UNIT-V

Phase equilibria, Nanomaterials and Instrumental methods of analysis

Phase equilibria – Gibbs phase rule; Concept of Phase component, degrees of freedom with examples;
Numericals. Application of Phase rule to i) one component system - water system; ii) two component
system - Pb-Ag system; Freezing mixtures - NaCl-water system
Nanomaterials - Introduction, size dependent properties (Surface area, Electrical, Optical, Catalytic and
Thermal properties). Synthesis of nanomaterials: top down and bottom-up approaches; Synthesis by sol-
gel and chemical vapor deposition methods. Nanoscale materials: Graphene and Carbon nanotubes -
properties and applications.
Instrumental methods of analysis - Principle, Instrumentation, and applications of Colorimetry
(Copper), Flame Photometry (Sodium), Potentiometry (Iron).
Self-study: Conductometry (mixture of strong acid and a weak acid with a strong base, strong acid with
strong base, weak acid with strong base)

UNIT-V: PHASE EQUILIBRIA

PHASE RULE

The Gibbs phase rule is a mathematical equation that relates the number of degrees of
freedom, number of components and number of phases. The equation was set up by
Gibbs in 1876 based on principles of thermodynamics. The Gibbs phase rule can be
stated as:

“If the equilibrium between any number of phases is not influenced by gravity, or electrical, or
magnetic forces, or by surface action but are influenced only by temperature, pressure and
concentration, then the number of degrees of freedom (F) of the system is related to the number of
components (C) and number of phases (P) by the following phase rule equation:

P+F=C+2

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Explanation of the terms involved in the phase rule

Phase (P): A phase is a homogeneous part of the system which is mechanically

separable and remains physically indistinct from the rest of the system.

Examples

1) A gaseous mixture will constitute one phase only.

2) If two liquids are immiscible (e.g., oil and water), they will constitute two separate
phases.

3) Two miscible liquids (e.g., water and alcohol) constitute one phase only.

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) At triple point, water consists of three phases.

6) Calcium carbonate decomposes as follows:

The above equilibrium has three phases (two solid and one gaseous)
7) Similarly, there are two solid phases, Fe and FeO and one gaseous phase consisting of
H2O(g) and H2(g). Hence, there are three phases in equilibrium.

Components (C): Component is the minimum number of independent constituents

necessary to define the composition of all the phases present in the system.
Examples
1) Water system has three phases.

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Each of these phases is a different physical form of the same chemical compound
represented by H2O. Hence, it is a one-component system.
2) 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.
3) In the dissociation of NH4Cl in a closed vessel, the following equilibrium occurs.

The system consists of two phases, viz., solid NH4Cl and homogenous gaseous mixture
consisting of NH3 and HCl. An equimolar mixture of NH3 and HCl in the vapour phase
may be regarded as NH4Cl in the vapour state, and hence it is a one-component system.
Addition of NH3 or HCl to the system makes it a two-component system because the
composition of the vapour phase can no longer be described by NH4Cl alone.

Degrees of Freedom (F): It is the smallest number of independent variables namely,

temperature, pressure and composition, which have to be fixed to specify the state of a
system. It is also called as variance.
Examples
1) In water system when all the three phases i.e., ice, water and water vapour, are in

equilibrium , the degree of freedom is zero and

the system is said to be invariant or non-variant. This is because the three phases coexist
at the triple point of water where the temperature and pressure are automatically fixed
and there is no need to specify any variable.

2) When , the degree of freedom is one and the system is

univariant. Only one variable, either temperature or pressure is to be specified to define
the position of the system because on specifying one variable the other automatically
becomes fixed.

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APPLICATION OF PHASE RULE
One-component system
Consider a one component system (C = 1) consisting of one phase (P = 1). Then, from
the phase rule,
F=C–P+2=1–1+2=2
Consider a one component system (C = 1) consisting of two phase (P = 2). Then, from
the phase rule,
F=C–P+2=1–2+2=1
Consider a one component system (C = 1) consisting of three phase (P = 3). Then, from
the phase rule,
F=C–P+2=1–3+2=0
Thus it can be seen that for a one component system,
i. With one phase, the system is bivariant.
ii. With two phases, the system is univariant.
iii. With three phases, the system is invariant.
iv. More than three phases cannot co-exist.
Phase Diagram
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.

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Phase Diagram for Water
The water system is a one-component system. It consists of three phases: ice, water and
water vapour. All these are represented by one chemical entity (H2O); hence C = 1.

The maximum number of degrees of freedom is two, hence, the phase diagram can be
conveniently represented by a two-dimensional diagram on paper using pressure and
temperature as variables.

Figure 1: Phase Diagram of Water System

The phase diagram consists of

1. Curves: OA, OB and OC
2. Areas: AOC, BOC and AOB
3. Points: O and A
4. Metastable curve

Curves: There are three curves in the phase diagram. Two phases exist in equilibrium
along each of these curves. Hence, according to the phase rule equation

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F = C – P + 2 = 1 – 2 + 2 = 1 (univariant or monovariant)
The system is univariant along each of these curves which means that to locate the
position of any point along these curves, only one variable, either pressure or
temperature needs to be specified. The various curves in the phase diagram are as
follows:
i. Curve OA: This curve is known as the vapour pressure curve of water or
vaporization curve. Along this curve, liquid water and water vapour coexist in
equilibrium. The curve has its upper limit at temperature 374 °C and pressure
218 atm. This is the critical point beyond which the liquid phase merges into the
vapour phase and they are no longer distinguishable from each other.
ii. Curve OB: This curve is known as the sublimation curve of ice. Two phases, ice
and its vapour, coexist in equilibrium along this curve. The lower limit of this
curve is –273 °C beyond which the vapour phase does not exist.
iii. Curve OC: This curve is known as the fusion or melting curve of ice. Two
phases, ice and water, coexist in equilibrium along this curve. The curve slopes
towards the pressure axis which means that the melting point of ice decreases
with the increase in pressure.

Areas: The phase diagram consists of three areas: BOC, AOC and AOB consisting of ice,
liquid water and water vapour, respectively. All these three areas consist of a single
phase only. Hence, according to the phase rule equation
F = C – P + 2 = 1 – 1 + 2 = 2 (bivariant)
The system in each of these areas is bivariant which means that to locate the position of
any point in these areas, it is essential to specify both the variables, that is, temperature
and pressure.
Triple Point: The point O where all the three curves meet is known as the triple point.
At the triple point, all the three phases, ice, water and water vapour, exist in
equilibrium. Hence, at O, the value of P = 3. According to the phase rule equation
F = C – P + 2 = 1 – 3 + 2 = 0 (invariant or non-variant)

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The degree of freedom at O is zero. The equilibrium is attained at a specific temperature
and pressure (0.0098 °C and 4.58 mm pressure). If either pressure or temperature is
varied even slightly, then at least one of the phases will disappear and all the three
phases will no longer coexist.

Metastable Curve OA': The dotted line OA' is the continuation of the vaporization
curve OA and represents the vapour pressure curve of supercooled water. This
equilibrium is said to be metastable because it can be achieved only by carefully cooling
water below O. This state cannot be achieved by the fusion of ice. Moreover, if an ice
crystal is added to this system, then immediate solidification occurs and the
temperature rises to 0 °C.

Two-component System
In a two-component system (C = 2), the degree of freedom of a two-component system
is given by
F=C–P+2
F=2–P+2=4–P
When P = 1, the degree of freedom has the highest value.
F=C–P+2
F=2–1+2=3
It means that three variables—temperature, pressure and composition are required to
explain the system completely. Such a three-dimensional diagram cannot be expressed
conveniently on paper. In the solid–liquid equilibrium of an alloy, usually the gas phase
is absent and the effect of pressure on the system is so small that it is neglected. Such
solid–liquid equilibrium with the gas phase absent is termed as the condensed system.
This will reduce the degree of freedom by one and for such a system, the phase rule
becomes
F=C–P+1

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This is known as the reduced or condensed phase rule and is widely applicable to solid–
liquid two component systems. The solid–liquid equilibria are represented on
temperature–composition diagrams.

Lead-Silver System
Lead–silver system is an example of a simple eutectic system. A eutectic system is a
homogeneous mixture of substances that melts or solidifies at a single temperature
lower than any of the constituents' melting points. This temperature is known as the
eutectic temperature, and it is the lowest feasible melting temperature for the included
component species for all mixing ratios. When molten silver and molten lead are mixed
together in all proportions, a single homogenous solution is formed without forming
any compound. The system consists of four phases:
(i) Solid silver
(ii) Solid lead
(iii) Solution of molten silver and lead
(iv) Vapour

Figure 2: Phase Diagram of Pb-Ag system

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1) Curves: Addition of Pb to pure Ag lowers the melting point of Ag; similarly, addition
of Ag to pure Pb lowers the melting point of Pb.
Curve AO: It represents the melting of Ag on gradual addition of Pb. Along this curve,
solid Ag and solution of lead and silver are in equilibrium.
Curve BO: It represents the melting of Pb on gradual addition of Ag. The curve
indicates that the melting point of Pb gradually falls on addition of Ag. Along this
curve, solid Pb and solution of lead and silver are in equilibrium.
Both AO and BO represent univariant systems
C = 2, P = 2
F = C – P + 1 ; 2 – 2 + 1 =1
2) Areas:
Area AOB: It consists of only one phase (liquid solution of lead and silver). On applying
the reduced phase rule equation, the degree of freedom comes out to be two. Hence, the
system is bivariant and both temperature and composition are required to be specified
to define the system completely
C = 2, P = 1 F = C – P + 1
=2–1+1=2
Area AOD: It contains two phases—solid Ag and solution containing Pb and Ag
Area BOE: It represents the phases—solid Pb + solution containing Pb and Ag. Both
these areas have two phases and are univariant.
F=C–P+1
C = 2 (Pb and Ag) ,P = 2 (Liquid + solid phase)
=2–2+1=1
Area below DOE: It represents a solid mixture of Pb or Ag with eutectic. The number of
phases is 2 (either Ag or Pb + eutectic) and the system is univariant.
C = 2, P = 2 F = C – P + 1
=2–2+1=1

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Eutectic Point O: The two curves AO and BO intersect at point O at a temperature of
303 °C. The point O is known as the eutectic point. At this point, three phases—solid
Ag, solid Pb and the melt are in equilibrium. On applying the phase rule equation, we
get
F=C–P+1
=2–3+1=0
Thus, the system at this point is invariant. Both temperature (303 °C) and composition
(Ag 2.6% and Pb 97.4%) are fixed at this point.

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 Figure 2. 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 crystallize 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.
Uses of Eutectic System: Used for creating low melting alloys which can be made into
safety fuses. Safety fuse is a device containing a small piece of low melting alloy that
melts under excessive heat or excessive current.
Examples
1) Safety valve in pressure cookers is made of an alloy having a definite
composition and definite eutectic temperature. As the temperature rises above
this temperature, the alloy melts, preventing any accident.

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 2) Safety fuses are employed for plugs in water sprayers in buildings. In case of
accidental fires, the plugs melt away and the water is released automatically to
extinguish the fire.
3) Fuse wire used in electric circuits melts away on over-heating.
4) Solders are readily fusible alloys which are applied to the point between metal
objects to unite them closely without heating the objects to their melting point.

NaCl-water system

Figure 3: Phase Diagram for NaCl-water system

The phase diagram for NaCl-water system is shown in figure 3. The point O represents
the melting of ice (0 ⁰C). When sodium chloride is added to ice, the melting point is
lowered and the curve 1 represents the melting point of ice in the presence of sodium
chloride. Along curve 1, ice and saturated sodium chloride solution are in equilibrium
and the system is invariant.
At eutectic point (-21.1 ⁰C), a new solid phase, NaCl.2H2O separates out from the
solution and is cryohydric point where ice, incongruent melting point (NaCl.2H2O (s))

and the NaCl solution are in equilibrium and the system is invariant.

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Below -21.1 ⁰C, only ice and NaCl.2H2O solid exist. Further, addition of NaCl, the
freezing point curve raises along curve 2, which is the solubility curve for dihydrate.

Freezing mixtures
A mixture of two or more substances (e.g. ice water and salt, or dry ice and alcohol)
which can be used to produce temperatures below the freezing point of solvent.
The principle behind it is the depression in freezing point.
Examples:
• Mixture of salt and ice. It can reduce the temperature up to -21.1 oC
NaCl is a non-volatile substance. When we combine salt with ice, it will first diffuse in
the liquid. So, it will decrease the freezing point of water beneath the temperature of ice.
So, ice will soften when we combine salt and ice, and extra water will be formed. So,
this will assist in dissolving more salt. Since the freezing mixture will not receive heat
from the external environment, it will absorb heat from the internal system and helps to
cool the internal system.
• Mixture of dry ice and alcohol. It can reduce the temperature up to −80 °C.

Applications: Freezing mixtures are utilized in labs for Cooling.

Salting of roads in cold-weather climates. By applying salt to an icy road, the melting
point of the ice is decreased, and the ice will melt more quickly, making driving safer
The radiator fluid in an automobile is a mixture of water and ethylene glycol. The
freezing-point depression prevents radiators from freezing in winter

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Questions
1. Define the terms (a) Phase (b) Component (c) Degree of Freedom. [6]
2. Define Phase and component with one example for each. [4]
3. Explain Phase diagram for water system. [6]
4. Explain Phase diagram for Lead-silver system. [5]
5. What is freezing mixture? Give an example [2]
6. Mention any two applications of freezing mixture. [2]
7. Calculate the number of phases present in the following systems:

i
ii
iii
iv
v
vi An emulsion of oil in water
8. How many degrees of freedom are present in the following systems?
i A gas in equilibrium with its solution in a liquid
ii A solution of a solid in a liquid in equilibrium with solvent vapour
iii Two partially miscible liquids in the absence of vapour

iv
v NH3 (g)

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