D. Y.

Patil College of Engineering, Akurdi, Pune-411 044

Office of Dean Academics

Engineering Chemistry: Model Answer Paper UT-III

Q 1. A) Explain different types of electronic transitions that occur in an organic molecule after
absorbing UV radiations. Identify in which of the following molecules show σ → σ*, π → π*, n → π* and
n → σ* transitions only: 7M
a. Ethylene b. Acetic acid c. Aniline d. Ethyl Methyl Ether e. diethyl ether
Ans:

Following are the principles of green chemistry:

1. σ → σ* transition:
a. σ electron from orbital is excited to corresponding anti-bonding orbital σ*.
b. The energy required is large for this transition.
c. e.g. Methane (CH4) has C-H bond only and can undergo σ → σ* transition and shows absorbance
maxima at 125 nm.

2. π → π* transition:
a. π electron in a bonding orbital is excited to corresponding anti-bonding orbital π*.
b. Compounds containing multiple bonds like alkenes, alkynes, carbonyl, nitriles, aromatic
compounds, etc undergo π → π* transitions.
c. e.g. Alkenes generally absorb in the region 170 to 205 nm.

3. n → σ* transition:
a. Saturated compounds containing atoms with lone pair of electrons like O, N, S and halogens are
capable of n → σ* transition.
b. These transitions usually requires less energy than σ → σ* transitions.
c. The number of organic functional groups with n → σ* peaks in UV region is small (150 – 250 nm).
d. e.g. Ethyl alcohol, Ethyl amine, etc

4. n → π* transition:
a. An electron from non-bonding orbital is promoted to anti-bonding π* orbital.
b. Compounds containing double bond involving hetero atoms (C=O, C≡N, N=O) undergo such
transitions.
c. n → π* transitions require minimum energy and show absorption at longer wavelength around 300
nm.
d. e.g. Acetone, Acetic acid, etc

1
 5. σ → π* & π → σ*transitions:
a. These electronic transitions are forbidden transitions & are only theoretically possible.
b. Thus, n → π* &π → π* electronic transitions show absorption in region above 200 nm which is
accessible to UV-visible spectrophotometer.
c. The UV spectrum is of only a few broad of absorption.

Compound a. Ethylene b. Acetic acid c. Aniline d. Ethyl Methyl Ether e. diethyl ether
Transitions π → π* n → π*, n → σ* n → σ* n → σ* n → π*, n → σ*

Q 1. B) Give reasons:
a) Benzene shows 𝛌𝐦𝐚𝐱 at 255 nm whereas phenol shows 𝛌𝐦𝐚𝐱 at 270 nm
b) HCl can undergo stretching vibrations only whereas CO2 undergoes stretching as well as
bending
c) Fundamental modes of vibrations for H2O are 3. 6M
Ans:
a) It is due to red shift due to presence of –OH. Presence of –OH group, more conjugation occurs that
leads to maximum wavelength of absorption.

b) HCl is linear molecule, where N = 2

∴ 𝑉𝑖𝑏𝑟𝑎𝑡𝑖𝑜𝑛 𝑑𝑒𝑔𝑟𝑒𝑒 𝑜𝑓 𝑓𝑟𝑒𝑒𝑑𝑜𝑚 = 3𝑁 − 5 = 3 × 2 − 5 = 1
Thus, HCl can only 1 stretching.
CO2 is linear molecule, where N = 3
∴ 𝑉𝑖𝑏𝑟𝑎𝑡𝑖𝑜𝑛 𝑑𝑒𝑔𝑟𝑒𝑒 𝑜𝑓 𝑓𝑟𝑒𝑒𝑑𝑜𝑚 = 3𝑁 − 5 = 3 × 3 − 5 = 4
Thus, CO2 can have 2 stretching and 2 bending vibrations.

c) H2O is non-linear molecule, where N = 3

∴ 𝑉𝑖𝑏𝑟𝑎𝑡𝑖𝑜𝑛 𝑑𝑒𝑔𝑟𝑒𝑒 𝑜𝑓 𝑓𝑟𝑒𝑒𝑑𝑜𝑚 = 3𝑁 − 6 = 3 × 3 − 6 = 3
Thus, HCl can have 3 modes of vibrations.
Q 1. C) Give principle of IR Spectroscopy. Explain function group region and finger print region. 5 M
Ans:
IR-spectroscopy or (vibrational spectroscopy) involves the interaction of infrared radiation with matter.
The IR spectroscopy theory utilizes the concept that molecules tend to absorb the specific frequencies of
light that are characteristic of the corresponding structure of the molecules.
If molecule absorbs IR radiation, it gets excited to higher vibrational level, which depends upon the type
of atom and chemical bond in the molecules.
a) Functional group region :
The fundamental vibrations occur in this region and the common functional groups show
absorption in this region. Hence, this region is called as functional group region. The bands that occur in
this region are mainly due to stretching vibrations of functional groups such as OH, NH, C–H, SH in
the range 2500  3700 cm–1.

b) Finger print region :

The region between 7.7 to 11  (i.e. 1300  909 cm–1) is known as finger print region. This is
the most complex part of IR spectrum and contains number of absorption bands. These absorption
bands appear due to stretching and bending vibrations. This region is not much helpful for

2
 interpretation. But it is useful for comparing the samples to know whether they are chemically
identical or not. If the finger print region of two samples is identical, then these samples are also
identical.

Q 2. A) What are the conditions of absorption of IR radiations by the molecule? Draw a block diagram
of IR spectrophotometer. Explain any four components of IR Spectrophotometer with their functions.
7M
Ans:
Conditions of absorption of IR radiations:
a) Correct Wavelength of Radiation:
A molecule absorbs radiation only when the natural frequency of vibration of some part of a
molecule i.e. atoms or group of atoms comprising it is the same as the frequency of the incident
radiations.

For example, the natural frequency of vibration a HCl molecule is about 8.7  1013 sec–2 (2890 cm–1)
when IR radiation is permitted to pass through a sample of HCl and the transmitted radiation is analysed
by the IR spectrometer. It is observed that part of the radiation which has a frequency of 8.7  1013 sec-
1 has been absorbed by HCl molecules where as the remaining frequencies of the radiation are
transmitted. Thus, the frequency 8.7  1013 sec–1 is characteristic of HCl molecule.

b) Dipole Moment:
When the molecule having electric dipole is kept in the electric field i.e kept in a beam of IR
radiation, this field will exact forces on the electric charges in the molecule. The electric field of IR
radiation is changing its polarity periodically when these charged atoms vibrate; they absorb IR radiation
from the radical source. If the rate of vibration of charged atoms in a molecule is fast, the absorption of
radiation is intense and thus the IR spectrum will have intense absorption bonds. On other hand, when
rate of vibration is slow, there will be weak bonds in the IR spectrum.

IR Spectrophotometer:

Construction:
1. Source: For IR radiation, one of the following sources can be used.
Nerst Filament: It consists of a ceramic rod that heated to incandescence. Ceramic rod consists of
mixture of rare earth metal oxides such as zirconium oxide, yttrium oxide and erbium oxide.

Globar: It is a silicon carbide rod of 5 to 10 mm width and 20 to 50 mm length which is electrically

heated up to 1,000 to 1,650°C (1,830 to 3,000°F).

3
 2. Sample cells and sampling of substances:
IR Spectra can be obtained for solid, liquid or gases doped in NaCl, KBr, LiF, etc which are IR
inactive.
Sampling of solid: It can be done by
Solid run in solution: Solid substances are dissolved in non-aqueous solvent. A drop of solution is
placed on the disc of alkali halide. Solvent is dried to give the film on the surface.

3. Detector:
In IR spectrophotometer, thermal detectors are used like
Thermocouple: Two metal wires are joined together as a junction. When it absorbs IR radiation, it
gets heated and produces potential difference results to detect.

Bolometer: Platinum or nickel is used to form bolometer, which is resistant thermometer to detect
weak thermal radiation. Change in resistance is observed due to change in temperature.

4. Amplifier and Recorder:

It applies the signals from detector and sends to recorder. It gives IR spectra of a compound as a
graph of percentage transmission of IR radiation vs wavelength or frequency or wavenumber.

Q 2. B) Give Reasons-
a) p-nitrophenol shows red shift in alkaline medium
b) Pyridine shows absorption intensity less than 2-methyl pyridine
c) Methane does not absorb IR radiation 6M
Ans:
a) In alkaline medium, p-nitrophenol shows red shift. Because negatively charged oxygen delocalizes
more effectively than the unshared pair of electron.
– –
O + O O + O
N N

-
OH

Alkaline
medium -
OH O

b) Introduction of auxochrome to the compounds like –CH3, which shows hyper-conjugation effect,
causes more effective delocalization than pyridine.

N N CH3

c) It contains C and H which has nearly the same electronegativity leads to no dipole moment. Also it
is symmetrical and non-polar in nature, therefore it does not absorb IR radiation.

4
Q 2. C) Give Reasons-
i. Calculate possible number of fundamental vibrations in CO2, CH4
ii. What are chromophores? Identify chromophoric group in following
a) CH2=CH2-SH b) C4H-OH c) CH3-CN 5M
Ans: i.

Sr. No Compound Geometry No. of atoms Fundamental vibrations

1. CO2 Linear 3 3𝑁 − 5 = 3 × 3 − 5 = 4
2. CH4 Non-linear 5 3𝑁 − 6 = 3 × 5 − 6 = 9

ii. Chromophore: The part of a molecule responsible for imparting color, are called as chromospheres.
Or The functional groups containing multiple bonds capable of absorbing radiations above 200 nm due to n →
π* & π → π* transitions.

Compound a) CH2=CH2-SH b) C4H-OH c) CH3-CN

Chromophoric group C=C C=C 𝐶≡𝑁

Q 3 A) i) What is galvanizing? Explain galvanizing with neat labeled diagram to protect iron from
corrosion. 4M
Ans:
Galvanizing: The process of coating iron or steel (base metal) with a thin coat of zinc by hot dipping to
prevent base metal corrosion is called as galvanizing.

Zinc is anodic with respect to base metal (steel). On exposure to the corrosive media, only zinc
undergoes corrosion, protecting base metal.

The process involves following steps:

1. The metal article is cleaned & degreased by using organic solvents.
2. It is treated with dil. H2SO4 (pickling) for 15 – 20 min. at 70 – 90oC to remove any rust or scale.
3. It is then washed with water & dried.
4. The metal article is then dipped in bath of molten zinc, maintained at 425 – 430oC. The surface of both is
covered with flux (NH4Cl + ZnCl2). Flux cleans the metal surface before coating for better adhesion and
prevents the oxidation of molten coating metal after the coating.
5. It is then passed through pair of hot rollers to remove excess zinc and produce thin uniform coating.
6. It is then annealated at 650oC & cooled to room temperature slowly.
7. This coating protects the base metal against corrosion and provide excellent base for applications of
paints, oils, enamels etc.

5
Q3 A) ii) What is metal cladding? How is it carried out? Which are cladding metals commonly used?
3M
Ans:
Cladding is the bonding together of dissimilar metals. It is the process by which a dense, homogeneous
layer of coating metal is bonded firmly and permanently to the base metal on one or both sides.

It is achieved by arranging thin sheets of the coating metal and the base metal sheet in the form of
sandwich, which is then passed through rollers, under the action of heat and pressure. Due to this,
coating metal gets bonded firmly and permanently to the base metal.

Example: A plate of duralumin is sandwiched between two layers of 99.5% pure aluminum. It is
called as ‘Alcad’, which is widely used for aircraft industry.

Q 3 B) Define Corrosion. State the conditions under which wet corrosion occurs. Explain oxygen
absorption mechanism of wet corrosion. 5 M
Ans:
Corrosion is the destruction of metal due to unintentional chemical or electrochemical attack on the
surface of metal by its environment.

The reactions involved in the Galvanic cell are as follows:

1. Anodic reaction: Metal undergoes oxidation with release of electrons.
Fe  Fe2+ + 2e−
3. Cathodic reaction: At the cathodic region, electrons are absorbed and cause reduction of constituents.

There are following possible conditions in which reduction takes place.

• If the solution is aerated and almost neutral, oxygen is reduced in the presence of H2O to OH− ions.
O2 + 2 H2O + 4 e−  4OH−
• If the solution is aerated and acidic in nature
4H+ + O2 + 4 e−  2 H2O
• If the solution is de-aerated and almost neutral, then H2 is liberated along with OH− ions.
2 H2O + 2 e− H2  + 2OH−
• If the solution is deaerated and acidic, H+ ions are reduced to hydrogen gas.
2H+ + 2e−  H2 

Oxygen absorption mechanism:

This type of corrosion occurs when electrolyte is neutral aqueous solution or alkaline solution containing
dissolved oxygen.

e.g. Consider a steel plate lying on the ground & is exposed to the atmosphere. In a due course of time
oxide layer will form on the surface of steel plate and drops of water may be collected over a small crack
on the oxide film present on the surface of steel. As shown in fig below.

In this case water act as an electrolyte, Fe plate underlying through the crack act as anode & oxide scale
on steel surface act as cathode as:

6
 At Anode:
The steel goes into solution as ferrous ions (Fe+2).
+2 -
Fe Fe +2e

At Cathode:
The electrons flow from anode to cathode. These electrons are interrupted by dissolved oxygen present
in the electrolyte, forming hydroxyl ion.

1 - -
H2O + /2 O 2 + 2 e 2 OH

The Fe+2 ions at anode & OH- ions at cathode diffuse & combine to form ferrous hydroxide. It is
observed that outward diffusion of Fe+2ions is more rapid as they have small size as compared to OH-
ions. Therefore corrosion takes place at anode; rust deposition takes place at cathode.
+2 -
Fe + 2 OH Fe(OH) 2

The following diagram shows the oxygen absorption mechanism as:

If enough oxygen is present in the electrolyte, ferrous hydroxide is easily oxidized to ferric hydroxide.
4 Fe(OH) 2 + 2 H 2O + O 2 Fe(OH) 3

Q3 C) Define Electroplating. Explain the process with neat labeled diagram and its applications. 5 M
Ans:
Electroplating: Electroplating or electro-deposition is the process by which the coating metal is
deposited on the base metal by passing a direct current through the solution of an electrolyte containing
soluble salt of coating metal.

Process of Electroplating:
1. The base metal article to be coated is cleaned to remove oils, greases, oxides, scales etc.
2. The metal article to be plated is made at cathode while coating metal is made at anode.
3. The number of cathodes & anodes can be suspended alternatively for getting uniform deposition of over
the entire surface.

7
 4. Cathode & anode are dipped in the electrolyte (normally a salt solution of coating metal), containing
soluble concentration of mineral acid to increase the electrical conductivity & suppress the hydrolysis of
salt.
5. pH of electrolyte is adjusted & suitable current density is chosen for electrolysis.
6. As electrolysis proceeds, the node metal gets oxidized and enters the electrolytic solution. The metal
ions get reduced & deposited on the surface of base metal (cathode).

+2 -
At anode: Ni Ni + 2 e Oxidation
+2 -
At cathode: Ni +2e Ni Reduction

Salts for electrolyte: NiCl2 or NiSO4

Applications:
1. Electroplating can be used for getting decorative surface. e.g. gold, chromium, brass coating on steel are
used in ornaments, wrist watches, belts, pens, etc
2. It is used for protecting surface against corrosion. e.g. chromium plating on steel.
3. Non-metals like wood, paper and glass can be electroplated for decoration, preservation of surface, for
obtaining conducting surface etc.
4. Automobile, aircraft, radio & ammunition industries use parts by electroforming (thick layer of metal by
electroplating).

Q 4. A) What is anodic coating and cathodic coating? Which is more protective and why? 4M
Ans:
Anodic Coating: It is the coating of metal (on the surface of base metal), which has higher position in
electrochemical/Galvanic series with respect to the base metal.
Examples: Coating of Zn, Al, Cd on steel.

Cathodic Coating: It is the coating of metal on the surface of base metal, which has slightly lower
position in the electrochemical series with respect to base metal.
Example: Coating of Sn on steel.

8
 Anodic Coating is better than cathodic coating.

In case of any pores present in coating, the base metal gets exposed to an environment. As Zn has higher
position in electrochemical series, it will get consumed first, then corrosion starts at base metal.
Therefore, base metal gets protected even if it has pores.

In case of any pores present in coating, the base metal gets exposed to an environment. As Sn has
slightly lower position in the electrochemical series, it allows corrosion of base metal. Therefore, base
metal starts corroding if any pores are present.

Thus, in anodic coating, coating metal gets corroded and in cathodic coating base metal starts to corrode.
Hence, anodic coating is better than cathodic coating.

Q 4. A) ii) Explain with the help of any three factors how nature of metal affects the rate of corrosion.
3M
Ans:
1. Electrode potential: The extent of corrosion depends upon the position of the metal in the
electrochemical series and galvanic series. The metal placed higher in the galvanic series becomes
anodic and suffers corrosion. The rate, extent and severity of corrosion depend upon the potential
difference of the two metals. More the two metals are apart in the galvanic series, the greater will be the
difference in their oxidation potential and hence, the faster will be the corrosion of the anodic metal.

2. Relative areas of anode and cathode: The rate of corrosion is directly proportional to the ratio of areas
of the cathodic part and anodic part. If the ratio of the cathodic area to anodic area is greater, then the
rate of corrosion is greater. Corrosion is more rapid, severe and localized, if the anodic area is smaller,
because the current density at the smaller anodic area is much greater. The great demand for electrons,
by the larger cathodic area, can be met by the smaller anode only by undergoing more corrosion.

3. Purity of metal: As pure metal have high resistance for corrosion as compared to impure metal. The
impurities present in the metal form minute galvanic cell with the metal under appropriate environment
and anodic part get corroded.
e.g. impurities such as Pb, Fe in Zn.

Q 4. B) Give Pilling-Bedworth ratio and its significance. Give the oxidation reactions involved and state
the type of film formed on the surface in case of Mg, Cr and Mo when they undergo oxidation corrosion.
5M
Ans:
Pilling-Bedworth ratio can be given as:
Volume of metal oxide
Pilling  Bedworth ratio 
Volume of metal consumed

Significance:
 It helps to identify whether metal is porous or non-porous thereby film formed is protective or
non-protective.
 Example “If the volume of metal oxide is smaller than the volume of metal consumed in the
metal oxide formation, then the film is porous & non-protective.”
 “If the volume of metal oxide is larger than the volume of metal consumed in the metal oxide
formation, then the film is non-porous & protective.”

9
 Corrosion of Mg by oxygen:
When magnesium forms oxide due to presence of oxygen, the volume of magnesium oxide is less than
the volume of magnesium. Thus, according to Pilling-Bedworth rule, it is porous and non-protective.
1
Mg + /2 O 2 MgO

Porous Oxide film, Non-protective

Corrosion of Cr by oxygen:
When chromium forms oxide due to presence of oxygen, the volume of chromium oxide is more than
the volume of chromium. Thus, according to Pilling-Bedworth rule, it is non-porous and protective.
3
2 Cr + /2 O 2 Cr 2O3

Corrosion of Mo by oxygen:
When molybdenum forms oxide due to presence of oxygen, it forms the volatile oxide film which
evaporated and then the second layer will be there to oxidize in presence of oxygen.
4 Mo + 3 O 2 2 Mo 2O 3 Evaporation slowly
Q.4 C) What is the principle of cathodic protection? Explain cathodic protection with any one method
and state its advantages. 5M
Ans:
Principle – In electrochemical corrosion, anode is the one which undergoes corrosion and cathode
remains protected from corrosion. In cathodic protection, the metal to be protected is forced to behave
like a cathode.

Sacrificial anodic or galvanic protection;-

The structure to be protected is connected to a small block or piece of more active/anodic metal. The
more active metal works as anode. The corrosion attack is concentrated at this more active metal and it
slowly undergoes corrosion. The main structure to be protected acts as cathode and remains protected
from corrosion.

The more active metal so employed is called Sacrificial anode. The corroded sacrificial anode block is
replaced by fresh one, when consumed completely. To increase electrical contact, sacrificial anodic
metal is placed in back fill (coke breeze or gypsum). Metals commonly used as sacrificial anodes are
Mg, Zn, Al and their alloys.

Advantages: The advantages of sacrificial anode method over others are they do not need external power
source, are easy to install, the anode and surface require low voltage and current.

===============================================================================

10
 Other Questions and Answers:

Q 1. Explain the mechanism of corrosion due to oxygen with respect toNa, Mg, Au, Cr & Mo metals
and state Pilling-Bedworth rule.
Mechanism of Corrosion due to presence of oxygen:
At Anode:
Oxygen adsorbs on metal surface & metal (M) gets oxidized to form metal ion as:
+2 -
M M + 2e Oxidation
At Cathode:
Oxygen gains electrons to form oxide ion as:
1 - -2
/2 O 2 + 2 e O Reduction
Net Reaction:
Thus, the net reaction involves the formation of metal oxide as:
1
M + /2 O 2 MO

1) Corrosion of Na by oxygen:
When sodium forms oxide due to presence of oxygen, the volume of sodium oxide is less than the volume
of sodium. Thus, according to Pilling-Bedworth rule, it is porous and non-protective.
1
2 Na + /2 O 2 Na 2O
Porous Oxide film, Non-protective

2) Corrosion of Mg by oxygen:
When magnesium forms oxide due to presence of oxygen, the volume of magnesium oxide is less than the
volume of magnesium. Thus, according to Pilling-Bedworth rule, it is porous and non-protective.
1
Mg + /2 O 2 MgO
Porous Oxide film, Non-protective

3) Corrosion of Au by oxygen:
When gold forms oxide due to presence of oxygen, it is unstable in nature and it decomposes back into the
metal and oxygen, the net corrosion is zero.
1
2 Au + /2 O2 Au 2O
Unstable oxide film

4) Corrosion of Cr by oxygen:
When chromium forms oxide due to presence of oxygen, the volume of chromium oxide is more than the
volume of chromium. Thus, according to Pilling-Bedworth rule, it is non-porous and protective.
3
2 Cr + /2 O 2 Cr 2O3

Non-Porous Oxide film, Protective

5) Corrosion of Mo by oxygen:
When molybdenum forms oxide due to presence of oxygen, it forms the volatile oxide film which
evaporated and then the second layer will be there to oxidize in presence of oxygen.
4 Mo + 3 O 2 2 Mo 2O 3 Evaporation slowly

11
Pilling-Bedworth Rule:
This rule gives an idea about the nature of oxide film, whether it is porous or nonporous. The rule states
that –
“If the volume of metal oxide is smaller than the volume of metal consumed in the metal oxide
formation, then the film is porous & non-protective.” And
“If the volume of metal oxide is larger than the volume of metal consumed in the metal oxide formation,
then the film is non-porous & protective.”
Volume of metal oxide
Pilling  Bedworth ratio 
Volume of metal consumed

Q 2. What is electrochemical corrosion? Explain electrochemical corrosion by evolution of hydrogen &

absorption of oxygen gas.
Electrochemical corrosion:
Electrochemical corrosion occurs due to electrochemical reaction between metal & electrolyte which can
be an aqueous salt solution, acid, alkali. When the metal comes in contact with the solution, potential difference
is developed and galvanic cell is formed. Greater the difference in the potential of the cathode & anode, greater
will be the corrosion.

Hydrogen evolution mechanism:

1) This type of corrosion occurs usually in acidic environment like industrial waste, solution of non-oxidizing
acids.
2) e.g. a steel tank containing acid industrial waste and a small copper scrap are in contact is considered.
3) The piece of copper and steel tank in contact with each other in presence of acidic electrolyte gives rise to an
electrochemical cell.
4) In this cell, steel acts as anode and copper acts as a cathode. It is observed that the steel tank portion in
contact with copper piece is corroded.

This can be represented by following reactions:

At Anode: At steel tank: Iron passes into solution as Fe+2 ions.
+2 -
Fe Fe + 2 e Oxidation
The free electrons are accumulated at cathode.

12
At cathode: At copper piece: Hydrogen ions from acidic electrolyte take up the free electrons and hydrogen
gas formed is liberated in the form of bubbles at cathode.
+ -
2H +2e Reduction H 2(g)
 Net Cell Reactions: Corrosion of this mechanism involves displacement of hydrogen ions from acidic
electrolyte by metal ions.
+ +2
Fe + 2 H Fe + H 2(g)
Thus, all metals above hydrogen in electrochemical series will have tendency to get dissolved in acidic
electrolyte with simultaneous liberation of hydrogen gas.

Oxygen absorption mechanism:

This type of corrosion occurs when electrolyte is neutral aqueous solution or alkaline solution containing
dissolved oxygen.
e.g. Consider a steel plate lying on the ground & is exposed to the atmosphere. In a due course of time
oxide layer will form on the surface of steel plate and drops of water may be collected over a small crack on the
oxide film present on the surface of steel. As shown in fig below.

In this case water act as an electrolyte, Fe plate underlying through the crack act as anode & oxide scale
on steel surface act as cathode as:

At Anode:
The steel goes into solution as ferrous ions (Fe+2).
+2 -
Fe Fe +2e
At Cathode:
The electrons flow from anode to cathode. These electrons are interrupted by dissolved oxygen present in the
electrolyte, forming hydroxyl ion.

1 - -
H2O + /2 O 2 + 2 e 2 OH

The Fe+2 ions at anode & OH- ions at cathode diffuse & combine to form ferrous hydroxide. It is
observed that outward diffusion of Fe+2ions is more rapid as they have small size as compared to OH- ions.
Therefore corrosion takes place at anode; rust deposition takes place at cathode.
+2 -
Fe + 2 OH Fe(OH) 2

The following diagram shows the oxygen absorption mechanism as:

If enough oxygen is present in the electrolyte, ferrous hydroxide is easily oxidized to ferric hydroxide.
4 Fe(OH) 2 + 2 H 2O + O 2 Fe(OH) 3

13
Q 3. Discuss the factors which affect the corrosion.
A. Nature of metal:
4. Electrode potential: The extent of corrosion depends upon the position of the metal in the electrochemical
series and galvanic series. The metal placed higher in the galvanic series becomes anodic and suffers
corrosion. The rate, extent and severity of corrosion depend upon the potential difference of the two metals.
More the two metals are apart in the galvanic series, the greater will be the difference in their oxidation
potential and hence, the faster will be the corrosion of the anodic metal.

5. Relative areas of anode and cathode: The rate of corrosion is directly proportional to the ratio of areas of
the cathodic part and anodic part. If the ratio of the cathodic area to anodic area is greater, then the rate of
corrosion is greater. Corrosion is more rapid, severe and localized, if the anodic area is smaller, because the
current density at the smaller anodic area is much greater. The great demand for electrons, by the larger
cathodic area, can be met by the smaller anode only by undergoing more corrosion.

6. Purity of metal: As pure metal have high resistance for corrosion as compared to impure metal. The
impurities present in the metal form minute galvanic cell with the metal under appropriate environment and
anodic part get corroded.
e.g. impurities such as Pb, Fe in Zn.

B. Nature of Environment:
1. Temperature: The rate of chemical reactions and the rate of diffusion increases with temperature. As
corrosion involves a series of chemical reactions. Hence, in general, corrosion increases with temperature.
Thus, corrosion enhances with rise in temperature.

2. Humidity: The corrosion of metal is very fast in humid atmosphere than in dry atmosphere. This is because;
moisture acts as a solvent for atmospheric gases like oxygen, carbon dioxide and some salts. This produces
an electrolyte which is essential for setting up galvanic cell or corrosion cell. Thus, metal like Mg, Al, Zn,
Cr, Fe get corroded in the presence of moisture even in the absence of oxygen.

3. pH of the medium: Acidic media are more corrosive than alkaline & neutral media. The corrosion of iron is
slow above pH 5 and in absence of oxygen. The presence of oxygen increases the rate of corrosion. Most of
the metals are readily attacked by acids but are resistant to alkalis. The corrosive tendency of such metals
can be reduced by increasing the pH of the medium. The corrosion of aluminum is minimum at pH 5.5 but it
is maximum in alkaline pH.

Q 4. Account for cathodic protection with respect to principle, method & applications.
Principle – In electrochemical corrosion, anode is the one which undergoes corrosion and cathode remains
protected from corrosion. In cathodic protection, the metal to be protected is forced to behave like a cathode.
Cathodic protection is of two types:
1. Sacrificial anodic or galvanic protection
2. Impressed current cathodic protection

Sacrificial anodic or galvanic protection;-

The structure to be protected is connected to a small block or piece of more active/anodic metal. The
more active metal works as anode. The corrosion attack is concentrated at this more active metal and it slowly
undergoes corrosion. The main structure to be protected acts as cathode and remains protected from corrosion.

The more active metal so employed is called Sacrificial anode. The corroded sacrificial anode block is
replaced by fresh one, when consumed completely. To increase electrical contact, sacrificial anodic metal is

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placed in back fill (coke breeze or gypsum). Metals commonly used as sacrificial anodes are Mg, Zn, Al and
their alloys.

Applications:
The method can be applied for the protection of
1) Buried pipelines
2) Underground cables
3) Marine structures, ship hulls, piers
4) Water tanks.

Q 5. Distinguish between cathodic& anodic coating.

Anodic coating Cathodic coating
1. It protects the underlying base metal by scarifying 1. It protects the underlying base metal due to its
itself. noble character offering higher corrosion
resistance.
2. Coating metal has higher oxidation potential than 2. Coating metal has lower oxidation potential than
that of base metal. that of base metal.
3. In case of any cracks or pores in the coating, the 3. In case of cracks or pores in the coating, there will
base metal is not corroded till the coating metal is be faster corrosion of base metal.
consumed.
4. e.g. coating of zinc on iron (galvanized steel.) 4. e.g. Coating of tin on iron (tin coated steel)

Q 6. What is electroplating? Explain process of electroplating, its advantages & applications.

Electroplating: Electroplating or electro-deposition is the process by which the coating metal is deposited on
the base metal by passing a direct current through the solution of an electrolyte containing soluble salt of
coating metal.

Process of Electroplating:
7. The base metal article to be coated is cleaned to remove oils, greases, oxides, scales etc.
8. The metal article to be plated is made at cathode while coating metal is made at anode.
9. The number of cathodes & anodes can be suspended alternatively for getting uniform deposition of over
the entire surface.

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 10. Cathode & anode are dipped in the electrolyte (normally a salt solution of coating metal), containing
soluble concentration of mineral acid to increase the electrical conductivity & suppress the hydrolysis of
salt.
11. pH of electrolyte is adjusted & suitable current density is chosen for electrolysis.
12. As electrolysis proceeds, the node metal gets oxidized and enters the electrolytic solution. The metal
ions get reduced & deposited on the surface of base metal (cathode).

+2 -
At anode: Ni Ni + 2 e Oxidation
+2 -
At cathode: Ni +2e Ni Reduction

Salts for electrolyte: NiCl2 or NiSO4

Advantages:
1. Coating thickness can be controlled.
2. Coating of metal having high melting points like Cr, Ni, Ag, Au can be easily applied.
3. Process is not expensive.
4. Fine coating can be obtained with improved hardness.

Applications:
1. Electroplating can be used for getting decorative surface. e.g. gold, chromium, brass coating on steel are
used in ornaments, wrist watches, belts, pens, etc
2. It is used for protecting surface against corrosion. e.g. chromium plating on steel.
3. Non-metals like wood, paper and glass can be electroplated for decoration, preservation of surface, for
obtaining conducting surface etc.
4. Automobile, aircraft, radio & ammunition industries use parts by electroforming (thick layer of metal by
electroplating).

Q 7. Explain Galvanizing & tinning process with diagram.

Galvanizing: The process of coating iron or steel (base metal) with a thin coat of zinc by hot dipping to prevent
base metal corrosion is called as galvanizing.
Zinc is anodic with respect to base metal (steel). On exposure to the corrosive media, only zinc
undergoes corrosion, protecting base metal.

The process involves following steps:

1. The metal article is cleaned & degreased by using organic solvents.
2. It is treated with dil. H2SO4 (pickling) for 15 – 20 min. at 70 – 90oC to remove any rust or scale.

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3. It is then washed with water & dried.
4. The metal article is then dipped in bath of molten zinc, maintained at 425 – 430oC. The surface of both is
covered with flux (NH4Cl + ZnCl2). Flux cleans the metal surface before coating for better adhesion and
prevents the oxidation of molten coating metal after the coating.
5. It is then passed through pair of hot rollers to remove excees zinc and produce thin uniform coating.
6. It is then annealated at 650oC & cooled to room temperature slowly.
7. This coating protects the base metal against corrosion and provide excellent base for applications of paints,
oils, enamels etc.

Uses – Galvanized sheets are used for roofing sheets, wires, pipes, bolts, screws, tubes, buckets etc.

Tinning – The process of coating iron or steel with a thin coat of tin (Sn) by hot dipping to prevent base
metal corrosion is called tinning.

The process involves following steps

1. The clean surface of metal article is treated with dil. H2SO4 to remove any oxide film, washed with water
and dried.
2. It is immersed in a flux (ZnCl2 and NH4Cl) which will facilitate better adhesion of coating.
3. The metal article is then passed through a tank of molten tin maintained at about 2400C
4. Finally it is passed through a series of rollers kept submerged in the palm oil. Rollers remove excess of tin
to produce thin, uniform coating. Palm oil protects the hot tin coated surface against oxidation.

Uses – Tinning is used for coating iron, steel, copper, brass used for manufacturing containers to store food
stuffs, oils, ghee, kerosene etc.

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