Department of Chemistry, BIT, Mesra

CH101: Chemistry

Module V: Phase and Chemical equilibrium [9 Lectures]

Phase Rule: Terms Involved, Phase diagram of one component (Water) & two component (Pb/Ag)
system & their applications. Law of chemical equilibrium, equilibrium constants and their
significance, Weak and strong electrolytes, Standard electrode potential and its application to different
kinds of half cells, EMF and its measurement and application, Batteries and Fuel Cells, Chemical and
Electrochemical corrosion, Factors affecting the rate of corrosion.

Phase Rule
The phase rule is a generalization given by Williard Gibbs (1876) which seeks to explain the equilibria
existing in heterogeneous systems. It is well known that, in homogeneous systems the reactants and
the products are in same or one phase, while in heterogeneous systems the reactants and the products
are in different or two phase. With the application of phase rule it is possible to predict qualitatively by
means of a diagram the effect of changing pressure, temperature and concentration on a heterogeneous
system in equilibrium. Before starting the rule the involved terms like phase, component and degree of
freedom need to be explained.

Terms involved
Phase is defined as any homogenous and uniform in composition, physical distinct portions of matter,
which is mechanically separated from other such parts of the system by definite boundary surfaces.
Following are the examples;
Water consists of three phases
Ice (S) ↔ Water (L) ↔ Water vapour (g)
A pure substance (solid, liquid or gas ) made of one chemical species , is considered as one phase.
Thus oxygen(O2), benzene(C6H6) and ice (H2O) are all one-phase system.
A gaseous mixture, miscible in all proportions, will constitute only one phase, e.g., mixture of
hydrogen and oxygen or air etc.
The two immiscible liquids (benzene and water) will form two liquid phases.
The two miscible liquids (i.e. alcohol and water) will form one separate phase.
A solution of a substance in a solvent consists of one phase only e.g.: Sugar solution in water.
A heterogeneous mixture like
CaCO3 (S) → CaO(S) + CO2 (g)
Consists of three phases (i.e. two solids and one gaseous).
Mixture of solids: Sulphur is a mixture of rhombic and monoclinc sulphur. These allotropes of
sulphur consists of same chemical species but differ in physical properties. Thus a mixture of two
allotropes is a two-phase system.

Component is defined as the smallest number of independent variable constituents, in terms of which
the composition of each phase can be expressed in the form of chemical equation. The concept of
component can be explained with the help of following examples;
In the water system, the chemical composition of all the three phases is H2O. Hence, it is one
component system.
Ice (S) ↔ Water (L) ↔ Water vapour (g)
A solution of a salt in a solvent consists of two component system, e.g, NaCl in water.
A saturated solution of NaCl consists of solid NaCl, NaCl solution, and water vapour. The chemical
composition of all the three phases is NaCl & H2O. Hence, it is a two component system.
Consider the thermal decomposition of MgCO3 in closed vessel

1 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
There are three phase and two component system (two solid and one gases) but two components, since
any two of the three substances are sufficient to express the composition of each of three phases. For
example if we choose CO2 and MgO as two component, then;
The composition of MgO phase can be expressed as nMgO
The composition of CO2 phase can be expressed as nCO2
The composition of MgCO3 can be expressed as xMgO+xCO2
Similarly, if we choose MgO and MgCO3 as two component, then;
The composition of MgO phase can be expressed as nMgO
The composition of CO2 phase can be expressed as nMgCO3+nCO2
The composition of MgCO3 can be expressed as xMgCO3
Suppose a solid dissociate into number of gaseous substances in a closed vessel, e.g.,

The overall composition of the dissociate vapor (NH3, HCl) is exactly the same with the udissociate
substances (NH4Cl). Thus the number of component is one with three phases. However, if NH3 or
HCl is introduced into the system then it should be a two component system, i.e., NH4Cl and the
excess NH3 or HCl.
NH4Cl (s)  NH3 (g) + HCl (g)
[NH3] = [HCl]
Keq = [NH3] [HCl] / [NH4Cl] = [NH3] [HCl]
[Because the active mass of NH4Cl (s) is constant ]
Now, the number of components = No. of constituents – no. of equation relating to
concentration of constituents = 3(NH4Cl, NH3, HCl) – 2
= 1 i.e, it is a single component system.

When NH4Cl is heated in a closed vessel along with NH3 or HCl then :
[NH3] ≠ [HCl]
Keq = [NH3] [HCl]
Therefore, only one equation relates the concentration of constituents

Hence, no. of components ( C ) = 3 – 1 = 2

Therefore it is a two component system.
The sulphur system consists of four phases, rhombic, monoclinic, liquid and vapour, the chemical
composition of all the phases is ‘S’. Hence, it is also one component system.

Degree of freedom is defined as the minimum number of independently variable factors, such as
pressure temperature and composition (concentration or volume), which can completely define the
equilibrium of a system. The least number of variable factors (concentration, pressure & temperature)
which must be specified so that the remaining variables are fixed automatically and the system is
completely defined.
❖ A system with F=0, is known as nonvariant or having no degree of freedom.
❖ A system with F=1, is known as univariant (having one degree of freedom)
❖ A system with F=2, is known as bivariant (having 2 degrees of freedom).
For examples;
A system consisting of pure gas or gas mixture, is a one phase system. If the temperature and
pressure are specified, then volume can be known. So, the degree of freedom for the system is two.
For a gaseous mixture of N2 and H2, we must state both the temperature and pressure. Hence, the
system is bivariant (degree of freedom is two).

2 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
 In the water system
Ice (S) ↔ Water (l)↔ Vapour (g)
Three phases will be in equilibrium only at particular temperature and pressure. If any of the variable,
i.e., temp & pressure is altered, three phases will not remain in equilibrium and one of the phases
disappears. Therefore the system is nonvariant (F=0) The system is, zero variant, or non-variant or
invariant and has no degree of freedom.
For a system consisting of water in contact with its vapour.
Water (l)↔ Vapour (g)
We must state either temperature or pressure to define the system completely. Hence; the degree of
freedom is one (or) the system is univariant.
For a system consisting of
NaCl (S) ↔ NaCl – Water (aq) ↔ Water vapour (g)
We must state either temperature or pressure. Hence the system is univariant (degree of freedom is
one).
For pure gas: From gas law, PV = RT, if the values of Pressure (P) and Temperature (T) be
specified, Volume (V), the third variable is fixed automatically. Hence degree of freedom (F) = 2

Phase rule
Phase rule can be stated as, in heterogeneous systems, if equilibrium between phases are not
influenced by gravity, magnetic & electrical forces, but are influenced only by pressure, temperature
and concentration, then the number of degree of freedom (F) of the system is related to number of
components (C) and number of phases (P) by the following phase rule equation

Merits of phase rule

1. It is applicable to both physical and chemical equilibria.
2. It is a convenient method of classifying the equilibrium states in terms of phases, components and
degree of freedom.
3. It indicates different system with same degree of freedom behave similarly.
4. It helps us to predict the behaviours of a system, under different sets of variables.
5. It helps in deciding whether the number of substances remains in equilibrium or not.
Limitations of phase rule
1. Phase rule is applicable only for those systems which are in equilibrium. It is not of much use for
those systems which attains the equilibrium state very slow.
2. Only three variables like P, T, & C are considered, but not electrical, magnetic and gravitational
forces.
3. It is applied only to a single equilibrium system.
4. It requires utmost care in deciding the number of phases existing in equilibrium.
5. Solid and liquid phases must not be in finely – divided state; otherwise deviations occur.

Derivation of phase Rule

Consider a heterogeneous system in equilibrium , having C components in which P phases are present.
According to the definition of the degree of freedom, F- is the minimum number of independent
variables which must be fixed arbitrarily to define the system completely.

No. of independent variables = Total no. of variables – no. of

relations between them at equilibrium

Now let us calculate total no. of independent variables:

(1) Temperature: At equilibrium ,temperature of every phase is same, so there is only one
temperature variable of the entire system.

3 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
 (2) Pressure: At equilibrium , each phase has the same pressure, so there is only one pressure
variable of the entire system.
(3) Concentration: Concentration of each components is generally expressed in terms of mole
fractions
For example , if there are two components A & B in one phase and if we know the
concentration of one (say A), the concentration of other (i.e.,B) can be automatically found because
sum is unity. Similarly, if we have three components and if the composition of two is known , then the
composition of third can be easily found out. Thus , if we have C components , we must know the
concentrations of C – I components . So for P phases the total composition variables are P(C – I).
Hence, total number of variables
= 1 (for temperature) + 1(for pressure) + P(C - 1) (for composition)
= P(C – 1) + 2

When P phases are present , (P – 1) equations are available for each component & for C component ,
the total no. of equations are C(P – 1).
[If there is one component in two phases, it is possible to write one equation amongst the variables and
if there is one component in three phases , it may be represented with the help of two equations.
Therefore in general when P phases are present , (P – 1) equations are available for each
components and for C components , the total no. of equations are C(P – 1).]

F = total no. of variables – no.of equations between them at equilibrium

F = [P(C-1) + 2] – [C (P-1) ]
Hence, F (Degree of freedom) = C – P + 2

Phase diagram
Phase diagram is a graph obtained by plotting one degree of freedom against another. If temperature is
plotted against pressure, the diagram is called P-T diagram. Similarly, a plot of temperature against
composition is known as T-C diagram. By the phase diagram, we may understand the behaviour of the
system, stability and equilibrium between phases. Systems are classified, on the basis of number of
components, into three types.
1. One component systems
2. Two component systems
3. Three component systems

Phase diagram of one component system

In any system, the minimum number of phases is one. It is evident from the phase rule equation
F=C-P+2 =1-1+2=2
For one component system the maximum number of degree of freedom is two. The maximum number
of phases in any system is three, from the phase rule equation
F=C-P+2 =1-3+2=0
The minimum number of degree of freedom is zero for one component system. From the above
calculations, it is clear that for any one-component system the maximum number of degree of freedom
is two. Therefore, such a system can be presented completely by a two dimensional diagram. Hence,
we may draw the phase diagram by taking pressure and temperature as the two axes. These are known
as pressure-temperature (P-T) diagrams, concentration (or) composition remains constant.
The Water system:
Water can exist in three possible phases, namely, solid, liquid and vapour. Hence, there can be three
equilibriums with two phases for each equilibrium:
1. Liquid ↔ vapour
4 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
2. Solid ↔ Vapour
3. Solid ↔ Liquid

The curve OA is called the vapourization curve of water; it represents the equilibrium between liquid
water and vapour. At any point on the curve the following equilibrium will exist.
Liquid water ↔ vapour
The degree of freedom of the system is one, i.e., univariant. This is predicted by the phase rule.
F=1-2+2; F=1
This equilibrium will extend up to the critical temperature (374OC). Beyond the critical temperature,
the equilibrium will disappear only water vapour will exist.
The curve OB is called the sublimation curve of ice; it represents the equilibrium between ice and
vapour. At any point on the curve the following equilibrium will exist.
Ice ↔ Vapour.
The degree of freedom of the system is one i.e., univariant. This is predicted by the phase rule.
F=C-P+2; F=1-2+2; F=1
This equilibrium will extend up to the absolute zero.
Triple point: The vaporization curve (OA) and the sublimation curve (OB) meet at point O, where
three phases, namely solid, liquid and vapour will coexist. Such a point is known as the “triple point”.
Temperature and pressure at the triple point of water are 0.0098 OC and 4.58 mm respectively,
according to phase rule, the degree of freedom is zero i.e., invariant.
F=C-P+2; F=1-3+2; F=0
The curve OC is called the fusion curve of ice; it represents the equilibrium between ice and water. At
any point, on the curve the following equilibrium will exist.
Ice ↔ water
The curve OC shows how is the melting point of ice increased by increasing pressure. The degree of
freedom of the system is one, i.e., univariant.
The curve OA’ is called vapour pressure curve of the super-cool water (or) metastable equilibrium.
Some times water can be cooled below 0OC without the formation of ice; this water is known as super-
cool water. The super-cool water can be preserved if the system is not subjected to stirring (or)
“Seeding” by solid. At any point on the curve the following equilibrium will exist.
Super-cool water ↔ vapour
The degree of freedom of the system is one i.e., univariant.
Area AOB, AOC and BOC contain vapour, liquid and ice phases respectively, with in these single-
phase areas, the system is bivariant. This is predicted by the phase rule.
F=C-P+2; F=1-1+2; F=2
To locate any point in an area, temperature and pressure needs to be known.

5 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
Phase diagram of Two-component systems
For binary mixtures of two chemically independent components,
C = 2 so that F = 4 – P
In addition to temperature and pressure, other variables are the composition of each phase, often
expressed as mole fraction or mass fraction of one component. As an example, consider the system of
two completely miscible liquids such as toluene and benzene, in equilibrium with their vapours. This
system may be described by a boiling-point diagram which shows the composition (mole fraction) of
the two phases in equilibrium as functions of temperature (at a fixed pressure). Four thermodynamic
variables which may describe the system include temperature (T), pressure (p), mole fraction of
component 1 (toluene) in the liquid phase (x1L), and mole fraction of component 1 in the vapour phase
(x1V). However since two phases are in equilibrium, only two of these variables can be independent (F
= 2). This is because the four variables are constrained by two relations: the equality of the chemical
potentials of liquid toluene and toluene vapour, and the corresponding equality for benzene. For given
T and p, there will be two phases at equilibrium when the overall composition of the system (system
point) lies in between the two curves. A horizontal line (isotherm or tie line) can be drawn through any
such system point, and intersects the curve for each phase at its equilibrium composition. The quantity
of each phase is given by the lever rule (expressed in the variable corresponding to the x-axis, here
mole fraction). For the analysis of fractional distillation, the two independent variables are instead
considered to be liquid-phase composition (x1L) and pressure. In that case the phase rule implies that
the equilibrium temperature (boiling point) and vapour-phase composition are determined. Liquid-
vapour phase diagrams for other systems may have azeotropes (maxima or minima) in the composition
curves, but the application of the phase rule is unchanged. The only difference is that the compositions
of the two phases are equal exactly at the azeotropic composition.

Phase diagram of two component: reduced phase rule (or) condensed phase rule
In a two – component system, minimum number of phases is one, i.e., P = 1, according to the phase
rule equation, the maximum degree of freedom is three
F = C – P + 2; F = 2 – 1; F = 3
So, the phase diagram of a binary system should be represented by a three dimensional diagram of
temperatures, pressure and composition, which can not be drawn on paper. Generally solid-liquid
equilibrium of an alloy has “no gas phase” and the effect of pressure is small. Therefore, experiments
are conducted under atmospheric pressure. Thus, the system in which the pressure is constant (vapour
phase is not considered) is known as condensed system. The phase rule becomes.
F’=C-P+1
This is known as reduced phase rule (or) condensed phase rule. The phase diagram can be drawn by
taking temperature and composition as the two axis. This is known as (T-C) diagram. The reduced
phase rule is used only when atmospheric pressure is larger than actual vapour pressure of the
component. Depending upon the solubility of the two components and their reactive ability, two
component systems are classified into three types

6 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
1. Simple Eutectic formation: 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).
2. Solid solution formation: 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%.
3. Compound formation: Under some conditions, two metals chemically react to give one or more
compounds with definite proportions. Of the compounds, a compound is said to possess congruent
(constant) melting point, if it melts exactly at a constant temperature into liquid, having the same
composition as that of solid.

Pb-Ag system:
It is a two-component Simple Eutectic system. Here four possible phases are solid Ag, Solid Pb,
solution of Ag-Pb and vapor. However, at the constant atmospheric pressure, the vapor phase is absent
and reduced phase rule is applicable as F=C-P+1. The phase diagram of the Pb-Ag system is shown in
the figure below;

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. 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 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
(303OC) 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.
Let us consider a point p, which represents a sample of lead containing less than 2.6% silver. On
cooling the temperature falls gradually till point p’. On further cooling lead begins to separate and the
concentration of Ag increase in the solution till the point O is reached, after that whole mass solidifies
(2.6% Ag; 97.4% pb). This process is utilized in the pattinson’s process of desilverization of lead.
7 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
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.

Applications
Pattinson’s process: If a sample of argent ferrous lead, containing less than 2.6% Ag is allowed to
cool gradually, lead will separate out and the solution will become progressively richer in Ag, till the
percentage 2.6 of Ag is reached; and on further cooling, the whole mass will solidify as such. On the
other hand, if lead-silver allow containing Ag greater than 2.6% is allowed to cool, and then pure
silver separates along the curve AO, till the eutectic composition at O is reached.

Thermal analysis or cooling curve: The shape of the cooling curve can be determined by thermal
analysis. Thermal analysis is a method involving a study of cooling curves of the various compositions
of a system during solidification. The cooling curve is obtained by plotting fall of temperature with
time. The principle of the method can be understood from the following examples. In that addition, a
compound is said to possess incongruent melting point, if it decomposes completely at a temperature
below its melting point yielding a new solid phase with a composition different from that of the
original.

1. When a pure substance in the liquid state is allowed to cool slowly and the temperature is noted at
definite times. The cooling curve (fig) shows the rate of cooling is continuous up to the point ‘b’ the
solid begins to separate, and the temperature will remain constant, until the liquid is completely
solidified (indicated by the line ‘b’). Thereafter, the fall in temperature will again become continuous
(indicated by the line ‘cd’).
2. If a mixture of two solids in the liquid state is cooled slowly and the cooling curve is obtained in a
similar manner (fig). The cooling curve shows the rate of cooling is continuous up to the point ‘b’. At
the point ‘b’ one of the solids begins to separate, this separation will extent up to the point ‘c’. At the
point ‘c’ the eutectic compound begins to separate. The temperature remains constant along cd until
the solidification completes. Thereafter the fall of temperature becomes uniform, but the rate of fall is
quite different from the previous one.
Uses
1. Melting point and eutectic temperature can be noted from the cooling curve.
2. Percentage purity of the compounds can be known.
3. The behaviour of the compounds can be clearly understood from the cooling curves.
4. The procedure of thermal analysis can also be used to derive the phase diagram of any two
component system.

Heat treatment of steel: Heat treatment involves the combination of heating and cooling of a metal or
alloy in one or more temperature cycles to confer desirable physical properties to the metal or alloy.
Heat treatment of steel may be carried out under near equilibrium conditions to improve the ductility
or under non equilibrium conditions to enhance the hardness. During heat treatment the size and shape
of the grains or the composition of the phase undergoes changes with respect to the micro constituents
and also in addition, the internal stresses will be relieved.
8 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
Hardening: Hardening involves the transformation of austenite to martensite or the bainite phase,
O
making the steel hard. If steel is quenched by plunging into water or oil to 204 C or lower temperature
the carbon atoms do not have sufficient time to form cementite but remain trapped in the lattice. The
excess carbon precipitates out in hot metal and prevents the slipping of the planes. Thus quenched
steel is quite hard and strong but has lower ductility. This heat treatment is called transformation
hardening. Further the quenched steel is not useful for construction purposes, because of its brittleness.
Therefore quenching is always followed by another heat treatment process called tempering. The
quenched steel is tempered by reheating to below α–iron or γ–iron transition temperature. Normally on
0
tempering, the steel becomes tougher and ductile. Tempering is carried out at about 200 C to make
O
hard steel resistant to abrasion or at higher temperature (~ 540 C) to make tough steel capable of
withstanding shock loads.

Case hardening: is a surface treatment by which the inside soft core of steel is hardened on the
surface. Low carbon steels are case hardened because they cannot be hardened by quenching.

Cyaniding: also produces case hardened, medium carbon steel articles. Here the article is immersed in
O
a molten bath of sodium or potassium cyanide at about 850 C for some times to facilitate the
adsorption of both carbon and nitrogen and then quenched in oil or water.

Nitriding: produces a hard surface on alloy steels. The process involves heating the alloy in the
O
presence of ammonia to about 550 C. Ammonia decomposes and nitrogen formed combines with
alloying elements to form hard nitrides on the surface of the alloy.

Annealing: Annealing involves heating and holding the steel at a suitable temperature for some times
to facilitate the dissolution of carbon in γ–iron followed by a slow cooling in a controlled manner in a
furnace. Steel is softened and becomes ductile and machineable. However annealing decreases the
hardness and strength of steel. Annealed hypereutectoid steels contain cementite. They are not soft but
can be machined easily. In contrast annealed hypo eutectoid steels contain ferrite and are relatively
soft and malleable.

Chemical equilibrium
When reactants are mixed in exact stoichiometric proportion to perform a chemical reaction, it is
believed that all the reactants would be converted into products with the release or absorption of
energy. This is not true in all cases. Chemical reactions can be classified as: Irreversible and
Reversible reactions.
Most of the reactions occur only in one direction. They are called irreversible reactions. For example;
Carbon is burnt in air:
Neutralisation reaction:
Precipitation rectaion:
Strictly speaking all reactions are considered to be reversible. But the rate of reaction in one particular
direction is extremely small compared to the other. Thus the reaction proceeds practically in one
direction to near completion, leaving a negligibly small amount of reactant at the end.
A reaction is said to be reversible if under certain conditions of temperature and pressure, the forward
and reverse reactions occur simultaneously.
Forward reaction:
Backward recation:
Total rectaion:

9 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
Many chemical reactions proceed only to a certain extent and stop. When analysed, the resulting
mixture contains both the reactants and products. It is because when reactants combine to form
products, the products also start combining to give back the reactants. When such opposing processes
take place at equal rates, no reaction appears to take place and it is said that a state of equilibrium has
reached.
A reversible reaction is said to be in the equilibrium state when the forward and backward reaction
occur simultaneously at the same rate in a closed system and the concentrations of reactants and
products do not change with time. In a chemical reaction, chemical equilibrium is the state in which
both reactants and products are present in concentrations which have no further tendency to change
with time. The chemical equilibrium is achieved when the rate of forward reaction is same as the
reverse reaction. Since the rates are equal, there are no net changes in the concentrations of the
reactant(s) and product(s). This state is known as dynamic equilibrium. The entire process can be
graphically represented by this diagram.

Characteristics of equilibrium state. The state of equilibrium has following characteristics properties:
(i) Chemical Equilibrium is dynamic in nature. The chemical equalibrium is the result of two equal but
opposite processes occurring in the forward and reverse directions and there is no “net” change
occurring in the system.
(ii) Equilibrium can be attained from either side. The same state of equilibrium (characterized by its
equilibrium constant which is discussed later can be reached whether the reaction is started from the
reactants or products side. For example, the same equilibrium.

(iii) Equilibrium can be attained only in a closed system. Equilibrium can be attained only if no
substance among, reactants or products, is allowed to escape i.e. the system is a closed one. Any
system consisting of gaseous phase or volatile liquids must be kept in a closed container.
Gaseous phase or volatile liquids must be kept in a closed container:
Non-volatile liquid and solid phases even in an open container:
(iv) A catalyst can not change the equilibrium state. Addition of a catalyst speeds up the forward and
reverse reactions by same extent and help in attaining the equilibrium faster. However, the equilibrium
concentrations of reactants and products are not affected in any manner.

Law of chemical equilibrium

Chemical Equilibrium can easily be understood by understanding Chemical Kinetics. It is the study of
the rate of the reactions under various conditions. Another concept that forms the basis is the Law of
mass action. Law of mass action states that the ‘Rate of a chemical reaction is directly proportional to
the product of the concentrations of the reactants raised to their respective stoichiometric coefficients’.
At equilibrium forward and backward rates are equal and the ratio of the rate constants is a constant
and is known as an equilibrium constant. In a reaction mixture at equilibrium, the concentrations of the
reactants and products are related by an equilibrium constant. So, Given a reaction:

10 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
The Law of Chemical Equilibrium is defined as, the ratio of product of concentration of the products
to the product of concentration of the reactants, with each concentration term is raised to the power by
its coefficient in overall balanced chemical equation, is a constant quantity at a given temperature and
it is called equilibrium constant.

Equilibrium constants and their significance

The concentrations values in the law of equilibrium are the equilibrium concentrations of reactants and
products. Kc is called the concentration equilibrium constant. In case of gases their partial pressures
can also be used in place of molar concentrations (since the two are directly proportional to each
other) in the law of equilibrium. The new equilibrium constant, Kp , is called the pressure equilibrium
constant. For the reaction between H2 and I2

Here all are the equilibrium partial pressures of H2 , I2 and HI respectively. For the general gas phase
reaction:

The equilibrium constant of a reaction has a constant and characteristic value at a given temperature.
The changes in starting concentration, pressure and the presence of a catalyst do not change the value
of the equilibrium constant. However if the temperature is changed. The value of the equilibrium
constant also changes. The magnitude of the equilibrium constant is a measure of the extent upto
which a reaction proceeds before the equilibrium is reached. The magnitude of K is large when the
products are present in larger amounts than the reactants in the equilibrium mixture. For example;

A large value of Kc for the second reaction indicates that amount of products is much more than the
reactants present at the time of equilibrium. Thus the magnitude of equilibrium constant tells us about
the position of the equilibrium.
If a system is subjected to a change in concentration of one or more reactants, or a change in
temperature or pressure, the equilibrium condition of the system is altered. In 1884, a French Chemist
and Engineer, Le Chatelier, showed that in every such case, the new equilibrium state partially reduces
the effect of change that brought it about. This principle is known as Le Chatelier’s Principle. The
principle states that, if a system at equilibrium is subjected to a change of pressure or temperature or
number of moles of the component, there will be a tendency for a net reaction in the direction that
reduces the effect of this change. Generally we can say that;
An increase in the concentration of the reactants shifts the equilibrium in the forward direction and a
decrease in the concentration of the reactants shifts the equilibrium in the backward direction.
Similarly, an increase in concentration of the products shifts the equilibrium in the backward direction
and a decrease in the concentration of the products shifts the equilibrium in the forward direction.

The pressure dependence of the equilibrium constant is usually weak in the range of pressures
normally encountered in industry, and therefore, it is usually neglected in practice. This is true for
condensed reactant/products (i.e., when reactants and products are solids or liquid) as well as gaseous
ones. In gas phase reaction the Change in pressure affects equilibrium involving gaseous phase either
in a homogeneous or hetrogeneons system.
Case I: When the number of moles of products is more than the total number of moles. Increase in
total pressure keeping the temperature constant, will cause a decrease in volume. This means that the

11 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
number of moles per unit volume will increase. A net change will take place in the equilibrium in the
direction where the number of moles decrease i.e. backward direction.
Case II: When the number of moles of products is less than reactants. Increase in total pressure will
bring a net change to the equilibrium in the direction where the total number of moles is decreasing.
Decrease in total pressure will bring the net change to equilibrium in the direction where the total
number of moles is increasing i.e. backward direction.
Case III: When there is no change in the total number of moles of reactant and product as in the
following state of equilibrium. There is no net change in equilibrium state when pressure is changed.
Case I Case II Case III

Equilibrium Constant & Gibbs Free energy:

The Equilibrium constant is related to the standard Gibbs free energy change for the reaction. The
relation is given by the equation:

Where, R is the universal gas constant, T is the temperature and Keq is the equilibrium constant. Using
the definition of Gibbs free energy & Gibbs free energy Isotherm equation, we have:

Where, Keq is the equilibrium constant at temperature T, ΔH⊖ and ΔS⊖ are constants and
are enthalpy and entropy of the system respectively. This graph of this equation is called the Van‘t
Hoff plot. The plot is used to estimate the enthalpy and entropy of a chemical reaction. From the plot
between “ln Keq” & “1/T“, we have −ΔH/R as the slope, and ΔS/R as the intercept of the linear fit.
Equilibrium constant Kc depends on the temperature of the reaction and the relation is given by Van’t
Hoff equation.

K1 is the equilibrium constant at absolute temperature T1, K2 is the equilibrium constant at absolute
temperature T2, R is the ideal gas constant, ΔH reaction enthalpy assumed to be constant over the
temperature range. This equation can be used to estimate a new equilibrium constant at a new absolute
temperature assuming a constant standard enthalpy change over the temperature range. Let’s
understand the change in the equilibrium constant for two different kinds of reactions: Endothermic &
Exothermic.

12 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
Types of Chemical Equilibria
There are two types of chemical equilibria: Homogeneous equilibria and Heterogeneous equilibria
Homogeneous Equilibria. The equilibrium reactions in which all the reactants and the products are in
the same phase are known as homogeneous equilibrium reactions. These are divided into two
categories:
The number of product molecules is equal to the number of reactant molecules. For example:

In the above equation, Δn = (number of moles of gaseous products)− (number of moles of gaseous
reactants) in the balanced chemical equation and while calculating Kp, pressure should be expressed in
bar (1 bar = 105 Pa = 105 Nm−2)
Heterogeneous Equilibria. The equilibrium reactions in which the reactants and the products are
present in different phases are known as heterogeneous equilibrium reactions. For example;

The concentrations of pure solids like [CaO] and [CaCO3] in the above case or the pure liquids to be
considered as constant and do not appear in Kp expression.

Weak and strong electrolytes

A redox reaction involves the transfer of electrons from one chemical species to another. Amount
(moles) of the salt that has made the solution saturated per liter of solution is called the solubility of
the salt. For salt AB.

Those substances which allow the passage of electricity by way of the aqueous solution or the fused
state and undergo chemical decomposition are called electrolytic conductors. Some examples are the
aqueous solution of acids. bases and salts. Following are the two types of electrolytes;
• Strong electrolytes: Those electrolytes which completely ionise or dissociate into ions are
known as strong electrolytes. Some of the examples of strong electrolytes are HCl, NaOH,
K2SO4.
• Weak electrolytes: Those electrolytes that dissociate partially (ex < 1) are known as weak
electrolytes. Some of the examples of weak electrolytes are CH3COOH, H2CO3, NH4OHH2S,
etc.

13 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
The energy from a redox reaction can be used to accomplish work by constructing an electrochemical
cell. In an electrochemical cell, the oxidation process and the reduction process are separated into two
half-cells connected by an external wire. The half-cell with the oxidation process is losing negative
charge (e− loss) while the half-cell with the reduction process is gaining negative charge (e− gain). To
maintain electrical neutrality in both half-cells, a salt bridge (or semipermeable membrane) must
connect the two half-cells to permit the transfer of ions between the two solutions. Thus, the salt
bridge completes the electrical circuit between the half cells.
The transfer of electrons through the external wire create a current that can do work. The driving force
pushing the electrons through the wire is the difference in the attraction for electrons in the two half-
cells. This voltage difference is called the cell potential (Ecell) and is measured in volts. The cell
potential (Ecell) is directly related to the magnitude of the equilibrium constant for the overall
oxidation-reduction reaction occurring in the cell. A reaction that more strongly favors product
formation (larger Keq) will have a higher cell potential (larger Ecell) than a reaction which only
moderately favors product formation.

Standard electrode potential and its application to different kinds of half cells
Standard cell potentials (E°cell) can be calculated from potentials (E°) for oxidation and reductions
reactions measured under standard conditions (1.00 M solutions, 1.00 atm pressure, 298 K). A positive
cell potential means the reaction proceeds spontaneously in the direction the reaction is written; a
reaction with a negative cell potential proceeds spontaneously in the reverse direction.

A galvanic cell is constructed from solutions in two beakers connected by a salt bridge and an external
wire. One beaker contains 0.15 M Cd(NO3)2 and a Cd metal electrode. The other beaker contains 0.20
M AgNO3 and Ag metal electrode. In the reaction, cadmium metal is oxidized (loses electrons) and is,
therefore, the anode. The silver ion is reduced (gains electrons) to form Ag0 (the cathode).

Cell Notation Rules:

1. The anode half-cell is described first; the cathode half-cell follows. Within a given half-cell, the
reactants are specified first and products last. As the reader's eye proceeds from left to right s/he is
reading a description of the oxidation reaction first and the reduction reaction last (in other words - the
direction of electron flow). Spectator ions are not included.
2. A single vertical line indicates that species are in different phases (e.g. solid electrode |liquid with
electrolyte), but in physical contact with each other. A double vertical line indicates a salt bridge or
porous membrane separating the individual half-cells.
3. The phase of the species (s, l, g, aq) is always shown in parentheses. If the electrolytes in the cells
are not at standard conditions, concentrations and/or pressure should be included with phase in
parentheses as shown in equation (8). If no concentration or pressure is noted, the electrolytes in the
cells are assumed at standard conditions (1.00 M or 1.00 atm and 298K).
Although many applications of electrochemical cells involve a flow of current between the two
electrodes, the most fundamental kind of measurement we can make is of the voltage, or electro-

14 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
motive force (EMF) between the electrodes in the absence of any cell current. This voltage, which we
usually refer to as the cell potential, is the potential difference between the electrodes, and is the
difference between the half-cell potentials of the right and left sides. Each of the half-cell potentials is
in turn a potential difference between the electrode and the solution, so for our example cell the above
relation can be expanded as follows;

It is important to understand that individual half-cell potentials are not directly measurable; there is no
way you can determine the potential difference between a piece of metal and a solution. Attaching one
lead of a voltmeter to the metal and dipping the other in the solution would simply create a new half-
cell involving the immersed metallic conductor.

EMF and its measurement and application

When the concentrations of solutes or partial pressures of gases are not at standard conditions, the cell
potential (Ecell) can be determined with the Nernst equation. For the general cell reaction occurring at
298 K, the Nernst equation can be rewritten as shown as follows;

The Standard Potential Table in your textbook lists many half-cell reactions and their voltages. These
potentials are measured relative to a selected standard half-reaction (usually the Standard Hydrogen
Electrode (SHE).
The fact that individual half-cell potentials are not directly measurable does not prevent us from
defining and working with them. If we cannot determine the absolute value of a half-cell potential, we
can still measure its value in relation to the potentials of other half cells. In particular, if we adopt a
reference halfcell whose potential is arbitrarily defined as zero, and measure the potentials of various
other electrode systems against this reference cell, we are in effect measuring the half-cell potentials
on a scale that is relative to the potential of the reference cell. As a reference cell we use the half cell
whose reaction is;

This is the hydrogen electrode, an example of a gas electrode as was discussed above. When this
electrode is set up under standardized conditions, it becomes the standard hydrogen electrode,
sometimes abbreviated SHE. In order to measure the relative potential of some other electrode
M2+/M, we can set up a cell

But since the difference Vsoln-VPt is by definition zero for the hydrogen half-cell, the cell potential we
measure corresponds to

By carrying out a series of measurements in which various other systems are substituted for the
M2+/M couple, we can construct a table in which the various half-cell reactions are arranged in order
of their potentials. The conventional way of doing this, as shown in Table , is to write the half-cell
reactions as reductions, and to place them in the order of increasing (more positive) potentials. The
resulting values are known as the standard half-cell potentials, denoted byE0.
15 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
Batteries
A battery is an electrochemical cell or series of cells that produces an electric current. In principle,
any galvanic cell could be used as a battery. An ideal battery would never run down, produce an
unchanging voltage, and be capable of withstanding environmental extremes of heat and humidity.
Real batteries strike a balance between ideal characteristics and practical limitations. For example, the
mass of a car battery is about 18 kg or about 1% of the mass of an average car or light-duty truck. This
type of battery would supply nearly unlimited energy if used in a smartphone, but would be rejected
for this application because of its mass. Thus, no single battery is “best” and batteries are selected for a
particular application, keeping things like the mass of the battery, its cost, reliability, and current
capacity in mind. There are two basic types of batteries: primary and secondary. A few batteries of
each type are described next.
Primary batteries are single-use batteries because they cannot be recharged. A common primary
battery is the dry cell (Figure). The dry cell is a zinc-carbon battery. The zinc can serves as both a
container and the negative electrode. The positive electrode is a rod made of carbon that is surrounded
by a paste of manganese(IV) oxide, zinc chloride, ammonium chloride, carbon powder, and a small
amount of water. The reaction at the anode can be represented as the ordinary oxidation of zinc:

Alkaline batteries (Figure) were developed in the 1950s partly to address some of the performance
issues with zinc–carbon dry cells. They are manufactured to be exact replacements for zinc-carbon dry
cells. As their name suggests, these types of batteries use alkaline electrolytes, often potassium
hydroxide. The reactions are;

16 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
Secondary batteries are rechargeable. These are the types of batteries found in devices such as
smartphones, electronic tablets, and automobiles.
Nickel-cadmium, or NiCd, batteries (Figure) consist of a nickel-plated cathode, cadmium-plated
anode, and a potassium hydroxide electrode. The positive and negative plates, which are prevented
from shorting by the separator, are rolled together and put into the case. This is a “jelly-roll” design
and allows the NiCd cell to deliver much more current than a similar-sized alkaline battery. The
reactions are

Lithium ion batteries (Figure) are among the most popular rechargeable batteries and are used in many
portable electronic devices. The reactions are

The lead acid battery (Figure) is the type of secondary battery used in your automobile. It is
inexpensive and capable of producing the high current required by automobile starter motors. The
reactions for a lead acid battery are;

Fuel Cells
A fuel cell is a galvanic cell that requires a constant external supply of reactants because the products
of the reaction are continuously removed. Unlike a battery, it does not store chemical or electrical
energy; a fuel cell allows electrical energy to be extracted directly from a chemical reaction. In
principle, this should be a more efficient process than, for example, burning the fuel to drive an
internal combustion engine that turns a generator, which is typically less than 40% efficient, and in
fact, the efficiency of a fuel cell is generally between 40% and 60%. Unfortunately, significant cost
and reliability problems have hindered the wide-scale adoption of fuel cells. In practice, their use has
been restricted to applications in which mass may be a significant cost factor, such as US manned
space vehicles. These space vehicles use a hydrogen/oxygen fuel cell that requires a continuous input
of H2(g) and O2(g), as illustrated in Figure. The electrode reactions are as follows:
The overall reaction represents an essentially pollution-free conversion of hydrogen and oxygen to
water, which in space vehicles is then collected and used. Although this type of fuel cell should
produce 1.23 V under standard conditions, in practice the device achieves only about 0.9 V. One of the
major barriers to achieving greater efficiency is the fact that the four-electron reduction
of O2(g)O2(g) at the cathode is intrinsically rather slow, which limits current that can be achieved. All
major automobile manufacturers have major research programs involving fuel cells: one of the most
important goals is the development of a better catalyst for the reduction of O2(g)O2(g).
17 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
A fuel cell requires an external supply of reactants as the products of the reaction are continuously
removed. In a fuel cell, energy is not stored; electrical energy is provided by a chemical reaction.

Corrosion
Metals have a natural tendency to revert back to combined states. During this process mostly, oxides
are formed though in some cases sulphides, carbonates, subparts etc. may result due to presence of
impurities. Any process of deterioration and loss of solid metallic material by chemical or
electrochemical attack by its environment is called corrosion. Corrosion is the reverse process of
metallurgy. Corrosion may be defined as the destruction of a metallic material by chemical,
electrochemical, or metallurgical interaction between the environment and the material. As for
example, iron when exposed to atmospheric conditions resulting rust is hydrated oxide
(Fe2O3.xH2O).

This is mainly two types; Chemical and Electrochemical corrosion.

Dry or Chemical corrosion

This type of Corrosion occurs mainly through the direct chemical action of atmospheric gasses (O2,
halogen, H2S, SO2. N2 or anhydrous inorganic liquid) with metal surpasses in immediate proximity.
Therefore it also known as, dry corrosion. Three types of chemical Corrosion are as (1) Oxidation
corrosion (2) Corrosion by hydrogen (3) Liquid metal corrosion
(1) Oxidation corrosion
This is carried out by the direct action of oxygen low or high temperatures on metals in absence of
moisture at ordinary temperature metals or very slightly attacked. The Exceptions are Alkali metals
and Alkaline earth metals. At high temperature all metals are oxidized, exception is Ag, Au and Pt.

At the surface of metal oxidation occurs and the resulting metal oxide scale forms a barrier which
restricts further oxidation. For oxidation to continue either the metal must diffused outwards through
the scale to the surface or the oxygen must defuse inwards through the scale to the underlying metal.
18 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
Both the cases are possible. But the outward diffusion of metal is generally more rapid than inward
diffusion of oxygen since metal ion is appreciably smaller than the oxygen ion and hence more
mobile. When oxidation starts, a thin layer of oxide is formed on the metal surface and the nature of
this film decides further action. If the film is,
a) Stable, it behaves has a protective coating in nature e.g., the oxide films on Al, Pb, Cu, Pt etc., are
stable and therefore further oxidation corrosion of prohibited.
b) Unstable that is the oxide layer formed decomposes back into metal and oxygen. So, oxidation
Corrosion is not possible. e.g., Ag, Au and Pt do not undergo oxidation Corrosion.
c) Volatile that is oxide layer volatilizes after formation and as such leaves the underlying metal
surface exposed further attack. This causes continuous which is excessive. e.g. Molybdenum oxide
(MoO3)
d) Porous that is the oxide layer formed having pores or cracks. In this case the atmospheric oxygen
passes through the pores or cracks of the underlying metal surface. This causes continuous corrosion
till complete conversion of metal into its oxide. In this addition the Porous and Non-Porous Oxide
Film or Pilling-Bedworth Rule is as follows;
If the volume of the oxide layer formed is less than the volume of metal consumed, the oxide layer is
porous in nature. As for example, the volumes of oxides of alkali and alkaline earth metals are less
than the volume of the metal consumed. Thus the oxide layer is porous and non-protective.
On the other hand, if the volume of oxide layer formed is greater than that of the volume of the metal
consumed, the oxide layer is non-porous in nature. For example, the volumes of oxides of heavy
metals such as Pb, Sn etc. are greater than the volume of the metal consumed and thus the oxide layer
is nonporous as well as protective.
(2) Corrosion by hydrogen
One process is Hydrogen embrittlement. It is the formation of cracks and blisters on the metal by
hydrogen gas when the metal comes into contact with H2S. Iron liberates atomic hydrogen by reaction
with H2S as follows;
Fe + H2S → FeS + 2H
These hydrogen atoms diffuse into the voids of metal matrix. When the pressure of the gas increases,
cracks and blisters developed on the metal.
The other process is Decarburisation. It is process of decrease in the carbon content of the steel.
When steel is exposed to the above H environment the carbon in steel reacts with the atomic
hydrogen;
C + 4H → CH4
Hence, carbon content in steel decreases. The collection of methane gas in the void space of the steel
develops pressure and cause cracking for extreme level.
(3) Liquid metal corrosion
It is due to the chemical action of the following liquid metals at high temperature. It involves due to
(a) dissociation of a solid metal by the liquid metal or (b) penetration of liquid metal into the solid
metals.

Wet or Electrochemical corrosion

This type of Corrosion occurs where a conducting liquid is in contact with the metal or when two
dissimilar metals or alloys are dipped partially in a solution. This corrosion occurs due to the existence
of separate anodic and cathodic parts, between which current flows through the conducting solution.
At anodic area, oxidation reaction occurs thereby destroying the anodic metal either by dissolution or
formation of compounds. Hence corrosion always occurs at anodic parts. At cathodic part, reduction
reaction (electro nation) occurs. It does not affect the cathode, since most metals cannot be further
reduced. At cathodic part, the dissolved constituents in the conducting medium accepts the electrons
forming ions (OH-, O2-). The metallic ions formed at anodic part and the ions formed at cathodic part
diffuse towards each other through conducting medium and form a corrosion product somewhere
between anode and cathode.

19 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
Mechanism
Electrochemical corrosion involves flow of electrons between anode and cathode. The anodic reaction
involves dissolution of metal liberating free electrons.

Reduction reaction can occur in the cathode at different environment. In acidic environment the
hydrogen is evolved at the cathode;
2H+ + 2e- → H2
In neutral or slightly alkali medium hydroxide ion is formed in the cathode;
½O2 + 2e- + O2 → H2O + 2OH-
The cathodic reaction consumes electrons with either (a) evolution of hydrogen or (b) absorption of
oxygen which depends on the nature of corrosive environment.
(a) Evolution of hydrogen
This type of corrosion occurs in acidic medium e.g., considering the metal Fe, anodic reaction is
dissolution of iron as ferrous ions with liberation of electrons.

The electrons released flow through the metal from anode to cathode, whereas H+ ions of acidic
solution are eliminated as hydrogen gas.

This type of corrosion causes displacement of hydrogen ions from the solution by metal ions. All
metals above hydrogen in electrochemical series have a tendency to get dissolved in acidic solution
with simultaneous evolution of H2 gas. The anodes are large areas, whereas cathodes are small areas.
(b) Absorption of oxygen
For example rusting of iron in neutral aqueous solution of electrolytes in presence of atmospheric
oxygen. Usually the surface of iron is coated with a thin film of iron oxide. If the film develops cracks,
anodic areas are created on the surface. While the metal parts act as cathodes. It shows that anodes are
small areas, while the rest metallic part forms large cathodes.

20 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
Types
There are two types (1) Galvanic corrosion and (2) Differential aeration or Concentration cell
corrosion.

(1) Galvanic corrosion

When two dissimilar metals are electrically connected and exposed to an electrolyte, the metal higher
in electrochemical series undergoes corrosion. This type of corrosion is called Galvanic corrosion
.e.g., Zinc (higher in electrochemical series) forms the anode and is attacked and gets dissolved;
whereas Fe or copper (lower in electrochemical series) acts as cathode. For example, steel screw in a
brass marine hardware easily undergo corrosion. Fe has potential -0.44V and that of Cu is +0.34V. Fe
corrodes in reference to Cu.

Mechanism: If the solution is acidic then corrosion occurs by hydrogen evolution process and if the
solution is neutral or slightly alkaline in nature then corrosion occurs by oxygen absorption process.
The electrons flow from the anodic metal to the cathodic metal.

(2) Differential aeration or Concentration cell corrosion

This type of corrosion is due to electrochemical attack on the metal surface exposed to an electrolyte
of varying concentrations or of varying aeration. The most common type of concentration cell
corrosion is the differential aeration corrosion which occurs when one part of metal is exposed to
different air concentration from other part. This causes a difference in potential between the differently
aerated areas. Experimentally it has been observed that poor oxygenated parts are anodic. Differential
aeration of metal causes a flow of current called the differential current. If a metal e.g., Zn is partially
immersed in a dilute solution of a neutral salt e.g., NaCl and the solution is not agitated properly, then
the parts above and adjacent to the waterline are strongly aerated and hence become cathodic. Whereas
parts immersed show a smaller oxygen concentration and become anodic. So there is a difference of
potential which causes flow of current between two differentially aerated areas of same metal. Zinc
will dissolve at anodic areas and oxygen will take up electrons at the cathodic areas forming hydroxyl
ion. Following are the facts about differential aeration corrosion:
(a) Less oxygenated part is the anode. Therefore cracks serve as foci for corrosion.
(b) Corrosion is accelerated under accumulation of dirt, scale or other contaminations. This restricts
the access of oxygen resulting an anode to promise greater accumulation. The result is localized
corrosion.
(c) Metals exposed to aqueous media corrode under blocks of wood or glass which restricts the access
of oxygen.

21 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
The examples of different aeration corrosion are as follows;
(a) Waterline corrosion: This is also known as differential oxygen concentration corrosion. In
general, when water is stored in a steel tank, it is observed that the maximum amount of corrosion
takes place along a line just beneath the level of the water meniscus. The area above the waterline
(highly oxygenated) acts as cathodic and is not affected by corrosion. However, if the water is
relatively free from acidity, little corrosion occurs. The problem of waterline corrosion is a matter of
concern for marine engineers. This type of corrosion is prevented to a great extent by painting the
sides of the ships by antifouling paints.
(b) Pitting corrosion: It is a localized accelerated attack, resulting in the formation of cavities around
which the metal is relatively unattacked. Thus the corrosion is a localized accelerated attack resulting
in the formation of pits, holes or cavities. Pitting corrosion therefore results in the formation of
pinholes, pits and cavities in the metal. The pitting corrosion may be due to following reasons:
a) Metal surface are not homogeneous.
b) External environment is not homogeneous.
c) Films are not perfectly uniform.
d) Crystallography directions are not equal in the reactivity.
e) Environment is not uniform with respect to concentration.
Pitting is usually the result of the breakdown or cracking of the protective film on a metal at specific
points. This gives rise to the formation of small anodic and large cathodic areas. In process of correct
environment this produces corrosion current. e.g., Stainless steel and aluminum show characteristic
pitting on chloride solution. Pitting is caused by the presence of sand, dust scale and other extraneous
impurities (like sand, dust, scale etc.), present on the metal surfaces. Because of differential amount of
oxygen in contact with the metal, the small part (underneath the impurity) becomes the anodic areas
and the surrounding large parts become the cathodic areas. Intense corrosion takes place in the anodic
areas underneath the impurity. Once a small pit is generated, the rate of corrosion will be increased. If
the presence of some extraneous impurities like sand, dust and scale is checked, pitting can be
reduced. If the concentration of oxygen is uniform, then also pitting is reduced. Otherwise differential
aeration corrosion takes place leading to pitting.

(c) Crevice corrosion: Let a crevice or crack between two different metallic objects be contact with a
liquid. The crevice acts like anode due to less oxygen and corrodes. The exposed area acts as a
cathode. Examples are rivets, joints etc.

(d) Pipeline corrosion: Buried pipelines or cables passing from one type of soil (clay, less aerated) to
another type of soil (sand, more aerated) get corroded due to different aeration.
(e) Corrosion on wire fence: In a wire fence the wires at the crossings are less aerated than the rest of
the fence and so, corrosion takes place at the wire crossings which become anodic.

22 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
(f) Stress corrosion: stress corrosion is the combined effect of static tensile stresses and the corrosive
environment on the metal. It is characterized by a highly localized attack occurring, when overall
corrosion is negligible. For stress corrosion to occur:
1. Presence of tensile stress, and
2. A specific corrosive environment are necessary.
The corrosive agents are highly specific and selective such are;
a. Caustic alkalis and strong nitrate solution for mild steel.
b. Traces of ammonia for brass,
c. acid chloride solution for stainless steel.
This type of corrosion is seen in fabricated articles of certain alloys like high-zinc brasses and nickel
brasses due to the presence of stresses caused by heavy working like rolling, drawing or insufficient
annealing. However, pure metals are relatively immune to stress corrosion. Stress corrosion involves
in a localized electrochemical corrosion, occurring along narrow paths, forming anodic areas with
respect to the more cathodic areas at the metal surface. Presence of stress produces strains, which
result in localized zones of higher electrode potential. These become so chemically-active that they are
attacked, even by a mild corrosive environment, resulting in the formation of attack, which grows and
propagates in a plant, until failure occurs or it may stop, after progressing a finite distance.

(g) Erosion corrosion: Erosion corrosion results by the combined effect of the abrading action of
vapours, gases and liquids and the mechanical rubbing action of solids over the surface of metals. This
type of corrosion is caused by the breakdown of a protective film at the spot of impingement and its
subsequent inability to repair itself under existing abrading action removes protective films from
localized spots on the metal surface, thereby resulting in the formation of differential cell at such areas
and localized corrosion at anodic points of the cells. Erosion corrosion is most common in agitators,
piping, condensers, tubes and vessels in which steams of liquids or gases emerge from an opening and
strike the side walls with high velocities.

Difference between Dry or Chemical and Wet or Electrochemical corrosion

Dry or Chemical Corrosion Wet or Electrochemical corrosion
1. It occurs in dry condition. 1. It occurs in presence of moisture or
electrolyte
2. It occurs by the direct chemical attack on 2. It occurs by formation of a large number
the metal by the environment. of anodic and cathodic areas.
3. Even a homogenous metal surface is 3. Only heterogeneous or bimetallic metal
corroded. surface is corroded.
4. Corrosion products gather at the place of 4. Corrosion occurs at the anode while the
corrosion. products form elsewhere.
5. It is self controlled process. 5. It is a continuous process.
6. It takes place by adsorption mechanism. 6. It follows electrochemical reaction.
7. Example: mild scale formation on iron 7. Example: rusting of iron under moist
surface. atmosphere.

23 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
Factors affecting the rate of corrosion
The rate and extent of corrosion depends on the (1) nature of the metal and (2) nature of corroding
environment.
(1) Nature of the metal
a. Position in galvanic series: When two metals or alloys are in electrical contact in presence of an
electrolyte the more active metal having higher position in the galvanic series undergoes corrosion.
The greater is the difference in position, the faster is the corrosion.
Galvanic Series: it is used to provide sufficient information in predicting the corrosion behavior in a
particular set of environmental conditions. Oxidation potential measurement of various metals and
alloys has been made using standard calomel electrode as the reference electrode and immersing the
metals and alloys in sea water. These are arranged in decreasing order of activity and this series is
known as the galvanic series.

b. Area of anode and cathode: Corrosion will be severe if the anodic area is smaller and cathodic area
is larger. The larger cathodic area demands more electrons and so the anodic area corrodes faster.
c. Purity of metal: 100% pure metal will not corrode, e.g., pure Zn does not corrode. The trace amount
of impurity or other metal helps for corrosion, e.g., Zn with Fe or Cu impurity forms a electrochemical
cell and easily corrodes.
d. Over voltage: reduction in overvoltage of the corroding metal accelerates the corrosion rate. As for
example, the Zn in 1N H2SO4 undergoes corrosion slowly because of high overvoltage of Zn metal
(0.7 V) which reduces the effective potential to a small value. In presence of CuSO4 the corrosion rate
of zinc is accelerated.
e. Nature of surface/oxide film: In aerated atmosphere, all metals get covered with a thin surface film
of metal oxides. The ratio of the volumes of metal oxides to the metal is known as specific volume
ratio. Greater is this value lesser is the oxidation corrosion rate. Specific volume ratios of Ni, Cr and
W are 1.6, 2.0 and 3.6 respectively suggesting Tungsten has least corrosion. Further the corrosion
depends on nature of oxide film. Metals like Al have a firm oxide film in comparison to Fe and hence
Al in less corrosive means it follows Pilling-Bed worth Rule. The iron oxide is porous in nature and
this leads to extension of corrosion to inner surface.
f. Nature of Corrosion Product:
Solubility of corrosion products: In electrochemical corrosion if the corrosion product is soluble in the
corroding medium then corrosion is rapid. If the corrosion product is insoluble, then acts as barrier
thereby suppressing further corrosion.
Volatility of corrosion products: If the corrosion product is volatile, then the underlying surface is
exposed for further attack. This causes rapid and continuous corrosion. E.g. MoO3 is volatile.
(2) Nature of corroding environment
a. Temperature: As the temperature of environment is increased the reaction rate is increased thereby
accelerating corrosion. The effect of temperature on the corrosion rate is complicated because of the
fact that it affects the various factors in different ways. The rate of chemical reaction increases, with
rise in temperature but the solubility of gases, like oxygen which affect corrosion, decreases. The
temperature may affect the protective coatings in different ways. In general, the rate of corrosion due
to oxygen or oxidizing agents is decreased with rise in temperature but the rate of hydrogen type
corrosion is increased.
b. Effect of pH: In the corrosion reaction described H+ or OH- are also involved. Therefore the effect
of pH is obvious. It can be easily seen from the chemical equation for a reaction the direction in which
it will shift by change in concentration of H+ or OH-. As a general rule, acids are more corrosive than

24 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
neutral or alkaline solutions. Exceptions to the rule are amphoteric metals, aluminium, zinc and lead,
which form anions as well as cations. In acid solutions these react quickly like other metals but in
alkaline solutions they form complex ions and go into solution. Consequently these metals most
resistant to corrosion in neutral solutions. In the case of other metals the corrosion rate is higher in
acidic solutions than in alkaline solutions. The corrosion of iron or steel is quite slow in alkaline
solutions and gradually increases as acidity increases and becomes rapid when the pH value is below,
say, 4.5 to 3. This is the reason why the pH value of water for boiler feed or for cooling systems is
kept in the alkaline range. The Fe corrosion with pH is shown in figure below.

c. Effect of Oxidant: Oxidizing agents may increase or decrease corrosion rates. Systems handling
water, e.g., boilers, heat exchangers, etc., are faced with serious corrosion problems due to dissolved
oxygen. In high pressure boilers less than 0.005 mg/l of dissolved oxygen is permissible. The
oxidizing agents oxidize materials and are themselves reduced at cathodes and, thereby support
cathode reaction and promote corrosion. It is not4eworthy that on some metals, like stainless steels.
Aluminum and magnesium, a thin film of oxide is deposited on the surface rendering the metal
resistant to corrosion and makes it passive. Such metals and alloys are more resistant in oxidizing
environments. Monel metals corrode rapidly in the presence of air whereas 18-8 stainless steel
corrodes rapidly in the absence of air. It has been reported that in an experiment using 5% sulphuric
acid at 30OC the corrosion rate of Monel metal was 240 mdd (mg per square decimeter per day). When
the acid solution was saturated with air, but on exposure to the same solution free from air corrosion
was 40 mdd. Under similar conditions the corrosion rates of stainless steel were 2 and 300 mdd. This
illustrates the sharp difference in the behaviors of Monel and stainless steel both of which are known
for their resistance to corrosion. Hence, care needs to be taken while using materials.
d. Humidity of air: critical humidity is defined as the relative humidity above which the atmosphere
corrosion rate of metal increases sharply. The value of critical humidity depends on nature of metal
and corrosion products. Corrosion of a metal is furnished in humid atmosphere because gases (CO 2,
O2) and vapours present in atmosphere furnish water to the electrolyte essential to establish an
electrochemical corrosion cell. The oxide film on the metal surface has the property to absorb
moisture. In presence of this absorbed moisture, corrosion rate is enhanced. Rain water may also wash
away the oxide film from the metal surface. This leads to enhanced atmospheric attack. The
exceptions are Cr, Al. A mild steel equipment handling water gets corroded at a faster rate as the
temperature increases, because of a higher rate of chemical reaction, reaching the maximum rate 80 0.
Above this temperature the effect of lower solubility of oxygen in water becomes dominant and the
rate of corrosion falls sharply. Similar results have been reported for the corrosion of Monel metal in
dilute sulphuric acid in the presence of air. The effect of temperature on the corrosion of zinc in
distilled water is interesting. Up to 50O the protective coating formed by the corrosion protects zinc.
Above 50O the protective coating gives way and rapid corrosion takes place up to about 65O. Above
65O the effect of decreasing solubility of oxygen becomes pronounced and the corrosion rate falls.
e. Corrosive gases: Acidic gases like CO2, SO2, H2S etc. produce electrolyte and increase corrosion.
f. Presence of suspended particles: Particles like NaCl, (NH4)2SO4 etc. along with moisture are
powerful electrolyte and increase the rate of corrosion.

25 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi
 Question Bank
Department of Chemistry, BIT, Mesra
CH101: Chemistry
Module V: Phase and Chemical equilibrium

1. Discuss the following terms: Phase, Component, Degree of Freedom.

2.a. Calculate the number of components in the following systems:
i)KCl-NaCl-H2O
ii)CaCO3(s)→ CaO(s)+CO2(g)
b.Calculate the number of degrees of freedom in the following systems
i) 2KClO3(s)→2KCl(s) +3O2(g)
ii) An aqueous solution of sodium chloride
c. What is the maximum degree of freedom for a:
i) Single component system.
ii) Pure substance under equilibrium.
5. Draw a neat phase diagram of water system, Discuss the behaviour of various equilibrium
involved in the system with varying pressure and temperature. How does the melting point of
ice change with the pressure and why?
6. What is condensed system? Why in such a case the phase rule equation is F=C-P+1?
7.Construct the phase diagram of lead-silver system and describe its use in understanding:
i) Eutectic point ii) Desilverization of argentiferrous lead
8. Define and compare the terms triple point and Eutectic point.
9. What is “ reduced phase rule”? Explain the terms involved in it.
10.Give the cooling curves ( not to scale- temp vs time) for the following:
i) 100% pure Ag
ii) 50% Pb & 50% Ag
iii) 97.4% Pb & 2.6% Ag
11. What is chemical equilibrium? Explain with example.
12. What are the characteristics of equilibrium state?
13. State and explain the law of chemical equilibrium.
14. What is equilibrium constant? What is Kp and Kc? What are their significances?
15. What is the relation between Kp and Kc?
16. What is the relation between equilibrium constant & Gibbs free energy? Hence explain about endothermic
and exothermic reactions.
17. What are two types of chemical equilibrium? Explain about Homogeneous equilibria and Heterogeneous
equilibria.
18. What is EMF? Describe the measurement of EMF of a cell.
19. Write short note on batteries.
20. Describe about primary and secondary batteries with example.
21. Write short note on;
(a) Zinc-carbon battery
(b) Alkaline battery
(c) Nickel-cadmium battery
(d) Lithium ion battery
(e) Lead acid battery
22. Describe the principle of fuel cell.
23. Define corrosion of metals. What are different types of corrosion?
24. Explain the electrochemical theory of wet corrosion.
25. Write short notes on a) pitting corrosion b) stress corrosion c) oxidation corrosion
26. Write short notes on Pitting corrosion and Stress corrosion.
27. Write a note on bimetallic corrosion.
28. Write a note on corrosion inhibitor.
29. Give reason why stainless steel is not used to build sea-going ship.
30. Differentiate between chemical corrosion and electrochemical corrosion.
31. What is Galvanization corrosion? Explain with example.
32. What are the factors affecting the rate of corrosion?

26 Prepared by Dr. P. Kar, Asst. Prof., Dept. Chem., BIT Mesra, Ranchi