UNIT – II – Part B

Redox Reactions and Electrochemistry

This document contains the important key points for the topics discussed in “Unit II -
Redox Reactions and Electrochemistry”. Student can use this document to revise the topics
they have learned previously in Unit II.
Electrochemistry
Electroplating: It is the process by which the coating metal (act as an anode) is deposited on
the base metal (act as a cathode) by passing a direct current through an electrolytic solution
containing the soluble salt of the coating metal.
 The anode is made up of coating metal (M) itself, Electron flow

the concentration of the electrolytic bath remains Power supply

unaltered during electrolysis since the metal ions

deposited on the cathode from the bath are Anion

replenished continuously by the reaction of the Canion

Cathode
free anions of the electrolyte with the anode Anode

metal.
General Procedure:
 Pretreatment of plating surfaces
o The article to be electroplated is first treated with organic solvents to remove oil,
grease, etc. Then it is treated with dil HCl or H2SO4 to remove surface scales, oxides,
etc ( HCl is used for Ni and Cu plating while for Cr plating H 2SO4 is used).
 The cleaned article is made as a cathode of an electrolytic cell. The anode is either the
coating metal itself or an inert material of good electrical conductivity like graphite.
The electrolyte is a coating metal salt solution.
 When direct current is passed, coating metal ions migrate to the cathode and get deposited
over the cathode. Thus a thin layer of coating metal is obtained on the article made as to
the cathode.
 For brighter and smooth deposits, favorable conditions such as low temp, medium current
density and low metal ion concentrations are used.
Electroplating of copper
 Cathode - Cleaned article; Anode - Copper and electrolyte - CuSO4
Electrolyte it ionizes as

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 On passing current Cu2+ ions go to the cathode (the article to be plated) and get
deposited there. The free sulfate ions migrate to the Cu anode and dissolve an equivalent
amount of the Cu to form CuSO4. Thus, the CuSO4 formed dissolves in the electrolyte thus
there is continuous replenishment of electrolytic salt during electrolysis.

Note: Other protective methods give only a coarse coating, electrodeposition gives a fine
deposit. To get a fine deposits
o Current density should be high
o Rate of deposition should be low
o The temperature should be low
o The concentration of free metal ions in the electrolyte should be low
Electroless Plating: It is a technique of depositing noble metal (noble metal salt solution) on
a catalytically active metal surface by using a suitable reducing agent without using electric
current. The reducing agent reduces the metallic ions to metal, which gets coated over the
catalytically activated surface to give a uniform thin coating.
Metal ions + Reducing agent Metal (deposit) + Oxidized product
Example:
Electroless plating of Nickel
 The first step is the pretreatment and activation of the surface
o Al, Cu, Fe, brass etc., can be directly nickel platted without activation.
o Stainless steel is activated by dipped in a hot solution of 1:1 H 2SO4.
o Mg alloy is pretreated by giving thin layer of Zn and Cu.
o Plastics, glass, quartz etc., are activated by dipping in the SnCl2 solution
containing HCl at 25°C and followed by dipping in palladium chloride solution.
During, a thin layer of Pd is formed on the surface
 Preparation of bath solution
The plating bath consists of the following constituents
o Coating solution NiCl2
o Reducing agent Sodium hypophosphite
o Complexing agent Sodium succinate
o Buffer Sodium acetate
o Optimum pH 4.5
o Optimum temperature 93°C

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  The activated object is completely immersed in the plating bath for the required time.
The following reduction reaction occurs and Ni gets deposited over the object

Electroless plating of copper

 The first step is the pretreatment and activation of the surface
 Composition of bath solution:
o Coating solution Copper sulphate solution
o Reducing agent Formaldehyde
o Complexing agent cum Exhaltant EDTA
o Buffer Sodium hydroxide
o Optimum pH 11.0
o Optimum temperature 25°C
 Reactions

Plating on Plastics
 Plating on plastic has first gained widespread use in the automotive industry in the
1960s. The application of platting on plastic provides good finishes on fashion items
as well as on consumer electronics products including laptop cases and cell phones.
As the plastic is not conductive, the direct electroplating of plastic is not possible.
 Steps involved in plating on plastic
 Conditioning- The selected material is first etched in a chromic acid solution to
enhance its adhesive capabilities.
 Pickling and etching – this is performed to remove any deformities left from the
previous stage and prepare the surface ready for deposition
 Activating the surface – This is done to create a chemically reducing surface. For
example in electroless plating of copper over the plastic board, palladium is used
to initiate the reduction of copper ions. The board is sensitized with a stannous
chloride solution and dipped in acidic palladium chloride.
 The surface of the material is coated with either nickel or copper from an
electroless plating solution.

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  The material is now ready for electroplating using standard plating technology.
 Apply conductive paint onto the plastic and then electroplate it.
 Examples of plastic materials that are plated successfully: ABS (first plated material-
90%metal plating plastic application) thermoplastics like Teflon (to manufacture non-
stick cookware), phenolic resin (laminates), polycarbonate (automotive, aerospace, data
storage and construction applications), polysulfone (filtration media and dielectrics in
capacitors), etc.
 Various metals used for plating on plastics:
 Copper: It has excellent electrical conductivity, so it is employed for metallizing non-
conductive metal surfaces. Copper plating can also be used as a heat stop-off for
masking. Compared to gold and silver, copper plating is relatively cheap
 Gold or silver: Gold or silver plating on plastic will improve the appearance aesthetic
appeal, provide corrosion resistance and a conductive coating on electronic parts and
components, and impart excellent heat-shielding properties that make it suitable for
high-temperature applications.
 Nickel: Nickel is bright, less toxic so it can serve as a substitute for chrome to plate
plastic automotive parts. Nickel also provides protection against corrosion and wear.
Alloying nickel with other metals such as tin and tungsten can increase the hardness
of the nickel deposit and enhance its corrosion and wear resistance capabilities.
 Chrome: Chrome provides a smooth surface finish, good corrosion resistance and
strong aesthetic appeal. However, the chrome plating process is highly complex and
also highly carcinogenic.
 Benefits of Plating on Plastic
 Plating plastic with a metal surface enhances the appearance of the material and
creates the impression of higher quality. Hence it is used in decorative purposes
 Plating on plastic increases the strength, wear resistance, corrosion and chemical
resistance

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Corrosion
Corrosion is defined as “the gradual destruction and deterioration and consequent loss of
solid metallic material through an unwanted chemical or electrochemical attack by its
environment at its surface”.
A general chemical process of corrosion reaction may be represented as

It may be noted that the corrosion is the reverse reaction of extraction of metals. The pure
metals are always at the higher energy state and release its energy during corrosion reaction,
this process is thermodynamically more favored than the extraction reaction, which makes
them a spontaneous reaction.
 Examples:-
i) Rusting of iron – when the iron is exposed to the atmospheric conditions, a layer of
reddish scale and powder of Fe3O4 is formed.
ii) Formation of a green film of basic carbonate- [CuCO3 + Cu(OH)2] is formed on the
surface of copper when it is exposed to moist air containing CO2.
Classification or Theories of corrosion
i. Dry or Chemical corrosion
ii. Wet or Electrochemical corrosion
Dry or Chemical corrosion - This type of corrosion is mainly due to direct chemical
reactions take place between metals and the corroding agents.
Metal + Corroding agents Metallic products
Corroding agents: Atmospheric gases such as O2, halogens, H2S, SO2, N2, or anhydrous
inorganic liquids.
Metallic products: Metal oxides, Metal hydroxides, etc.
Types of chemical corrosion
i. Oxidation corrosion or corrosion by oxygen
ii. Corrosion by hydrogen
iii. Liquid metal corrosion
Oxidation corrosion or corrosion by oxygen
 This corrosion is caused by the direct chemical attack of oxygen on a metal surface at
low or high temperatures and in the absence of moisture.

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 Chemical reactions involving in Oxidation corrosion are
i. Formation of metal ions (M2+) at the surface of the metal due to oxidation.

ii. Atmospheric oxygen accepts the electrons from the metal surface to form oxide ion

iii. The oxide ions react with the metal ion to form the metal oxide film at the surface of
the metal.

Mechanism of oxidation corrosion:

 Oxidation occurs first at the surface of the metal and a scale of metal oxide is formed
on the surface of the metal and it tends to act as a barrier for further oxidation.
 Therefore, for oxidation to continue either the metal must diffuse outwards through
the scale to the surface or the oxygen must diffuse inwards through the scale to the
underlying metal.
 Both transfers occur, but the outward diffusion of the metal is generally much more
rapid than the inward diffusion of oxygen. Since the metal ion is appreciably smaller
than the oxide ion, therefore the metal ion has much higher mobility.

Factors influencing oxidation corrosion

i. Reactivity of metal:
Highly reactive metals: Metals having more negative standard reduction potentials
are highly reactive and hence corrode very fast.
Example: Lithium catches fire at ambient conditions very vigorously.
Similarly metals such as Na, K and Ca also react with air or moisture so rapidly that
these metals can not be stored under open conditions.
Slow reactive metal: Metals having a comparatively more positive reduction
potential values react slowly.
Example: Zn, Fe, etc
Inert metal: Metals whose standard reduction potentials are very high positive
values, it will not undergo corrosion even after heating in an oxygen atmosphere.
Example: Au, Pt, etc.

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 ii. Temperature
 At high temperatures - All metals are attacked by oxygen and are oxidized (except
noble metals like Ag, Au, and Pt).
 At ordinary temperature - All the metals are slightly attacked. However alkali
metals – Li, Na, K, Rb, etc. and alkaline earth metals – Be, Ca, Sr, etc. are attacked
very rapidly and get oxidized readily.
iii. Nature of the oxide formed: It plays an important role in the further oxidation
corrosion process.

Types of oxide films

 Stable layer: - A stable layer is fine-grained in structure and can get adhered tightly to
the parent metal surface. Hence such a layer can be impervious. Such a film behaves
as a protective coating, thereby shielding the metal surface. Consequently further
oxidation corrosion is prevented.
Example: Al, Sn. Pb, Cu, etc. form stable oxide layers on the surface thus preventing
further oxidation.
 Unstable Layer: The oxide layer formed decomposes back into metal and oxygen

Consequently oxidation corrosion is not possible in such cases.

Example: Ag, Au and Pt do not undergo oxidation corrosion.
 Volatile Layer: The oxide layer volatilizes as soon as it is formed, thereby leaving
the underlying metal surface exposed for further attack. This causes rapid and
continuous corrosion.
Example: Mo forms a volatile MoO3 layer.
 Porous Layer: It contains pores and cracks. Atmospheric oxygen can easily enter into
the underlying surface of the metal through the pores or cracks of the layer, it
continues until the entire metal is converted to its oxide.
Example: Iron when attacked by H2S at high-temperature forms porous FeS layer.
 Non-porous Layer: In this case, the rate of oxidation is almost zero, since oxygen
cannot easily enter into the oxide layer.
 Pilling – Bedworth rule:

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 The nature of the oxide layer formed depends on the ratio of the volume of oxide
formed to the volume of metal consumed.
According to Pilling-Bedworth rule
If the volume of the oxide layer is less than the volume of metal, the oxide layer is
porous and hence non-protective. Hence it cannot prevent the access of oxygen to
the fresh metal surface below. If the specific volume ratio is small, then the rate of
corrosion is large.
Example: The volume of oxides of alkali and alkaline earth metals like Li, Na, K,
Mg is less than the volume of metals.
If the volume of the oxide layer formed is greater than the volume of the metal, then
the oxide layer is non-porous or protective.
Example: The volume of oxides of heavy metals such as Al, Sn, Pb etc., is greater
than the volume of the metal. Hence the oxide layer formed is tight–adhering non-
porous and protective.
Corrosion by hydrogen
 Hydrogen embrittlement: This type of corrosion occurs when the metal is exposed
to the hydrogen environment.
Example: Iron reacts with H2S at ordinary temperature to liberate atomic hydrogen

This liberated atomic hydrogen diffuses readily into the metal and collects in the voids
present in the metal, where it recombines to form molecular hydrogen

Hydrogen gas collected in the voids develops high pressure which causes cracking and
blistering of the metal and this process is called Hydrogen embrittlement.
Decarburization: Hydrogen molecules undergo thermal decomposition to produce
atomic hydrogen at high temperatures which readily reacts with carbon present in the
boiler material (steel) at high temperature to produce high-pressure methane gas CH4 gas
enters into the voids present in the boiler and produces high pressure causes cracking and
blistering in steel. The process of decrease in carbon content in steel is called as
decarburization

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Liquid metal corrosion
 It is due to the chemical action of flowing liquid metal at high temperature on the
solid metal. It takes place in two ways: (i) dissolution of solid metal by a liquid metal
or (ii) due to internal penetrating of the liquid metal into the solid metal. In both
cases solid metal becomes affected.
Wet (or) electrochemical corrosion:-
This type of corrosion is observed when
 A conducting liquid is in contact with a metal (or)
 When two dissimilar metals (or) alloys are either immersed (or) dipped partially in a
solution.
Mechanism
The corrosion occurs due to the existence of separate anodic and cathodic areas or parts
between which current flows.
At Anode: Oxidation takes place and the anodic metal is destroyed by dissolving (or)
forming a compound such as an oxide.

At cathode: Reduction takes place. The metal which is acting as the cathode is in its
reduced form only. Therefore it cannot be further reduced. Therefore cathodic reactions
do not affect the cathode.
 Hence at cathodic part dissolved constituents in the conducting medium accept the
electrons to form some ions like OH -, O2- etc.
 The metallic ions from the anodic part and non-metallic ions from the cathodic part
diffuse towards each other through conducting medium and form a corrosion product
somewhere between anode and cathode.
 The e-s which are set free at the anodic part flow through the metal and finally
consumed in the cathodic region.
Based on the mechanism, the electrochemical reactions may be classified as under
acidic, alkaline, or neutral media.
 The evolution of hydrogen takes place in acidic environments.
At anode: Iron undergo dissolution to give Fe2+ with the liberation of electrons.

At cathode: The liberated electrons flow through the metal from anode to cathode
(acidic region) where H+ ions get reduced to H2 gas.

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 The overall reaction is

 This type of corrosion causes “displacement of hydrogen ions from the acidic solution
by metal ions. In hydrogen evolution type corrosion, the anodes are very large areas,
whereas cathodes are small areas. All metals above hydrogen in the electrochemical
series tend to get dissolved in acidic solution with the simultaneous evolution of
hydrogen.
 Absorption of oxygen type corrosion:
Example: Rusting of Fe in the neutral aqueous solution of electrolytes like NaCl in
the presence of atmospheric oxygen. The iron surface will be usually coated with a
thin film of iron oxide. However, if this oxide film develops some cracks, anodic
areas are created on the surface to the rest of the metal part which acts as the cathode
At anode: Iron metal dissolves as Fe2+ ions with the liberation of electrons.

At cathode: The liberated electrons flow from anodic to cathodic areas through iron
metal, where the electrons are accepted by the dissolved oxygen to form the
hydroxide.

Overall reaction: The Fe2+ions and OH- ions diffuse and form ferrous hydroxide
precipitate when they meet with each other.

If enough O2 is present Fe(OH)2 is easily oxidized to Fe(OH)3 (ferric hydroxide)

The product called yellow rust corresponds to Fe(OH) 3.H2O. If the supply of O2 is
limited, the corrosion product maybe even black anhydrous magnetite Fe3O4.
Types of electrochemical corrosion
I. Galvanic corrosion or Differential metal corrosion (DMC): When two different kinds
of metals are in contact with each other in the presence of an electrolyte or moist air,
galvanic corrosion occurs. Most active metal acts as anode and the less active metal act as
the cathode. Examples:

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  In Fe-Cu couple – Fe (more active metal) dissolves in preferences to copper (less
active metal). i.e. Fe acts as anode undergoes corrosion and Cu act as cathode.
 Zn-Cu Couple
 Steel screw in a brass marine hardware
 Lead-Antimony solder around a copper wire
 Steel pipe connected to copper plumbing
II. Concentration cell corrosion or Differential aeration corrosion (DAC): This type of
corrosion occurs due to electrochemical attack on the surface of the metal, exposed to
varying concentrations of electrolyte or of varying aeration (various concentration
of oxygen).
 When the metal is partially dipped in a solution, the metal inside the solution has very
poor aeration (act as an anode) compared with the metal that is outside the solution
(more aerated - act as a cathode). Hence corrosion will take place at the anodic area.
 Example: Zinc metal is partially immersed in a dilute solution of a neutral salt (NaCl)
Some more examples of differential cell corrosion
a. Waterline corrosion: When water is stored in a steel tank, the area below the
waterline (poor oxygenated) acts as the anode and affected by corrosion, the area
above the waterline (highly oxygenated) act as the cathode and comparatively
unaffected by corrosion.
b. Pitting corrosion or Localised corrosion: It is a localized accelerated attack at
some places on the metal surface, resulting in the formation of pits or holes or
cavities on the surface of the metal, leaving the rest of the metal surfaces
unaffected. Example: Consider a drop of NaCl solution resting on metal surfaces.
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 the high oxygen concentration. The rate of corrosion will
be more when the area of cathode is larger and the area of the anode is smaller.
Therefore more and more material is removed from the same spot. Thus a small
pit is formed on the surface of the metal.
c. Crevice corrosion: If a crevice (narrow opening crack) between different
metallic objects or between a metal and a nonmetallic in contact with liquids, the
crevice becomes the anodic region and gets corroded because of less oxygen

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 concentration. The exposed area has high oxygen concentration and acts as a
cathode.
d. Pipeline corrosion: Buried pipelines or cables passing from one type of soil to
another type of soil may get corroded due to differential aeration corrosion. This
type of corrosion occurring in pipelines is called pipeline corrosion. Example:
Pipeline passing from clay (less aerated) to sand (more aerated) may get corroded
due to differential aeration
III. Biofouling and biocorrosion: Some types of bacteria can promote corrosion of metals
even in the absence of a high concentration of oxygen (anaerobic condition). This is
known as microbial corrosion, biocorrosion, or microbially influenced corrosion. Mostly
iron pipes used in underground applications undergo biocorrosion.
Steps involved in the biocorrosion formation:
 Formation of the bacterial colony on the metal surface leading to the biofilm
formation where the bacterial colonies are covered by an extracellular membrane
(ECM) made up of polysaccharides, lipids, nucleic acids and/or proteins.
 Depending on the type of bacterial species and the surrounding condition, one of the
following mechanisms may take place:
o Localization of microbial adsorption creates the area of low oxygen exposure
which acts as anode and other locations with high oxygen exposure, acts as a
cathode. Finally, this results in differential aeration corrosion.
o Organic or inorganic acids released by the microbial species may alter the
local environment of the metal and hence the locations where bacteria adsorb.
Enhanced corrosion is observed at places where bacteria adsorb.
o Corrosion may occur due to the presence of bacteria such as Shewanella sp.
that can directly involve in electron transfer reactions to the metal surface
leading to breakage of the metal surface.
o Bacteria like Desulfuromonas sp. and Desulfobactor sp. can convert sulfur and
its oxides to sulphuric acid. Even a small amount of sulphuric acid formed at
the metal site can corrode the metal.
Microbial induced concrete corrosion: It is a special case of biocorrosion observed in
concrete structures. In this corrosion of concrete structures occurs due to the reaction of
chemical ingredients of cement such as calcium carbonate, silicate and aluminate with
water and the products released by microorganisms. Moreover, the strength of the

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 structure is decreased by the reaction of steel present inside the concrete with corroding
agents. The mechanical stress induced in the concrete structure due to the formation of
corrosion products also increases the biocorrosion.
 Biodeterioration of concrete structures is caused by microorganisms that grow in
environments on concrete surfaces under the following favorable conditions such as
 water availability
 low pH
 elevated relative humidity
 long cycles of humidification and drying, freezing and defrosting, high carbon
dioxide concentrations. (e.g., carbonation in urban atmospheres)
 high concentrations of chloride ions or other salts (e.g., marine environments)
 high concentrations of sulfates and small amounts of acids (e.g., sewer pipes or
residual water treatment plants).
Example:
 Iron used in concrete applications can corrode when microorganisms are present.
 Preventive measures against concrete corrosion
 Adding biocides
 Applying protective coatings such as water repellents
 Changing the composition of the concrete mixture which includes
 Alkalinity - Corrosion rate is inversely related to alkalinity
 Silica fume - it improves the strength efficiency and durability of concrete
 Polymer-modified mortar and concrete - improve the durability of concrete sewer
pipes.
Corrosion control methods
Though the metal surface cannot be protected from corrosion completely, corrosion can be
minimized by
 Modification of the environment, proper design and selection of materials –
Corrosion can be avoided by
o choosing construction materials as pure and homogeneous materials
o avoiding direct contact with nobler metals, dissimilar metals, moisture and eliminating
internal stresses
o using moisture-absorbing materials, isolation of dissimilar metals by insulation (to
avoid direct contact) and well-annealed articles to minimize internal stresses

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 o controlling the pH, conductivity, oxygen content of the aqueous environment
o choosing construction materials preferably from lower down or dissimilar metals in
such a way that they are as close as possible in the galvanic series
o minimizing sharp edges and corners, avoiding crevices in joints
o using smooth surfaces, good ventilation, maintaining a small cathodic and large anodic
area

 Cathodic and anodic protection

o Cathodic protection – In this the metal structure to be protected from corrosion is
made to act as a cathode by connecting with the auxiliary anode. In this method, the
metal structures, equipment, underground pipes, ocean-going ships, water tanks, etc
are made cathodic by the following methods:
 Sacrificial anodic method
 Impressed current method
Sacrificial anodic method: Highly reactive but abundant metals such as magnesium,
zinc, etc are connected to the structure to be protected. This forms the galvanic cells
with high emf in which the metal of interest acts as cathode and magnesium as a
sacrificial anode. At regular time intervals, the corroded magnesium is replaced,
which would be much cheaper than replacing the entire metallic pipes.

Advantages:
 Efficient use of protective current,
 Cheap installation if installed at the time of construction
 Easy maintenance.
Limitation: Many anodes are required for poorly coated surface and the high
installation cost if the installation is done after construction

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 Impressed current cathodic protection method: In this method, the metallic
structure to be protected is made cathode of an electrolytic cell by connecting to a DC
bias where the metal of interest is connected to the negative terminal. The DC voltage
may be generated from the ac line through rectification. The anode used in such
methods can typically be a scrapped iron or such materials.

Advantages:
 Effective in protecting both uncoated and poorly coated surfaces,
 Applicable in high-resistivity environments
 The protection of large areas can be done by a single installation
Limitation: Require external power, periodic inspection and maintenance as
overprotection can cause coating damage.
o Anodic protection – In this the metal structure to be protected from corrosion is made
to act as an anode by applying an external impressed direct current. This leads to the
formation of the thin oxide film which suppresses further corrosion. This method is
suitable for the metals like Al, Cr, Ti, Ni, etc., The metal tank that has to be protected
from corrosion is connected to a potentiostat and is adjusted for a particular potential
and current. This causes the tank to behave as anode and causes the formation of a
corrosion-resistant oxide layer that protects the tank surface from further corrosion.

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 Use of corrosion inhibitors: Corrosion inhibitors are the organic or inorganic
substances which when added to the medium, minimizes the corrosion. It can be either
anodic inhibitor (example – metal phosphates, chromates, molybdates etc) or cathodic
inhibitor example - amines, substituted urea, thiocarbamides, mercaptans etc). Anodic
inhibitor forms a strongly adherent protective coating on the surface of the anode which
retards further corrosion. Cathodic inhibitors slow down the reactions occurring in the
cathodic area.
 Use of protective coatings: Organic or inorganic surface coating can be applied on the
metallic surfaces to avoid direct contact of the surface with surroundings by forming a
film over the metallic surface and retards the corrosion process.
Inorganic Surface coatings
1) Tinning: In this method, a thin and uniform coating of tin over the base metal surface
is applied by using hot-dipping or electroplating methods. Tinning is widely used in
food storage cans. As tin is cathodic to iron, any porosity on the tin-coated surface
causes the rusting.
2) Galvanization: Galvanization is the process of zinc coating over ferrous materials
such as steel or iron through the hot-dipping method. As zinc coating is anodic to iron
or steel material, it can prevent the corrosion of the underlying iron or steel material
even if the coating is porous.
3) Electrodeposition: In this method metallic structure is protected from corrosion by
depositing the coated metal over the base metal electrolytically using the coated metal
as the anode, the base metal (object) as the cathode and a suitable electrolyte(salt of
the coated metal). The fineness of the coat depends on a)the rate of deposition b)
current density c) concentration of free metal ions in the electrolyte and d) the
temperature of the electrolyte bath.
4) Anodizing: This method is suitable for protecting metals like Al, Cr, Ni, Zn, etc that
are capable of forming a self-protective passive oxide film in the oxidizing acid bath.
Example: Anodization of aluminum (ie. Anodic oxidation of Al) is the process by
which Al2O3 is formed on the aluminum surface, when the aluminum article (anode),
inert conducting electrode (cathode) are dipped in a bath of 10-15% H2SO4 and
electrolyzed. The porosity of the oxide layer is minimized by immersing in a boiling
water bath to enhance the strength and corrosion resistance. Anodized articles are
used for making aircraft parts, machine parts, household utensils, etc

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 Organic coatings
Organic coatings are the inert organic barriers formed between the metal surface and the
surrounding to shield the surface from corrosion and impart decorative value. Example -
paints, varnishes, lacquers and enamels, etc. The protective value of the organic coatings
depends on various parameters including the chemical inertness, environmental
components, porosity, method of coating method, etc.
Oil Paints: Paint is a mixture of pigments, vehicle or drying oil, a thinner, driers, fillers.
a. Pigments – It is the major ingredient of paint and increases its strength and life. It can
be natural or mineral pigments such as clay, mica, etc or it may be synthetic pigments
such as TiO2, ZnO, BaSO4, etc. The property of the paint depends on the composition,
size, shape, distribution, refractive index and the relative proportion of pigment to
vehicle.
b. Vehicle or Drying oil - It is the film-forming constituent of the paint that provides
toughness, adhesion, elasticity, and hyrophobicity. They are mostly high molecular
fatty acids such as oleic acid, linoleic acid, etc.
c. Thinners – These are used to reduce the viscosity, penetration of vehicle and to get
desired consistency of the paint favoring its easy and uniform applicability. Example -
turpentine, petroleum spirit, etc.
d. Drier - A drier is needed in the paint to enhance the drying of oil film by carrying
oxygen, which leads to oxidation, polymerization, or condensation reactions. The
drier may be resinates, borates, or tungstates of Co, Mn, Zn or Pb. Apart from this, the
paint may consist of extenders or fillers (to reduce the cost, increase durability, etc),
plasticizers (for minimized cracking by elasticity), and anti-skinning agents (for
preventing gelling).

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