PHASE EQUILIBRIA

Notes on

PHASE EQUILIBRIA
Physical Chemistry
B.Sc.III (SEM VI)

Dr. Megha U. Patil

DR. MEGHA U. PATIL

DEPARTMENT OF CHEMISTRY
PDVP COLLEGE TASGAON

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Notes provided by-Dr. Megha Patil, Assist. Prof. Department of chemistry, PDVP COLLEGE
 PHASE EQUILIBRIA

Table of Contents
INTRODUCTION ..................................................................................................................... 3
DEFINITIONS ....................................................................................................................... 4
System .................................................................................................................................... 4
Equilibrium ........................................................................................................................ 4
True Equilibrium ................................................................................................................ 4
Metastable Equilibrium: ..................................................................................................... 4
PHASE RULE: .......................................................................................................................... 5
PHASE (P): ............................................................................................................................ 5
a) Gaseous phase (g): ......................................................................................................... 5
(b) Liquid Phase (l): ........................................................................................................... 5
(c) Solid Phase (s): ........................................................................................................ 6
COMPONENT (C): ............................................................................................................... 6
DEGREE OF FREEDOM (F) ................................................................................................ 7
One Component system ............................................................................................................. 8
Water system .......................................................................................................................... 8
Sulphur System: ....................................................................................................................... 11
TWO–COMPONENT SYSTEMS ........................................................................................... 15
The Silver–Lead System .......................................................................................................... 15
Ferric Chloride -water system .............................................................................................. 17
KI water system ................................................................................................................... 20
Three Component System ........................................................................................................ 21
Objective Questions ................................................................................................................. 25

After study this unit you should able to,

• Explain Phase, Phase rule

• Draw and explain Phase diagram.

• Elucidate one component system, two component systems two component alloy

system (or) multi component equilibria, Reduced phase rule (or) condensed
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system

Advantages of Phase Rule :

• Phase rule is applicable to both Chemical and Physical equilibriums.

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• • Phase rule is applicable to macroscopic systems and hence no information is

required regarding molecular or micro structure.

• • We can conveniently classify equilibrium states in terms of phases, components

and degrees of freedom

INTRODUCTION
For a system at equilibrium the phase rule relates:

P = number of phases that can coexist, to

C = number of components making up the phases, and
F = degrees of freedom.
Where these three variables are related in the equation
P+F=C+2
The degrees of freedom represent the environmental conditions which can be
independently varied without changing the number of phases in the system.
Conditions include:
▪ Temperature
▪ Pressure
▪ Chemical Composition

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DEFINITIONS
System: An assemblage of materials that is isolated in some manner from rest of the
universe.

• isolated system: one that does not exchange matter or energy with its
surroundings.
• closed system: one that exchanges only energy with its surroundings.
• open system: one that exchanges both matter and energy with its surroundings.
Equilibrium: The lowest energy state of a system in which there is no tendency for a
spontaneous change.
True Equilibrium: In any system same state is obtained by approach from any
direction.
e.g. ice(s) ⇔ water(l)
At given pressure the temperature at which two phases are in equilibrium is the
same (at 1atm pressure and 0℃) irrespective of the fact that weather equilibrium is
obtained by partial melting of ice or partial freezing of water, system thus exist in true
equilibrium.

Metastable Equilibrium:
state of a equilibrium can be obtained by careful approach from one direction.
It is possible to obtain water at -4℃ by careful colling of water. It is not possible to
have water at -4℃ by melting of ice.

All chemical reactions are broadly classified into 2 types:

1) Irreversible Reactions:
Zn + H2SO4 −−−−−> ZnSO4 + H2↑
2) Reversible reactions:
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(a) Homogeneous reversible reactions

Eg: N2(g )3H2(g) 2NH3(g)

(b) Heterogeneous reversible reactions

Eg: CaCO3(s) CaO(s) + CO2(g)

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The reversible reactions are represented by 2 arrows in the opposite directions.

The homogeneous reversible reactions can be studied by the law of mass action and
the heterogeneous reversible reactions using the phase rule, given by Willard Gibbs
(1874) which is defined as,

PHASE RULE:
If the equilibrium between any numbers of phases is
not ‘influenced by gravitational/electrical/ magnetic forces but is
influenced by pressure, temperature and concentration, then the number of degrees of
freedom (F) is related to the number of components (C) and the number of phases (P)
as:
F=C−P+2
Explanation of terms with examples
PHASE (P):
PHASE is defined as, ―any homogeneous physically distinct and mechanically
separable portions of a system which is separated from other parts of the system by
definite boundaries.
a) Gaseous phase (g):
All gases are completely miscible and have no boundaries between them.
Hence all gases constitute a single phase.
Eg: Air, a mixture of O2, H2, N2, CO2 and water vapor, etc., constitutes a single
phase.
(b) Liquid Phase (l):
The number of liquid phases depends on the number of liquids present and their
miscibility’s.

(i) If two liquids are immiscible, they will form two separate liquid phases. (e.g.)
Benzene – Water system.
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(ii) If two liquids are completely miscible, they will form only one liquid phase.
(e.g.) Alcohol - Water system.

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(c) Solid Phase (s):

Every solid constitutes a separate single phase. (e.g.) Decomposition of CaCO3
CaCO3(s) CaO (s) + CO2(g)
It involves 3 phases namely solid CaCO3, solid CaO and gaseous CO2 Other examples:
1) A water system has 3 phases namely one solid, one liquid and one gaseous phase.
Ice(s) Water(l) Vapour(g)
2) A solution of a substance in a solvent constitutes only one phase. (e.g.) Sugar
solution in water.

3) An emulsion of oil in water forms two phases

4) MgCO3 (s) MgO (s) + CO2 (g)

It involves 3 phases, solid MgCO3, solid MgO and gaseous CO2.

5) Rhombic sulphur (s) −−−−> Monoclinic sulphur (s). It forms 2 phases.

6) Consider the following heterogeneous system.

CuSO4(s) + 5H2O (l) CuSO4 . 5H2O (s)

It involves 3 phases namely, 2 solids and 1 liquid phase.

COMPONENT (C):
Component is defined as, ―the minimum number of independent variable
constituents, by means of which the composition of each phase can be expressed in the
form of a chemical equation.
Examples:
(a) Consider a water system consisting of three phases.
Ice(s) Water(l) Vapour(g)
The chemical composition of all the three phases is H2O.
Hence the number of components is one.
(b) Sulphur exists in 4 phases namely rhombic, monoclinic, liquid and vapour, but the
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chemical composition is only sulphur. Hence it is a one component system.

(c) Thermal decomposition of CaCO3
CaCO3s) CaO (s) + CO2(g)

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The system has 3 phases namely, solid CaCO3, solid CaO and gaseous CO2and 2
components, as the composition of each of the above phases can be expressed as
equations considering any two of the three components present. When CaCO3and CaO
are considered as components, the chemical equations are:

Phase Components
CaCO3 CaCO3 + 0CaO
CaO 0CaCO3 + CaO
CO2 CaCO3 − CaO

(d) PCl5(s) ⇔ PCl3(l) + Cl2(g)

This system has 3 phases and 2 components namely, PCl3 and Cl2.

(e) An aqueous solution of NaCl is a two-component system.

The constituents are NaCl and H2O.

(f) CuSO4. 5H2O(s) CuSO4. 3H2O(s) + 2H2O(g)

It is also a two-component system as components are CuSO4.3H2O and H2O. (g)
In the dissociation of NH4Cl, the following equilibrium occurs.
NH4Cl (s) NH3 (g) + HCl (g)
The system consists of 2 phases namely solid NH4Cl and the gaseous mixture
containing NH3 + HCl.
When NH3and HCl are present in equivalent quantities the composition of both
the phases can be represented by NH4Cl and hence the system will be a one component
system.
DEGREE OF FREEDOM (F)
Degree of freedom is defined as, ―the minimum number of independent
variable factors like temperature, pressure and concentration, which must be fixed in
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order to define the system completely‖.

A system having 1, 2, 3 or 0 degrees of freedom are called as univariant,
bivariant, trivariant and non-variant systems respectively.
Examples:

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(a) Consider the following equilibrium

Ice(s) Water(l) Vapour(g)
These 3 phases will be in equilibrium only at a particular temperature and
pressure.
Hence, this system does not have any degree of freedom, so it is non-variant (or) zero-
variant (or) in-variant system.
(b) Consider the following equilibrium
Liquid Water(l) Water- vapour(g)
Here liquid water is in equilibrium with water vapour. Hence any one of the
degrees of freedom such as temperature (or) pressure has to be fixed to define the
system. Therefore, the degree of freedom is one.
(d) For a gaseous mixture of N2 and H2, both the pressure and temperature must be
fixed to define the system. Hence, the system is bivariant.
One Component system
Water system

Draw and Explain neat labelled phase diagram for water system

Dr. Megha U. Patil

Phases:
The water system consistes of three phases-

ICE(S) WATER(L) WATERVAPOUR (g)

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Since H2O is the only chemical compound involved.

Therefore it is single or one component system.

From phase rule, when c=1;

F=c−p+2=1−P+2=3−PF=c−p+2=1−P+2=3−P
ie the degree of freedom depends on the number of phase present at equilibrium

The three different cases are possible

1)P=1;F=2 (bivariant system)

2) P=2;F=1 (univariant system)

3) P=3;F=0 (invariant system)

From above, It is clear that for any one component system, the maximum number of
degrees of freedom is two

Such a system can be represented completely by a two dimensional diagram.

The most convenient variables are the pressure and temperature.

Curve:

1. OC Ice & Water

2. OA Water & Vapor F=1−2+2=1F=1−2+2=1
3. OB Ice and Vapor (univariant)

Metastable Curve:
A) Ice & Water F=1−2+2=1F=1−2+2=1 (univariant)
i)Curve OA−−−−−−−−Curve OA_: It is vaporization curve. The curve OA terminates
at A.Its critical point is 218atm. & temperature is 374∘c374∘c.It represents vapor
pressure of liquid at different temperatures.
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Two phases water & water vapors consists coexist in equilibrium along the curve
p=2,c=1.

.....F=C−P+2=1−2+2=1F=C−P+2=1−2+2=1 ..... univariant

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Vapor pressure is 1 atm. The corresponding temperature in degree centigrade is the

Boiling point of water i.e.1000C

ii).Curve OB−−−−−−−−Curve OB_:It is sublimation curve. The curve OB terminates

at B, the absolute zero -2730C temperature. It shows vapor pressure of solid ice at
different temperature.
The two phase's solid-ice & water-vapor coexist in equilibrium.

.....F=1 & system is monovariant.

iii). Curve OC−−−−−−−−:Curve OC_: It is Fusion curve.

The curve OC terminates at C, the critical pressure.

The two phase's solid-ice & liquid-water coexist in equilibrium. The curve indicates
melting point of Ice decreases with increases in pressure. At one atm. Line meets the
curve at 0∘c0∘c. ....F=1 & system is monovariant.
Areas:

1. BOC Ice
2. COA Water F=1−1+2F=1−1+2 (bivariant)
3. AOB Vapor

The area AOC, AOB & BOC The curve or areas between the curves show the conditions
at temperature & pressure under which a single phase i.e, ice, water & water vapor is
capable of stable existence.

AOC-Represent liquid phase....F=C−P+2F=C−P+2

AOB-Gaseous phase =1−1+2=1−1+2
BOC-Solid phase =2

Hence each system has two degree of freedom i.e. system is bivariant or divariant.
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Point Point:
O Triple Point Ice, Water & Vapor F=1−3+2=0F=1−3+2=0 (invariant
TRIPLE POINT:All the three curve OA, OB & OC meet at pt O called as triple point,
where all the three phases solid, liquid & vapor are in simultaneously in equilibrium.
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The triple point occurs at 0.0075∘c0.0075∘c & 4.58 mm Hg pressure.

Since there are three phases & one component,

.......F=C−P+2=1−3+2=0F=C−P+2=1−3+2=0 ....system is zero variant.

METASTABLE CURVE OA:
This curve is also known as super coding (water/vapors)curve.

This is extension of curve OA i.e. vapors pressure curve. That is, water can be super
cooled by eliminating solid particles carefully which includes crystallization. The super
cooled water system is unstable i.e. metastable,

The metastable vapor pressure of super cooled water is higher than vapor pressure of
ice.

APPLICATIONS:
1. In one component system the equilibrium condition may be represented with the
help of diagram taking pressure & temperature as two areas. The diagram is
called as pressure-temperature diagram.

2. In this diagram any line or curve represents a univariant system because

equilibrium conditions at any point on line could be completely defined by just
fixing either pressure or temperature.

3. All areas represent bivariant system because to define the system completely, at
any point in the area, both temperature & pressure should be fixed.

Sulphur System:
It is a one-component, four-phase system. The four phases are :
(a) Two solid polymorphic forms :
(i) Rhombic Sulphur (SR)

(ii) Monoclinic Sulphur (SM)

(b) Sulphur Liquid (SL)
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(c) Sulphur Vapour (SV)

All the four phase can be represented by the only chemical individual ‘sulphur’ itself
and hence one component of the system.
The two crystalline forms of sulphur SR and SM exhibit enantiotropy with a
transition point at 95.6ºC. Below this temperature SR is stable, while above it SM is

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Notes provided by-Dr. Megha Patil, Assist. Prof. Department of chemistry, PDVP COLLEGE
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the stable variety. At 95.6ºC each form can be gradually transformed to the other and
the two are in equilibrium. At 120ºC, SM melts.
Thus,

The phase diagram for the sulphur system is shown in Fig. The salient features of the
phase diagram are described below.
(i) The six curves AB, BC, CD, BE, CE, EG
(ii) The three Triple points B, C, E (iii) The four areas :
ABG marked ‘solid Rhombic’
BEC marked ‘solid Monoclinic’
GECD marked ‘liquid Sulphur’
ABCD marked ‘Sulphur vapour’
Let us now proceed to discuss the significance of these features :
(1) The curves AB, BC, CD, BE, CE, EG
These six curves divide the diagram into four areas.
Curve AB, the Vapour Pressure curve of SR. It shows the vapour pressure of solid
rhombic sulphur (SR) at different temperatures. Along this curve the two phases SR and
sulphur vapour (SV)
are in equilibrium. The system SR/SV has one degree of freedom,
F=C–P+2=1–2+2=1
i.e., it is monovariant.

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Notes provided by-Dr. Megha Patil, Assist. Prof. Department of chemistry, PDVP COLLEGE
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Curve BC, the Vapour Pressure curve of SM. It shows variation of the vapour pressure
of monoclinic sulphur (SM) with temperature. SM and SV coexist in equilibrium along
this curve. The system SM/SV is monovariant.
Curve CD, the Vapour Pressure curve of SL. It depicts the variation of the vapour
pressure of liquid sulphur (SL) with temperature. SL and SV are in equilibrium along CD.
The two phase system SL/SV is monovariant. One atmosphere line meets this curve at a
temperature (444.6ºC) which is the boiling point of sulphur.
Curve BE, the Transition curve. It shows the effect of pressure on the transition
temperature for SR and SM. As two solid phases are in equilibrium along the curve, the
system SR/SM is monovariant.
Curve CE, the Fusion curve of SM. It represents the effect of pressure on the melting
point of SM. The two phases in equilibrium along this curve are SM and SL. The system
SM/SL is monovariant. Thus the curve CE slopes slightly away from the pressure axis.
The curve ends at E because SM ceases to exist beyond this point.

Curve EG, the Fusion curve for SR. Here the two phases in equilibrium are SR and SL.
The number of phases being two, the system SR/SL is monovariant.
(2) The Triple points B, C, E
Triple point B. 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. Thus the temperature
corresponding to B is the transition temperature (95.6ºC).
Triple point C. 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
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nonvariant. The temperature corresponding to C as indicated on the phase diagram is

120ºC. This is the melting point of SM.
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
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SL are in equilibrium and the system at the point E is nonvariant. This point gives the
conditions of existence of the system SR/SM/SL at 155ºC and 1290 atmospheres pressure.
(3) The Areas
The phase diagram of the sulphur system has four areas or regions. These are labelled
as rhombic sulphur, monoclinic sulphur, liquid sulphur and vapour. 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.
(4) Metastable Equilibria
The change of SR to SM takes place very slowly. If enough time for the change is not
allowed and SR is heated rapidly, it is possible to pass well above the transition point
without getting SM. In that case, there being three phases (SR, SL, SV) only and one
component, the phase diagram, like that of water system, will consist of three curves,
one triple point and three areas.
The dashed curve BF, the Vapour Pressure curve of metastable SR. This is a
continuation of the vapour pressure curve AB of stable SR. The metastable phases SR
and SV are in equilibrium along this curve. It is a monovariant system.
The dashed curve CF, the Vapour Pressure curve of supercooled SL. On
supercooling liquid sulphur, the dashed curve CF is obtained. It is, in fact, the back
prolongation of DC. The curve CF represents the metastable equilibrium between
supercooled SL and SV. Thus it may be designated as the vapour pressure curve of
supercooled SL. It meets the dashed curve BF at F.

The dashed curve FE, the Fusion curve of metastable SR. The two metastable phases
SR and SL are in equilibrium along this curve and the system is monovariant. This shows
that the melting point of metastable SR is increased with pressure. Beyond E, this curve
depicts the conditions for the stable equilibrium SR/SL as the metastable SR disappears.
The metastable Triple point F. At this point, three metastable phases SR, SL and SV
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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).

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TWO–COMPONENT SYSTEMS
When a single phase is present in a two-component system, the degree of freedom is
three, F = 2 – 1 + 2 = 3 This means that three variables must be specified in order to
describe the condition of the phase.
Thus in such a system, in addition to pressure and temperature the concentration of one
of the components has also to be given.
For graphic representation of these variables, three coordinate axes at right angles to
each other would be required.
Therefore the phase diagram obtained would be a solid model. For the sake of having
simple plane diagrams we generally consider only two variables, the third one being a
constant.
For example, for a solid/liquid equilibrium, the gas phase in usually absent and the
effect of pressure on the equilibrium is very small.
Thus when a two-component system consists of solid and liquid phases only, the effect
of pressure may be disregarded.
Then it is necessary to take into account the remaining variables viz., temperature and
concentration. Such a solid/liquid system with the gas phase absent is called a
condensed system.
The experimental measurements of temperature and concentration in condensed
systems are usually carried out under atmospheric pressure. Since the degree of freedom
in such a case is reduced by one, we may write the Reduced Phase rule as F' = C – P +
1 where F' gives the remaining degrees of freedom of the system.
The reduced phase rule is more convenient to apply to solid/liquid two-component
condensed system. Since the only variables for two-component solid/liquid systems are
temperature and composition, the phase diagrams for such systems consist of
Temperature-Concentration graphs (TC graphs).
Dr. Megha U. Patil

The Silver–Lead System

This system has two components and four phases. The phases are : (i) solid silver; (ii)
solid lead; (iii) solution of molten silver and lead; and (iv) vapour. The boiling points
of silver and lead being considerably high, the vapour phase is practically absent. Thus

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Ag/Pb is a condensed system with three phases. In such a case, pressure can have no
effect on the system. Therefore we need consider only the two remaining variables,
namely the temperature (T) and concentration (C). The complete TC diagram of the
system Ag/Pb is shown in Fig

The salient features of the diagram are : (a) Two curves, AC and BC (b) Eutectic point,
C (c) Three areas : (i) above ACB; (ii) below AC; (iii) below BC Curve AC; the
Freezing point curve of Ag. A represents the freezing point or melting point of solid
silver (961ºC) and the curve AC shows that the addition of lead lowers the melting point
along it. The phases in equilibrium along AC are solid silver and solution of silver and
lead. Applying the reduced phase rule equation F' = C – P + 1 = 2 – 2 + 1 = 1 Thus the
system Ag/solution is monovariant. Curve B; the Freezing point curve of Pb. B
represents the melting point of solid lead (327ºC) and the curve BC shows that the
melting point is lowered by addition of silver. The phases in equilibrium along BC are
solid lead and solution. The system is monovariant. The Eutectic point C. The curves
AC and BC intersect at C, which is called the eutectic point. Here three phases solid
Ag, solid Pb, and solution are in equilibrium. Applying the reduced phase rule equation
F' = C – P + 1 = 2 – 3 + 1 = 0 Thus the system Ag/Pb/solution at C is nonvariant. Both
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the variables, temperature (303ºC) and composition (97.5% Pb, 2.5% Ag) are fixed. If
you raise the temperature above the eutectic temperature, the solid phases Ag and Pb
disappear and if you cool below it, you will land in the solid Ag/Pb area where solution
phase is nonexistent. The Area above AOC. This region represents the single phase

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 PHASE EQUILIBRIA

system, the solution of molten Ag and Pb. Applying the reduced phase rule equation,
we have F' = C – P + 1 = 2 – 1 + 1 = 2 Thus the system solution Ag/Pb is bivariant. The
area below AC represents the phases Ag + solution, while that below BC the phases Pb
+ solution. The area below the temperature 303º, represents solid Ag + solid Pb. All
these areas
temperature (– 22.0ºC). Alternatively, we may start with a concentrated solution of the
salt represented by point X on the phase diagram. As we withdraw heat by adding ice,
we travel along the dashed line XY. At Y which lies on the solubility curve BO, the
solution becomes saturated with the salt. On further withdrawing heat, we go along with
the curve BO until the eutectic point is reached. Thus the same minimum temperature
can be attained with a freezing mixture, whether we add salt to ice or ice to salt solution.
The eutectic temperatures of some salt/ice systems are listed below.

Ferric Chloride -water system

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KI water system

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Three Component System

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Objective Questions

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