) lies well above atmospheric pressure.
➢ Liquid carbon dioxide does not exist under normal conditions.

➢ Slope of melting curve is +ve

➢ The melting temperature of solid carbon dioxide rises as the pressure is increased.
➢ The critical temperature 304.2 K (31.0°C) and pressure 73 atm are readily accessible
➢ Carbon dioxide is cheap.
➢ Supercritical carbon dioxide, scCO2, is the center of attention for an increasing number of solvent-based
processes.
Polymorphism: The occurrence of the same substance in more than one crystalline forms

➢ The individual crystalline forms of an element (Compounds) are referred to as polymorphs or allotropes.
➢ Rhombic and monoclinic sulphur are two allotropes of sulphur.
➢ The allotropic forms of an element have distinct physical properties and constitute separate phases.
Allotropy can be divided into three types :
(a) Enantiotropy, (b) Monotropy and (c) Dynamic allotropy.

a. Enantiotropy
➢ One polymorphic form (or allotrope) can reversibilily change into another at a definite temperature when
the two forms have a common vapour pressure.
➢ This temperature is known as the transition temperature.
➢ One form is stable above this temperature and the other form below it.
b. Monotropy
➢ It occurs when one form is stable and the other metastable.
➢ The metastable form changes to the stable form and the change is not reversible.
➢ There is no transition temperature as the vapour pressures are never equal.

Metastable stable Stable

c. Dynamic allotropy:
Several forms which can coexist in equilibrium over a range of temperature.
➢ The amount of each is determined by the temperature.
➢ The separate forms usually have different molecular formulae but the same empirical formula.
➢ Dynamic allotropy is reversible but there is no fixed transition point.
➢ Liquid sulphur which consists of three allotropes Sµ (S8), S (S4) and S (unknown).
➢ The composition of the equilibrium mixture vary between 120ºC and 444.6ºC and there is no transition point
The Sulphur System: C=1 and maximum number of P = 4
Two solid polymorphic forms :
1. Rhombic Sulphur (SR) stable above 95.6ºC enantiotropy
2. Monoclinic Sulphur (SM) stable below 95.6ºC
3. Sulphur Liquid (SL) stable above 120 ºC
4. Sulphur Vapour (SV)

The salient features of the phase diagram are described

below.
(i) The four areas :
ABG marked ‘solid Rhombic’
BEC marked ‘solid Monoclinic’
GECD marked ‘liquid Sulphur’
ABCD marked ‘Sulphur vapour’
(ii)The six curves AB, BC, CD, BE, CE, EG
(iii) The three Triple points B, C, E
(i) The Areas
➢ The phase diagram has four areas or regions representing rhombic
sulphur, monoclinic sulphur, liquid sulphur and vapour.
➢ The areas represents the P and T conditions at which each form exist
independently
➢ These represent single phase systems which have two degrees of freedom,
F=C–P+2=1–1+2=2
➢ That is, each of the systems SR, SM, SL, and SV are bivariant.
(ii)The six curves AB, BC, CD, BE, CE, EG: All are monovariant
Curve AB: Vapour Pressure curve of Rhombic SR at different temperatures.
➢ The two phases SR  SV are in equilibrium and monovariant (sublimation curve).
➢ At a given T only one value of Vapour pressure
➢ At 95.6 oC, rhombic sulphur will change in to monoclinic sulphur (Transition T)
Curve BC: Vapour Pressure curve of SM at different temperatures
➢ SM  SV coexist in equilibrium along this curve (sublimation curve).
➢ The system SM/SV is monovariant.
➢ At 120 oC, monoclinic sulphur melts completely to liquid sulphur (melting point of SM)
Curve CD: Vapour Pressure curve of liquid sulphur at different temperatures (boiling curve).
➢ SL and SV are in equilibrium along CD.
➢ One atmosphere line meets this curve at a temperature (444.6ºC) which is the boiling point of sulphur.
Curve BE (Transition curve ): The effect of pressure on the Transition Temperature for SR and SM.
➢ Transition temperature increases with increasing pressure (+ve slope)
➢ The transformation of SR and SM is accompanied by increase of volume (density of SR = 2.04; SM = 1.9) and
absorption of heat.

𝑑𝑃 Htr
=
𝑑𝑇 𝑇 (Vf − Vi )

Curve CE (Fusion curve of SM ): Represents the effect of pressure on the

melting point of SM.
SM ⇄ SL.
➢ The melting of SM is accompanied by a slight increase of volume.
➢ The melting point will rise by increase of pressure (Le Chatelier’s
principle).
➢ The curve ends at E because SM ceases to exist beyond this point.

Curve EG, the Fusion curve for SR.

SR ⇄ SL.
➢ At high pressure, rhombic sulphur directly melts without forming monoclinic
(iii) The Triple points B, C, E
Triple point B (The transition point 95.6ºC).
➢ This is the meeting point of the three curves AB, BC and BE.
➢ Three phases, solid SR, solid SM and SV are in equilibrium at the point B.
➢ There being three phases and one component, the system SR/SM/SL is nonvariant.
F=C–P+2=1–3+2=0
At B, SR is changed to SM and the process is reversible.

Triple point C (The melting point of SM at 120ºC)

➢ The curves BC, CD, CE meet at this point.
➢ The three phases in equilibrium are SM, SL and SV.
➢ There being three phases and one component, the system SM/SL/SV is nonvariant.

Triple point E.
➢ The two lines CE and BE, having different inclinations away from the pressure axis, meet at E where a third
line EG also joins.
➢ The three phases SR, SM and SL are in equilibrium
➢ This point gives the conditions of existence of the system SR/SM/SL at 165ºC and 1290 atmospheres pressure.
(4) Metastable Equilibria
SR ⇄ SM takes place very slowly (crystal structure rearrangement).
➢ If Rhombic sulphur is heated rapidly, transition to SM will not happen

The dashed curve BF, the Vapour Pressure curve of metastable SR.
➢ BF is the continuation of the vapour pressure curve AB of stable SR.
Metastable SR ⇄ SV
➢ It is a monovariant system.
The dashed curve CF, the Vapour Pressure curve of supercooled SL.
➢ Slow cooling of sulphur liquid can avoid the formation of SM until the point F where SR starts precipitating.
Metastable (supercooled) Sliq. ⇄ SV.
➢ The curve CF meets the dashed curve BF at F.
The dashed curve FE, the Fusion curve of metastable SR.
SR ⇄ SL the system is monovariant.
➢ The melting point of metastable SR is increased with pressure.
➢ Beyond E, there is a stable equilibrium SR ⇄ SL as the metastable SR disappears.

The metastable Triple point F.

➢ At this point, three metastable phases SR, SL and SV are in equilibrium.
➢ The system is a metastable triple point with no degree of freedom.
➢ The corresponding temperature is the melting point of metastable SR (114ºC).
Phase diagram for pure substances Phase diagram for mixtures

[Water System]
[CO2 System]
[Sulphur System]

[Pb-Ag System]

[Zn-Mg System] [Na2SO4-H2O System]

[Cu-Ni System]
Two–component Or Binary Systems C = 2
➢ The phase rule become F = 2 – P + 2 = 4-P
➢ Minimum no of phase = 1, => the maximum number of degrees of freedom, F =2–1+2=3
➢ Three variables (Temperature, Pressure and Composition) must be specified in order to describe the condition
of the phase
3D ➢ For condensed system, measurements of Temperature and composition (Mole
diagram fraction)is done at atmospheric pressure (P is constant)

➢ For a solid/liquid equilibrium, the gas phase in

usually absent (condensed system)
➢ The effect of pressure on the equilibrium is very
small

F’ = C-P + 1➔ Reduced Phase Rule

The reduced phase rule for two component system
F’ = 2-P + 1 In Binary systems,
❖ Simple Eutectic (Isomorphous) system
F’ = 3-P
❖ Systems that forms a stable Compound
Construction of Phase diagram by Thermal analysis (or) cooling curve
➢ Cooling curves of various compositions of a system during solidification is studied.
➢ A molten liquid with two components (A and B) is cooled slowly
➢ At Temperature ‘b’ one substance (A or B) begins to solidify (exothermic) out of the melt
➢ A break is indicated by change of the rate of cooling (different heat capacities)

➢ Further cooling, second compound also begins to solidify

(break point ‘c’).
➢ The temperature remains constant until the liquid melt gets
completely solidify, which forms the eutectic mixture
The temperature of horizontal line ‘cd’ gives the temperature of the eutectic.
Minimum temperature at which A+B exist as liquid
Cooling curve of a mixture of varying composition
➢ Freezing commence at different temperatures for different mixtures which
differ in composition
➢ The main phase diagram =>
➢ The compositions in X-axis and Temperature (point b) in Y-axis.
➢ Any point on the line indicates the appearance of solid phase from the
liquid.
➢ The area above this curve is only liquid phase.
Cooling curve of six alloys of different compositions

Time (t)
➢ The liquidus is the line above which the entire sample is liquid
➢ The solidus is the line below which the sample is entirely solid.

➢ The fusion temperature and the liquidus and solidus temperature (Y axis) are then plotted as a function
of composition (X-axis)to form the phase diagram
1. Simple Eutectic Isomorphous (easy melting) system-
➢ Two elements are completely miscible in each other in liquid and solid state
➢ Both pure materials have same crystal structure
➢ Atoms have similar radii
➢ Similar electronegativity (otherwise may form a compound instead)
➢ Solute should have higher valence Eg: Pb-Ag, Pb-Sn, Pb-Mg, Ag-Au, Zn -Cd etc.
The phase diagram of 2-component condensed system
Reduced phase rule F’ = 2-P + 1 = 3-P

The phase diagram consists of

➢ Regions (Areas), One phase
F’ = 3-P = 3-1 ➔ bivariant
➢ Lines (Bounderies), Two phases
F’ = 3-P = 3-2➔ univariant
➢ Point (Junction between lines), Three phases
F’ = 3-3➔ nonvarient
The Ag–Pb System The phase diagram of Ag/Pb system.

➢ This system has two components and four phases.

➢ Solid silver(M.P. 961 oC) and Solid lead (M.P. 327 oC)
➢ Solution of molten silver and lead
➢ Vapour. (The boiling points of silver and lead being
considerably high, the vapour phase is practically absent)
➢ Thus Ag/Pb is a condensed system with three phases and P is
constant.
➢ Only the two remaining variables, Temperature (T) and
Concentration (C).

The salient features of the diagram are :

(a) Two curves, AC and BC
(b) Eutectic point, C (At 303 0C with a composition 2.5% Ag in Pb)
(c) Three areas : (i) above ACB; (ii) below AC; (iii) below BC
The Ag–Pb System The phase diagram of Ag/Pb system.

Curve AC; Freezing point curve of Ag.

➢ The point A represents the freezing point of Ag (961 oC) .
➢ The freezing point of Ag falls by the addition of Pb along AC.
➢ Thus along AC, the solid Ag is in equilibrium with the liquid
solution of Pb in Ag. F’ = 3-2= 1, Univariant

Curve BC; Freezing point curve of Pb

➢ The point B shows the freezing point of Pb (327 oC).
➢ Curve BC exhibits the fall of freezing point by the addition of Ag to Pb.
➢ Along BC, solid Pb is in equilibrium with the liquid solution of Ag in Pb.
➢ The degree of freedom is one i.e., both equilibria are monovariant.
The Eutectic point C Reduced phase rule F’ = C-P + 1
(easy melting at 303 oC with 2.5% Ag in 97.5% Pb).

➢ At C, solids Ag and Pb (of composition 2.5Ag in 97.5 Pb) is in

equilibrium with the solution phase having same composition.
➢ The number of phases is 3 and the reduced phase rule become,
F' = C – P + 1 = 2 – 3 + 1 = 0, nonvariant.
➢ The temperature corresponding to C gives the lowest
temperature TE (303o C )where the mixture of Ag and Pb melts
➢ The point C is therefore, called the Eutectic temperature (TE)
and corresponding composition is the eutectic composition (CE)

The eutectic mixture, although it has a definite melting point, is not to be regarded as a compound.
(i) The components are not in stoichiometric proportions
(ii) Eutectic solid is a two-phase system
(iii)It crystallizes out in a nearly homogeneous mixture of microcrystals and
(iv) X-ray diffraction studies reveal the existence of separate crystals of the components.
The Areas Reduced phase rule F’ = C-P + 1
The Area above the line AC and BC.
➢ The two components Ag and Pb are present as liquid solutions of Z
varying compositions.
➢ A homogeneous solution of Ag and Pb constitutes one phase only.
F = C – P + 1 = 2 – 1 + 1 = 2, Bivariant
➢ To define the system at any point in this area, both temperature and
composition have to be specified.
The Areas between AC and TE line: - univariant
➢ Two phases exist viz., solid Ag and solution of varying
composition of Ag and Pb
➢ Below TE line no liquid can exist, the entire area below this line
would represent the system solid Ag and solid Pb (univariant) x
Effect of Cooling
➢ A solution of Ag and Pb at point (X) in the area ➢ If the solution just above the eutectic point is cooled (Z), a
above ACB is cooled, the cooling dashed line meets solid mixture (eutectic mixture) of eutectic composition CE,
the curve AC at Y (composition x). will be obtained.
➢ Solid Pb separates and the equilibrium shifts down along the curve YC till the eutectic point and then solid Ag
starts to separate along with a eutectic mixture.
Pattinson’s Process for the Desilverisation of Argentiferous Lead –
This process of recovery of silver from argentiferous lead (0.1% Ag in Pb)
Applications of Eutectic systems
Safety fuses, Safety plugs, Fire alarms, Pressure cooker valves
➢ Wood metals melts at 75 0C - Eutectic alloy of 50% bismuth, 26.7% lead, 13.3% tin, and 10% cadmium by
mass.
➢ Rose's metal consists of 50% bismuth, 25–28% lead and 22–25% tin. (Melting point is between 94 and 98
°C). The alloy does not appreciably contract or expand on solidification because of the presence of Bismuth
(https://www.chemistrylearner.com/rose-metal.html#google_vignette)
Solder
➢ Pb-Sn solder (37-67% of Pb, 31-60% of Sn and Sb in 0.12- 0.2% (used in soldering electrical connection)
➢ Brazing alloy Sn-92%, Sb-5.5% and Ca-2.5 % (used in tinning)
➢ Tin man’s solder Sn-66% and Pb- 34% (used in soldering electrical connection)
➢ Plumber solder Sn-50% and Pb- 50%

Examples of some other Eutectic systems

➢ NaCl (801 oC) and water (5 oC) form a eutectoid when
the mixture is 23.3% salt by mass with a eutectic point
at -21.2 oC.
➢ The system is used to melt ice and snow.