Applied Chemistry MS-133

1|Chemical Kinematics & Catalysis
Unit 3
Thermodynamics & Electrochemical
Phenomenon
Thermodynamics
(Greek word thermos = Heat and dynamics = movement or flow)
The term thermodynamic is derived from Greek words thermos meaning heat and dynamic
meaning movement or flow. So chemical thermodynamics concerns with the study of the
flow of heat energy during a chemical reaction. OR
The study of flow of heat or any other form of energy into or out of a system as it undergoes
a physical or chemical transformation, is called thermodynamics.
Thermodynamics terms and concepts
1. System and Surrounding
A system is that part of the universe which is under experimental study and the rest of the
universe is surroundings.
2. Boundary
The real or imaginary surface separating the system from the surroundings is called
boundary. For example, boiling water in a beaker
When a reaction is carried out in a beaker, the content of the beaker constitutes the system
while the entire reaming part of the universe is surrounding. The surface of the liquid
contents in the beaker
3. Types of system
There are three types of system.
a) Open system
A system which can exchange both matter and energy with the surroundings is called an
open system. Due to these exchanges, matter and energy do not remain constant in open
system. For example, water in a beaker placed on a table.
b) Closed system
A system which can exchange energy but not matter with the surroundings is called a closed
system. For example, a liquid in equilibrium with its vapours in a closed vessel.
c) Isolated system
A system which can neither exchange matter nor energy with the surroundings is called an
isolated system. For example, boiling water in a thermos-flask.
4. Thermodynamics process
The path or operation by which a system changes from one state to another. The various
processes are
i. Isothermal process
It is the process in which temperature of the system reamians constant during each step.
This is achieved by placing the system in a thermostat.
Mathematically T = Constant dT = 0
ii. Adiabatic process
A process in which no heat is exchanged between the system and its surroundings, is called
adiabatic process. Such a process is achieved by insulating the system from its
surroundings.
Mathematically q = Constant dq = 0
iii. Isobaric process
It is the process in which pressure of the system remains constant during each step.
Mathematically P = Constant dP = 0
iv. Isochoric process
It is the process in which volume of the system remains constant. In this process no external
work is done. Mathematically V = Constant dV = 0
v. Cyclic process
A process which brings back a system to its original state after a series of changes is called
a cyclic process.
As the internal energy (E) and enthalpy (H) depend only on their states, it means that in
cyclic process, the changes in E and H are zero.
Mathematically E = Constant dE = 0
And H = Constant dH = 0
5. State function
The thermodynamic parameters which depend only upon the initial and final states of the
system and are independent of the how the change is accomplished are called state
functions. For example internal energy (E), enthalpy (H), entropy (S), free energy (G),
pressure (P), temperature (T), and volume (V) etc. Heat (q) and work (W) are path
dependent, are not the state functions. A system in which the state functions (variables)
have constant values throughout is said to be in a state of thermodynamic equilibrium.
Nature of Heat, Work and Energy
Work
It is defined as the produce of force and distance. Mathematically
W=F  S
Work is motion against an opposing force. Doing work is equivalent to raise a weight
somewhere in the surroundings. An example of doing work is the expansion of the gas that
pushes out a piston and raises a weight.
Unit of work
In CGS system the unit of work is erg. Since the erg is small, a bigger unit, joule (J) is now
used. Work is measured in joules in SI units.
1J = 107 erg
1 erg =107 J
We often use Kilojoule (kJ) for large quantities of work
1 kJ =1000 J
Energy
The energy of a system is its capacity to do work.
Heat
The quantity of energy that flows across the boundary of a system during a change in its
state due to difference in temperature between the system and its surroundings.
Unit of Heat
The unit of heat is calorie (cal). SI unit of heat is joule (J).
1 joule = 0.2390 calories
1 calorie = 4.184 J
1 kcal = 4.184 kJ
Sign convention of heat
The symbol of heat is q. If the heat flows from the surroundings into the system, it is taken as
+q. If the heat flows from the system into the surroundings, it is taken to be –q.
Sign convention of work

The symbol of work is w. if work is done on a system by the surroundings and the energy of
the system is increased, it is taken to be positive +w. If work is done by the system on the
surroundings and energy of the system is decreased, it is taken to be negative, -w.
Summary of sign convention
Heat flows into the system, q is +ve Heat flows out of the system, q is –ve
Work is done on the system, w is +ve Work is done by the system, w is –ve
Pressure-volume Work
Consider a gas contained in a cylinder fitted with a
frictionless piston. The pressure of the gas P, exerts
a force on the piston. This can be balanced by
applying an equal but opposite pressure Pext from
outside on the piston. It is important to remember
that it is the external pressure, Pext and not the
internal pressure of the gas itself which is used in
evaluating work.
If a gas expands at constant pressure, the piston
would move through a distance  ,
Work = Force  distance
W=F  
Since pressure is force per unit area
F
P=
A
F = Pext  A
Where A is the cross sectional area of the piston
F = Pext  A  
F = Pext  V
Where V is the increase in volume of the gas.

Since the system (gas) is doing work on the surroundings (piston), it bears negative sign.
Thus
W = - Pext  V
In the same way equation for work done in compression of gas can be calculated as
W = Pext  V
It may be noted that the work done by a system is not a state function.
Reversible and Irreversible process
Reversible Process
A thermodynamic reverse process is one that takes place infinitesimally slowly and its
direction at any point can be reversed by an infinitesimal change in the state of the system.
In fact, a reversible process is considered to proceed from the initial state to the final state
through an infinite series of infinitesimally small stages. At the initial, final and all
intermediate stages, the system is in equilibrium state. This is so because an infinitesimal
change in the state of the system at each intermediate step is negligible.
Irreversible Process
When a process goes from the initial to the final state in a single step and cannot be carried
in the reverse order, it is said to be irreversible process.
Here the system is in equilibrium state in the beginning and at the end, but not at points in
between.
Example:
Consider a certain quantity of a gas contained in a cylinder having a weightless and
frictionless piston. The expansion of gas can be carried out by two methods illustrated in
Figure.
Let the pressure applied to the piston be P and this is equal to the internal pressure of the
gas. Since the external and internal pressures are exactly counterbalanced, the piston
remains stationary and there is no change in volume of the gas. Now suppose the pressure
on the piston is decreased by an infinitesimal amount dP. Thus the external pressure on the
piston being P – dP, the piston moves up and the gas will expand by an infinitesimal small
amount. The gas will, therefore, be expanded infinitely slowly, i.e. by a thermodynamically
reversible process. At all stages in the expansion of the gas, dP being negligibly small the
gas is maintained in a state of equilibrium throughout. If at any point of the process the
pressure is increased by dP, the gas would contract reversibly.
On the other hand, the expansion is irreversible (see Fig. 7.6b) if the pressure on the piston
is decreased suddenly. It moves upward rapidly in a single operation. The gas is in
equilibrium state in the initial and final stages only. The expansion of the gas, in this case,
takes place in an irreversible manner.
Difference between Reversible and Irreversible Process

Reversible Process Irreversible Process
1. It takes place in infinite number of 1. It takes place in finite time.
infinitesimally small steps and it would
take infinite time to occur.
2. It is imaginary as it assumes the 2. It is real and can be performed actually.
presence of frictionless and weightless
piston.
3. It is an equilibrium state at all stages of 3. It is equilibrium state only at the initial
the operation. and final stages of the operation.
4. All changes are reversed when the 4. After this type of process has occurred all
process is carried out in reversible changes do not return to the initial state
direction. by themselves.
5. It is extremely slow. 5. It proceeds at measurable speed.
6. Work done by a reversible process is 6. Work done by an irreversible process is
greater than the corresponding smaller than the corresponding reversible
irreversible process. process.
Work done in an isothermal reversible expansion of ideal gas
Consider an ideal gas confined in a cylinder with
a frictionless piston. Suppose it expands
reversibly from volume V1 to V2 at a constant
temperature. The pressure of the gas is
successively reduced from P1 to P2.
The reversible expansion of the gas takes place
in a finite number of infinitesimal small
intermediate steps. To start with the external,
Pext is arranged equal to the internal pressure of
the gas, Pgas and the piston remains stationary.
If Pext is decreased by an infinitesimal amount
dP the gas expands reversibly and the piston
move through a distance d .
Since dP is so small, for all practical purpose
Pext  Pgas  P
The work done by the gas in one infinitesimal

step dw , can be expressed as
dw  P  A  d  (A = cross sectional area of piston)
= P  dV
Where dV is the increase in volume
The total amount of work done by the isothermal reversible expansion of the ideal gas from
V1 to V2 is, therefore,
V2
w    PdV
V1
By the ideal gas equation

PV  nRT
nRT
P
V
V2
nRT
w   dV
V1
V
V2
dV
w   nRT 
V1
V
On integration we get
V2
w   nRT ln
V1
Since
PV
1 1  PV
2 2
V2 P1

V1 P2
P1
w   nRT ln
P2
P1
w  2.303nRT log
P2
First law of thermodynamics

The first law of thermodynamics is the law of conservation of energy. This law may be stated
in various forms.
Energy can neither be created nor destroyed but one form of energy can be converted into
another form of energy.
The total energy of the universe remains constant.
When one form of energy disappears, exactly the same amount of energy appears in some
other forms.
The net energy change of a closed system is equal to the heat transferred to the system
minus the useful work done by the system on the surroundings.
Mathematical formulation of first law of thermodynamics
Let us consider that the internal energy of system is E1. If the system is supplied with q
amount of heat then the internal energy of the system will increase to E 1 + q. If work (W) is
now done on the system, then the final internal energy is E2 is given by
E 2  E1  q + W
E 2 - E1  q + W
E = q + W
If heat is absorbed by the system (endothermic process), q is positive i.e.  is positive
If heat is evolved by the system (exothermic process), q is negative i.e.  is negative
If work is done on the system, W is positive.
If work is done by the system, W is negative.
Internal energy
The sum of all kinds of energies of the particles of the system is called internal energy.
The total of all possible kinds of energy of a system is called its internal energy.
The definite amount of energy which is stored in a system is called internal energy.
The energy stored in a system which is available for conversion into heat is called the heat
content or enthalpy of the system.
Absolute value of internal energy of a system cannot be measured. However, change in
internal energy ( E ) of a system can be measured. The internal energy is a state function
and depends only on the initial and final states of the system. Thus
E = E 2  E1
Where E1 and E2 are internal energies in the initial and final states of the system
respectively.
Enthalpy or heat content
The thermodynamic quantity (E + PV) is called the heat content or enthalpy of the system. It
is denoted by H.
Enthalpy is the sum of the internal energy and the product of its pressure and volume.
The total heat content of a system at constant pressure is equal to the sum of internal
energy E and product of PV.
H = E + PV
Where H = Enthalpy of system
P = pressure of system
V = volume of system
E = internal energy of system
Change in enthalpy
It is not possible to measure the absolute enthalpy how a change in enthalpy can be
measured accurately and is given by
We do not need the absolute value of the enthalpy. We only need the measurement of
enthalpy change. In thermodynamics processes, we are concerned with the change in
enthalpy H .
H1 = Enthalpy of system in initial state
H2 = Enthalpy of system in final state
Change in enthalpy, H = H 2  H1
Now H1 = E1 + P1V1 and H 2 = E 2 + P2 V2
H = (E 2 + P2 V2 )  (E1 + P1V1 )
H = (E 2 - E1 )  (P2 V2 + P1V1 )
H = E + PV
When P = Constant, then PV = PV
Hence
H = E + PV
H = E + (-PV) (Here the work is done by the system)
According to first law of thermodynamics
ΔE = q + PΔV
H = q + PV - PV
H = q
Since pressure is constant, so we can write
H = q P
This means that change in enthalpy is equal to the heat at constant pressure.
Relationship between H and  E
We know that H = E + PV
The difference between H and  E is a PV term related to work of expansion.
In case of solids and liquids, changes in state do not cause significant changes in the
volume i.e. V  0 . For such process, H and  E are approximately the same.
ΔH  ΔE (For solids and liquids only)
However, in case of gaseous reactants and products H and  E are quite different. For a
reaction suppose
10 | C h e m i c a l K i n e m a t i c s & C a t a l y s i s
n1 = moles of gaseous reactants
n 2 = moles of gaseous products

Then according to ideal gas equation at constant temperature and pressure
P1V1 = n1RT
P2 V2 = n 2 RT
PV2  PV1  n 2 RT - n 1RT
P (V2  V1 )  RT (n 2 - n1 )
PV = nRT
H = E + nRT
q P  q V + nRT
Equation shows the relationship between H and  E.
Units and sign convention of Enthalpy
H = H 2  H1
If H 2  H1 then H is positive and the reaction will be endothermic. If H1  H 2 then H is

negative and the reaction will be exothermic.
Entropy
It is measure of disorder or randomness of a system. Greater the disorder in a system,
higher is the entropy of the system. It is a state function and denoted by symbol “S”.
The entropy of a system varies directly with temperature.
q
S =
T
If heat is absorbed, then S is positive and there will be increase in entropy. If heat is
evolved, S is negative and there is a decrease in entropy.
Absolute entropy
Absolute entropy is also called standard entropy. It is denoted by S o and is the entropy of the
substance at 25oC (298K) and 1 atm pressure.
The change in entropy ( So ) for the reaction can be calculated by the following relation
ΔSo = S o
(products) - S o
(reactants)
sum of the standard abosute  sum of the standard absolute 

ΔSo =   -  
entropies of the products   entropies of the reactants 
Unit of entropy
As the entropy change is equal to the heat absorbed reversibly by the system divided by the
absolute temperature.
q (rev)
S = S(final) - S(initial) =
T
In SI system, the unit of entropy is joule per mole per degree i.e. J mol-1 K-1
Electrochemistry
Electrochemistry is the branch of chemistry which deals with the inter-conversion of electrical
to chemical energy and vice versa. For example
i) In battery, chemical energy is converted to electrical energy.
ii) In electroplating/electrolysis electrical energy is converted to chemical energy.
Electrochemical and galvanic series
Electrochemical reactions are predicted by electrochemical series. A metal having higher
position can replace (reduce) other metals that have lower position in the series. For
example
Zn + CuSO4 
 ZnSO 4 + Cu
i.e. Zn + Cu2 
 Zn2 + Cu
or in other words, zinc will corrode faster that copper.
Some exceptions have been observed in this generalization. For example, Ti is less reactive
than Ag.
Galvanic series is the series of metals that is made keeping in view the process of corrosion
of a metal in a particular atmosphere, i.e., seawater. In galvanic series, oxidation potential of
metals is arranged in the decreasing order of activity of a series of metals. The series is
towards the increasing noble nature.
More anodic: Mg, Mg alloys, Zn, Al, Cd, Fe, Pb, Sn, Ni-Mo-Fe-alloys, Brasses, Cu, Ni, Cr-
steel alloy, Ag, Ti, Au, Pt towards noble nature.
Electrochemical and galvanic series

In the electrochemical series, metals are arranged from top to bottom in increasing order of
their reduction potential. A metal high in the series is more anodic and undergoes corrosion
faster than the metal below it, i.e. Zn corrodes faster than Fe which in turn corrodes faster
than Sn. However, there are exceptions to this generalization, e.g, Ti is less corroded than
Ag (placed below Ti in electrochemical series). This is due to the fact that Ti develops
strongly adhering oxide layers on its surface, with the result it effective electrode potential
becomes more positive (or less negative). Thus electrochemical series does not account for
corrosion of all metals and alloys.
Hence a more practical series called galvanic series has been developed by studying the
corrosion of metals and alloys in a given environment like sea water. Thus, galvanic series
gives real and useful informations regarding corrosion of metals and alloys.
Comparison of Electrochemical and Galvanic Series

Electrochemical Series Galvanic Series
1. This series comprises of metals and non- 1. This series comprises of metals and
metals. alloys.
2. The position of a metal in this series is 2. Position of free metal and when present
permanently fixed. in the form of alloy is different.
3. It predicts the relative displacement 3. It predicts the relative corrosion
tendencies. tendencies.
4. Electrode potential is measured by 4. Corrosion of metals and alloys (without
dipping pure metals (without oxide films) oxide films) is studied in unpolluted sea
in their salt solution of 1M concentration. water.
5. Standard hydrogen electrode is used as 5. Calomel electrode is used as a reference
reference electrode. electrode.
CORROSION
Corrosion is defined as the slow and continuous destruction of metal or alloy due to the
chemical or electrochemical reaction with its environment.
The most familiar example of corrosion is rusting of iron when exposed to atmospheric
conditions. Similarly the formation of green film or basic carbonate [CuCO 3 + Cu(OH)2] on
the surface of copper when exposed to moist air containing CO2 and oxygen.
Causes of corrosion
Metal occurs in nature in two different forms. They are
1. Native state
2. Combined state
1. Native state
The metals occur in native, free, uncombined states or pure metal are highly stable and non-
reactive with the environment. They do not combine with other elements. They are noble
metals exist as such in the earth crust. They have very good corrosion resistance.
Examples are Au, Pt, Ag, Pd, Cu etc.
2. Combined state
Except noble metals, all other metals are reactive and form stable compounds as their
oxides, sulphides, chloride and carbonates. They exist in the form of stable compounds
called ore or mineral. Examples are FeO2, ZnO, PbS, CaCO3 etc.
Except noble metals, all other metals in the pure state are thermodynamically unstable as
they are considered in excited state i.e. higher energy state. Therefore, as soon as the
metals are extracted from their ores, the reverse process begins and form stable metallic
compounds, which are thermodynamically stable i.e. lower energy state.
corrosion (oxidation)
Metal (unstable) Metallic compound (stable)
The properties such as electrical conductivity, ductility, malleability etc. are lost due to
corrosion.
Over voltage
When a metal, which occupies a high position in galvanic series (say Zinc), is placed in
H2SO4 it undergoes corrosion forming a film and hydrogen gas.
The initial rate of reaction is quite slow, because of higher over voltage (0.70 V) of the Zn
metal, which reduces the effective electrode potential to a small value. However, because
some copper gets deposited on the zinc metal forming minute cathodes, where the hydrogen
over voltage is only 0.33 V, thus, reduction in over voltage of the corroding metal/alloy
accelerates the corrosion rate.
Zn has over hydrogen voltage due to which the rate of corrosion of Zn is very slow (Zn rod
dipped in ZnSO4). But when CuSO4 solution is added to H2SO4 Cu gets deposited on Zn rod
and acts as small cathode. For Cu higher over hydrogen voltage value is less. Hence rate of
corrosion of Zn in presence of Cu becomes more. Thus metals for which over voltage are
more get corrode slowly, where as those which have higher voltages, the rate of corrosion is
high.
For example, corrosion of Zn rod dipped in H2SO4 is very slow. When small amount of
CuSO4 solution is added to H2SO4, Cu gets deposited on the Zn rod and acts as cathode
and the rate of corrosion of Zn increases.
(over voltage of Zn metal is 0.73)
Differential Aeration Corrosion
This type of corrosion occurs when one part of the metal is exposed to a different air
concentration from other part of the metal. This develops a difference in potential between
differently aerated areas; the poor oxygenated parts act as anode. The flow of current
caused by differential aeration of metal is known as differential current.
Differential aeration corrosion occurs when metals are partially immersed in a solution just
below the waterline. Let us consider that a metal (say Zn) is partially immersed in a dilute
solution of a neutral salt (say NaCl) and the solution is not agitated properly. The parts
above and just below the waterline are strongly aerated and hence act as cathode, while the
parts immersed to a greater depth are weakly aerated and act as anode. Hence a difference
of potential is developed which causes a flow of current between the two differentially
aerated areas of the metal. Following reactions occur at the two areas (electrodes).
At anode  Zn 2 +
Zn  2e 
1
At cathode O2 + H2O + 2e  
 2OH
2
Similarly, corrosion of iron by water drops (or salt solution) can be easily explained. Areas
covered by droplets become anodic, while the other areas which are freely exposed to air
become cathodic.
From the above discussion, it is clear that oxygen concentration cell increases the corrosion
which occurs at the place where oxygen concentration is lower.
Differential aeration theory or concentration cell formation

theory
According to this theory, when a metal is exposed to varying concentration of air (oxygen) or
an electrolyte, concentration cell is formed. The metallic area which is exposed to less
amount of oxygen act as anode undergoes corrosion. The metallic area which is exposed to
greater amount of oxygen acts as cathode.
Corrosion of metal occurs due to difference in concentration of air or electrolyte. Hence this
theory is called differential aeration theory or concentration cell formation theory.
Examples
1. Corrosion on wire fence
In an iron fence the point where wire cross is less exposed to oxygen and becomes anode.
Therefore corrosion takes place at the point of contact where the wire crosses.
2. Metal partially immersed in water, the immersed portion is less exposed to oxygen and
becomes anode. Therefore corrosion takes place.
3. Metal are covered by drop of water, sand or dust.
The less oxygenated area acts as anode (gets corroded). The more oxygenated area acts
as cathode (protected from corrosion).
Reactions
at anode (less oxygenated area)
 Fe 2 + 2e 
Fe 
at cathode (more oxygenated area)

1
2 O 2 + H 2O + 2e  
 2OH 
Fe 2  2OH  
 Fe(OH) 2
Which is further oxidized to Fe(OH) 3. Since the anodic area is small and the cathodic area is
large, corrosion is more concentrated at the anode. Thus, a small hole is formed on the
surface of the metal. This type of intense localized corrosion is called pitting.
Factors influencing corrosion
There are two factors that influence the rate of corrosion. Hence a knowledge of these
factors and the mechanism with which they affect the corrosion rate is essential because the
rate of corrosion is different in different environment.
a) Nature of the metal b) Nature of the corroding environment
(a) Nature of the metal
i) Position in galvanic series
Metals and alloys placed higher in the galvanic series are more affected by the corrosion
than lower one.
ii) Purity of metal
Impurities in metal leads to the formation of small electrochemical cells. For example the rate
of corrosion of Aluminum in Hydrochloric acid with increase in percentage impurity is noted.
% purity of Al 99.99 99.97 99.2
Relative rate of corrosion 1 1000 3000
iii) Relative areas of anodic and cathodic parts

When two dissimilar metals or alloys are in contact, the corrosion of the anodic part is
directly proportional to the ratio of the cathodic and anoidic parts. So corrosion will be rapid
for smaller anodic area.
iv) Nature of surface film
The impervious, porous, volatile or non-adherent nature of film plays an important for
affecting the rate of corrosion.
v) Solubility of corrosion product
If the corrosion product is soluble in in the corroding medium, corrosion proceeds at a faster
rate. If it is insoluble corrosion will be suppressed, e.g. PbSO 4 formation on Pb surface in
H2SO4.
(b) Nature of the corroding environment
i) Concentration difference
ii) Temperature
The rate of corrosion is directly proportional to temperature i.e. rise in temperature increases
the rate of corrosion. This is because the rate of diffusion of ions increases with rise in
temperature.
iii) Humidity
The higher the humidity of the atmosphere the greater is the rate and extent of corrosion
because the moisture acts as solvent for O2 in air to produce the electrolyte which is required
for setting up a corrosion cell.
iv) Impurities
Atmosphere in industrial areas contains corrosive gases like CO 2, H2S, SO2 and fumes of
HCl and H2SO4. In the presence of these gases, the acidity of the liquid adjacent to metal
surfaces increases and its electrical conductivity also increases, thereby the rate of corrosion
increases.
v) Influence of pH
Generally, acidic media are more corrosive than alkaline and neutral media.
vi) Conductance of the corroding medium
This is important in case of underground or submerged structures. Since conductance of dry
sandy soils is lower than that of clayey and mineralized soils. Less damaged is caused to
underground lines buried under dry and sandy soils than in clay or mineralized soils.
Control of corrosion (Protection against corrosion)

Corrosion of metals causes tremendous loss of money and energy with a large scale
wastage of human resources. Complete stoppage of corrosion of all types is not possible,
however, it can be minimized by the use of different methods and by adopting some
preventive measures. The choice of the method depends upon the environmental conditions
and the nature of the corrosion.
Some useful and well known methods of avoiding and inhibiting corrosion are described
below:
1. Proper selection of metal
One of the simplest way to avoid corrosion is to use a metal giving better performance under
the requisite environment. For example “Tin” is completely inert to water, “lead” is resistant
to dilute H2SO4, aluminum resists atmospheric corrosion and Tantalum (Ta) is the most
suitable metal to resist most acids.
2. Using pure metal
Presence of impurities in a metal causes heterogeneity which makes it less resistant to
corrosion. For example pure aluminum develops an impervious protective oxide film on
exposure of atmosphere, which further protects the surface from corrosion as compared to
an impure sample of the metal.
3. Proper designing
Contact of dissimilar metals in presence of a corroding medium should be avoided. Similarly
sharp and cornels in piping system be minimized to avoid entrapment corrosive liquids at
such points. In the same way welding of tanks is preferable to riveting for avoiding crevice
corroding.
4. Use of metal alloys
Sometimes commonly used metals like Fe, Cu, Al and Zn etc easily undergo corrosion in
pure form. Their resistance to corrosion is much enhanced by alloying them with suitable
elements. For example Cr when alloyed with Fe produces a far better corrosion resistant
material than pure iron and is successfully used in cutlery, surgical instruments and springs
etc. corrosion resisting property is further improved by addition of Ni and Mo etc.
5. Cathodic and anodic protection
This method is usually applied to underground or submerged cables, pipe lines, ship hulls or
piers etc. It involved the principle of forcibly making the metal to act like a cathode. Here the
active metal parts are converted into non deteriorating cathodes by the application of
external current. The arrangement may be “cathodic” or “anodic” as illustrated below in the
diagram.
(i) Cathodic protection
In this arrangement the metal structure liable to be attacked is made cathode by impressing
a reversed flow of current so as to nullify the corrosion current. Usually the impressed
current is obtained from an external D.C source (battery or rectifier on A.C line) as in Figure.
(ii) Sacrificial or anodic protection
In this method the metal structure is connected by a wire to a more active anodic metal (like
Mg, Zn and Al etc). This more active metal itself get corroded and the parent structure is
saved from corroding. This sacrificial anode is then replaced when consumed.
6. By alteration of environment
Environment or medium is a strong determining factor for the severity of corrosion. Change
of concentration or removal/addition of substances which neutralize the corrosive
constituents of the medium considerably reduce the rate of corrosion. Use of “inhibitors” also
reduce the effectiveness of corrosion environment by
(a) Forming protective films
(b) Retarding evolution of H2 in acid media
(c) Reacting with corrosive agents
7. By using protective coatings
This is the old and most commonly method used for corrosion control. Coatings actually
isolate the metal surface from the corroding environment and are classified as detailed
below:
a) Organic coatings
Organic coatings like paints, varnishes, lacquers and enamels etc, when applied on the
clean metallic surface provide good protection and decoration to the metal. Their protective
value mainly depends on their chemical resistance to corrosion environment. Their use is
however, restricted where articles are subjected to friction and brazing/erosion etc.
b) Chemical conversion coatings
They include
(i) Oxide coatings (HgO and PbO etc)
(ii) Phosphate coatings
It is produced by treating base metal (Fe, Zn, Al, etc) with H3PO4 and phosphate of Zn or Mn.
It is usually applied on Fe, Al and Mg etc. They have good adherence. This process is also
known as “Phosphating”.
(iii) Chromatising
It is used as a passivating treatment after phosphatizing on Zn, Cd etc.
c) Organic linings
Now a days objects are protected by applying some rubber or plastic linings on metallic
surface. Rubber lining is accomplished by pressing a sheet of partially vulcanized rubber
against the steel surface and finally heating to 100 oC for vulcanization. Rubber layer is also
formed by dissolving soft rubber in petroleum along with sulphur and then applying the same
on the metal. Plastic lining are also cemented through suitable adhesives.
d) Ceramic coatings
Two types of such coatings are formed as detailed below:
i) Vitreous enamels
It is glass like material fixed on metallic surface by using wet and dry process. A slurry of
glass constituents or powder of the same is painted or dusted upon the steel object which is
then heated. A glass coating is bonded on the steel surface by means of ferrous silicate.
ii) Ceramic coating
They are obtained from high refractory oxides (Al 2O3, Cr2O3 etc). It is applied by dipping or
spraying and then heating for 3-15 minutes. Such coatings are used in utensils, sanitary
wares, table tops, bath tubs and for producing surfaces of thermal and electrical insulations.
e) Metallic coatings
This is an important method to provide a protective barrier against corrosion. A large number
of physical and electrochemical methods are used for the formation of desired metallic
coatings. These coatings may be ‘cathodic’ and ‘anodic’ in nature. Anodic coating is
obtained by using metals which are more anodic to the base metal (e.g. Zn and Al etc on
steel since their electrode potential is greater than that of Fe). On the other hand, ‘cathodic’
coatings are arranged by depositing a more noble metal (i.e. having lower electrode
potential) than the base metals (e.g. Sn coating on iron). These coatings act protective only
when completely ‘continuous’ and free from breaks.
Different methods of formation of metallic coatings are discussed blew:
i) Hot dipping
Hot dip coating of low melting point metals (Zn, Al, Sn etc) are obtained as given under.
a) Galvanizing
It is the process of producing thin coating of Zn on iron to protect from rusting steel article is
completely cleaned by treating it with dil.H 2SO4 for 15-20 minutes at 60-90oC and then are
dried. It is then dipped in molten zinc (425-430 oC) and passes through the rollers to squeeze
out superfluous zinc and ensure a thin, uniform layer.
b) Tinning
Here iron or steel articles are given a tin coating by passing them through tanks of mole tin
and finally through a series of rollers.
ii) Metal cladding
In this case a layer of metal is bonded firmly and permanently on one or both sides of the
base metal by sandwitching them together through rollers under heat and pressure. It finds a
wide use in aircraft industry.
iii) Metal spraying
It is the process in which molten metal is sprayed with the help of spray gun e.g. Zn and Al
wire or power is fed onto into oxyacetylene flame and throw on the steel surface by means of
compressed air.
iv) Cementation or diffusion coating
This process is employed for coating small, intricate shaped articles like nuts, bolts, screws,
nails and washers etc. The articles are packed and a rotary drum containing dust of coating
metal (Zn, Al, Cr etc) at a temperature just below their melting point and agitated strongly for
desired results. The process is called “Sherardizing”. If zinc is coated “calorizing” if aluminum
is used and “chormizing” when chromium is used.
v) Electrodeposition or electroplating
It is the best modern method of coating article industrially with protective metallic layer. In
this method the coating is deposited on the article by making it a cathode in an electrolytic
cell containing the soluble salt of the coating metal and then passing a DC current. The
anode is made of the coating metal or graphite. For example Ni may be electroplated on an
article (say a spoon) by using a solution of NiSO4 as shown in the diagram.
This method is popular and advantageously used for being quick, easy to control and for
depositing fine, smooth and uniform layers of a variety of metals (i.e. Ni, Cr and Ag etc).
Fuel cells
Fuel cell (rechargeable)
A fuel cell is a special type of galvanic cell in which reactants are continuously supplied as
they are consumed and the products are continuously removed. In fuel cell chemical energy
is converted into electrical energy. This type of cell finds importance in space vehicles. A fuel
cell is based on the reaction between oxygen and a gaseous hydrogen or methane. A fuel
cell is shown in figure. The electrodes are hallow tubes made up of porous compressed
carbon impregnated with platinum, which acts as a catalyst. The electrolyte is KOH. At
electrodes, hydrogen is oxidized to water and oxygen is reduced to hydroxide ions.
 H 2( g )  2OH  ( aq )  2 H 2O(l )   2 (at anode)

O2( g )  2 H 2O( l )  4e   4OH  (at cathode)
2 H 2( g )  O2( g ) 
 2 H 2O( l ) (overall reaction)
This fuel cell is operated at high temperature so that the water formed as a product of the
cell reaction evaporates and may be condensed and used as drinking water for an astronaut.
A number of these cells are usually connected together so that several kilowatts of power
can be generated.
The fuel cell produces electricity and pure water during space flights. Fuel cells are light,
portable and source of electricity. Many fuel cells do not produce pollutants. Some other cell
reactions in fuel cell are:
(i) 2 NH 3  3 O2 
 N 2  H 2O(l )
2
(ii) N 2 H 4  1 O2  N 2  2 H 2O( l )

2
(iii) CH 4  2O2   CO2  2 H 2O( l )
Fuel cells are very efficient. They convert about 75% of flues bond energy into electricity.
Advantages of Fuel cells
1. No emission of toxic gases. Chemical wastes are in safe limits. The reactants and
products are environmental friendly.
2. High efficiency of conversion of chemical energy to electrical energy. So can be used as
an excellent renewable energy resource.
3. No noise pollution like generators.
4. Low maintenance and fuel transportation costs.
5. Unlike nuclear energy, fuel energy is economical and safe.
6. Fuel cells are operable up to 200oC and so find applications in high temperature
systems.
Advantages of Fuel cells
1. The main limitation of fuel cells lie in high initial costs associated with electrode material
and design costs.
2. Large weight and volume of H2 gas fuel storage system.
3. High cost of H2 gas.
4. Lack of infrastructure for distribution and marketing of hydrogen gas.
5. Most alkaline fuel cells suffer from leakage of gasses.
Unit 5
Engineering Materials
GLASS
INTRODUCTION
Glass is an engineering material. It may be defined as an amorphous, rigid, brittle,
hard, transparent super cooled liquid. It is resistant to heat. It is a transparent mixture of
silicates of potassium or sodium.
It is produced by the fusion of certain basic oxides and acidic oxides, with sand and
other materials.
Composition of Glass
The composition of some common verities of glass is as follow.
1. Soda lime glass Na2O. CaO. 6SiO2
2. Potash lime glass K2O. CaO. 6SiO2
3. Potash lead glass K2O. PbO. 6SiO2
Raw material required for the manufacture of glass:
The raw materials for the manufacture of ordinary glass are of two kinds.
1. Acidic oxides: (SiO2), Boron oxides (B2O3)
2. Basic oxides: Sodium oxide (Na2O), Potassium oxides (K2O), calcium oxide (CaO),
Lead oxdies (PbO), Zinc oxide (ZnO), Magnesium oxide (MgO) and Aluminum oxide
(Al2O3).
Manufacture of Glass
Raw materials are:
1. Sand
2. Sodium carbonate
3. Calcium carbonate
Mixing
The raw materials are powdered well and they are mixed homogenously. With this some of
the broken glass powders are also added to get an intimate mixture known as “Batch”.
Fusion
The batch is then transferred to the tank or pot furnace. This batch is heated to 1400-
1500oC. at this temperature the substances present in the batch react together forming a
mixture of silicates. This mixture of silicates is known as glass.
Fining
The molten glass is kept at the highest temperature for some time to remove gas bubbles.
This is called fining.
Na2CO3 is often added to lower the viscosity of the molten glass. The impurities rise to the
top as scum and it is removed. Cullet, oxidizing agents, reducing agents and other materials
are also added to the molten glass according to the requirements.
Fabrication
Coloring material may be added to the molten glass to get desired coloured glass.
Molten glass is then moulded or fabricated into articles of desired shape by blowing,
moulding, or pressing.
Colouring materials colour
1. Cobalt oxides Blue
2. Cuprous salt Red
3. Chromium oxide Green
4. Ferric ion Yellow
5. Potassium dichromate Green
Annealing of glass
The method of slow cooling of glass is called annealing. If the manufactured hot glass
articles are cooled suddenly, it will easily break. To avoid this glass is cooled very slowly by
passing them through several hot chambers. The temperature of the hot chamber is in the
decreasing order gradually. This process of slow cooling of glass is called an annealing.
The annealing temperature varies for different types of glasses.
Photo chromatic glass
Photo chromic lenses are lenses that darken on exposure to specific types of light, most
commonly ultraviolet radiation. Once the light source is removed, the lenses will gradually
return to their clear state. Photo chromic lenses may be of glass, polycarbonate, or another
plastic. Traditional photo chromic eyeglasses are generally alkali boro-alumino silicates with
0.01 to 0.1% silver halide and a small amount of copper. Upon absorption of light, the silver
ion reduces to metallic silver, which nucleates to form colloids about 120 oA in size. This is
small enough to keep the glass transparent, but the colloids are dense enough to make the
glass look gray or black.
Windshield glass
A framed pane of usually curved glass or other transparent shielding located in front of the
occupants of a vehicle to protect them from the wind.
A shield placed to protect an object from the wind.
Modern windshield are generally made of laminated safety glass, a type of treated glass,
which consists of two (typically) curved sheets of glass with a plastic layer laminated
between them for safety, and are bonded into the window frame. Motorbike windshields are
often made of high-impact acrylic plastic.
Laminated glass is produced by permanently bonding two pieces of glass together with a
tough glass plastic interlayer (polyvinyl butyral, PVB) under heat and pressure. Once bonded
together, the glass and which acts as a single unit and generally appears very similar to
standard clear glass. The inter layer is virtually invisible when viewed in transmission with
glass on either side.
The benefit of laminated glass is that if broken, glass fragments will adhere to the PVB inter
layer rather than falling free, thereby reducing the risk of physical injury and property
damage. PVB also has properties that effectively filter over 99% of UV. It also reduces
transmission of sound. Hence the windshield glass in cars is a safety device just like
seatbelts and airbags. Laminated glass is commonly used in automobiles (for windshields),
airports, museums, sound studios, schools, green houses.
Windshield protects the vehicle’s occupants from wind and flying debris such as dust,
insects, and rocks, and provide an aerodynamically formed window towards the front.
Optical gas (Crown glass)
Optical glass is a type of optical glass used in lenses and other optical components. It has
relatively low refractive index ( 1.52 ) and low dispersion. Crown glass is produced from
alkali-lime (RCH) silicates containing approximately 10% potassium oxide and is one of the
earliest low dispersion glasses.
CERAMICS
INTRODUCTION
Ceramics find wide application in engineering, medical and domestic usage.
Ceramics are increasingly used in motor parts (e.g. ceramic disc, brakes, ceramic balls,
etc.). Ceramics engine does not require cooling system. They withstand heat up to 3300 oC.
One of the main application of ceramics is white pottery.
Ceramics
Ceramics are inorganic non-metallic materials that are processed at high
temperature and subsequent cooling.
Examples: Ceramic wash basin, ceramic tiles etc.
White pottery
They are ceramic materials of china clay which is in white colour after firing is called
white wares. They consist of a refractory body and glossy coating.
The raw materials used for manufacture of white pottery are given below:
1. China clay (kaolin) [Al(OH)4SiO5]
2. Feldspar [KAlSiO2]
3. Flint (SiO2)/quartz.
Manufacture of White Pottery
Step-I
Preparation of body ware
The raw materials are made into fine powder and mixed with water to form a paste.
The excess of water is removed by filtration. The article is prepared from the paste either by
hand moulding or by using potter’s wheel.
It is dried and then fired in a ‘biscuit’ oven to get porous were called ‘Bisque’.
Step-II
Glaze
In order to make the porous water (Bisque) into water-tight article, it is covered with
glaze by melting it over the surface of the body.
Slurry of glaze is prepared by mixing Feldspar, silica and boric oxide with water. now the
fired articles are dipped in the slurry of glaze and again fired. Now a smooth, glossy and
non-porous surface is formed on the articles.
Step-III
Decoration
To decorate the article, design are made on the article using pigments and fired
again. Examples are iron oxide pigments red colour, Cobalt oxides give blue colour
Uses of White ware
They are used for the preparation of
i. Spark plugs
ii. Electrical insulators
iii. Laboratory equipments
iv. Crucibles, dishes, insulators sanitary wares etc.
Glazing
Glazing is the process of giving a smooth, glossy, non-porous surface on the
articles using glazes.
A glaze is a fine powder consisting of glass forming materials like lead silicates, borosilicates
etc. They are colourless glazing and colour glazing mixtures. Colourless galzing is done with
glass forming materials like lead silicate and borosilicate. Colour glazing is done by mixing
coloured metal pigments with glass forming materials.
Examples: iron oxide for red and brown
Copper oxide for green
Cobalt oxide for blue
Purpose of glazing
i. To get decorative effect
ii. To make the surface impervious (non-porous) to liquids and water
iii. To improve appearance of the article
iv. To increase durability of ceramic materials
v. To get a smooth glossy appearance
vi. To protect the surface from atmospheric action
Methods of glazing
There are two methods of glazing
1. Salt glazing
2. Liquid glazing
1. Salt glazing
In salt glazing, common salt (sodium chloride) is used for getting glossy films over articles.
The process consists of throwing sodium chloride into furnace, when the article is in red-hot
condition. At high temperature sodium chloride
Vapours reacts with silica in the article to form a smooth glossy and impervious film of
“sodium silicate”. This is known as salt glazing.
2. Liquid glazing
Slurry of glaze is prepared by mixing Feldspar, silica and boric oxide with water. Now the
articles are dipped into the slurry of glaze and then fired. Now a smooth, glossy and non-
porous surface is formed on the articles. This is known as Liquid glazing.
REFRACTORIES
INTRODUCTION
Refractories find wide application in linings of the furnaces, tanks, convertor, kilns,
crucibles, ladles, etc. employed for the manufacture of metals, cement, glass, steel,
ceramics, paper, etc.
Refractories
Refractories are materials which can withstand very high temperature. They are
resistant to heat and corrosive action of gases, metallic liquids and slags. Examples: Fire
clay, Silica.
REQUIREMENT FOR A GOOD REFRACTORY
1. Refractoriness
It is the ability to withstand very high temperature without deformation during operation.
2. Strength or refractoriness under load (RUL)
They must possess high mechanical strength even at very high temperature and bear
maximum possible load without breakage.
3. Thermal expansion
A good refractory should have low thermal expansion under normal conditions.
4. Thermal conductivity
5. In general, a good refractory must have low thermal conductivity to reduce heat losses
by radiation. But when heat is to be supplied from outside, the refractory must possess
good conductivity.
6. Porosity
A good refractory should not be porous. In porous refractory, the molten metal and slag
enters and weaken the structure. But porosity helps in the thermal shock-resistance of
refractories.
7. Thermal spalling
A good refractory must have low thermal spalling. It is breaking, cracking, peeling off or
fracturing of the refractory under high temperature.
8. Chemical composition
A good refractory must be chemically inert.
CLASSIFICATION
The refractories are classified into three types based on the chemical properties.
1. Acid refractories
2. Basic refractories
3. Neutral refractories
S.No Type of Examples Uses
Refractory
1. Acidic Refractories Zirconia, silica Used in furnaces where the charge and
slag are acidic in nature.
2. Basic Refractories Magnesia, dolomite Used in furnaces where the charge and
slag are basic in nature.
3. Neutral Chromite, alumina Used in furnaces where the charge and
Refractories slag are either acidic or basic in nature.
Uses of few refractory bricks

a. Silica bricks
It contains 90-95% silica and about 2% lime.
i. They are used in open hearth furnaces, electric furnaces and glass furnaces.
ii. They are used in cock-ovens and gas retort settings.
iii. They are used in lining of acid convertors.
b. Fire clay bricks
It contains major portion of alumina and silica and small percentage of K 2O, FeO, CuO and
MgO.
i. They are used in blast furnaces and open hearth furnaces.
ii. They are used in stoves, crucibles, furnaces, kilns, regenerators and charging doors.
c. Alumina bricks
It contains more percentage of Al2O3.
i. They are used in vertical shaft kilns for burning lime.
ii. They are used in linings of rotary kiln in cement manufacture.
iii. They are used in brass melting reverberatories, lead-dressing, reverberatory
furnaces, and aluminum furnaces and in oil fired furnaces.
COMPOSITE MATERIALS
INTRODUCTION
Each class of basic engineering materials like metals, high polymers and ceramics
has its own outstanding and distinct characteristics as well as laminates. However very
stringent requirements of supersonic aircraft, gas turbines and high temperature reactors
have forces to develop a new class of materials called “composites”.
The composite materials are generally made by placing the dissimilar materials
together in such a manner that they work as a single mechanical unit. The properties of new
materials so produced are different in kind and scale from those of any constituents. Thus, it
has become possible to incorporate or alter properties, more than that, introduces a
combination of properties like high strength and stiffness at elevated temperatures.
Metals for instance, lose their strength at elevated temperatures. High polymeric
materials in general can withstand still lower temperatures. Ceramics, due to their brittleness
are unsatisfactory structural materials. This led to the exploration of combination of metals
and polymers with ceramics resulting in composites having required properties which seems
to be the hope for the future.
Composite material
A composite material contains two phases namely
i. Matrix phase
ii. Dispersed phase
Matrix phase
A continuous body constituent which encloses the composite and gives a bulk form is called
matrix phase.
The matrix acts as a medium which protects and binds the dispersed phase.
The matrix phase may be metals, ceramics or polymers.
Dispersed phase
The substance which is dispersed in the matrix phase is called the dispersed phase. It
constitutes the internal structure of the composite.
Definition
A multiphase material consisting of a mixture of two (or) more substances with
different properties which are mutually insoluble is called a composite material.
Concrete is the best example of composite
Thus, using composites it is possible to have such combination of properties like high
strength and stiffness, corrosion resistance and ability to withstand extreme high
temperature conditions.
Examples
i. Wood (A composite of cellulose fibers and lignin cementing materials)
ii. Rain proof cloth (A cloth impregnated with water-proof material)
iii. Bone (A composite of soft collagen and brittle and hard material apatite)
Advantageous properties of composite materials over metals and polymers
The important advantages of composite materials over metals and polymers are given
below:
1. Higher specific strength.
2. Lower specific gravity.
3. High specific stiffness.
4. Lower electrical conductivity.
5. Better corrosion and oxidation resistance.
6. Good impact and thermal shock resistance.
7. Can be fabricated easily.
General applications of composite materials
1. In fabrication of roof and floors.
2. In aeronautical applications like components of rockets, aircrafts, helicopter, etc.
3. In valves, pump parts, spray nozzles, etc.
4. In communication antennae, electronic circuit boards, etc.
5. In marine applications like propellers shaft, hulls and other ship parts.
6. In automobile industries, turbine engines, etc.
Corrosion control methods
Cathodic protection Surface coatings
Sacrificial anode method Organic surf ace coatings (paints)

Impressed current method Metallic coatings
Hot dipping Metal cladding Electro-plating
Galvanizing
Tinning
Metallurgy Corrosion
Ore Metal Corrosion product
(thermodynamically (thermodynamically (thermodynamically
stable) unstable) stable)
Different types of corrosion

There are different type of corrosion base on the reaction and physical state.
1. Galvanic corrosion
2. Pitting corrosion
3. Stress corrosion
4. Crevice corrosion
5. Erosion corrosion
6. Soil corrosion
7. Micro-biological corrosion
8. Water-line corrosion
9. Differential aeration corrosion
10. Intergranular corrosion
1. Galvanic corrosion
This type of electrochemical corrosion is also called bimetallic corrosion. When two
dissimilar metals are connected and exposed to an electrolyte, they will form a galvanic cell.
The anode metal will be oxidized and it will undergo corrosion. Zinc and copper metals
connected with each other in an electrolyte medium form a galvanic cell. Zinc acts as anode
and undergoes corrosion while cathode will be unaffected.
At anode  Zn2 + 2e  (oxidation) corrosion

Zn 
At cathode Cu + 2e 
 Cu (Reduction) unaffected
Examples of galvanic corrosion
i. Steel screws in brass marine hardware
ii. Steel pipe connected to copper plumbing
iii. Steel propeller shaft in bronze bearing
iv. Zinc coating on mild steel
v. Lead-tin solder around copper wires
Galvanic corrosion
When two dissimilar metals are electrically connected and exposed to an electrolyte, the
metal higher in electrochemical series (low reduction potential) undergoes corrosion and the
metal lower in electrochemical series (higher reduction potential) is protected. This type of
corrosion is called Galvanic corrosion.
For example when Zn and Cu are connected and exposed to corroding environment, Zn
(higher in electrochemical series) forms the anode, undergoes oxidation and gets corroded.
Cu (lower in electrochemical series) acts as cathode, undergoes reduction and protected as
the electrons released by Zn flows towards Cu.
Concentration cell corrosion

This type of corrosion occurs due to electrochemical attack of the metal surface exposed to
electrolyte of varying concentrations or varying aeration. This type of corrosion is due to
i. Difference in concentration of metals ions.
ii. Difference in the exposure to air/oxygen (Differential aeration corrosion)
iii. Difference in temperature
Differential aeration corrosion is the most common type of concentration cell corrosion.
When a metal is exposed to different air concentrations, it has been found that poorly
oxygenated part of the metal becomes anodic and well oxygenated part becomes cathodic.
The potential difference is created which causes the flow of electrons from anode (metallic
part immersed in NaCl solution) to cathode (exposed to atmosphere).
For example Zn rod immersed deep in NaCl solution: Anode
Zn rod above NaCl solution: Cathode
Pitting corrosion
A cavity, pinholes and cracks on the protective film developed on the metal surface creates
the formation of small anodic areas in the less oxygenated parts and large cathodic areas in
well oxygenated parts. The flow of electrons is from anode to cathode and ions move
through atmosphere moisture medium.
Carry over
The boiler water concentrated with dissolved salts is carried along a steam or in the
form of droplets of water which gets deposited on the turbine plates. The metal under the
drop becomes anodic due to high concentration of the dissolve salts and gets corroded. The
remaining large areas of turbine plate becomes cathodic.
Caustic embrittlement
Boiler feed water contains certain amount of Na 2CO3 which decomposes to NaOH
under the high pressure of the boilers.
Na2CO3 + H2O 
 2NaOH + CO2 
NaOH gets deposited in the cracks/pits of the boilers plate creating a concentration cell. The
metal deposited with NaOH becomes anodic while the metal surround the drop becomes
cathodic.
Underground corrosion
Underground corrosion is due to the corrosiveness of the soil. As the acidity of the
soil increases, the rate of corrosion increases.
Stress corrosion
Stress corrosion is due to the combine effect of the stratic tensile stresses and the corrosive
environment of the metal. The tensile stress is usually observed in fabricated articles like
alloys of Zn and Ni.
Inter granular corrosion
This corrosion occurs along grain boundaries. The grain boundary where the metal is
sensitive undergoes corrosion attack. The grain boundary contains a material which shows
more anodic potential. The metal at the grain boundary decays as it becomes anodic and the
center of the grain becomes cathodic which is protected.
Season cracking
It is applied to stress corrosion of copper alloys brass. Pure copper metal is less sensitive to
stress corrosion. However, presence of alloying impurities like P, Zn, Al etc. results in
marked sensitivity for corrosion. Some of the alloys like brass are made of Zn and Cu. In
presence of ammonia or amines, Zn and Cu undergo inter-granular cracking. These metals
form complexes [Cu(NH3)4]++ and [Zn(NH3)4]++ which appear as corrosion products. Stress
corrosion may be reduces by:
i. applying protective coatings
ii. using corrosion inhibitors
iii. stress relief heat treatments
Crevice corrosion
If surface of painted metal is scratched, it will undergo corrosion. The scratched portion acts
as small anode and the rest part will act as cathode forming a local cell. Crevice corrosion is
formed near joints, rivets and bolts. Changes in the concentration of oxygen/acidic medium
causes crevice corrosion.
Erosion corrosion
Due to mechanical wear and tear, corrosion occurs on the surface of a metal and is called
erosion corrosion.
Soil corrosion
Underground pipes, cables etc. corrode to soil corrosion.
It is caused due to moistures, pH of soil and micro-organisms. The differential aeration is
also the cause of corrosion.
Microbiological corrosion
Some types of bacteria consume oxygen and cause differential aeration type of system
which results in corrosion. The corrosion occurs at the portion poor in oxygen concentration.
For example, the bacillus, algae diatoms
Waterline corrosion
It has been observed in the case of an iron tank containing water, that the portion of iron
tank just below the water level undergoes corrosion. It is due to the difference in oxygen
concentration. Corroding portion is poor in oxygen and acts as anode.
Anodic Protection
This an electrochemical method of corrosion control in which an external potential control
system, called potentiostat, is used to produce and maintain a thin non-corroding, passive
film on a metal or an alloy. The use of potentiostat is to shift corrosion potential into passive
potential so that the corrosion of the metal is stopped.
The potential of the object (say acid storage tank) to be protected is controlled by potential
controller (potentiostat) so that under certain potential range, the object becomes passive
and prevents further corrosion. This potential range depends upon the relationship between
the metal and the environment.
Applications:
i. Used in acid coolers in dilute sulphuric acid plants
ii. Used in storage tanks for sulphuric acid
iii. Used in chromium in contact with hydrofluoric acid
Limitations:
i.This method cannot be applied in the case of corrosive medium containing
aggressive chloride.
i. This cannot be applied if protection breaks down at any point, it is difficult to
reestablish.
Cathodic protection
The method of protecting the base metal by making it to behave like a cathode is called as
cathodic protection. There are two types of cathodic protection.
(a) Sacrificial anodic protection
(b) Impressed current cathodic protection
(a) Sacrificial anodic protection
In this technique, a more active metal is connected to the metal structure to be protected so
that all the corrosion is concentrated at the more active metal and thus saving the metal
structure from corrosion. This method is used for the protection of sea going vessels such
as ships and boats. Sheets of Zn and Mg are hung around the hull of the ship. Zn and Mg
being anodic to iron get corroded. Since they are scarified in the process of saving iron
(anode), they are called sacrificial anodes. The corroded sacrificial anode is replaced by a
fresh one, when consumed completely.
Metals commonly employed as sacrificial anode are Mg, Zn, Al and their alloys which
possess low reduction potential and occupy higher position in electrochemical series.
Important applications of sacrificial anodic protection are as follows:
A ship hull which is made up of steel is connected to sacrificial anode (Zn-blocks) which
undergoes corrosion leaving the base metal protected.
The underground water pipelines and water tanks are also protected by sacrificial anode
method.
By referring to the electrochemical series, the metal with low reduction potential is connected
to the base metal which acts as anode.
(b) Impressed current cathodic protection

In this method, an impresses current is applied in an opposite direction to nullify the
corrosion current and converting the corroding metal from anode to cathode. This can be
accomplished by applying sufficient amount of direct current from a battery to an anode
buried in the soil and connected to the corroding metal structure which is to be protected.
The anode is in a backfill (composed of gypsum) so as to increase the electrical contact with
the soil. Since in this method current from external source is impressed on the system, this is
called impressed current method.
This method is used for buried structures such as water tanks, water and oil pipelines,
transmission line towers etc.
Comparison of sacrificial anode method with impressed current cathodic method

Sacrificial anode method Impressed current method
1. External power supply is not required. 1. External power supply is required.
2. The cost of investment is low. 2. The cost of investment is high.
3. This requires periodic replacement of 3. Replacement is not required as anodes
sacrificial anode. are stable.
4. Soil and microbiological corrosion effects 4. Soil and microbiological corrosion effects
are not considered. are taken into account.
5. This is the most economical method 5. This well suited for large structures and
especially when short term protection is long term operations.
required.
6. This is a suitable method when the 6. This is a suitable method even when the
current requirement and the resistivity of current requirement and the resistivity of
the electrolyte are relatively low. the electrolytes are high.
Corrosion inhibitors
There are some chemicals which reduce the rate of corrosion. These chemicals are called
corrosion inhibitors. They are two types, anodic and cathodic. Phosphate, chromate,
tungsten protect anode. They form sparingly soluble products which are adsorbed on the
surface of metal and hence check corrosion. Cathodic protection is done by organic amines,
mercaptans, thiourea and substituted urea. The above chemicals retard reduction reaction
taking place at cathode.
Also, by the use of salts of Mg, Zn or Ni, the insoluble hydroxides of Mg, Mg, Ni are
deposited preventing corrosion.
1
At cathode: H2O + O 2 + 2e  
 2OH
2
Mg2 2OH 
 Mg(OH)2
(precipitate)
INHIBITORS
Inhibitors are organic or inorganic substances which decrease the rate of corrosion. Usually
the inhibitors are added in small quantities to the corrosive medium. Inhibitors are classified
into
i. Anodic inhibitors (chemical passivators)
ii. Cathodic inhibitors (adsorption inhibitors)
iii. Vapour phase inhibitors (volatile corrosion inhibitors)
Anodic inhibitors
Inhibitors which retard the corrosion of metals by forming a sparingly soluble
compound with a newly produced metal cations. This compound will then adsorb on the
corroding metal surface forming a passive film or barrier. Anodic inhibitors are used to repair
a) the crack of the oxide film over the metal surface
b) the pitting corrosion
c) the porous oxide film formed on the metal surface.
Examples: Chromate. Phosphate, tungsten, nitrate, molybdate etc.
Cathodic inhibitors
Depending upon the nature of the cathodic reaction in an electrochemical corrosion,
cathodic inhibitors are classified into
a) In an acidic solution: the main cathodic reaction is the liberation of hydrogen gas,
the corrosion can be controlled by slowing down the diffusion of H+ ions through the
cathode. For example, amines, mercaptans, thiourea etc.
2 H + 2e 
 H2 
b) In a neutral solution: in a neutral solution, the cathodic reaction is the adsorption of
oxygen or formation of hydroxyl ions.
The corrosion is therefore, controlled either by eliminating oxygen from the corroding
medium or by retarding its diffusion to the cathodic area.
The dissolved oxygen can be eliminated by adding reducing agents like Na2SO3.
The diffusion of oxygen can be controlled by adding inhibitors like Mg, Zn or Ni salts. For
example, Na2SO3, N2H4, Salts of Mg, Zn or Ni.
1
H2O + O2 + 2e  
 2OH
2
c) Vapour phase inhibitors
These are organic inhibitors which are readily vapourized and form a protective layer on the
metal surface.
These are conveniently used to prevent corrosion in closed spaces, storage containers,
packing materials, sophisticated equipment etc.
For examples, dicyclohexylammonium nitrate, dicyclohexyl ammonium chromate,
benzotriazole, phenylthiourea etc.
PROTECTIVE COATINGS
Protective coatings are used to protect metals from corrosion. The main types of protective
coatings are classified as follows:
Protective Coatings
Metallic Coatings Non-metallic Coatings Organic Coatings
1. Hot dipping 1. Surface or Chemical 1. Paint

conversion coatings
(a) Galvanizing 2. Varnishes
(b) Tinning (a) Chromate coating
3. Lacquers
2. Metal spraying (b) Phosphate coating
4. Enamels
3. Cladding (c) Oxide coating
2. Anodizing
4. Cementation
(a) Sherardizing
(b) Chromizing
(c) Calorizing
5. Electroplating or
Electrodeposition
The protective coatings must be chemical inert to the environment and also sufficiently thick.
Besides protection from corrosive conditions, such coatings can also give decorative
appearance to the base metals. To be more effective, these coatings should adhere well to
the surface.
Metallic coatings
Surface coatings made up of metals are known as metallic coatings.
These coatings separate the base metal from the corrosive environment and also function as
an effective barrier for the protection of base metals.
The metal which is coated upon is known as the base metal.
The metal applied as coating is referred to as coat metal.
The different methods used for metal coating are:
1. Hot dipping
a) Galvanizing
b) Tinning
2. Metal spraying
3. Cladding
4. Cementation
a) Sheardizing – Cementation with Zinc powder is called Sheardizing.
b) Chromizing – Cementation with 55% Chromium powder & 45% Alumina is called
Chromizing.
c) Calorizing – Cementation with Aluminum and Alumina powder is called
Calorizing.
5. Electroplating or electrodepositon
Hot dipping
In the process of hot dipping, the metal to be coated is dipped in the molten bath of the
coating metal. Such hot dip coatings are generally non-uniform. The common examples of
hot dip coatings are galvanizing and tinning.
1. Galvanization
The process of coating a layer of zinc over iron is called galvanization. The steel article is
first pickled with dilute sulphuric acid to remove traces of rust, dust, etc. at 60-90 oC for about
15-20 minutes. Then this metal is dipped in a molten zinc bath maintained at 430oC.
When zinc is coated over iron, zinc and iron forms a galvanic cell. The electropositive zinc
forms the anode and undergoes corrosion. Hence iron is protected from corrosion by
sacrificial protection method.
The surface of the bath is covered with ammonium chloride flux to prevent oxide formation
on the surface of molten zinc. The coated base metal is then passed through rollers to
correct the thickness of the film.
It is used to protect roofing sheets, wires, pipes, tanks, nails, screws, etc.
2. Tinning
The coating of tin over iron is called tin plating or tinning.
Tinning is done to protect iron, steel and copper from corrosion. It is also called tinplating.
Since tin is non-toxic, it is mainly used in food industry for coating food containers. Tin-
coated utensils are used for storing foodstuffs, pickles, oils, etc.
Tin is noble metal (more cathodic) than iron. It is more resistant to atmospheric corrosion.
Thus uniform layer of tin protects iron from corrosion. Tinning the base metal is first pickled
with dilute sulphuric acid to remove surface impurities. Then it is passed through molten tin
covered with zinc chloride flux. The tin coated article is passed through a series of rollers
immersed in a palm oil bath to remove the excess tin. Galvanizing is preferred to tinning
because tin is Cathodic to iron, where zinc is anodic to iron. So, if the protective layer of the
tin coating has any cracks, iron will corrode. If the protective layer of the zinc coating has any
cracks, iron being Cathodic and is not corroded. The corrosion products fill up the cracks,
thus preventing corrosion.
DIFFERENCE BETWEEN GALVANIZING AND TINNING
Galvanizing Tinning
1. A process of covering iron or steel with a 1. A process of covering iron or steel with a
thin coat of ‘Zinc’ to prevent it from thin coat on ‘Tin’ to prevent it from
rusting. corrosion.
2. Zinc protects the iron sacrificially. (Zinc 2. Tin protects base metal without undergo
undergoes corrosion) any corrosion (non-sacrificially)
3. Zinc continuously protects the base metal 3. If any break, in coating causes rapid
even if broken at some places. corrosion of base metal.
4. Galvanized containers cannot be used 4. Tin is non-toxic in nature of any medium.
for storing acidic foodstuffs as Zinc
becomes toxic in acidic medium.
Electroplating (Refer Electrochemistry)
Electroplating is process in which the coat metal is deposited on the base metal by passing a
direct current through an electrolytic solution by means of electrolysis.
Objectives of Electroplating
i. to increase corrosion resistance
ii. to get better appearance
iii. to increase the hardness
iv. to change the surface properties of metals and non-metals
Process
In electroplating, the cleaned base metal is made as the cathode and the coat metal
is taken as the anode. A solution of the coat metal salt is taken as the electrolyte. The
electrodes are connected to the battery and DC current is passed. Now electrolysis takes
place and the coat metal is deposited over the base metal.
The nature of coating depends on
1) the current density
2) time
3) temperature and
4) the concentration of the electrolyte
For example, to electroplate a spoon made of copper with silver, the copper spoon is taken
as the cathode. A silver plate is taken as the anode. Silver thiocyanate solution is the
electrolyte. When the electrodes are connected to a DC source of electricity, silver deposited
over the copper spoon.
Electroplating diagram
The following electrolytes are used for coating other metals.

Copper sulphate – Copper
Nickel sulphate – Nickel
Chromic acid – Chromium
Factors affecting Electroplating
The following are the factors affecting electroplating.
1. Cleaning of the article is essential for a strong adherent electroplating.
2. Concentration of the electrolyte is a major factor in electroplating.
3. Low concentration of metal ions will produce uniform coherent metal deposition.
4. Thickness of the deposit should be minimized in order to get a strong adherent
coating.
5. Additives such as glue and boric acid should be added to the electrolytic bath to get a
strong adherent and smooth coating.
6. The electrolyte selected should be highly soluble and should not undergo any
chemical reaction.
7. The pH of the electrolytic bath must be properly maintained to get the deposition
effectively.
INORGANIC COATINGS
Anodizing
Anodizing is the process of coating aluminum oxide on the surface of aluminum or its
alloy.
This type of coating is produced on non-ferrous metals like Al, Zn, Mg and their alloys, by
anodic oxidation process, by passing direct electric current through a bath in which the metal
is suspended from anode. Here the base metal behaves as an anode. For anodizing 8%
sulphuric acid is used as the electrolyte. Since it is a good oxidizing agent, it oxides
aluminum (at the anode) into aluminum oxide. The electrolytes are sulphonic, chromic,
phosphoric, oxalic or boric acid.
Anodized coatings have more corrosion resistance due to thicker coating.
“Aluminum oxide coatings” are formed by the oxidation taking place on the aluminum surface
at moderate temperatures (35-40oC) and moderate current densities. The formed oxide film
is initially thin and gain thickness by the continuous oxidation of aluminum anode. The
surface of oxide film contains pores, which may cause corrosion. The pores can be sealed
by exposing to boiling water, when the oxide is converted into monohydrate (Al 2O3. H2O).
This process is called sealing process.
The anodized aluminum and its alloys are used in
1. Aircrafts
2. Window frames
3. Machine parts
4. Fancy article and
5. Refrigerator, etc.
ORGANIC COATINGS
INTRODUCTION
Organic coating includes paints and varnishes. In this lesson, we are going to study
about paint and its components. A little introduction to special paints used is also discussed.
Further, we are going to study about varnishes its types and their preparation.
Paints
Definition
Paint is a dispersion of pigment in drying oil.
Paint coating is given to both metallic and wooden articles to protect them from
corrosion and to give better surface appearance. Paint convers the manufacturing defects in
the articles.
When paint is applied to a metal surface, the thinner evaporates while the drying oil
slowly oxidizes forming of pigmented film.
Components of paints and their functions
The important constituents of paint are as follows.
1. Pigments
2. Vehicle or drying oils or medium
3. Thinners
4. Driers
5. Fillers or extenders
6. Plasticizers
7. Antiskinning agents
1. Pigment
A pigment is a solid and colour-producing substance which gives desired colour to the paint.
Example
White pigments – Titanium oxide, zinc oxide
Black pigments – Graphite, Carbon black
Red pigments – Red lead, Indian red (Fe2O3)
Functions
The following are the functions of the pigment.
a. A pigment gives opacity and colour to the film.
b. It covers the manufacturing defects.
c. A pigment gives strength to the film.
d. It protects the film by reflecting the destructive ultraviolet rays.
2. Vehicle or drying oils or medium
The liquid portion in which the pigment is dispersed is called a medium or vehicle.
Example
Linseed oil, dehydrated castor oil, soybean oil and fish oil.
Functions
a. Vehicles hold the pigment particles together on the metal surface.
b. They form the protective film by evaporation or by oxidation and polymerization of the
unsaturated constituents of the oil.
c. Vehicles give better adhesion to the metal surface.
d. They impart water repellency, durability and toughness to the film.
3. Thinner
Thinners are added to paints to reduce the viscosity of the paints in order to make it easy to
apply on the metal surface.
Example
Turpentine, kerosene and petroleum spirit.
Functions
a. Thinners reduce the viscosity of the paint to render it easy to handle and apply to the
metal surface.
b. They dissolve the oil, pigments etc. and produce a homogeneous mixture.
c. Thinner evaporate rapidly and help the drying of the film.
d. They increase the elasticity of the film.
4. Driers
Driers are used to speed up the drying process and accelerate the drying of the oil film by
oxidation, polymerization and condensation.
Example
Naphthentates and Resinates of lead, cobalt and manganese.
Functions
Driers act as oxygen carrier catalysts which help the absorption of oxygen and catalyze the
drying of the oil film by oxidation, polymerization and condensation.
5. Fillers or extenders
Fillers are used to increase the volume of the paint and to reduce the cost. It increases the
durability of the paint.
Examples
Asbestos, talc, china clay, calcium sulphate and calcium carbonate.
Functions
a. Filler serve to fill the voids in the film.
b. They reduce the cracking of the paints.
c. Fillers increase the durability of the paints.
d. They reduce the cost of the paint.
6. Plasticizers
Plasticizers are chemicals added to increase elasticity of film and to prevent cracking of the
film.
Example
Tertiary amyl alcohol, triphenyl phosphate, triglyceryl phosphate.
7. Antiskinning agents
They are chemicals added to the paint to prevent skinning of the paint.
Example
Polyhydroxy phenols, guaiacol, etc.
VARNISHES
Definition
Varnish is a homogenous colloidal dispersion of natural or synthetic resin in
oil or spirit medium.
It the medium is oil it is known as oil varnishes.
If the medium is spirit it is known as spirit varnishes.
It is used as protective and decorative coating to the wooden surfaces. It is provides a hard,
transparent, glossy appearance and durable film to the coated surface.
There are two types of varnishes
1. Oil varnishes
2. Spirit varnishes
Preparation of oil varnishes
Oil varnishes are more difficult to manufacture. Resins that are used in the
preparation of oil varnishes are high molecular weight substances and are not easily soluble
in oil. The resin is taken in an aluminum vessel and heated over a fire pit or in small furnace.
When resin melts, the temperature is slowly increased to about 300 oC. This process is
known as gum running. Some cracking or depolymerization of the resin takes place and
about 25% of the resin is lost in the form of fumes.
The required quantity (about 25% of the weight of the resin) of boiled oil or linseed oil
along with driers is separately heated to 200 to 220 oC and is slowly added to the heated
resin with constant stirring until thorough combination has taken place. This operation is
known as cooking. Overheating must be avoided as it causes discolouration of the varnish.
The kettle is removed from the furnace and allowed to cool, while spirit is then added (which
is a petroleum fraction, boiling between 150oC and 200oC). It is the most common thinner.
The varnish is stored in tanks for some days for maturing. Foreign matter and particles of
resin, which have not dissolved, settle during this period. During maturing, the colour of the
varnish also improves and it becomes more homogenous. The varnish is filtered and packed
for marketing.
Spirit varnishes
A spirit varnish is a dispersion of resin in spirit.
Preparation
The resin and spirit are placed in a cylinder drum, plasticizer and other components
are added. The resin is dissolved by agitating the mixture or by rotating the drum. It is then
filtered and used. The final product is called spirit varnish.
DIFFERENCE BETWEEN PAINT AND VARNISH

Paint Varnish
1. Paint has pigment. 1. There is no pigment in varnish.
2. It can be applied to both metals and 2. It can be applied only to wooden articles.
wooden articles.
3. It is opaque. 3. It is transparent.
Special paints
In addition to the normal ingredients some special chemicals are incorporated to
paints for some specific purposes. They are commonly known as special paints.
1. Luminous paints
Luminous paints are visible in the dark. Since it contains luminophor pigments (like CdS,
ZnS) that are used for visibility in the dark. They absorb light radiations and emit them in the
dark. The active components in luminous paint are specially prepared phosphorescent
materials like CdS, ZnS, etc. For colour effect in luminous paints, certain chemicals like
copper salt (green), silver salt (blue), cerium and uranium salts (yellow),etc. are prepared.
Uses
They find application in inks, advertising signboards, road marks, road traffic signs,,
number plates of vehicels, watch dials, map, chart, etc.
Fireretardant Paints
The paints which retard the fire are called fire-retardant.
This paint contains the chemicals PVC, Chlorinated rubber, urea formaldehyde and
carbonate pigments which are fire resistant in nature. These substances at higher
temperatures breakdown to give the non-inflammable gases like CO 2, NH3, HCl and HBr.
These gases are non-combustible and do not support combustion. Thus the fire is retardant.
Uses
Mainly used defence, industrial, commercial, education and residential complexes.
The most frequent source of a fire in any hotel, restaurant or residence. The walls, doors and
even kitchen counters should be protected against the spread of fire.
False ceiling, Lift, Equipment Rooms, Aircraft Safe deposit vaults, lockers. Computer
Server Rooms, Power plants Chemical Plants, Storage Tanks, structures in Sugar Mills,
Textile Mills and Floorings.
Aluminum Paints
The base material in aluminum paint is a fine powder of aluminum. The ground fine
powder of aluminum is suspended in either spirit varnish or an oil-varnish depending on the
requirement. When paints are applied, the thinner evaporates and oil, if any, undergoes
oxidation and polymerization. A bright adhering film of aluminum is obtained on the painted
surface.
Uses
Wooden and metallic article for interior and exterior decoration.
Advantages of aluminum paints
1. It possesses a good covering power.
2. It imparts very attractive appearance to the surface.
3. It has fairly good heat-resistance.
4. It has very good electrical resistance.
5. The painted film is water proof.
6. The electrical surface is visible even darkness.
7. Corrosion protection for iron and steel surface is better than all other paints.
Distemper
Distempers are water paints. They contain chalk powder, glue and pigment dissolved
in water. They are very cheap and can be easily applied on walls. They are durable and give
pleasing finish to walls. The ingredients of distemper are
i. Whitening agent or chalk powder (the base)
ii. Glue or casein (the binder)
iii. Colouring pigment and
iv. Water (the solvent or thinner)
Advantages
1. Distempers are cheaper than paints and varnishes.
2. They can be applied easily on plasters and wall surfaces in the interior of the
buildings.
3. They are durable.
4. They give smooth and pleasing finish to walls.

Applied Chemistry MS-133

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Applied Chemistry MS-133

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1|Chemical Kinematics & Catalysis

Sign convention of work

Where V is the increase in volume of the gas.

Difference between Reversible and Irreversible Process

The work done by the gas in one infinitesimal

By the ideal gas equation

First law of thermodynamics

Now H1 = E1 + P1V1 and H 2 = E 2 + P2 V2

n 2 = moles of gaseous products

If H 2  H1 then H is positive and the reaction will be endothermic. If H1  H 2 then H is

sum of the standard abosute  sum of the standard absolute 

Electrochemical and galvanic series

Comparison of Electrochemical and Galvanic Series

Differential aeration theory or concentration cell formation

at cathode (more oxygenated area)

iii) Relative areas of anodic and cathodic parts

Control of corrosion (Protection against corrosion)

 H 2( g )  2OH  ( aq )  2 H 2O(l )   2 (at anode)

(ii) N 2 H 4  1 O2  N 2  2 H 2O( l )

Uses of few refractory bricks

Corrosion control methods

Cathodic protection Surface coatings

Sacrificial anode method Organic surf ace coatings (paints)

Hot dipping Metal cladding Electro-plating

Different types of corrosion

At anode  Zn2 + 2e  (oxidation) corrosion

Concentration cell corrosion

(b) Impressed current cathodic protection

Comparison of sacrificial anode method with impressed current cathodic method

Metallic Coatings Non-metallic Coatings Organic Coatings

1. Hot dipping 1. Surface or Chemical 1. Paint

The following electrolytes are used for coating other metals.

DIFFERENCE BETWEEN PAINT AND VARNISH

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