Corrosion

Many metals exist in nature in combined form as their oxides, carbonates,

sulphides, chlorides and silicates (except noble metals) such as Au (gold), Pt (Platinum) etc.
During extraction process these are reduced to their metallic state from their ores and during
extraction of ores considerable amount of energy is required. Compounds are in lower energy
state than the metals. Hence when metals are put into use in
various forms, they get exposed to environment such as dry gases, moisture, liquids etc. and
slowly the exposed metal surface begin to decay by conversion into a compound.
Definition: - Any process of deterioration or destruction and consequent loss of a solid metallic
material through an unwanted chemical or electrochemical attack by its environment at its
surface is called corrosion. Thus corrosion is a reverse process of extraction of metals.
Examples:-
i) Rusting of iron – when iron is exposed to the atmospheric conditions, a layer of reddish
scale and powder of Fe3O4 is formed.

ii) Formation of green film of basic carbonate- [CuCO 3 + Cu(OH)2] on the surface of
copper when exposed to moist air containing CO2.
Theories of corrosion: - Corrosion can be explained by the following two theories.
 Dry or chemical corrosion.
2. Wet or electrochemical corrosion
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.
 The corrosion occurs due to the existence of separate anodic and cathodic areas or parts
between which current flows through the conduction soln.
 In the anodic area oxidation reaction takes place so anodic metal is destroyed by
dissolving (or) forming a compound such as an oxide.
 Hence corrosion always occurs at anodic areasAt Anode
M –--------> Mn+ + ne –
At cathode
Mn+ +ne – –--------> M
  In cathodic area, reduction reaction (gain of e – s) takes place. The metal which is
acting as cathode is in its reduced form only. Therefore it cannot be further
reduced. Therefore cathodic reactions do not affect the cathode.
 So at cathodic part dissolved constituents in the conducting medium accept the
electrons to form some ions like OH-, O2- etc.
 The metallic ions from anodic part and non- metallic ions from cathodic part
diffuse towards each other through conducting medium and form a corrosion
product somewhere between anode and cathode.
 The electrons which are set free at anodic part flow through the metal and are
finally consumed in the cathodic region.
 Thus we may sum up that electrochemical corrosion involves:
i) The formation of anodic and cathodic areas.
ii) Electrical contact between the cathodic and anodic parts to enable the conduction
of electrons.
iii) An electrolyte through which the ions can diffuse or migrate this is usually
provided by moisture.
iv) Corrosion of anode only
v) Formation of corrosion product is somewhere in between cathode and anode. Define
metallic corrosion.
Q. Explain the electrochemical theory of corrosion byHydrogen evolution and
oxygen absorption.
A.
Evolution of hydrogen: occurs
 In acidic environments.
 For eg in the corrosion of iron metal the anodic reaction is dissolution of Fe as
ferrous ions with liberation of e-s.
Fe –-----> Fe+2 + 2e- oxidation.
 These electrons flow through the metal from anode to cathode (acidic region) where H +
ions are eliminated as H2 gas.
2H+ + 2e- –------> H2 reduction.
 The overall reaction is
Fe + 2H+ –------> Fe2+ + H2
  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, where as cathodes
are small areas.
 All metals above hydrogen in the electrochemical series have a tendency to get dissolved
in acidic solution with simultaneous evolution of hydrogen.

Q. Explain the corrosion of iron by dilute mineral acids.

Absorption of oxygen type corrosion:
Rusting of Fe in neutral aqueous solution of
electrolytes like NaCl in the presence of atmospheric oxygen is a common example of this
type of corrosion.

The surface of iron 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.
  While pure metal parts act as cathode.
 Thus anodic areas are very small surface parts.
 The rest of the surface of the metal forms cathodes.
 Thus at the anodic part iron metal dissolves as Fe+2 ions with the liberation of e- s.
Fe –-----> Fe+2 + 2e-
 The liberated e- s flow from anodic to cathodic areas through iron metal during which
they interact with dissolved oxygen and moisture.
½ O2 + H2O + 2e- → 2OH-
 The Fe+2 ions and OH- ions diffuse and form ferrous hydroxide precipitate when they
meet with each other
Fe+2 + 2OH- –------> Fe(OH)2
 If enough O2 is present Fe(OH)2 is easily oxidized to Fe(OH)3 (ferric hydroxide)
4 Fe(OH)2 + O2 + 2H2O –-----> 4Fe(OH)3
The product called yellow rust actually corresponds to Fe(OH)3.H2O.

 If the supply of O2 is limited, the corrosion product may be even black anhydrous
magnetite Fe3O4.
Q. Explain the factors which influence the rate of corrosion?
Factors influencing corrosion:
A.
i) Nature of metals
ii) Nature of the corroding environment.
Nature of metals:
1) Position in galvanic series:-The metal higher in series is more active and suffers
corrosion. The rate and extent of corrosion is directly proportional to electrode potential
difference between them.
2) Over voltage: - when a metal, which occupies a high position in galvanic series (say
Zinc), is placed in H2SO4, it undergoes corrosion forming a film and hydrogen gas.
The initial rate of reaction is quite slow, because of high over voltage (0.70 V) of the zinc metal,
which reduces the effective electrode potential to a small value. However, if few drops of copper
sulphate (CuSO4) are added, the corrosion rate of zinc is accelerated, because some copper gets
deposited on the zinc metal forming minute cathodes, where the hydrogen over voltage is only
0.33 V, thus, reduction in over voltage of the corroding metal/ alloy accelerates the corrosion
rate.
3) Purity of metal: - Impurity of a metal generally causes heterogeneity and form minute
electrochemical cells and the anodic part gets corroded. For eg: Zn metal containing
impurity such as Pb ( or) Fe undergoes corrosion.
The rate and extent of corrosion increases with extent of impurities.
4) Nature of the surface film: - when metals are exposed to atmosphere, practically all
metals get covered with a thin surface film of metal oxide. The ratio of the volume of
metal oxide to the metal is known as specific volume ratio. Greater the specific volume
ratio, lesser is the oxidation corrosion rate. For eg: the specific volume ratio of Ni, Cr, W
are 1.6, 2.0 and 3.6 respectively. Consequently the rate of oxidation corrosion is least for
(w) tungsten.

5) Nature of the corrosion product:- a) Solubility of corrosion products : If the corrosion

product is soluble in the corroding medium, then corrosion proceeds at a faster rate otherwise if
it is insoluble, corrosion will be suppressed e.g: PbSO 4 formation in case of Pb in H 2SO4
b)Volatility of corrosion products : - If the corrosion product is volatile , it evaporates as soon
as it is formed, there by leaving the underlying metal surface exposed for further attack.
This causes rapid and continuous corrosion.
For eg: Mo forms MoO3 volatile oxide.
Nature of the corroding environment:-
i) Temperature: With increase of temperature, the corrosion rate also increases because the
reaction as well as diffusion rate of ions in the corrosion medium increases.
ii) Humidity: The higher the humidity of the atmosphere the greater is rate and extent of
corrosion because the moisture acts as medium for O2 in air and behaves as an electrolyte.
For eg: atmospheric corrosion of iron is slow in dry air compound to moist air. Iron
combines with O2 and water to form ferrous hydroxide which combines with atmospheric
CO2 to form ferrous bicarbonate.
2Fe+O2+2H2O–------->2Fe(OH)2
Fe(OH)2 + CO2 –------>Fe(HCO3)2
Effect ofpH: - Generally acidic media are more corrosive than alkaline and neutral media.
Hence metals may be virtually classified according to pH range in which they will be
affected (or) resistant. However atmospheric metals like Al, Pb etc. are corroded in alkaline
medium and the corrosion rate of iron in O 2 free water is slow, until the pH is below Zn is
rapidly corroded in weakly acidic solutions.

Q. What is sacrificial anode? Mention its role in control.

1) Cathodic protection : The principle involved in this method is to force the metal to be
protected to behave like a cathode thereby corrosion doesn’t occur. There are two types of
cathodic protection.
i) Sacrificial anodic protection method: - In this method the metallic structure to be
protected is connected by a wire to a more anodic metal, so that all the corrosion is
concentrated at this more active metal implies the more active metal itself gets corroded
slowly. While the parent structure which is cathodic is protected .The more active metal so
employed is called “sacrificial anodic” whenever the sacrificial anode is consumed
completely. It is replaced by a fresh one. Metal commonly employed as sacrificial anodes
are Mg, Zn, Al and their alloys. Sacrificial anodes are used for the protection of buried pipe
lines underground cables, marine structures, ship hulls, water tanks etc.

What is the principle of cathodic protection? Explain impressed current method of

protection. (0r) How are metals protected by impressed current method?
Impressed current – cathodic protection: - In this method an impressed current is applied in
opposite direction to nullify the corrosion current and current the corroding metal from anode to
cathode. Usually the impressed current is derived from a direct current source (like battery or
rectifier on ac line) with an insoluble anode, like graphite, high silica iron, scrap iron, stainless
steel or platinum. Usually a sufficient d.c is applied to an insoluble anode, buried in the soil ( or
immersed in the corroding medium) and connected to the metallic structure to be protected. The
anode is buried is a backfill such as coke breeze or gypsum to increase the electrical contact
between itself and the surrounding soil.
Applications:- This type of protections is used in buried structures such as tanks and pipelines,
transmission line towers, marine piers, laid up ships etc.,
Advantages: - They can be automatically controlled which reduce maintenance and operational
costs.