Module 4: Phase Rule & Analytical Techniques

Phase Rule: The phase rule, also known as the Gibbs phase rule, relates the number of
components and the number of degrees of freedom in a system at equilibrium by the formula
F=C–P+2
Where,
F equals the number of degrees of freedom or the number of independent variables,
C equals the number of components in a system in equilibrium and
P equals the number of phases.
The digit 2 stands for the two variables, temperature and pressure.

Terminology:
1. Phase: In general terms, a “phase” is a homogeneous, physically distinct, mechanically
separable portion of a material with a given chemical composition.
Examples:
 Ice cubes in water constitute a two-phase system (ice and liquid water), unless we include
the vapour above the glass in our system, which would make it a three-phase system.
 A mixture of oil and water would also be a two-phase system. Just as oil and water
represent two distinct liquid phases.
 Two regions of a solid with distinctly different composition or structure separated by
boundaries represent two solid phases.
Required conditions for phase: A phase must fulfil the following three conditions
i. It should be physically homogeneous.
ii. In case of more than one phase, all phases must be separated from each other by surface
of contact (interface) at equilibrium.
iii. A dynamic equilibrium must be established between phases of the system through
exchange of chemical species.
2. Components (C): The number of components ‘C’ of a system at equilibrium is the
smallest number of independently variable chemical constituents by means of which the
composition of all the phases present in the system can be expressed either directly or in
the form of a chemical equation.
 In case of chemically reactive system where various chemical reactions take place
between the species, the number of components is calculated by the relation C=S-R.
Where S=number of chemical species present in the system and R=number of chemical
relations among the chemical species.
 Example 1:
Water exist in three phase as Solid (ice) ↔ Liquid (water) ↔ Gas (vapour); each phase
can be represented by H2O. Thus, the number of components is one.
 Example 2: Thermal decomposition of calcium carbonate in a sealed tube, represented
as CaCO3 (s) ↔ CaO (s) ↔ CO2 (g);
There are three phases, three species and one relation. Here S=3, R=1;
Therefore C=S-R=3-1=2; Hence the number of components is two.
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 Since it is a two-component system, hence all the phases in the equilibrium can be
expressed by choosing only any two constituents.
 Example 3: Consider the decomposition of ammonium chloride as
NH4Cl (s) ↔ NH3 (g) ↔ HCl (g)
If the reaction is carried out in a closed vessel or in vacuum then the number of
components is one. However, if the reaction is carried out in excess of NH3 or HCl then
the number of components of the system will be 2.
 If ions are also present in the system then the condition of electroneutrality (number of
positive and negative charged ions should be equal) is also considered. Hence the number
of components may be calculated by the modified relation as C=S-(R+1)
 For example, In the system NaBr-KCl-H2O;
Here the number of species is nine NaBr, KCl, NaCl, KBr, H2O, Na+, Br-, K+, Cl- (the
dissociation of water is ignored). The number of independent reactions/relations is four.
NaBr ↔ Na+ + Br-
KCl ↔ K+ + Cl-
Na+ + Cl- ↔ NaCl
K+ + Br- ↔ KBr
Therefore, number of components C=S-(R+1)=9-(4+1)=4

3. Degree of Freedom (F): It is the least number of independent variables (temperature,

pressure and concentration), which may be altered without changing the number of
phases. It is also called variance. These variables describe the state of the system.
 Example 1: Consider a system containing a gas enclosed in a cylinder provided with a
movable piston. It is a single-phase system having one component. To describe the
system completely, we need only temperature and pressure because the volume is
automatically known from the equation of state. So, we may change only temperature
and pressure. Hence it is a bivariant i.e., degree of freedom is two (F=2).
P+F=C+2
F= C – P + 2 = 1 – 1 + 2 = 2
Example 2: In the reaction involving the decomposition of calcium carbonate on heating,
there are three phases – two solid phases and one gaseous phase.
CaCO3 (s) ↔ CaO (s) ↔ CO2 (g);
Here P=3 & C=2; Therefore F = C – P + 2 = 2 – 3 + 2 = 1
Therefore, only one variable, either temperature or pressure, can be changed
independently.
4. A phase diagram is a type of chart used to show conditions at which thermodynamically
distinct phases can occur at equilibrium. Common components of a phase diagram are
lines of equilibrium or phase boundaries, which refer to lines that mark conditions under
which multiple phases can coexist at equilibrium. Phase transitions occur along lines of
equilibrium.

5. Triple points are points on phase diagrams where lines of equilibrium intersect. Triple
points mark conditions at which three different phases can coexist. For example, the water
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 phase diagram has a triple point corresponding to the single temperature and pressure at
which solid, liquid, and gaseous water can coexist in a stable equilibrium

Two-Component System: A two-component system may be defined as “a system in which it

is possible to express the composition of all phases present in the system in terms of two
constituents”. For a two-component system, the phase rule equation may be put in the form
F = 2 – P + 2 = 4 – P Or F + P = 4
In a two-component system, when P=1, the degree of freedom (F) has the highest value:
F=4– 1=3

Because the maximum number of degrees of freedom in a two-component system is three,

the phase behaviours of a binary system may be represented by a 3D diagram of pressure,
temperature, and composition, which cannot be conveniently shown on a paper.

The Phase Rule for Two-Component Systems: In general, the phase rule equation is
P+F=C+E. Where, E is the number of external variables such as temperature, pressure, and in
unusual cases electric field and magnetic field. Solid-liquid equilibrium of an alloy has
practically no gas phase, and the effect of pressure is negligible on this type of equilibrium.
Thus, keeping the pressure constant of a system in which vapour phase is not considered is
known as a condensed system.
As such, the phase rule becomes F = C – P + 1. This is known as the condensed phase rule.
The solid-liquid equilibriums are represented on temperature-composition diagrams.

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lead-silver system (example for 2-component system)
 Both lead and silver are completely miscible and form homogeneous mixture.
 The melting point of pure lead is 327 oC. It is lowered by the addition of silver.
 The melting point of pure silver is 961 oC. It is lowered by the addition of lead.
 The Phase diagram of lead-silver is as shown in the Figure.

1. Curves:
i. Curve BO: It represents the melting point or freezing point curve of Pb by
addition of small amount of Ag. Along this curve two phases solid Pb and
liquid melt co-exist.
Solid Pb (s) ↔ liquid melt (l)
F = C – P + 1 = 2 – 2 + 1 = 1; the system is uni-variant (F=1)

ii. Curve AO: It represents the melting point or freezing point curve of Ag by
addition of small amount of Pb. Along this curve two phases solid Ag and
liquid melt co-exist.
Solid Ag (s) ↔ liquid melt (l)
F = C – P + 1 = 2 – 2 + 1 = 1; the system is uni-variant (F=1)

2. Areas:
i. Area above the curve AOB: In this region only one phase i.e., liquid alloy (melt of
Ag & Pb) co-exist.
F = C – P + 1 = 2 – 1 + 1 = 2; the system is bi-variant (F=2) in this region
(Temperature & Composition).

ii. Area BOE: In this area solid lead and liquid melt co-exists.
Degree of freedom=F=C-P+1=2-2+1=1; Therefore the system is uni-variant.

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 iii. Area AOF: In this area solid silver and melt exist. as similar in case of area BOE.
It is also uni-variant system as the degree of freedom is one.

3. Points:
i. Points ‘A’ & ‘B’: Point A & B represents the melting point of pure silver (961 oC)
and pure lead (327 oC) respectively.
ii. Eutectic point ‘O’: It is a point where two curves AO & BO meet. At this point solid
mass (lead + silver) is in equilibrium with the fused mass. There are three phases
present. F=C-P+1=2-3+1=0; Hence the system is invariant. This point ‘C’ represents
the lowest possible temperature (303 oC) below which a liquid phase cannot exist and
beyond which the liquid phase cannot be enriched in either component by freezing
out the other component. Such type of a liquid mixture of two components Pb & Ag
which has the lowest freezing point correspond to all other liquid is called eutectic
mixture and temperature corresponding to this mixture is called eutectic
temperature. This temperature is always less than the melting point of the
constituents.

Application: desilverisation of lead/Pattinsons process

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Working principle of pH sensor & determination of pH of an analyte by using
a glass electrode:

Part A: Working principle of pH sensor:

The sensor works by comparing the electric potential of a pH-

sensitive system to the potential of a stable reference system. The
sensing system uses a pH-sensitive glass bulb which changes
voltage proportionally to the concentration of hydrogen ions. A
sensing electrode measures the potential of the glass bulb.

The glass bulb, made up of SiO2, is designed in such

a way that oxide ions emerges on the surface. Also,
H+ ions cannot diffuse through the bulb, but forms a
hydrated gel layer on the surface as shown in figure.

Case 1: Analyte is acidic solution i.e outer hydrated gel layer is more positive than the inner
hydrated layer.

In such cases,

 the metal, Ag undergo oxidation to give

electrons and Ag+ ions.
 Ag+ ions replaces H+ ions (of HCl,
inner solution) & free H+ ions moves into
inner hydrated gel layer
 Ag+ ions & Cl- ions combine and forms
AgCl
 Since, Ag, wire is conducting, electrons will give rise to electric current and change the
potential of the glass electrode.
 The change in potential of the glass electrode is measured with respect to the reference
electrode, saturated calomel electrode

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Case 2: Analyte is Basic solution i.e outer hydrated gel layer is less positive than the inner
hydrated layer.

In such cases,

 H+ ions releases from the inner hydrated

gel
 AgCl dissociates into Ag+ ions &
Cl- ions
+
 H ions reacts with Cl ions to from HCl
-
+
 The electrode donates electrons to Ag
ions. Ag+ ions reduces to Ag
 The electrode donates its electrons to
Ag+ ions, as a result potential of the glass
electrode changes.
 The change in potential of the glass electrode is measured with respect to the reference
electrode, saturated calomel electrode

summary,

 the concentration of H+ ions in the outer solution affects the binding H+ ions on the inner
hydration layer.
 The binding or release of H+ ions on the inner hydration layer affects the oxidation of Ag
metal or reduction of Ag+ ions.
 The oxidation of Ag metal or reduction of Ag+ ions causes the glass electrode to either
loss or gain electrons (This changes the voltage/potential of the electrode)
 The change in potential of the glass electrode is measured with respect to the reference
electrode, saturated calomel electrode

Part B: Application of pH sensor (glass electrode) in the determination of pH of an analyte

solution:

The glass electrode is immersed in a solution of which pH is to be

determined. It is combined with a reference electrode such as a
calomel electrode through a salt bridge. The cell assembly is
represented as:
Calomel electrode || Solution of unknown pH | glass electrode
or
Hg | Hg2Cl2 (s) | KCl (sat.) || Solution of unknown pH | glass | HCl (0.1M) | AgCl | Ag(s)

The EMF of the above cell, Ecell is measured using an electronic

potentiometer. Ecell measured is the difference between potential
of glass electrode (EG) and calomel electrode (ESCE). The potential
developed at the glass electrode is higher than the reference
calomel electrode (EG > ESCE).

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 𝐸 =𝐸 −𝐸

𝐸 =𝐸 −𝐸

𝐸 = 𝐸 − 0.0591𝑝 − 𝐸

(𝐸 − 𝐸 − 𝐸 )
𝑝 =
0.0591

Where, 𝐸 & and ESCE are constants. By substituting Ecell value, pH of an unknown solution is
calculated.

Note: 𝐸 value is evaluated by dipping the glass electrode in a solution of known pH and
measuring EMF of the cell formed when combined with calomel electrode.

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Optical Sensors: working principle & applications

Part A: Working principle of photodiode

Optical sensor is a devise that measures the quantity of light rays physically present and turns
that information into an electrical signal that can be interpreted by a person or an electronic
instrumentation. Commonly used optical sensor is a photodiode.

The photodiode is made up of two layers of P-type

and N-type semiconductor. In this, the P-type
material is formed from diffusion of the lightly
doped P-type substrate. Thus, the layer of P+ ions
is formed due to the diffusion process. N-type
epitaxial layer is grown on N-type substrate. The
P+ diffusion layer is developed on N-type heavily
doped epitaxial layer. The contacts are made up of
metals to form two terminal cathode and anode.

When the junction of Photodiode is illuminated by

the light source, the photons strike the junction
surface. The photons impart their energy in the form
of light to the junction. Due to which electrons from
valence band get the energy to jump into the
conduction band and contribute to current. In this
way, the photodiode converts light energy into
electrical energy.
When the Photo diode operates in reverse biased
mode, it is called Photoconductive mode. In this, the
current flowing in diode varies linearly with the
intensity of light incident on it.

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Part B: Application of optical sensor in colorimetry
Example: determination of copper

When a solution containing cupric ions is treated with ammonia solution, a soluble complex with
characteristic deep blue colour is formed.

Cu2+ + 4NH3 → Cu[(NH3)4]2+

 A series of standard Copper solutions are prepared

 Copper solutions are treated with ammonia to form a complex as shown in above scheme
 Absorbance of each solution is measured at 620nm using blank as a reference solution.
 The colorimeter is used to record the absorbance of each solution.
 A graph (calibration or standard graph) of absorbance against concentration of copper
(standard solutions) is plotted, which gives a linear graph passing through origin.
 For the unknown solution, ammonia solution is added to form a complex.
 The absorbance of the test solution is recorded by using colorimeter.
 The concentration of copper in the unknown solution is determined with the help of
standard graph.

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Potentiometric Sensors: working principle & applications

Part A: Working principle of potentiometric sensor

Potentiometric sensors measure the potential difference between the two electrodes (working &
reference electrodes) under the conditions of no current flow. The measured potential may then
be used to determine the analytical quantity of interest, generally the concentration of some
component of the solution. The working electrode potential must depend on the concentration
of the analyte.
In the potentiometric sensor, the ion selector electrode is coupled
with the reference electrode to complete the circuit and the sensor
measure the potential difference between two electrodes.

The signal of a general potentiometric sensor is based on the

Nernst equation. This equation predicts a linear dependence of the
sensor response, E, on the logarithm of a function of the activity
of the ion in solution:

𝑅𝑇
𝐸=𝐸 + 𝑙𝑛 (𝑎 )
𝑛𝐹

To measure electrode potential experimentally, a galvanic cell must be formed by coupling a

reference electrode (Ex: saturated calomel electrode or glass electrode) with the working
electrode. The scheme of resulting cell is given by:

Reference electrode ││ Working electrode

A(-) C(+)

Potential of the reference electrode is constant. But, the potential of the working electrode
changes as the concentration of the analyte changes. Hence, EMF of the cell changes as the
potential of the working electrode changes.

Part B: Application of optical sensor

Example: Estimation of iron (To determine the weight of Mohr’s salt solution (FAS)
Potentiometrically, by titrating with standard K2Cr2O7 solution)

Titration of Mohr’s salt solution with K2Cr2O7 solution is a redox titration. Mohr’s salt is a
reducing agent and K2Cr2O7 is an oxidizing agent. Inert Platinum electrode is used as working
electrode, potential of which is a function of ratio of concentration of reduced species to the
concentration of oxidized species of a specimen (metal ion or a compound).

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till the end point: When working electrode (platinum electrode) is immersed in FAS solution,
gives rise to the redox electrode of ferric ferrous system: Pt(s) │ Fe3+, Fe2+
The potential developed at this electrode is given by the Nernst equation shown below:

E Fe 3 / Fe 2  E Fe
0
 0.0592 log
Fe 
2

3
/ Fe 2 
Fe 
3

Fe2+ ions are oxidized to Fe3+ions, when dichromate solution is added. Thus, the ratio,
[Fe2+]/[Fe3+] gradually decreases and hence the electrode potential of working electrode
gradually increases in accordance with the Nernst equation. This occurs until the end point. The
formal potential of this system is +0.68 V in 1M H2SO4 w.r.to SHE

after end point: After the endpoint, dichromate remains in solution, because Fe2+ ions do not
exist in solution to react with it. Hence potential of the redox electrode is determined by Cr2 O72
∕ Cr3+ couple after the endpoint. Potential of this electrode is given by the Nernst equation shown
below:

ECr 6 / Cr 3  E 0

0.0592
log

Cr 3  2

Cr 6  / Cr 3
6 Cr2 O72 H   14

The formal potential of Cr2O72 ∕ Cr3+ system is about +1.3V w.r.to SHE. Hence a steep change
in the electrode potential results at the endpoint. Potential increases gradually after the endpoint
with the addition of dichromate in accordance with above equation.

𝑵𝑲𝟐𝒄𝒓𝟐𝑶𝟕 𝒙 𝑽𝑲𝟐𝑪𝒓𝟐𝑶𝟕 𝑵𝑲𝟐𝒄𝒓𝟐𝑶𝟕 𝒙 𝑽𝑬𝒒

𝑵𝒐𝒓𝒎𝒂𝒍𝒊𝒕𝒚 𝒐𝒇 𝑭𝑨𝑺 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 = 𝑽𝑭𝑨𝑺
= 𝟓𝟎
𝑵
𝑾𝒆𝒊𝒈𝒉𝒕 𝒐𝒇𝑭𝑨𝑺/𝒍 = 𝑵𝑭𝑨𝑺 𝒙 𝑬𝒒𝒖𝒊𝒗𝒂𝒍𝒆𝒏𝒕 𝒘𝒆𝒊𝒈𝒉𝒕 𝒐𝒇 𝑭𝑨𝑺 (𝟑𝟗𝟐) 𝒈

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