SUB:ENGG CHEMISTRY

MODULE-2

CORROSION AND METAL FINISHING

1.What is Corrosion? Explain the Electrochemial theory of corrosion by taking iron as an
example. (7M)

Corrosion is the deterioration of metal as result of chemical reaction with the surrounding.
Corrosion is broadly classified in two types:.

 Dry corrosion: if the corrosion takes place when oxygen or other gases in the air react with
metal in the absence of moisture /liquid, the corrosion is known as dry corrosion.
The basic reaction involved in dry corrosion is:

M → Mn+ + ne-

 The metal loses electrons to form an ion and some free electrons .The metal ions can there
react with oxygen to from a metal oxide.
 Wet corrosion: if the corrosion takes place when oxygen and moisture from the
surrounding react with metal, the corrosion is known as wet corrosion, wet corrosion is
explained on the basic of electrochemical theory.

Electrochemical Theory of Corrosion;

A large number of minute galvanic cells (anodic and cathodic regions) are formed on the surface of
metal due to surface heterogeneties.

At anode, iron is oxidized liberating Fe2+ ions and electrons,

Fe → Fe2+ + 2e-

At cathode,The chemical species present in the surrounding of cathode undergoes reduction by

accepting electrons coming through metal from the anodic region .Depending on the surrounding
medium; there are four possible reductions at cathodic region.

 If the medium is acidic and deaerated,

2H+ + 2e → H2
 If the medium is neutral and aerated.
O2 + 21/2 H2O+ 4e- → 4OH-

 If the medium is neutral and deaerated.

2H20+2e → H2+20H-

2H20 → 2H++ 20H-

2H++2e → H2
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Fe+2 ion formed at anode react with OH-formed at cathode, forming ferrous hydroxide ,Ferrous
hydroxide on further reaction with oxygen and water ,lead to the formation of corrosion product
(hydrated ferric oxide) or rust

2Fe2++4OH- →2Fe(OH)2

2Fe (OH)2+(n-2)H2O+O2 → Fe2 O3.nH2O (oxide rust )

2.Expain the factors affecting the rate of corrosion? (any three) (6M)

 Ratio of anodic to cathodic areas: If the anode area is small and cathode area is large, the
rate of corrosion increases.

Example: Tin coating protects iron from corrosion as value of tin (0.14v)is higher than iron (0-44v)
if some areas of iron is not covered by tin ,the exposes iron act as a small anode and tin layer act as
large cathode .As cathode is larger ,demand for electrons will be very high and intense corrosion
occurs on the exposed anodic area.

 Nature of corrosion product: If corrosion product (oxides) is highly insoluble ,stable,

stoichiometric, non-porous with low ionic and electrical conductivity, the formed layer
prevents further corrosion of the metal by acting as protective barrier.

Example: Corrosion product of Al .Cr, Ti, etc.

* pH: The rate of corrosion increases with decrease in pH.

* pH<3. Severe corrosion occurs even in the absence of oxygen due to evolution of hydrogen at the
cathode.

* pH 3to 10.corrosion occurs only in the presence of oxygen.

* pH 10 and above, corrosion is less likely for most of the metals.

* Conductivity of medium: As the conductivity of corrosion medium increase, the corrosion rate
also increases, 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 ,Therefore the rate of corrosion is faster will e the exchange of electrons at
the electrode surfaces, Therefore the rate of corrosion is faster in the sea water that in fresh water.

3.Explain types of corrosion (any two ) (6M)

1. Differential Metal Corrosion;

 When two dissimilar metals are in contact with each other in corrosive environment ,that
metal with lower electrode potential act as anode and undergo corrosion ,whereas the metal
with higher electrode.Potential act as cathode and remain unaffected. Larger the potential
difference between the two metals higher is the rate of corrosion.
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Example: when Fe (Eo =0.44v)is in contact

with Cu (Eo=0.34V). Iron having lower electrode potential becomes anodic and undergoes
corrosion. Whereas copper becomes cathodic and remain unaffected.

2. Differential Aeration Corrosion;

 When a metal exposed to different concentration of oxygen or air, the areas which are
exposes to lower concentration of O2 becomes anode and undergo corrosion, whereas the
areas which are exposes to higher concentration of oxygen becomes cathodic and remain
unaffected.

Example: Iron rod partially immersed in NaCI solution .Part of the metal which is inside the
solution is exposed to lower concentration of oxygen becomes anodic and undergo corrosion
whereas the part of the metal which is concentration of more oxygen becomes cathodic and
remain unaffected Differential aeration corrosion is broadly classified into two types as
described below.

 Waterline corrosion :
Water line corrosion is observed in ships ,water storage tanks ,etc In water storage tanks, the
part of medical just below the water line is anodic (less oxygenated )and undergo
corrosion ,while the part just above the waterline is anodic (less oxygenated )and undergo
corrosion, while the part just above the waterline is cathodic (more oxygenated) and remain
unaffected .Corrosion ,here it is called waterline corrosion.
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 Pitting Corrosion:

Pitting corrosion is observed when dust particles get deposited on a metal surface. The portion
covered by the dust will be anodic (less oxygenated) and undergo corrosion, whereas the portion
not covered by dust will be cathodic(more oxygenated ) and remain unaffected.

4.Explain the types of corrosion control (any two) (6M)

Corrosion can be controlled by preventing the formation of anodic areas in metals. The most
common methods used are given below:

 Inorganic coatings -Anodizing

 Metal coating -Galvanizing
 Cathodic protection- i. Sacrificial anode method.

ii. Impressed current method

Anodizing of Aluminum;

 Anodizing is a conversion coating made by oxidation of outer layer of metal through the
process of electrolysis. Oxide layer formed on the metal act as protective barrier preventing
corrosion.
 In anodization of alminium, clean, polished aluminum is taken as anode and immersed in an
electrolytic cell containing 5-10% chromic acid inert electrodes like stainless steel and bath
is maintained at 35o C
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A current density of 10-20m A/cm2 is applied to oxidize the outer layer of aluminum to aluminum
oxide, which is porous; the pores are finally sealed by dipping in hot water to produceA1203H20
which acts as a non porous protective layer preventing corrosion.

Anodic reaction:

2Al + 3H2O → A12O3+6H++6e-

Cathode reaction:

6H+ + 6e- → 3H2

Galvanizing (Anodic Metal Coating):

Coating a layer of Zinc on iron by hot dipping is known as galvanization .The following are the
involved in galvanization process:

 The iron
sheet is degreased by passing through organic solvent.
 Then it is washed with dilute sulphuric acid to remove rust and oxide impurities.
 The metal is then treated with flux materials such as NH4C1 or Zn C12 for improving
adhesion property and avoids oxidation of zinc and dried.
 The metal is dipped in molten zinc maintained at 430-4700C
 The excess zinc present on iron surface is removed by rolling or by passing blast of air.

Cathodic Protection;
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Cathodic protection is a method of protecting a metal against corrosion by making the entire metal
cathodic by supplying electrons from external source.

There are two different methods to supply electrons.

(a)Sacrificial anode method:

* In this method, the metal to be protected (for example iron) is connected to a more active anodic
metal like magnesium or zinc. The anodic metal undergo oxidation and sacrifice itself to provide
electrons to the metal to be protected. Hence, the method is known as sacrificial anode method.

* Once the sacrificial anodes are completely corroded, they should be replaced with fresh anodes.

* For example, a zinc or magnesium block connected to a buried oil storage tank or pipeline.

* Sacrificial anode method is used to protect buried pipelines, ship hulls, etc.

(b)Impressed
current method;

 In this method, the metal to be protected is connected to negative (cathodic) terminal of a

DC source. The positive (anodic) terminal is connected to an inert anode like graphite. DC
current is applied to supply electrons to the metal to be protected.
 Impressed current or voltage method is used to protect marine structures, water storage
tanks and oil pipe lines.
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5.What do you mean by metal finishing? Mention any five technological importance.(6M)

Metal finishing is a surface process carried out in order to modify the surface properties of a metal
by deposition of a layer of another metal or an alloy or a polymer film.

Eg: electroplating of metals, Electroless plating, chemical conversion coating etc.

Technological importance of metal finishing:

Metal finishing imparts desirable surface characteristics such as

1. Imparting higher corrosion resistance.

2. Imparting improved wear resistance.
3. Imparting thermal resistance, hardness, improved solderablity etc.
4. Providing optical or thermal conducting surface.
5. Manufacturing electrical and electronic components such as PCB, capacitors etc.
6. Electroforming of articles.
7. In electro polishing and electrochemical etching.

6.Define and explain any two terms; (6M)

Polarization: ‘’It is a process where in, there is a variation of electrode potential, owing to the
inadequate diffusion of species from the bulk of the electrolytic solution to the vicinity of the
electrode’’.

The electrode potential is given by the Nernst’s equation

E = E0 + O.O592/n log [ Mn+]

E0 = standard electrode potential and [ M n+] is the metal ion concentration surrounding the
electrode surface at equilibrium. When electric current is passed, the value of [ M n+] in the
vicinity of the electrode surface decreases, due to continuous reduction of the metal ions to metal
atoms. Thus

Mn+ + ne- M

So there is a change in the value of the electrode potential. However, the equilibrium is re-
established as the metal ions from the bulk of the solution diffuse towards the electrode, due to the
existence of a concentration gradient between the bulk of the solution and around the electrode
surface. But the rate of diffusion is usually slow, and hence there is a variation in electrode
potential. Under such conditions, the electrodes said to be polarized.

Polarization depends on the following factors:

1. Size of electrode
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2. Nature of electrode surface

3. Concentration of electrolyte

4. Temperature

5. Conductivity of electrolytic solution

6. Stirring of electrolytic solution.

7. Nature of the ions deposited on electrodes

8. Use of depolarizer.

Always large electrode surface, low concentration of electrolyte and highly conducting solutions
decreases the polarization effect.

Decomposition potential or decomposition voltage:

“ The minimum potential which must be applied between the two electrodes immersed in the given
electrolytic solution in order to bring about continuous electrolytic decomposition is called the
decomposition potential of the electrolyte.’’

Thus decomposition potential is equal to back emf.

Ed = Eb = Ecathode - Eanode

For the determination of the decompositional voltage the following arrangement has to be made. It
is as shown in the fig. The two electrodes A and B are connected to a voltmeter V through ammeter
M to measure the strength of the current. E is the external source of the emf. The voltage applied to
the cell can be regulated with the help of a variable resistance C and this voltage in turn can be
measured with the help of a voltmeter V.

To get decomposition potential the current flowing in the cell is plotted against the applied voltage.
The curve AB represents the current below the decomposition potential and the points Band E there
are a sudden increase in the current and hence the current takes a sharp turn upwards. The point of
intersection of BD and ED is the decomposition potential.
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8.Explain the electroplating of chromium? (7M)

Electroplating of chromium (Decorative and Hard)

There are two types of chromium coating.

 Decorative chromium coating: thin coating of chromium with thickness range of 0.25-
0.75umimpart bright and decorative look to the materials.

Plating bath composition: chromic acid (CrO3) and H2SO4 in 100:1 proportion.

Current density: 145-430mA/cm2

Temperature: 45-55oc

Current efficiency: 8-12%

Anode: Insoluble anodes Pb-Sn or Pb-Sn coated with PbO2 or stainless steel.

Cathode: Object to be plated

 Hard chromium coating: Hard or thick coating of chromium with a thickness range 300pm
impart wear and tear resistance to materials

Plating bath composition: chromic acid (CrO3) and H2SO4 in 100:1 proportion.

Current density: 290-580mA/cm2

Temperature: 45-55oc

Current efficiency: 8-12%

Anode: Insoluble anodes Pb-Sn or Pb-Sn coated with PbO2 or stainless steel.

Cathode: Object to be plated

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 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 CrO 3 in the bath solution. This is
converted into trivalent Cr (III) by a complex anodic reaction in the presence of sulphate
ions and 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.

8.Difference between electro less and electroplating? Mention advantages of electrolessplating? (6M)

Property Electroplating Electroless plating

Decrease in free energy due to

Driving force Electrical energy
autocatalytic redox reaction.

Electron source Direct current Reducing agent

Object with catalytically active

Cathode Object to be electro plated.
surface.

Anode Separate anode Catalytic surface of sustrate

Not satisfactory for objects having

Satisfactory for all objects and
Nature of deposit intricate parts, but purity of
purity is less.
deposit is high
Conductors, semiconductors and
Applicability Only to conductors
insulators.

Advantages of electro less plating:

1. Does not require electrical power source.

2. It is applicable to conductors, semiconductors and non-conductors like plastics.
3. Electro less plating are less porous than electroplates and posses unique characteristic
chemical, mechanical and magnetic properties.
4. Electro less plating baths have better throwing power and deposit a more uniform metal
coating over an article irrespective of its shape or size.
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9.Explain the electroless plating of nickel? (7M)

Electroless plating of nickel:

 Electro less plating of nickel: The surface to be plated is first degreased by using organic
solvents or alkali, followed by acid treatment.
 Al, Cu, Fe and brass need no activation.
 Stainless steel surface is activated by dipping in hot solution of 50% dilute H2SO4.
 Mg surface is activated by giving zinc or Cu coating.
 Non-metallic articles are activated by dipping in SnCl2 + HCl solution, followed by dipping
in PdCl2 solution. Then it is dried.

Composition of the bath:

Coating solution: NiCl2 solution (20g/L)

Reducing agent: sodium hypophosphite (20g/L)

Buffer: Sodium acetate (10g/L)

Complexing agent: Sodium succinate (15g/)

PH: 4.5

Temperature: 93oc

Reactions: At cathode: Ni2+ + 2e- Ni

At anode: H2PO2- + H2O H2PO3- + 2H+ + 2e-

Net redox reaction: Ni2+ + H2PO2- + H2O Ni + H2PO3- + 2H+

 Both oxidation and reduction takes place on the same substrate surface. In the reaction there
is liberation of H+ ions, which alter the PH this may affect the quality of plating. Hence
buffer solution is essential.
 Plating process will starts at a temperature of 70 oc and it is maximum at 93 oc. Further rise in
temperature may lead to the decomposition of organic additives; hence temperature range
should be 70-93oc.

Applications:

1. Electro less Ni plating is extensively used in electronic appliances (egs knobs of hi-fi
equipments).
2. Finds application in domestic as well automotive fields (egs: consume jewellery, car trims,
tops of perfume bottles etc.).
3. Electro less Ni coated polymers (like ABS plastics) find preferred decorative as well as
functional applications.
4. Also used in instrumentation and computers in view of its magnetic properties.
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5. Heat-treated electro less nickel-plated appliances finds applications in hydraulic
compressors, pressure vessels, pumps and fuel injection assemblies.

10.Explain the electroless plating of copper? (7M)

Electroless plating of copper:

Pretreatment and activation of the surface: 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 pretreatment.

2. Non-metallic materials (e.g. glass, plastics, printed circuit boards, PCB) are activated by first
dipping in SnCl2 and HCl solution, followed by dipping in PdCl2 solution and dried.

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: 11.0

Temperature: 25oc

Reactions:

Cathode: Cu2+ + 2e- Cu

Anode: 2HCHO + 4OH- 2HCOO- +2H20 + H2 +2e-

Net redox reaction: Cu2+ + 2HCHO + 4OH- Cu +2HCOO- +2H20 + H

Applications:

1. Mainly used in printed circuit boards (PCB).

2. For plating on non-conductors.
3. Applied on wave-guides and for decorative plating on plastics.