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Engineering Chemistry-II
Unit-I, Electrochemistry

2 Marks

1. Classify the types of conductors.

Types of conductors:
1. Metallic conductors or Electronic conductors.
Metallic conductors are solid substances, which conduct electric current due to the
movement of electrons from one end to another end. The conduction decreases with
increase of temperature.
Examples: All metals, Graphite
2. Electrolytic conductors.
Electrolytic conductors conduct electric current due to the movement of ions in
solution or in fused state. The conduction increases with increase of temperature.
Examples: Acids, Bases, Electrovalent substances.

2. Write Difference between metallic and electrolytic conductors

Sl. No. Metallic Conductor Electrolytic Conductor

1 It involves the flow of electrons in It involves the movement of ions in a
a conductor. solution.
2 It does not involve any transfer of It involves transfer of electrolyte in the
matter. form of ions.
3 Conduction decreases with Conduction increases with increase in
increase in temperature. temperature.
4 No change in chemical properties Chemical reactions occur at the two
of the conductor. electrodes.

3. Define the following terms a) single electrode potential (E) b) standard electrode
potential (Eo)
Single electrode potential:
It is the measure of tendency of a metallic electrode to loss or gain electrons, when it is in
contact with a solution of its own salt.
Standard electrode potential:
It is the measure of tendency of a metallic electrode to loss or gain electrons, when it is in
contact with a solution of its own salt of 1 molar concentration at 25o C.

4. Define reference electrode give one example.

Reference electrode is the one, the potential of which is known (or) arbitrarily fixed as
zero. It is used to measure the electrode potential of another unknown electrode by
combining with it.
Examples: Standard hydrogen electrode (SHE) – Primary reference electrode.
Saturated Calomel electrode - Secondary reference electrode.

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5. What is emf series or electro chemical series? Write its significance.

Electrochemical Series
When various metals are arranged in the order of their increasing values of
standard reduction potential on the hydrogen scale, then the arrangement is called
electrochemical series.
Significance:
(i) Std emf of the cell can be calculated.
(ii) Equilibrium constant can be calculated.
(iii) Spontaneity of redox reactions can be predicted.

6. Write the Nernst equation and its applications.

Nernst equation for reduction potential,
E = Eo red + (0.0591/n) log [ Mn+]
Nernst equation for oxidation potential,
E = Eo oxi - (0.0591/n) log [ Mn+]
Where, n – number of electron involved in the electro chemical reaction,
[ Mn+] – Concentration of metal ion.
Applications:
(i) Nernst equation is used to calculate electrode potential of unknown metal.
(ii) Corrosion tendency of metal can be predicted.

7. Define corrosion. Give example and types.

Corrosion:
“Corrosion can be defined as a process of gradual destruction or deterioration of
metals or alloys by the chemical or electrochemical reaction with its environment”.
Example:
The most familiar example of corrosion is “rusting of iron”, when exposed to the
atmospheric condition, a layer of reddish scale and powder of oxide (Fe3O4) is formed
and iron becomes weak.
Types:
Based on the environment corrosion is classified into two types.
1. Chemical or dry corrosion
2. Electrochemical or wet corrosion

8. State and explain pilling and bed worth rule. (Or) What is pilling – Bed worth
ratio?
Pilling – bed worth rule:
The ratio of the volume of the oxide formed to the volume of the metal consumed
is called“Pilling – bed worth rule”.

According to it, if the volume of the oxide layer is less than the volume of metal,
the oxide layer is porous and hence non protective.
Example: Oxides of alkali and alkaline earth metals such as Na, Mg, Ca etc.

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On the other hand if the volume of oxide layer is greater than the volume of the
metal the oxide layer is non porous and protective.
Example: Oxides of heavy metals such as Pb, Sn etc.

9. What is hydrogen embrittlement? Where it is caused?

Hydrogen embrittlement is the effect of atomic hydrogen on metals at ordinary
temperature causing cracks and blisters by occupying the voids of the metals.
When metals contact to H2S at ordinary temperature causes evolution of atomic
hydrogen.
Fe + H2S FeS +2H
This atomic hydrogen diffuse readily into the metal and collects in the voids,
where it recombines to form molecular hydrogen
H+H H2
Collection of these gases in the voids causes cracks and blisters on the metal. This
process is called hydrogen embrittlement.

10. What is ‘decarburization’?

The process of decrease in carbon content in steel is termed as “decarburization”
of steel.
At high temperature atomic hydrogen is formed by the thermal dissociation of
molecular hydrogen.
H2 2H
When steel is exposed to this environment the atomic hydrogen readily combine
with carbon steel and produce methane gas.
C + 4H CH4
Collection of this gas in the voids develops very high pressure, which cause
cracking. Thus the process of decrease in carbon content in steel is termed as
“decarburization” of steel

11. What is electrochemical corrosion?

Wet corrosion or electrochemical corrosion occurs in the following conditions.
(i) When two dissimilar metals or alloys are in contact with each other in the
presence of an aqueous solution or moisture.
(ii) When a metal is exposed to varying concentration of oxygen or any
electrolyte.
Under the above condition, one part of the metal act as anode and another part act as
cathode.

12. Distinguish between dry corrosion and wet corrosion.

Sl. No. Dry or chemical corrosion Wet or Electrochemical corrosion
It occurs in presence of moisture or
1 It occurs in dry state.
electrolyte
It follows adsorption It follows the mechanism of electro
2
mechanism chemical reaction.

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Corrosion product accumulates

Corrosion occurs at anode while products
3 on the same spot, where
gather at cathode.
corrosion occurs.

13. In electrochemical corrosions, what is the general anodic reaction of a metal M?

What is the cathodic reaction in basic aqueous solution containing dissolved
oxygen?
In anodic part, oxidation or dissolution of metal occurs
Anodic reaction: M M2+ + 2e-

In cathodic part reduction occurs, which depends on the nature of the corrosive
environment.
1. If the corrosive environment is acidic, hydrogen evolution occurs at the cathodic
part
2H+ + 2e- H2
2. If the corrosive environment is slightly alkaline (or) neutral, hydroxide ion forms
at cathodic part
Cathodic reaction: ½ O2 + H2O + 2e- 2OH-
14. What is concentration cell corrosion? Give an example.
Concentration cell corrosion:
The concentration cell corrosion occurs when a metal is exposed to varying
concentration of oxygen or any electrolyte on the surface of the base metal.

The more aerated part becomes cathodic .The metal part inside the solution is less
aerated and thus become anodic and suffer corrosion.
Ex: Metals partially immersed in a water or conducting solution. (called water
line corrosion)
Examples for this corrosion are
1. Pitting or localized corrosion.
2. Crevice corrosion
3. Pipeline corrosion
4. Corrosion on wire fence

15. What is pitting corrosion?

Pitting corrosion:
Pitting is a localized attack, resulting in the formation of a hole around which the
metal is relativity unattacked.
Example:
Metal area covered by a drop of water, sand, dust, scale etc., Let us consider a
drop of water or aqueous NaCl resting on a metal surface, the area covered by the drop of
water acts as an anode due to less oxygen concentration and suffer corrosion .The
uncovered area acts as cathode due to high oxygen concentration.
16. How does the galvanic corrosion occur? How to prevent the galvanic corrosion?

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When two dissimilar metals or alloys are in contact with each other in the
presence of an aqueous solution or moisture galvanic corrosion occurs. It can be
minimized by the using the following steps.
1. Selecting the metals as close as possible in the electrochemical series.
2. Providing smaller area for cathode and larger area for anode.
3. Inserting an insulating material between the two metals.
20. How does a drop of water oil, dust, resting on an iron surface lead in
corrosion of the metal?
The area covered by the drop of water acts as an anode due to less oxygen
concentration and suffers corrosion. The uncovered area (freely exposed to air) acts as a
cathode due to high oxygen concentration.
The rate of corrosion will be more when the area of the cathode and the area of
anode is smaller. Therefore, more and more material is removed from the spot. Thus a
small hole or pit is formed on the surface of the metal

21. What is a sacrificial anode? How does it function?

Sacrificial anode:
A sacrificial anode is more active metal than the anodic part of the corrosion cell.
When the sacrificial anode is connected to the anode of the corrosion cell, the corrosion
will concentrate only on the active metal and protects the basic metal. The artificially
made anode thus gradually gets corroded protecting the original metallic structure. Hence
this process is otherwise known as sacrificial anodic protection.
Examples:
Al, Zn, Mg are used as sacrificial anodes
22. What is corrosion inhibitor? Give examples.
Corrosion inhibitor:
Corrosion inhibitor is a substance or chemical which decrease the corrosion of
metal, when it is added to the corrosive environment.
Types of inhibitors:
(i) Anodic inhibitors: E.g., Chromates, nitrates, phosphates,
(ii) Cathodic inhibitors: E.g., amines, mercaptans, Na2SO3, hydrazine
(iii) Vapour phase inhibitors: It readily vapourises and forms a protective layer
on the metal surface. E.g., Dicyclohexylammonium nitrate, benzotriazole, etc.,
23. Why is ‘Back fills’ used in the impressed current cathodic protection
method?
‘Back fill’ is the medium which is made of coke, breeze, gypsum, and sodium
sulphate in which graphite anode is placed so as to increase the electrical contact with the
surrounding environment.
24. How corrosion of metals controlled by impressed current cathodic
protection method?
In this method, an impressed current is applied in opposite direction to nullify the
corrosion current and convert the corroding metal from anode to cathode.
As sufficient direct current is applied to an inert anode (graphite), buried in the
soil and connected to the metallic structure to be protected. The anode is usually, a back
fill, composed of coke, breeze and gypsum, so as to increase the electrical contact with

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the surrounding soil.

Battery

Insulated
copper wire Ground level

Pipe line to be protected

Back
fill Anode
(Graphite)
Fig: Impressed current cathode protection

25. What are protective coatings? How are they classified?

Protective coatings:
Protective coatings are used to protect the metals from corrosion. It acts as a
physical barrier between the coated metal surface and the environment.

Properties:
1. They import some special properties such as hardness, electrical properties,
oxidation-resistance and thermal insulation to the protected surface.
Uses:
It is used for decorative purposes.
Classification: Protective coatings

Inorganic Coating Organic Coatings

Metallic coatings Non-metallic coatings

1. Hot dipping 1. Surface or chemical

i) Galvanising conversion coating Paints
ii) Tinning (a) Chromate Varnishes
2. Metal cladding (b) Phosphate Lacquers
3. Cementation (c) Oxide Enamels
1. Sherardising 2. Anodizing
2. Chromising 3. Porcelain enamel coating
3. Calorising
4. Electroplating

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26. What is the principle of Electro-plating?

Principle:
Electroplating is the process in which the coating metal is deposited on the base
metal by passing a direct current through an electrolytic solution containing the soluble
salt of the coating metal.

Anode Cathode (Material to be electroplated)

(Material to be
Deposited)

Electrolyte

The base metal to be plated is made cathode of an electrolytic cell, whereas the
anode is either made of the coating metal or inert material of good electrical conductivity.
27. What are the objectives of electroplating?
On metals:
1. To increase the resistance to corrosion of the coated metal.
2. To improve the hardness and physical appearance of the article.
3. To increase the decorative and commercial values of the article.
4. To increase resistance to chemical attack
5. To improve the properties of the surface of the article.
On Non-metals:
1. To increase strength
2. To preserve and decorate the surfaces of non-metals like plastics, wood, glass
etc.,
3. For making the surface conductivity by utilization of light weight, non-
metallic materials.
28. What is the principle of electroless plating?
Electroless plating is a technique of depositing a noble metal on a catalytically
active surface of the metal to be protected, by using a suitable reducing agent without
using electrical energy.

The most reducing agent reduces the metallic ions to metal, which gets plated
over the catalytically activated surface giving a uniform thin coating.

Metal ions + Reducing agent Metal + oxidized products.

(Deposited)

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29. What are the advantages of electroless plating over electroplating?

The electroless plating is more advantageous when compare to electroplating. The
advantages of electroless plating are given as follows. They are
1. No electricity is required.
2. Electroless plating on insulators and semiconductor can be easily carried out.
3. Complicated parts can also be plated uniformly.
4. Electroless coating possess good mechanical, chemical and magnetic
properties.
30. What are the applications of electroplating?
Electroplating is widely used for
1. Decorative purposes: Au, Ag, Cu, Ni, Cr, and etc .are the most widely used
metals for decorative plating. The base metals used are steel, Zn, Cu, Al, etc.
2. Corrosion protection: Fe and steel are protected from corrosion by
electroplating them with Cu, Ni, Cr, etc.
3. Ni plating used as an undercoat for articles, which are finally to be chromium-
plated.
4. Cu plating used as a protective coating for steel article.
5. Cu plating is coated at the bottom of stainless steel cooking utensils to effect
better heat transfer.

31. What are the applications of electroless plating?

1. Electroless nickel plating is extensively used in electronic appliances (e.g.,
knobs of hi-fi equipments)
2. Heat treated electroless Ni plated appliance finds preferred applications in
hydraulic compressors, pressure valves, pumps and fuels injection assemblies.
3. Plastic cabinets coated with Cu and Ni finds applications in digital as well as
an electronic instruments.
4. Electroless Cu plating is used in double or multilayered boards (PCB) in
which plating through holes is required .Such holes cannot be Cu
electroplated.
32. What are the uses of lacquers?
Lacquer is a colloidal dispersion of cellulose derivatives, resins and plasticizers
in solvents and diluents. Lacquers dry by the evaporation of the solvent and diluents. It is
used for the following purposes.
1. They are used for the interior decoration like painting wood work and
furniture.
2. It is used in the preparation of artificial leather goods.
3. It is mainly used in giving finishing coat to automobile.
33. What are varnishes? Write about two types of varnishes ?
Varnishes:
Varnishes are homogenous colloidal solution of natural or synthetic resins in
thinner or oil or both. Varnishes are used to protect the metal surfaces from
environmental destructions like corrosion, erosion etc., and also used to decorate the
metal surfaces.

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Types of varnishes:
1. Oil varnishes:
Oil varnish is prepared by dissolving natural or synthetic resins in a drying oil and
volatile solvent.
2. Spirit varnishes:
It is prepared by dissolving natural or synthetic resins in a volatile solvent (spirit)

34. What is meant by fire retarding paints?

These paints contain chemicals such as chlorinated rubber, carbonate pigments,
urea- formaldehyde, chalk, borax, which decompose at elevated temperature producing
non-inflammable gases HCl, CO2 and NH3 respectively. These gases act as a barrier
between air and inflammable substrate of the paint and thus retard the rate of burning.

Fire proof materials like clay, asbestos etc. in fine powder form are used in same
paints. Silicone paints are also fire retarding paints.

35. What is meant by water repellent paints?

They are made by the hydrolysis and condensation of organo ethoxy silanes and
organo chloro silanes. The resultant molecular mass alkoxy silicane is thinned with a
suitable solvent and then applied by brushing or spraying. It undergoes hydrolysis to form
cross- links. The resin is formed inside the capillaries making the latter water-repellent.

Development of full water repellency takes place with in 24 hours, but its
maximum repellency is attained in two weeks.

Water repellent paints are mainly used in ships, boats and marine equipments.

36. What is meant by temperature indicating paints?

These paints contain thermochromes (meaning, thermo – temperature, chromes -
colour), i.e., thermochromes are the substances which undergo colour changes at different
temperatures. These paints play a vital role in industries where the different in the heating
zones of the furnace have to be known.
The ingredients added are Mercury iodides, complex amines of Cu, Fe, Co, Ni,
Mn, Cr etc.
With the help of such paint the temperature can be indicated between the range
450C and 14500C. These paints are used in the outer walls of the reactors and furnaces to
indicate the temperature of the reaction so that it can be stopped at a particular stage.
37. What is paint and what are the requisites of a good paint?
Paint:
Paint is a mechanical dispersion of one or more finely divided pigments in a
medium. When paint is applied to a metal surface, the thinner evaporates, while the
vehicle undergoes slow oxidation forming a pigmented film.
Requisites of a good paint:
1. It should spread easily on the metal surface.

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2. It should have high hiding power

3. It should not crack on drying
4. It should adhere well to the surface
5. The color of the paint should be stable

38. What is the function of drying oil in the paint?

This is a nonvolatile portion of a medium. This is the film forming constituent of
the paint. These are high molecular weight fatty acids present in vegetable and animal
oils
Functions:
1. They form a protective film by the oxidation and the polymerisation of the oil
2. They hold the pigment particles together on the metal surface.
3. They impart water repellency, toughness and durability to the film.
Examples:
Linseed oil, dehydrated castor oil.

Unit - III – Electrochemistry, Corrosion and Protective Coatings

Important big questions

1. Derive Nernst equation for electrode potential of an electrode. Discuss its

applications.
2. Describe the construction and working principle of std hydrogen
electrode and saturated calomel electrode.
3. What are the differences between the electrochemical cell and
electrolytic cell?
4. Describe the construction and working of a Galvanic cell.
5. What is mean by emf series? Explain its applications.
6. What is corrosion of metals? Explain the mechanism of oxidation
corrosion?
7. Describe the mechanism of electrochemical corrosion by hydrogen
evolution?
8. Differentiate between chemical and electrochemical corrosion. Mention
any four factors that affect electrochemical corrosion.
9. Describe the mechanism of dry corrosion or chemical corrosion with its
types
10.Explain the different types of electrochemical corrosion?
11.What are the factors that affect electrochemical corrosion rate? Discuss in
detail.
12.How will you control the rate of corrosion
13.How is corrosion prevented by cathodic protection? Explain.
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14.What is a corrosion inhibitor? Describe the types in it.

15.Explain the mechanism of drying oils?

16.What are the important constituents in paint? Explain the function of the
various constituents.
17.Write a short note on various special paints
18.What are the constituents present in paint, varnish and lacquer? Mention
their special qualities and uses?
19.How the hot dip process is carries out?
20.How are galvanizing and tinning are carried out? Bring out the
differences.
21.What is mean by electroless plating? Explain the various steps of
electroless plating.
22.What are surface conversion processes? how do they prevent corrosion?

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