Corrosion

 Corrosion is termed as the chemical or electrochemical

reaction between a material and its environment that leads
to deterioration of the material and/or its properties
 It is a process through which metals in manufactured states
return to their natural oxidation states
 This process is a reduction-oxidation reaction in which the
metal is being oxidized by its surroundings, often the oxygen
in air
 The reaction is both spontaneous and electrochemically
favoured.
 Corrosion is essentially the creation of voltaic, or galvanic,
cells where the metal in question acts as an anode and
generally deteriorates or loses functional stability.
 Effects of corrosion
 Loss of efficiency
 Contamination of product
 Damage of metallic equipments
 Inability to use metallic materials
 Loss of valuable materials such as blockage of pipes, mechanical
damage of underground water pipes
 Accidents due to mechanical loss of metallic bridges, cars, aircrafts
 Causes pollution due to escaping products from corrosion
 Depletion of natural resource
 Some of the major harmful effects of corrosion can be
summarized as follows:
• Reduction of metal thickness leading to loss of mechanical
strength and structural failure or breakdown.
• Hazards or injuries to people arising from structural failure
or breakdown (e.g. bridges, cars, aircraft).
• Loss of time in availability of profile-making industrial
equipment.
• Reduced value of goods due to deterioration of
appearance.
• Contamination of fluids in vessels and pipes
• Perforation of vessels and pipes allowing escape of their
contents and possible harm to the surroundings
• Mechanical damage to valves, pumps, etc, or blockage of
pipes by solid corrosion products
 Common metals and Alloys
 Iron:
• Main corrosion product is rust or iron oxides
• The most familiar form of rust is the reddish coating that forms
flakes on iron and steel (Fe2O3)
• Rust also comes in other colors, including yellow, brown,
orange, and even green! The different colors reflect various
chemical compositions of rust.
 Steel:
• These contain Fe, C, Cr, Ni, Mo, etc
• Main corrosion product is rust or
iron oxides, those similar to iron
• Along with iron, other alloying
metals (Ni, Cr, Mo) also get
corroded due the formation of
corresponding oxides
 Copper:
• Main corrosion products are CuCO3 + Cu(OH)2, patinas as Cu2O;
posnjakite (Cu4SO(OH)6H2O), brochantite (Cu4SO4(OH)6H2O), and
antlerite (Cu3SO4(OH)4)s
 Brass and Bronze:
• Brass contains Cu, Zn
• Bronze contains mainly Cu, Sn
• Main corrosion products are
similar to copper corrosion
products
 Reasons of corrosion
 In nature, most metals (except Au, Pt, etc) prefer existing as
thermodynamically more stable compounds, such as, their oxides,
carbonates, chlorides, silicates, etc.
 But, during the extraction process at high temperature, the
metallic compounds are reduced to their pure metallic state which
is, thermodynamically unstable state.
 Hence, the extracted/reduced pure metal will always have a
strong tendency to convert itself into the more stable metallic
compound oxidized state through corrosion.
 The Gibbs free energy changes of forming oxide and sulphides are
negative, so oxidation reaction is usually spontaneous
 Types of corrosion
 Corrosion is classified on the basis of nature of the corrodent,
mechanism of corrosion, and appearance of the corroded
metal
 Dry corrosion (chemical corrosion):
Classified depending on the corroding agent:
(i) Corrosion by oxidation,
(ii) Corrosion by gases other than oxygen
(iii) Corrosion by liquid metals.
 Wet corrosion (electrochemical corrosion):
(i) Evolution of hydrogen-type corrosion,
(ii) Absorption of oxygen-type corrosion,
(iii) Galvanic or bimetallic corrosion,
(iv) Concentration cell corrosion (or water line corrosion).
 Dry Corrosion
 This corrosion occurs due to the direct chemical attack of
atmospheric gases such as O2, halogens, H2S, SO2 or
anhydrous inorganic liquids on the metal surface.
 Dry corrosion occurs when there is no moisture or water to
aid corrosion
 This process is very sensitive to temperature
 Under hot conditions, dry corrosion occurs at a much faster
rate as compared to normal conditions
 Corrosion is due to adsorption, and the corrosion products
accumulate in the same spot where corrosion occurs
 Main types of this corrosion are
• Corrosion by oxygen (or) oxidation corrosion.
• Corrosion by other gases like H2S, SO2, CO2, F2 etc.
• Liquid metal corrosion (or) Erosion Corrosion
 Oxidation Corrosion
 Direct action of oxygen in the absence of moisture at low (or)
high temperatures leads to oxidation corrosion
 At high temperatures all metals are attacked by oxygen and
are oxidized – except noble metals like Ag, Au, and Pt
 At ambient temperature generally all the metals are slightly
attacked.
 Alkali metals and alkaline earth metals get oxidized readily
 The reactions in the oxidation corrosion are
Oxidation of metals

4 Fe + 3 O2 → 2 Fe2O3

2 Mg + O2 → 2 MgO

4 Al + 3 O2 → 2 Al2O3

2 Cu + O2 → 2 CuO

4 Na + O2 → 2 Na2O

2 Zn + O2 → 2 ZnO
 Mechanism of oxidation corrosion
 Oxidation takes place first at the surface of the metal
 Adsorption of oxygen on to the metal surface
 Loss of electron from the metal and gain of electron by
oxygen
 Dissociation of oxygen
 Formation of oxide layer onto the metal surface
 Types of oxide layers
 Nature of the oxide formed plays an important part in
oxidation corrosion process
• As the oxide layer grows the rate of electron transfer
decreases
• The corrosion stops and the metal is made passive
 Stable oxide layer (or stable protective oxide layer)
• It is a fine grain of oxide layer which is non-porous and
adheres strongly to the metal
• Oxides of Al, Pb, Cu, Ni and Cr which form stable, non-porous
and tightly adhering impervious metal-oxide films (<300 Å or
30 nm thick) to the pure metallic surface.
• Such layers prevents oxygen from diffusing through the metal
and further attack is stopped.
• Further oxidation corrosion is stopped
 Unstable oxide layer
• Oxide layers produced on noble metal surfaces (Pt, Ag,
etc) immediately decompose back into the metal and
oxygen, thereby preventing oxidation corrosion

Metallic oxide Metal + Oxygen

 Porous oxide layer:
• These oxide layers have minute pores and are not
impervious layers.
• Oxygen will diffuse through these pores and cracks
promoting further corrosion.
• Fe is a good example of this type of corrosion
• Iron when attacked by H2S at high temperature forms
porous FeS layer
 Volatile oxide layer:
• These are oxide layers which volatilize (evaporate) as soon
as they are formed and hence further corrosion is
facilitated.
• The underlying metal surface is exposed for further
corrosion. After some time the metal itself will disappear.
• Molybdenum (Mo) is an example of volatile oxide layer
corrosion. MoO3 is volatile (MoO2 is non-volatile.).
 Pilling-Bedworth rule (P-B ratio):
 The protective or non-protective nature of the oxide film is
determined by Pilling-Bedworth rule
 The ratio of the volume of the oxide formed to the volume
of the metal consumed is called as Pilling-Bedworth ratio or
P-B ratio
ρ
ρ
RPB = Pilling–Bedworth ratio,
M = atomic or molecular mass,
n = number of atoms of metal per one
molecule of the oxide
ρ = density, and
V = volume.
 Cases
 On the basis of the P-B ratio, it can be judged if the metal is
likely to passivate in dry air by creation of a protective oxide
layer
o PB ratio <1: the oxide coating is broken, no protective
effect. (example: magnesium)
• Alkali and alkalline earth metals: PB < 1 → tensile stresses
in oxide film → brittle oxide cracks
o PB ratio > 2: the oxide coating chips off, no protective
effect (example: iron)
o PB ratio between 1 and 2: the oxide coating is passivating
(examples: aluminum, titanium, chromium containing
steels).
 Rules
 If the volume of the oxide layer is greater than the
volume of the metal, the oxide layer is protective and
non-porous
• Aluminium forms Aluminium oxide whose volume is greater
than the volume of the metal (Al). Hence these do not
undergo corrosion rapidly
 If the volume of the oxide layer formed is less than the
volume of the metal, the oxide layer is non protective
and porous
• Alkali and alkaline earth metals like Li, Na, K, Mg forms
oxides of volume less than volume of metals. Hence these
undergo corrosion more rapidly
 Corrosion by other gases
 In dry atmosphere CO2, Cl2, SO2, F2, NOx etc. are gases which can
attack the metal and corrode
 Extent of corrosion depends on the affinity of the metal to the
gas.
 These gases chemically react with the metal forming either
porous or non-porous layers of films
 Protective or non-porous layer prevents from further attack.
 Non-protective or porous layer expose the underlying fresh
metal surface for further attack.
 H2S gas attacks steel and make them brittle
2 Ag + Cl2 → 2 AgCl non-porous layer
Fe + H2S → FeS + H2 porous layer
Sn + 2 Cl2 → SnCl4 volatile layer
 Hydrogen embrittlement
 Hydrogen Embrittlement is a process whereby metals become
brittle and fracture as a result of the introduction and diffusion of
hydrogen into the material
 When metals are in contact with H2S, at ordinary temperature
causes evolution of atomic hydrogen
 This atomic hydrogen diffuses readily into the metal and collects in
the voids, where it recombines to form molecular hydrogen

Fe + H2S → FeS + 2 H·
2 H· → H2 ↑

 Collection of these hydrogen gases

in the voids develops very high
pressure, which causes cracks and
blisters on metal leading to
hydrogen embrittlement.
 Liquid - Metal corrosion or Erosion- corrosion
 This type of corrosion is experienced in pipe lines used in
oil and refineries.
 In metallic pipelines, the fast flow of corrosive liquid or
aggressive fluid completely removes the underlying layer
of metal in the pipeline due to mechanical abrasion
 Corrosion by liquid metal or
Liquid metal embrittlement
 Liquid metal (Hg, Zn, Sn, Pb, Cd etc.) flowing at high
temperature over the solid metal or alloy can result in
• Dissolution of the solid metal by the liquid metal (Gold
can be corroded by mercury) or
• Internal penetration of the liquid metal into the solid
metal.
 Molten metal atoms penetrate the grain boundaries and
fracture the metal.
 Such corrosion is found in devices used in nuclear power
plants. It causes brittle failure of metal structure
 Types of corrosion
 Corrosion is classified on the basis of nature of the corrodent,
mechanism of corrosion, and appearance of the corroded
metal
 Dry corrosion (chemical corrosion):
Classified depending on the corroding agent:
(i) Corrosion by oxidation,
(ii) Corrosion by gases other than oxygen
(iii) Corrosion by liquid metals.
 Wet corrosion (electrochemical corrosion):
(i) Evolution of hydrogen-type corrosion,
(ii) Absorption of oxygen-type corrosion,
(iii) Galvanic or bimetallic corrosion,
(iv) Concentration cell corrosion (or water line corrosion).
 Electrode potential
Electrode Potential
(1) When a metal (M) is placed in a solution of its ions (M++), either of the following
three possibilities can occurs, according to the electrode potential solution pressure
theory of Nernst.
(i) A metal ion Mn+ collides with the electrode, and undergoes no change.
(ii) A metal ion Mn+ collides with the electrode, gains n electrons and gets converted
into a metal atom M, (i.e. the metal ion is reduced).

Mn+(aq) + ne− → M(s)

(iii) A metal atom on the electrode M may lose a electrons to the electrode, and enter
to the solution as Mn+, (i.e. the metal atom is oxidised).
M(s) → Mn+(aq) + ne−
Thus, “the electrode potential is the tendency of an electrode to lose or gain electrons
when it is in contact with solution of its own ions.”
 Mechanism of Wet Corrosion is based on Nernst theory
• (2)
. The magnitude of electrode potential depends on the following factors,

(i) Nature of the electrode,

(ii) Concentration of the ions in solution,
(iii) Temperature.

(3) Types of electrode potential : Depending on the nature of the metal electrode to lose
or gain electrons, the electrode potential may be of two types,
(i) Oxidation potential : When electrode is negatively charged with respect to
solution, i.e., it acts as anode. Oxidation occurs. M → Mn+ + ne
(ii) Reduction potential : When electrode is positively charged with respect to
solution, i.e. it acts as cathode. Reduction occurs. Mn+ + ne− → M
(4) Standard electrode potential : “If in the half cell, the metal rod (M) is suspended in
a solution of one molar concentration, and the temperature is kept at 298 K, the electrode
potential is called standard electrode potential, represented usually by Eo”. ‘or’
The standard electrode potential of a metal may be defined as “the potential difference in
volts developed in a cell consisting of two electrodes, the pure metal in contact with a
molar solution of one of its ions and the normal hydrogen electrode (NHE)”.
Standard oxidation potential for any half-cell = − (Standard reduction potential
Standard reduction potential for any half-cell = − (Standard reduction potential
(5) Reference electrode or reference half – cells

It is not possible to measure the absolute value of the single electrode potential directly.
Only the difference in potential between two electrodes can be measured experimentally. It
is, therefore, necessary to couple the electrode with another electrode whose potential is
known. This electrode is termed as reference electrode or reference half – cells. Various
types of half – cells have been used to make complete cell with spontaneous reaction in
forward direction. These half – cells have been summarised in following table,
- 0.74 V 0.34 V
Types of electrochemical corrosion

 Uniform or General corrosion

 Hydrogen evolution type corrosion
 Oxygen consumption type corrosion
 Galvanic corrosion
 Concentration cell corrosion
 Pitting corrosion
 Stress corrosion
 Wet or Electrochemical Corrosion
 In this type of corrosion, a conducting liquid (electrolyte) is in
contact with a metal or
 Two dissimilar metals or alloys are partially dipped in the
electrolyte
 It occurs when electrons from metal surface are transferred to a
suitable electron acceptor or depolarizer. Water must be present
to serve as a medium for the transport of ions
 The most common depolarizers are oxygen, acids, and the cations
of less active metals
 Because the electrons flow through the metallic object itself, the
anodic and cathodic regions can be at widely separated locations.
 Anodic regions tend to develop at locations where the metal is
stressed
 Contact with a different kind of metal, either direct or indirect, can
lead to corrosion of the more active one
 Criteria for Electrochemical Corrosion
1. Formation of galvanic cells on the surface of metal
generating anodic and cathodic areas.
2. Presence of conducting liquid with the formation of
electrochemical cells.
3. At anode of metal surface, oxidation [Corrosion] takes
place by liberating electrons.
4. At cathode, reduction [No corrosion] takes place
 The rate of the electrochemical corrosion will depend on:
• If the corrosion product is soluble in the medium, rate
of corrosion will be high.
• If the corrosion product is insoluble in the medium,
rate of corrosion will be very low.
 Mechanism of Wet Corrosion is based on Nernst theory
• According to which all metals have a tendency to pass into
solution.
• If a metal having higher electrode potential comes into
contact with another metal having a lower electrode
potential, a galvanic cell is set up
• The metal having the higher electrode potential becomes
anodic and goes into solution to a measurable extent. The
other becomes cathodic and does not enter solution
• The extent of galvanic corrosion depends upon the difference
in the electrode potential of the two electrodes and their
respective areas.
o The greater the difference in the potentials of the cathode and
anode, the greater will be the corrosion.
o Also the smaller the area of the anode as compared to the
cathode, the more will be the attack.
 Corrosion Cells and Reactions
 Oxidation and reduction steps occur at separate locations on the
metal. This is possible because metals are conductive, so the
electrons can flow through the metal from the anodic to the
cathodic regions
 The presence of water is necessary in order to transport ions to
and from the metal
 Uniform or General corrosion
 The electrochemical reactions (in aqueous or atmospheric
media) proceed uniformly over the entire exposed metal
surface over a large area
 General corrosion represents the greatest destruction of
metal
 General corrosion is less dangerous than the other corrosion
forms because the life of equipment or structures can be
accurately estimated from simple corrosion tests and
sometimes by visual inspection.
 Hydrogen evolution type corrosion
 It occurs when base metals are in contact with an acidic solution
 Rusting of iron metal in acidic environment takes place in the
following way
• Anode: Oxidation occurs
Fe → Fe2+ + 2 e-
• Cathode: Reduction occurs
2 H+ + 2 e- → H2 ↑
• The overall reaction is:
Fe + 2 H+ → Fe2+ + H2 ↑
 Metal ions produced at the anode dissolves in the electrolyte
while hydrogen evolves at the cathode.
 Hence, this type of corrosion causes “displacement of hydrogen
ions from the acidic solution by metal ions”
 In this case anodic areas are large and cathodic areas are small.
 Oxygen consumption type corrosion
 It occurs when base metals are in contact with neutral solutions
like water with dissolved oxygen (DO)
 Rusting of iron is an example of this type of corrosion
• Anode: Oxidation occurs
Fe → Fe2+ + 2 e–
These electrons move from anode to cathode and
react with the electrolyte and oxygen giving
• Cathode: Reduction occurs
O2 + 2 H2O + 4 e– → 4 OH–

 The Fe2+ at the anode and OH – at the cathode diffuse and react to
produce Fe(OH)2 which gets further oxidized to Fe(OH)3 (rust):
Fe + 2 OH – → Fe(OH)2 (green)
4 Fe(OH)2 + O2 + 2 H2O → 4 Fe(OH)3 or 2 (Fe2O3.3H2O)
If the supply of oxygen is limited, the corrosion product
may be even black anhydrous magnetite Fe3O4
 In acidic solution, the cathodic reaction leads to water formation
O2 + 4H+ + 4 e– → 2 H2O
 In basic or neutral solution reduction leads to hydroxyl ion
O2 + 2 H2O + 4 e– → 4 OH–
 In deaerated and acidic solution H+ ions reduced to hydrogen gas
 Rust is a non-sticking compound i.e., it does not stick to the
surface. It peels off exposing fresh iron surface for further rusting.
 Small Fe2+ diffuses more rapidly than large OH- ions. So, corrosion
occurs at anode, but rust is deposited at or near the cathode
 Smaller the area of anode compared to cathode will lead to
faster corrosion of anode.
• The corrosion current at anode and at cathode are same. But for
small anodic area the current density will be large at anode and
larger cathodic area will demand more electron which will be
fulfilled by fast reaction at anode (oxdidation), i.e. rapid
corrosion.
 Difference between chemical (dry) corrosion and
electrochemical (wet) corrosion
Chemical (dry) corrosion Electrochemical (wet) corrosion
Chemical corrosion occurs in the dry Electrochemical corrosion occurs the
state. presence of moisture or electrolyte.
Corrosion products accumulate at the It involves the setting up of a huge
same spot where corrosion occurs. number of tiny galvanic cells.
It involves the direct chemical attack It follows mechanism
of the metal by the environment. electrochemical reactions.
It follows absorption mechanism. It occurs only on heterogeneous
metal surface.
It occurs on both homogeneous and Corrosion occurs at the anode but
heterogeneous surfaces. products gather at the cathode.
Uniform corrosion takes place. Pitting is more frequent especially
when the anode area is small.
It is slow process It is fast process
 Differential metal corrosion or Galvanic corrosion
or Bi-Metallic Corrosion
 Galvanic corrosion, or dissimilar metal corrosion, occurs when two
different metals are located together in a corrosive electrolyte
 A galvanic couple forms between the two metals, where one
metal becomes the anode and the other the cathode
 Metal with lower reduction potential (anode) undergoes
oxidation and the metal with higher reduction potential (cathode)
undergoes reduction
 The anode or sacrificial metal, corrodes and deteriorates faster
than it would alone, while the cathode deteriorates more slowly
than it would otherwise
 Anodic area always undergoes corrosion and cathodic area
remains unaffected
 Galvanic corrosion can only occur when there exists an electric
conducting path connecting the metals, eg., an electrolyte
Three conditions must exist
for galvanic corrosion to
occur:
• Electrochemically dissimilar
metals must be present
• The metals must be in
electrical contact, and
• The metals must be
exposed to an electrolyte
- 0.74 V 0.34 V
 Anodic

Cathodic
 A metal placed high in the electrochemical series is said
to be anodic to the one placed below it
 Thus, iron is anodic to copper, nickel and tin.
 On the other hand, iron acts as a cathode in contact with
zinc and magnesium
 In Zn-Cu, Zn acts as anode (oxidized) and Copper acts as
cathode (reduced)
 Steel screws in a brass marine hardware.
 Lead-antimony solder around a copper wire
 Steel pipe connected to copper plumbing.

 When Zinc metal is dipped in 1N H2SO4, the initial rate of corrosion

is quite slow. Upon the addition of copper powders and/or copper
salt like copper sulphate, the rate of corrosion increases
significantly.
 Prevention of Galvanic corrosion
 Selecting materials with similar electrode potentials [e.g.,
Joining Cu metal and Bronze]
 Breaking the electrical connection by insulating [plastic washer,
Paint] the two metals from each other.
 Applying coatings to both materials. The coating on the cathode
is the most important and must be in good condition, otherwise
the galvanic corrosion could be worsened.
 Separating the two materials by inserting a suitably sized
spacer.
 Installing a sacrificial anode that is anodic to both metals.
 Adding corrosion inhibitor to the environment. The inhibitor
will adsorb on the metal surface there by preventing the
contacts of anode and cathode surface with electrolyte or
aqueous medium.
 Ways to Avoid Galvanic Corrosion
 This mostly includes obstructing the electrical path in the
metallic or electrolyte parts of the system, removing oxygen
from the electrolyte, and the introduction of corrosion
inhibitors
 1. Insulation
• One of the most effective ways of breaking the electrical path
in the electrochemical cell is to place a non-conductive
material between the contact points of the coupling metals.
• Insulation material blocks the flow of electrons, thus
preventing oxidation and reduction reactions from occurring
• Insulation is typically achieved by using polymer or
elastomer-based bushings, washers, gaskets and coatings.
• For example, in the oil and gas industry, non-conductive glass
reinforced epoxy (GRE) gaskets are used
 2. Electrolyte Isolation
• Therefore, protective measures that involve isolating
the contacting metals and the electrolyte can prove to
be effective in preventing galvanic corrosion.
• This is achieved by using water-repellent compounds
that act as barriers between the metal substrate and
the electrolyte solution.
• Paints, coatings, oils and greases have all been used in
numerous industries to great effect.
 3. Selection of Appropriate Contacting Metals
• Galvanic corrosion can also be avoided by minimizing
the potential difference between the metals.
• The electrons flow from the anode to the cathode
due to the potential difference, which acts as the
driving force.
• The higher the potential difference, the greater the
induced galvanic current, and the more severe the
corrosion rate. The opposite is true for metals with a
low potential difference between them.
• The objective is to select contacting metals with
similar electrode potentials, i.e., metals that are close
to each other in the galvanic series, to reduce the
possibility of galvanic corrosion.
 4. Corrosion Inhibitors
• Corrosion inhibitors are compounds (usually liquid)
that are added to the electrolyte to suppress the
chemical reactions that cause galvanic corrosion.
• Inhibitors work in a number of ways – most involving
complex chemical processes.
• Inhibitors that are most effective against galvanic
corrosion are those that remove dissolved oxygen
from the electrolyte solution.
• Removing oxygen reduces the possibility of reduction
taking place at the anode. Since the cathodic reactions
are dependent on anodic reactions, the galvanic
process is halted.
 5. Minimizing the Area Ratio
• The larger the area of the cathode in relation to the
anode (i.e., the higher the cathode to anode ratio), the
greater the rate of reduction at the anode, thus the
more severe the resulting galvanic corrosion.
• By contrast, the smaller the cathode to anode area,
the less detrimental the ensuing deterioration.
• During the preliminary design stages, it is worthwhile
to ensure that the area of the anodic metal is made as
large as possible in relation to the cathode.
• For example, steel fasteners in an aluminum plate will
produce better results than aluminum fasteners in a
steel plate.
 Concentration cell corrosion
 Concentration Cell: Electrolytic cell that is comprised of two half-
cells with the same electrodes, but differing in concentrations.
 Here more concentrated solution gets diluted and diluted solution
gets concentrated, creating a voltage till an equilibrium is attained
 This is achieved by electron transfer from cell with the lower
concentration to the cell with the higher concentration.
 Concentration cell corrosion is the deterioration of parts of a
metal surface at different rates, due to the parts of the surface
coming into contact with different concentrations of the same
electrolyte.
 In other words, when a metal is exposed to varying concentration
of electrolyte or varying concentration of oxygen, a concentration
cell is formed.
 The extent of this corrosion reaction is proportionate to the
difference in concentrations at contact points
 The difference in the concentration of electrolyte or oxygen (air)
over the surface of base metal result in some parts of the metal
acquiring different electric potentials and in turn develops galvanic
cells which initiates corrosion.
 If an area of the electrolyte close to the metal shows a lowered
concentration of metal ions, the region turn anodic and thus, this
part of the metal corrodes faster, so as to increase the local ion
concentration in electrolyte
 Concentration cell corrosion
 Types of concentration cell corrosions include Crevice
Corrosion, Pitting corrosion, Water-line corrosion, Cracking of
concrete cover, corrosive damage of pipes buried in soil, etc.
 Concentration cell corrosion is most prevalent in the
presence of oxygen. In this case Oxygen Concentration Cells
develops. Also known as Differential Aeration Corrosion
 Parts of metal that are covered by scale will corrode faster
because the contact with oxygen for these parts is restricted
 Differential Aeration Corrosion
 Differential Aeration Corrosion takes place when there is an
uneven supply of oxygen to areas of the same metal component
 When a poorly oxygenated area is adjacent to an area with a good
supply of oxygen, an anodic/cathodic reaction occurs
 The less aerated or less oxygenated part behaves anodic while the
more oxygenated part cathodic. Since cathodic reactions involve
consumption of oxygen, the more oxygenated part behaves
cathodic and less oxygenated pan behaves anodic
 Corrosion starts at the anode (dissolves)
 This type of corrosion occurs when metals are partly dipped in
solutions or partly covered with dust, oil marks, sand etc
 Oxygen screening, crevice corrosion and poultice action are other
terms for this type of corrosion
 It is the most common type of concentration cell corrosion
 Corrosion of metals partly immersed in solution
 When a metal piece is partly immersed in an electrolyte or
water, the part of the metal above the surface of the solution
is more aerated and behaves cathodic while the metal part
immersed inside water has less accessibility to oxygen [only
with Dissolved oxygen] and behaves anodic.
 The difference of potential thus created causes the flow of
current between the two regions which results in corrosion
 Corrosion of metals partly covered with
dirt, dust, sand, scale, oil

 Metals partly covered with dirt, dust, sand, scale, oil marks
become oxygen deficient area – Anode:
M → Mn+ + 2 e- (Fe → Fe2+ + 2 e- )
 The other area which is more exposed to oxygen becomes
oxygen rich and acts as cathode.
O2 + 2 H2O + 4 e- → 4 OH-
 Drops of water or salt solution

Anode: Fe → Fe2+ + 2 e- Cathode: O2 + 2 H2O + 4 e- → 4 OH-

 Water-line corrosion
 Waterline corrosion occurs when differential aeration is present
in a neutral medium.
 It is usually found in steel guttering, pipes, tanks, ships floating
in seawater for long periods of time
 The part of the metal below the water line is exposed to only to
dissolved oxygen while the part above the water is exposed to
higher concentration of oxygen
 Water-line corrosion

Anode: Fe → Fe2+ + 2 e- Cathode: O2 + 2 H2O + 4 e- → 4 OH-

 Crevice corrosion
 Crevice corrosion is defined as a form of localized corrosion
occurring at locations where easy access to the bulk
environment is prevented, such as the mating surfaces of
metals or assemblies of metal and non-metal, for example,
gaskets, couplings, and joints.
 It may occur also at washers, under barnacles, at sand grains,
under applied protective films, and at pockets formed by
threaded joints
 Intense localized corrosion, ranging from small pits to
extensive corrosion over the whole surface, can occur within
narrow cervices
 The mechanism of crevice corrosion generally involves
differential aeration cell in which the freely exposed metal
outside the crevice is predominately cathodic while the metal
within the crevice is anodic
Aloha airline
accident in
1988.
The fuselage
broke off
during take off
due to crevice
corrosion
 Pitting Corrosion
 Pitting is a type of corrosion that occurs in materials that have
protective films.
 It is an attack with localized holes on the metal's surface.
 The attack can penetrate the metal very rapidly, while some parts
of the metal surface remain free from corrosion
 The protective oxide layer on the metal surface gets damaged at
specific points due to chemical attack, scratches or cut edges,
thereby giving rise to the formation of small anodic and large
cathodic parts.
 Due to rapid penetration of oxygen through some cracks in the
oxide film or pin holes on metallic surfaces, pitting takes place
leading to corrosion.
 Pitting start at the oxygen poor region at the bottom of the pit is
Anodic. Pit tends to deepen leading to premature failure due to
fatigue or brittle fracture
 Pitting corrosion is characterized
by the formation of small cavities
(pits) in the metal.
 The pits can vary greatly by
depth and shape and be
scattered on the surface with a
different frequency.
 The resulting cavities may be
very small and be covered by
corrosion products.
 The area covered by the drop of water acts as an anode due to less
oxygen concentration and suffers corrosion. The uncovered area
acts as a cathode due to high oxygen concentration
 This creates differential aeration cell on metal surface
 Larger cathodic area than the anodic area, accelerate corrosion at
the same spot wherein the water drop is resting
 The removal more metal from the same spot leads to the
formation of pits and hence this is known as pitting corrosion
 Factors influencing corrosion
The rate and extent of corrosion mainly depends on
(i) Nature of the metal
(ii) Nature of the environment
Nature of the metal Nature of the environment
1) Position in the galvanic series 1) Temperature
2) Purity of metal 2) Conductance of medium
3) Physical state of metal 3) Humidity
4) Nature of surface film 4) Presence of impurities
5) Nature of corrosion product 5) pH
6) Relative areas of the anodic
and cathodic parts
7) Overvoltage
 Nature of the metal
 Position in the galvanic series:
• To account for complete Anodic
corrosion behavior of metal
and its alloy system a separate
chemical series is required
called galvanic series.
• When two dissimilar metals
are in contact, the more
anodic metal (Higher up in the
series) will corrode.
• The extent of corrosion
depends on how far apart are
the two metals in the galvanic Cathodic

series.
 Purity of metal:
• Purer the metal, lesser is the rate of corrosion.
• The 100% pure metal will not undergo any type of corrosion.
This is known as homogeneity on metal
• But, the presence of impurities in a metal creates
heterogeneity and thus local galvanic cells are set up with
distinct anodic and cathodic area in the metal.
• Higher the percentage of impurity, faster is the rate of
corrosion of the anodic metal.
 Physical state of metal:
• The rate of corrosion will depend on the physical state of the
metal such as grain size, orientation of crystals, stress etc.
• The smaller the grains in size, the greater will be its solubility
and hence greater will be its corrosion. Different faces of a
metal have different corrosion rate.
 Nature of surface film (Pilling-Bedworth rule):
• Corrosion depends on the nature of surface film i.e. the
oxide film is stable or unstable or volatile or porous or non-
porous will decide the rate of corrosion of the metal.
 Nature of the corrosion product:
• If the corrosion product is soluble in the environment in
which the metal is working, then the corrosion will
proceed faster.
• If the product is insoluble in the environment, then the
corrosion is very slow since the corrosion product becomes
a protective layer on the metallic surface. Eg. PbSO4.
• If the corrosion product is volatile, it evaporates as soon as
it is formed exposing fresh metal for corrosion and hence
the corrosion becomes very rapid and the metal will
disappear over a period of time, eg. MoO3, SnCl4.
 Relative areas of the anodic and cathodic parts:
• When two dissimilar metals are in contact, the rate of
corrosion is directly proportional to the ratio of cathodic
part to anodic part
• If the anodic area is small, corrosion is more rapid and
severe and localized because the current density at a
smaller anodic area is much greater
• The demand for electrons (by larger cathodic areas) can be
met by smaller anodic areas only by undergoing corrosion
is more rapid
• The rate of corrosion will be more, when the cathodic area
is larger. When the cathodic area is larger, the demand for
electrons will be more and this results in an increased rate
of corrosion (dissolution) of metals at anodic area
 Nature of the environment
 Temperature:
• Rate of corrosion is directly proportional to temperature.
• This is because, the rate of chemical reaction and the rate
of diffusion of the ions increases with rise in temperature.
Hence the rate of corrosion increases with temperature
 Humidity in environment:
• The rate of corrosion will be more, when the humidity in
the environment is high.
• The moisture acts as a solvent for the oxygen in the air to
produce the electrolyte, which is essential for setting up a
corrosion cell
 Presence of impurities in the atmosphere:
• Gases like CO2, SO2, H2S and fumes of HCl, H2SO4 provide
conductive environment for enhancing the electrochemical
corrosion.
• In marine environment, the Cl- is responsible for enhanced
rate of corrosion
• Particles of NaCl, (NH4)2SO4 along with moisture act as strong
electrolyte and accelerate the electrochemical corrosion
• Conductance of the corroding environment
• An increase in the electrical conductivity of the electrolyte will
therefore increase the corrosion rate.
• In corrosion of underground and submerged structures, the
conductance of the medium plays a critical role in corrosion.
• In sea water the chloride content causes rapidly increased
conductivity.
 Formation of oxygen concentration cell:
• If one part of the metal is exposed to higher levels of
oxygen, it becomes cathode and the other part which is
exposed to lesser levels of oxygen will become anode.
• This is called oxygen concentration cell which promotes
corrosion by anodic oxidation/dissolution
2 H2O + O2 + 4e - → 4 OH- (Cathodic reaction-higher O2)
• This OH- will move to the cathode where Fe2+ reacts to
form Fe(OH)2 which later converts into rust (Fe2O3.3H2O)
• Buried pipelines, cables etc., experience this kind of
electrochemical corrosion.
 Effect of pH:
• Acid medium facilitates more corrosion than neutral and
basic media as a general rule.

• Acidic medium >>> high corrosion rate

• Basic medium >>> moderate corrosion

• Highly alkaline medium >>> corrosion ceases

• The corrosion rate of Fe in oxygen free water is very slow

up to pH 5.0 but in the presence of oxygen, the corrosion
at pH 5.0 enhances greatly
• Zinc corrodes rapidly in acidic solutions but the rate of
corrosion is relatively lower in alkaline medium (pH 11.0).
• Aluminium corrodes less at pH 5.5 but the rate of corrosion
is very high in pH 8.5.
 Electroplating
 It is the process by which the coating metal is deposited on the
base metal by passing a direct current through an electrolytic
solution containing the soluble salt of the coating metal
 Electroplating is done for improving
a) corrosion resistance
b) wear resistance
c) chemical resistance
d) surface hardness
e) appearance
 Both ferrous and non-ferrous metals are plated with Ni, Cr, Cu,
Zn, Pb, Al, Ag, Au, Sn etc.
 Electroplating is mainly used in automobile, aircraft,
refrigerator, chemical and electrical appliances etc.
 Theory of Electroplating
 The base metal to be plated is made cathode of an
electrolytic cell, whereas the anode is either made of the
coating metal itself or an inert material of good electrical
conductivity
 If the anode is made of coating metal itself in the
electrolytic cell, during electrolysis, the concentration of
electrolytic bath remains unaltered.
 Since the metal ions deposited from the bath on cathode
(Base metal) are replenished continuously by the reaction of
free anions with the anode.
 If the anode is made of an inert material like graphite,
electrolyte should be added continuously to maintain the
concentration of the coating metal ions in the bath.