Dr. Shweta J.

Malode
MODULE 2
CORROSION AND METAL FINISHING
Questions from previous exam papers
1. Explain the electrochemical theory with reference of iron.
Answer: Electrochemical Theory of Corrosion
Most of the corrosion takes place on the basis of electrochemical reactions on the surface of metal
such a type of corrosion is known as wet corrosion.
 Formation of galvanic cells: When a metal like iron is exposed to the environment, corrosion
of metal takes place due to the formation of anodic and cathodic regions on the same metal
surface or when the two metals are in contact with each other in a corrosive medium (like
moisture). These anodes and cathodes are formed due to the heterogeneities at the interfaces of
the metal and environment.
 At anode: oxidation takes place so that metal is converted into metal ions with the liberation
of electrons.
Fe Fe2+ + 2e-
 At cathode: reduction takes place. Since the metal at cathodic region cannot be reduced
further, so some constituents of the corrosive medium take part in the cathodic reaction. The
cathodic reactions are dependent on the nature of environment. Most common type of cathodic
reaction is (a) Liberation of hydrogen, (b) Absorption of oxygen.
(a) Liberation of Hydrogen type
(i) If the medium is acidic and in the absence of O2
2H+ +2e- H2
(ii) If the medium is neutral or alkaline in the absence of O2.
2H2O + 2e- 2OH- + H2
(b) Absorption of oxygen type
(i) If the medium is acidic and in the presence of O2.
4H+ + O2 + 4e- 2H2O
(ii) If the medium is neutral or alkaline and in the presence of O2.
2H2O + O2 + 4e- 4OH-
The metal ions (Fe2+) liberated at anode and some anions (OH-) formed at cathode diffuse towards
each other through the conducting medium and form a corrosion product somewhere between the
anode and cathode as,

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2Fe2+ + 4OH- 2Fe(OH)2
In an oxidizing environment, the insoluble Fe(OH)2 oxidised to ferric oxide as following reaction.

4Fe(OH)2 + O2 + 2H2O 2(Fe2O3 . 3H2O) + H2

Yellow rust
If the concentration of oxygen is limited, then Fe(OH)2 is converted into magnetic oxide of Fe and
is known as black rust.
3Fe(OH)2 + ½ O2 Fe3O4.3H2O
Black rust
A diagrammatic representation of rusting of iron is shown below.

2. Explain the following types of corrosion: a) Pitting corrosion b) Water line corrosion.
Answer: Water Line Corrosion: This is a case of differential aeration corrosion commonly
observed in steel water tanks, ocean going ships etc. in which portion of the metal is always under
water. The part of the metal below the water line is exposed to only to lower concentration of
oxygen becomes anodic and undergoes corrosion. While the part above the water is exposed to
higher concentration of oxygen becomes cathodic and remains unaffected. More intense corrosion
is observed just below the water line; hence it is called as water line corrosion. This type of
corrosion is commonly observed in ships floating in sea water for a long period of time.

Pitting Corrosion: Pitting corrosion is a localized and accelerated corrosion. When a small
particles of dust or oil drops etc are get deposited on a metal (like steel), the portion covered by
the dust will be less-aerated becomes anodic and undergoes corrosion and forms a pit. The
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adjacent area of the metal which is exposed to higher concentration of oxygen becomes cathodic
and remains unaffected. Once pit is formed the ratio of corrosion increases, because of the
formation of smaller anodic and larger cathodic area intense corrosion takes place.

3. Write a brief note on the effect of the following factors on the rate of corrosion. a)
Nature of corrosion product, b) Nature of medium, c) Ratio of anodic and cathodic area, d)
Nature of metal, e) Temperature.
Answer: 1) Nature of Metal: The metals with lower electrode potential values are reactive than
the metals with higher electrode potential values. The more reactive metals are susceptible for
corrosion. Thus the tendency of a metal to undergo corrosion decreases with increase in electrode
potential.
Examples: Active metals like K, Na, Mg, Zn etc have low electrode potential values are highly
susceptible for corrosion. The noble metals such as silver, gold, platinum etc., with higher
electrode potential values are less susceptible for corrosion. However, there are few exception for
this general trend as some metals show the property of passivity like Al, Cr, Ti, Ta etc.
2) Nature of Corrosion Product: The corrosion product is usually the oxide of the metal; the
nature of the product may or may not act as a protective film. If the corrosion product deposited is
insoluble, stable, uniform and non porous, it act as a protective film preventing the further
corrosion of metal. On the other hand if the corrosion product is soluble, unstable, non-uniform
and porous, the corrosion of the metal takes place continuously.
Examples: Metals like aluminium, chromium, titanium etc are highly passive as their oxides as
corrosion products form protective films on the metal surface, preventing further corrosion.
Metals such as iron, zinc, magnesium etc do not form any protective film and are highly
susceptible for continuous corrosion, when exposed to oxidizing environment.
3) Ratio of Anodic and Cathodic area: The rate of the corrosion is greatly influenced by the
relative sizes of cathodic and anodic areas. If the metal has smaller the anodic area and larger the
cathodic area exposed to corrosive atmosphere (i.e., the ratio of anodic to cathodic area is small),
then the corrosion is more intense and faster is the corrosion rate at the anodic region. As the ratio
decreases, the corrosion rate increases rapidly.This can be explained as follows; at anode,
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oxidation takes place and electrons are liberated. At the cathode, these electrons are consumed.
When anode is smaller and cathode region is larger all the liberated electrons at anode are rapidly
consumed. This process makes the anodic reaction to takes place at its maximum rate thus
increasing the corrosion rate. If the cathode is smaller and reverse process takes place decrease
rate of corrosion.
4) Nature of Medium:
pH: In general, higher the acidic nature of the environment (low pH) higher is the rate of
corrosion. At pH greater than 10, corrosion of iron practically ceases due to the formation of a
protective coating of hydrous oxides of iron. If the pH is lower than 3, severe corrosion occurs
even in the absence of air due to the continuous evolution of hydrogen at the cathodic region.
Conductance: The corrosion rate increases in the presence of conducting species in the
atmosphere. This is because corrosion is an electrochemical phenomenon. The rate of corrosion in
a dry atmosphere is less than that in a wet atmosphere since the latter is more conducting. Higher
the conductivity of the medium, faster the ions can migrate between the anodic and cathodic
regions of the corrosion cell, in turn, faster will be the exchange of electrons at the electrode
surfaces. This facilitates higher corrosion rate. Therefore, corrosion problem is more in the sea
water than in fresh water.
Temperature: The rate of corrosion increases with increase in the temperature. Increase in
temperature increases conductance of the aqueous medium and results in an increase in the
diffusion rate. Hence, corrosion progresses faster. In some cases, rise in temperature decreases the
passivity, which again leads to increase in the corrosion rate.

4. Explain the Galvanization process.

Answer: Galvanization is a process of coating a layer of zinc on iron by hot dipping. The
following steps are involved in the process,
 Iron sheet is passed through organic solvent to remove oil or grease present on it.
 Then it is washed with dil. H2SO4 to remove any rust (oxide layer) present on the surface
(pickling).
 Then it is treated with a mixture of aqueous solution of ZnCl2 and NH4Cl which acts as
flux and then dried.
 Finally it is dipped in molten zinc at 450 0C.
 Excess zinc present on iron sheet is removed by passing through rollers.

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Uses: For corrosion protection in roofing sheets, wires, pipes, in making electrical appliances.

5. Explain anodizing of aluminium.

Answer: Anodizing of Al: It is the process of oxidation of outer layer of metal to its metal oxide
by electrolysis. Oxide layer formed over the metal itself acts as a protective layer.
Procedure: In anodizing of aluminium, it is cleaned, degreased and polished and taken as anode
in an electrolytic cell. It is immersed in an electrolyte consisting of 5-10% chromic acid (H2CrO4).
Steel or copper is taken as cathode. Temperature of the bath is maintained at 35 0C. A current
density of 100 A/m2 or more is applied which oxidizes outer layer of Al to Al2O3 that gets
deposited over the metal.
Applications: Anodized aluminium is used as an attractive, highly durable, corrosion resistant
material in exterior for roofs, walls, buildings and also in many home appliances and consumer
products.

6. What is cathodic protection? Explain sacrificial anode and impressed current method
for prevention of corrosion.
Answer: Cathodic Protection: It is a method of protecting a metal or alloy from corrosion by
making the entire metal cathodic by providing electrons from an external source. This prevents
the oxidation of metal at anodic area. Thus anodic area of metal is converted to cathodic area.

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When whole metal becomes cathodic, it doesn’t undergo corrosion.There are two methods for
providing electrons for cathodic reactions.
i) Sacrificial Anode Method:
In this method, the protected metal surface is converted in to a cathode by connecting it to a more
active metal. This active metal acts as an auxillary anode. Zn, Mg and Al are the common
auxillary anodes used in this method. These metals being more active, acts as anode and undergo
preferential corrosion, protecting the metal structure. Since the anodic metals are sacrifices to
protect the metal structure, the method is known as sacrificial anode method. Exhausted sacrificial
anodes are replaced by new ones as and when required.
Examples: 1. A Mg or Zn block connected to a buried oil tank
2. Mg bars are connected to ocean going ships
Sacrificial anode methods are simple with low installation cost and do not require power supply
but involves recurring expenditure of replacement of consumed anodes.

ii) Impressed Current Method:

This is another method to provide cathodic protection by supplying electrons. These can be
provided by a source of direct current. The structure to be protected should be made negative
(connected to negative terminal of a D.C source). Resin bonded graphite rod, platinised Ti, Pb are
used as anode and connected to the positive terminal. The main structure being cathode does not
undergo corrosion, and anode being inert remains unaffected. This method is simple, can protect
large metal area with low maintenance cost but expensive, because it needs high current. This
technique is used to protect marine structure, water storage tanks and other gas or oil pipelines.

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7. Explain the principles governing electroplating process.
a) Polarization, b) Decomposition potential, c) Over voltage.
Answer: Polarization: During electrolysis, metal ions present at the vicinity of cathode get
reduced to metal atoms. Therefore concentration of metal ions at the vicinity of cathode
decreases. To maintain the same concentration, metal ions must be supplied from the bulk of the
solution to vicinity of the electrode. If metal ions are not supplied sufficiently, then the
concentration of metal ions at the electrode surface decreases. This leads to decrease in the
potential of electrode according to Nernst equation.
2.303RT
E = E0 + log [Mn+]
nF
This decrease in electrode potential due to insufficient supply of ions from bulk of the
solution to surface of the electrode is called as Polarization. Polarization occurs at anode also.
Potential required to overcome polarization of anode and cathode is called as polarization
potential. It depends upon, 1) Conductivity of the solution, 2) Current density applied, 3)
Temperature, 4) Rate of stirring of the electrolyte solution, 5) Nature of the electrode.
Effect of polarization can be minimized by stirring the electrolyte continuously, by using
electrodes of larger surface area and electrolytes of higher conductivity.

Decomposition Potential (ED): In an electrolytic cell, the following processes occur during
electroplating of metal: i) Cations are attracted towards cathode, ii) Anions are attracted towards
anode, iii) Cations are reduced to metal atoms at the surface of cathode, iv) Anions are oxidized at
the surface of anode.
Each of these steps has its own potential. If the externally applied potential is less than potential
of these processes, then electroplating of metal does not occur. Therefore, electroplating of metal
occurs smoothly and continuously when the applied potential is greater than the potential of all
these steps. The minimum external voltage that must be applied in order to carry out continuous
electrolysis in an electrolyte cell is called as decomposition potential (ED).
Decomposition potential is given by the equation: ED = EBack + ɳ
Where, ɳ is the over potential and EBack is the back EMF. EBack is the back difference in potential
of anodic and cathodic reactions occuring in the cell during electrolysis. The EMF opposes the
externally applied potential and hence it is called as back EMF.
EBack = Ecathode - Eanode

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It is more difficult to deposit the metal which has a higher decomposition potential.

Over Potential or Overvoltage (ɳ): In most of the cases, decomposition potential (ED) required
to carry out continuous electrolysis is greater than theoretical decomposition potential. This
difference between ED and theoretical decomposition potential (EBack) is called as over voltage
(ɳ).
Over potential = (Experimental decomposition potential – Theoretical decomposition potential)
i.e. ɳ = ED - EBack
Over potential can be defined as the excess potential that has to be applied above the
theoretical decomposition potential to bring about continuous electrolysis. Over voltage is mainly
due to polarization of electrodes and other side reactions that occur at the electrode surface during
electroplating. One of the main side reactions is liberation of hydrogen at cathode.

8. What is electroplating? Explain the process of electroplating of chromium for

engineering applications. Indicate the reasons for not employing chromium as anode.
Answer: It is a process in which a layer of metal is deposited on the surface of another metal by
applying electric current.
Composition of the bath: Plating bath solution: Chromic acid bath [Chromic acid (CrO3) and
H2SO4 in 100:1 proportion]
Temperature: 45-60 0C
Current density: 100-200 mA/cm2 for decorative chromium and 215 -430 mA/cm2 for hard
chromium
Current efficiency: 8-12 %
pH: 2-4
Anode: Insoluble anodes Pb-Sn or Pb-Sn coated with PbO2 or stainless steel.
Cathode: Object to be plated
Applications: Decorative chromium (imparts bright and decorative look to materials like
automotive bumps, wheel rims, taps, handles etc).
Hard chromium (imparts surface hardness and wear resistance to materials like in cutting edges of
milling and drilling tools, hand guns, aircraft landing parts, piston rings etc).
In chromium plating sulphate ion provided by the sulphuric acid is believed to act as a
catalyst. Cr is present in the hexavalent state Cr(VI) as CrO3 in the bath solution. This is
converted into trivalent Cr (III) by a complex anodic reaction in the presence of sulphate ions and
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then coated, as Cr on the cathode surface. The amount of Cr (III) ions should be restricted in order
to get proper deposit. Insoluble anodes are used to maintain the Cr (III) concentration as they
oxidize Cr (III) to Cr(VI). Chromium anodes are not used in Cr plating because Cr metal
passivates strongly in acid sulphate medium and Cr anode gives Cr (III) ions on dissolution. In the
presence of large concentration of Cr(III) ions, a black Cr deposit is obtained.
Reactions:
CrO3 + H2O H2CrO4
Chromium trioxide Chromic acid

2H2CrO4 H2Cr2O7 + H2O

SO42- (catalyst)
+
Cr2O72- + 14H + 6e
-
2 Cr3+ + 7H2O

2 Cr3+ + 6e- 2 Cr

9. What is electroless plating? Explain the process of electroless plating of copper on PCB.
Answer: Deposition of layer of metal from its salt solution on a catalytically active surface of the
object using a suitable reducing agent without using electric current is called electroless plating.
Electroless plating of Copper:
The surface to be coated is first degreased by organic solvents or alkali followed by acid
treatment.
1. Metals like Fe, Co, Ni etc do not need pre-treatment.
2. Non-metallic materials (e.g. glass, plastic etc) are activated by first dipping in SnCl 2 and HCl
solution, followed by dipping in PdCl2 solution and dried to get a thin layer of palladium
(acts as catalyst).
HCl
SnCl2 + PdCl2 SnCl4 + Pd
Composition of bath:
Coating solution: CuSO4 solution (12g/L)
Reducing agent: Formaldehyde (8g/L)
Buffer: NaOH (15g/L) + Rochelle salt (14g/L)
Complexing agent: EDTA (20g/L)
pH: 11
Temperature: 25 oC
Reactions:

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Anode: 2HCHO + 4OH- 2HCOO- +2H2O + H2 +2e-
Cathode: Cu2+ + 2e- Cu

Net redox reaction: Cu2+ + 2HCHO + 4OH- Cu +2HCOO- +2H2O + H2

Preparation of printed circuit boards (PCB’s): The activated board is immersed in plating bath
solution maintained at 25 0C. Plating is carried out at a rate of 1-5 µm/h, till 5-100 µm thickness is
obtained. Selected areas are protected and the rest of the copper is etched away to produce the
circuit pattern. The connection between both sides of track is made by drilling hole followed by
plating through holes by electro less plating. Double sided PCB’s are commonly used because of
feasibility of packing of more components in smaller space.
Applications: Mainly used in printed circuit boards (PCB’s) and for plating on non-conductors.

10. Explain the electroless plating of Nickel. Mention its applications.

Answer: Electro less plating process of Nickel:

Plating bath solution: A solution of NiCl2 20 g /litre,

Reducing agent: Sodium hypophosphate 20 g/litre
Buffer: Sodium Acetate 10 g/litre
Complexing agent: Sodium Succinate.
pH: 4.5
Temperature: 93 0C
Anodic reaction: H2PO2- + H2O H2PO3- + 2H+ + 2e-
Cathodic reactions: Ni2+ + 2e- Ni

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Overall reaction: Ni2+ + H2PO2- + H2O Ni + H2PO3- + 2H+.
Uses: To plate on industrial components such as pumps and valves, shafts, gears, reaction vessels
and other tools. To coat on steel, plastic, PCB’s etc.

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