UNIT 1: Electrochemistry: Electrode Systems and Corrosion

Electrochemistry: The branch of chemistry which deals with the study of inter-conversion of
chemical energy and electrical energy.

Electrode Systems
Terminology:
 Electrolysis: The chemical decomposition of an electrolyte upon passing electric current.
 Electrolyte: The substance which conducts electricity in molten or in aqueous solution.
 Single electrode: This may be a metal or non-metal which is in contact with a solution of its
own ions. It is also called as half-cell.
Ex: Zinc electrode can be constructed by introducing Zn rod in ZnSO4.
 Single electrode potential or electrode potential (E): The tendency of an electrode to lose
(oxidation potential) or gain (reduction potential) electrons when it is in contact with the
solution of its own ions.
Or
The potential developed when an electrode is in equilibrium with a solution of its own ions.
It is denoted by “E”.
 Standard electrode potential (E0): The potential developed when the electrode is in
equilibrium with 1M solution (1atm in case of gases) of its ions at 298K. It is denoted by ‘E 0’.
Ex: E0Zn = -0.76v & E0Cu = +0.34V
In oxidation: a species loses one or more electrons resulting in an increase in its oxidation
number. M ⟶ Mn+ + ne-
In reduction: the species gains one or more electrons; there is a decrease in oxidation
number. Mn+ + ne- ⟶ M
 Electromotive force (EMF) of a cell: The maximum potential difference between the
electrodes of galvanic cell that drives electric current. It is denoted by EMF or Ecell.
Ecell = ERHE – ELHE or Ecell = Ecathode – Eanode
 Electrochemical cell: It is a device used to convert spontaneous chemical energy in to electrical
energy or electrical energy in to non-spontaneous chemical energy.
 Galvanic cell or Voltaic cell: A device in which electricity is produced as a result of spontaneous
chemical reaction involving reduction-oxidation reactions.
Ex: Batteries and fuel cells
 Electrolytic cell: A device in which the electrical energy is converted into chemical energy.
Or
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An electrochemical cell in which a non-spontaneous chemical reaction is driven by an external
source of current.
Ex: electroplating of gold, silver, copper etc., electrorefining of metals, electrolysis of brine
solution in Nelson’s cell etc.
Nernst equation for single electrode potential.
The tendency of an electrode to lose (oxidation potential) or gain (reduction potential) electrons when
it is in contact with the solution of its own ions is called single electrode potential.

Nernst equation gives a relationship between single electrode potential and standard electrode
potential through concentration of metal ions at a particular temperature.
RT
E = E 0 + nF ln[Mn+ ] Nernst equation for single electrode potential.
substituting the value of R = 8.314 J/K/mol, T = 298 K, F = 96500 C/mol in equation (10) and
converting loge to log10, we get,
0.0591
E = E0 + log [Mn+ ] Nernst equation for single electrode potential at 298 K.
n
Note:
(i) If concentration of solution [Mn+] is increased, the electrode potential increases and vice
versa.
(ii) If temperature is increased, the electrode potential increases and vice versa.

Classification of cells
 Primary cell: In primary cell, the chemical energy is converted into electrical energy as long
as the chemical components are active. These are not rechargeable and once discharged have
no further electrical use. Ex: Zn- air cell, Zn-MnO2 cell and Li-MnO2 cell etc.
 Secondary cell: It is rechargeable. The cell reactions are reversible. After discharge,
secondary cells can be recharged electrically to their original condition by passing current
through them in the direction opposite to that of discharge current. The electrical energy is
stored in them in the form of chemical energy and hence these are also called storage cells.
Ex: Lead storage cells, Ni-MH cells, nickel-cadmium cells, Li-ion and Na-ion cells
 Concentration cells: A concentration cell is a galvanic cell which generates electrical energy
at the expense of chemical energy. Unlike galvanic cells, a concentration cell consists of two
electrodes of same material and same electrolyte but with different concentrations (hence
these cells are called as electrolyte concentration cells).

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Construction, working principle and applications of electrolyte concentration cell
with an example.
Construction: Electrolyte concentration cell is a
galvanic cell consisting of both anode and cathode
made up of same element (metal or nonmetal) in
contact with the solutions of the same electrolyte of
different concentration. A typical Copper
concentration cell is shown in figure. It consists of two
copper electrodes, immersed in CuSO 4 solutions of
two different concentrations. These two electrodes are externally connected by metallic wire
and internally by a salt bridge. The cell can be represented as,
Cu | Cu 2+ (C1) || Cu 2+ (C2) | Cu
Or Cu(s) / CuSO4 (C1) // CuSO4 (C2) / Cu(s) [where C2 > C1]

Working principle: By convention left hand electrode is the anode and right-hand electrode is
cathode.
At anode Cu → Cu 2+ (C1) + 2e
At cathode Cu 2+ (C2) + 2e → Cu
Net cell reaction Cu 2+ (C2) → Cu 2+ (C1)
The net cell reaction is merely the change in concentration; as a result, the current flows through
the circuit.

The Nernst equation for the EMF of a concentration cell is given by the equation:
0.0591 C2
Ecell = log [ ] at 250 ; C1 < C2
n C1

Applications: Used to determine the valence state of metal ions

Note:
1. In a concentration cell, the electrode with lower electrolyte concentration acts as the
anode and the one with higher electrolyte concentration acts as the cathode.
2. If the two solutions are of the same concentrations, then, Ecell = 0
3. When C2/C1 > 1, log C2/C1 is positive & electrode potential is positive.
Higher the ratio of C2/C1, greater is the value of EMF of the cell. i.e., ECell α C2/C1.

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Reference electrode
The potential of an electrode cannot be accurately directly measured. So the electrode is
connected to another electrode of known potential, such an electrode is termed as reference
electrode.
“Any electrode of constant and reproducible potential, used to determine the potential of other
electrode is called as reference electrode”.
There are two types of reference electrodes.
1) Primary reference electrode: The Standard Hydrogen Electrode (SHE) is called as primary
reference electrode, whose potential is arbitrarily taken as zero at all temperatures.
But it has two main limitations – a) difficulty in setting up of the electrode and b) the
electrode becomes inactive in presence of impurity gases present in hydrogen.
To overcome these difficulties involved in the use of SHE as reference electrodes,
secondary reference electrodes are used.
2) Secondary reference electrodes: These are the type of electrodes whose potential remains
constant and their potential with respect to SHE are known.
These have several advantages over SHE like a) these are very simple in construction b)
the potential is reproducible and stable over a long period and c) the electrode potential will not
vary with temperature.
Ex: Calomel electrode & Ag-AgCl electrode

Construction, working and applications of calomel electrode. Justify that it is a reversible

electrode.

Construction: Calomel electrode is a metal-metal salt ion

electrode. It consists of two glass tubes. In the inner tube a
paste of Hg and mercurous chloride (calomel – Hg2Cl2) and
above which mercury is placed. The remaining portion of both
inner and outer tube is filled with saturated KCl solution. A
platinum wire is dipped in the inner tube and is used to
provide external electrical contact. The porous plug at the
bottom of the outer tube acts as salt bridge.
Hg (s) | Hg2Cl2 (s) | KCl(Sat)

Working principle: Calomel electrode can act as anode or cathode depending on the nature of
the other electrode of the cell. The electrode reactions are represented as follows:

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 As anode: As cathode:
2Hg → Hg22+ + 2e- Hg2Cl2 → Hg22+ + 2Cl-
Hg22+ + 2Cl- → Hg2Cl2 Hg22+ + 2e- → 2Hg
2Hg + 2Cl- → Hg2Cl2 + 2e- Hg2Cl2 + 2e- → 2Hg + 2Cl-

The net reversible electrode reaction is

½ Hg2Cl2 + e- → Hg (l)+ Cl- (aq)

Electrode potential of calomel electrode is given by:

E = E0 – 0.0591 log [Cl-] at 298 K
Since the calomel electrode is reversible with respect to chloride ion its electrode potential
depends on the concentration of KCl solution. At 298K, the electrode potentials as follows:
KCl concentration 0.1N 1N Saturated
Electrode potential (V) 0.334 0.281 0.2422
Advantages of calomel electrode (a secondary reference electrode):
1. It is very simple in construction.
2. The potential is reproducible and stable over a long period.
3. Its electrode potential will not vary with temperature.
Applications of calomel electrode: It is the most commonly used as secondary reference
electrode for potential measurements of unknown electrodes.

Ion selective electrode

Ion-selective electrode is a membrane electrode which is selectively sensitive to a specific ion
in a mixture and potential developed at the electrode is a function of concentration of that ion
in the solution. The electrode generally consists of a membrane which is capable of exchanging
the specific ions with the solution with which it is in contact. Therefore, these electrodes are also
referred to as membrane electrodes. Example: Glass electrode, Nitrate electrode, Fluoride
electrode

Reference Solution to be Internal standard Reference

electrode 2 analysed [Mn+] = C2 solution [Mn+] = C1 electrode 1

External reference electrode Ion selective electrode

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Construction, working principle and applications of Glass
electrode.
Construction: A glass electrode consists of a long glass tube with a thin
walled glass bulb at one end. This glass can specifically sense hydrogen
ions up to a pH of about 9. The bulb contains 0.1 M HCl and Ag/AgCl
electrode (as internal reference electrode) immersed into the solution
and connected by a platinum wire for electrical contact.
The electrode is represented as:
Ag | AgCl (s) | HCl (0.1M) | Glass

Working principle: A glass bulb containing an acid is immersed in

analyte solution, a potential is developed across the glass membrane.
The potential difference, EB at the interface also referred to as the
boundary potential is the result of difference in potential (E2 - E1) developed across the gel
layer of glass membrane between the two liquids.
The boundary potential, EB can be related to the difference
in the hydrogen ion concentration of the two solutions by
the relation,
RT
EB = E2 − E1 = (ln C2 − ln C1 ) … 1
nF
Where C1 is the concentration of H+ ions of acid solution
inside the glass bulb and C2 is the concentration of the acid
solution into which the glass bulb is dipped.
RT RT
EB = − ln C1 + ln C2 … (2)
nF nF
If the concentration C1 of the solution inside the glass bulb is constant, then the first term on the
R.H.S. of equation (2) is constant. Therefore
RT
EB = constant + ln C2 … . . (3)
nF
Substituting the value of R and F at 298K,
EB = L + 0.0591 log C2 . . … (4)
Where, L is a constant, which depends primarily on the pH of the solution taken in the bulb and
glass electrode assembly.
Since C2 = [H+] of the solution, Equation (4) is written as,
EB = L − 0.0591pH … . (5)
The membrane undergoes an ion exchange reaction; Na+ ions on the glass are exchanged for H+
ions.
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The boundary potential established due to the above reaction is mainly responsible for the glass
electrode potential EG is given by
EG= EB + EAg/AgCl …………. (6)
From equation (1), EB = 0 when C1 = C2. But in practice, it has been observed that even when C1
= C2, a small potential is developed. This is called asymmetric potential (Easy). Hence, Equation
(6) can be written as
EG = EB + EAg/AgCl + Easy
EG = L - 0.0591 pH + EAg/AgCl + Easy
EG = EG0 - 0.0591 pH…………. (7)
Where EG0 is a constant equal to L + EAg/AgCl + Easy
Application of Glass electrode: Glass electrode is used to determine the pH of an unknown
solution

Advantages and limitations of glass electrode.

Advantages of glass electrode:
1. Glass electrode can be employed in the presence of strong oxidizing or reducing
substances and metal ions.
2. It is not poisoned easily.
3. Accurate results are obtained between pH range 1-9. However, by using special glass
electrodes, pH 1-13 can be measured.
4. It is simple to operate, can be used in portable instruments and therefore extensively
used in chemical, industrial, agricultural and biological laboratories.
5. Can be used in colored, turbid and colloidal solutions.
6. Attain equilibrium immediately

Limitations of glass electrode:

1. The glass membrane though it is very thin, it offers high resistance. Therefore, ordinary
potentiometers cannot be used; hence it requires sensitive electronic potentiometers.
2. This electrode cannot be used for solutions for pH less than 1and greater than 9.
3. Fluoride ions attack the glass electrode easily.
4. In strongly acidic solutions of pH<1, the salt effect due to anions is observed.
5. It can be used up to a pH of 13 but being sensitive to Na + ions above a pH of 9, the linear
relationship between glass electrode is altered. So, an alkaline error is introduced
beyond a pH of 9, which should be taken into consideration

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Determination of pH of the solution by using glass electrode
The glass electrode is immersed in a solution of which pH is to be determined. It is combined
with a reference electrode such as a calomel electrode through a salt bridge. The cell assembly
is represented as:
Calomel electrode || Solution of unknown pH | glass electrode
or
Hg | Hg2Cl2 (s) | KCl (sat.) || Solution of unknown pH | glass | HCl (0.1M) | AgCl | Ag(s)

The EMF of the above cell, Ecell is measured using an

electronic potentiometer. Ecell measured is the difference
between potential of glass electrode E G and calomel
electrode (Ecal). The potential developed at the indicator
glass electrode is higher than the reference calomel
electrode (EG > Ecal).

Hence, Ecell = Ecathode - Eanode

= EG -Ecal

Ecell = [EG0 - 0.0591 pH] - Ecal (Since, EG = EG0 - 0.0591 pH)

G 
0
0.0591pH = E ECALECELL
0
E
G E 
CALECELL
Therefore, pH = 0.0591
Where, E0G and Ecal are constants. By substituting Ecell value, pH of an unknown solution is
calculated.
Note: E0G value is evaluated by dipping the glass electrode in a solution of known P H and
measuring EMF of the cell formed when combined with calomel electrode.

CORROSION
Definition: “A process of destruction or deterioration and consequent loss of metal / alloy from
its surface through an unwanted chemical or electrochemical attack by its environment” is
called corrosion.

Electrochemical theory of corrosion taking rusting of iron as an example

When a metal, such as iron, is exposed to the environment, according to electrochemical theory
the following electrochemical changes occur gradually.

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  Anodic and cathodic areas are formed resulting in minute galvanic cells
 Oxidation (corrosion) takes place at the anodic area and electrons are liberated.
 The electrons released at the anodic area migrate to the cathodic area and reduction
takes place.
Step I: Reaction at anodic area
Metal Fe dissolves to give Fe+2 ions and electrons
Fe → Fe+2 + 2e- (oxidation reaction)
Step II: Reaction at cathodic area
Electrons released at the anodic area are conducted to the cathode and are responsible for
various cathodic reactions.
1. Absorption of oxygen (In the presence of oxygen): oxygen in the environment dissolves
in the moisture
a. In acidic medium, H+ ions reduced to H2O
4H+ + 4e- + O2 → 2H2O
b. In neutral or slightly alkaline medium, dissolved oxygen reduced to hydroxyl ions.
O2 + 2H2O + 4e- → 4OH-
Both the reactions involve absorption oxygen.
2. Liberation of hydrogen (In the absence of oxygen):
a. In acidic medium, H+ ions reduced to hydrogen gas
2H+ + 2e- → H2 ↑
b. In neutral or slightly basic medium, moisture reduced to hydroxyl ions
hydrogen gas
2H2O + 2e- → 2OH- + H2 ↑
Both the reactions involve evolution of hydrogen gas.
Step III: Formation of Fe (OH)2
Smaller Fe+2 ions diffuses faster than the larger OH- ions to the cathodic area through the
moisture and converted into insoluble Fe (OH)2. Hence, the corrosion current flows between
the anodic and cathodic areas through conducting media (metal).
Fe+2 + 2OH- → Fe (OH)2

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Step IV: Formation of Rust
a. In the presence of excessive amount of oxygen, Fe (OH)2 is converted into yellow rust
(hydrated ferric oxide), Fe2O3.3H2O.
4Fe (OH)2 + O2 + 2H2O → 2[Fe2O3.3H2O] (yellow rust)

b. In the limited amount of DO, Fe (OH)2 is converted into black rust (ferrouos ferric oxide),
Fe3O4.3H2O.
3Fe (OH)2 + ½ O2 → Fe3O4.3H2O (black rust)

TYPES OF CORROSION
1. Differential metal (galvanic or bimetallic) corrosion
2. Differential aeration corrosion (concentration cell corrosion)–
- a) waterline corrosion
- b) pitting corrosion
3. Stress corrosion - Caustic embrittlement in boilers.

1. Differential metal corrosion with an examples.

Galvanic corrosion is caused when two dissimilar
metals are in contact with each other in a corrosive
environment. The metal with lower electrode potential
or more active metal (higher in galvanic series) acts as
anode and undergoes corrosion. The metal with higher
electrode potential (lower in galvanic series) acts as
cathode and is free from corrosion.
For example, 1) if iron and copper are in contact with each other in presence of an electrolyte
then, iron which is higher in galvanic series (with lower electrode potential) forms the anode
and gets dissolved (corroded), while copper which is lower in galvanic series (with higher
electrochemical potential) acts as cathode and is protected.

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2) when Fe and Zn are in contact with each other, Zn becomes anodic and undergoes
corrosion and Fe remain unaffected.

Corrosion reactions:
At anode: Metal Fe dissolves to give Fe+2 ions and electrons as Fe Fe 2+ + 2e-
At cathode: Depending on the nature of the corrosion environment the cathode reaction may
be either hydrogen evolution or oxygen absorption.
2H+ + 2e- H2↑ or H2O + ½ O2 + 2e- 2OH-

2. Differential aeration corrosion with examples.

Corrosion of metals arising due to difference in oxygen or
air concentration on the metal surface is known as
differential aeration corrosion. The part of the metal
exposed to higher oxygen concentration acts as cathodic
region and part of the metal exposed to lower oxygen
concentration acts as anodic region. Consequently, poorly
oxygenated (anode) region undergoes corrosion.
At the anode (less O2 concentration);
M Mn+ + n e-
At the cathode (more O2 concentration); H2O + ½ O2 + 2e- 2OH-

Examples: Waterline corrosion and pitting corrosion

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Waterline corrosion:
Waterline corrosion is a case of
differential aeration corrosion that
occurs in ocean going ships, water
storage steel tanks, in which a
portion of the metal is always under
water. The part of the metal below
the water line is less aerated while
the part above the water is more
aerated. Thus, part of the metal below the water acts as anode and undergoes corrosion and part
above the waterline is free from corrosion. Rusting is observed along a line just below the level
of the stored water.
At anode Fe Fe 2+ + 2e- (oxidation)
At cathode H2O + ½ O2 + 2e- 2OH- (reduction)
2Fe (OH)2 + ½ O2 + H2O Fe2O3.3H2O (Rust)

Pitting corrosion
Pitting corrosion is a localized corrosion on the small area of the metal surface resulting in the
formation of pits or holes. The pitting corrosion is generally initiated by the deposition of sand,
water drop, dust etc. or due to the breakdown of the protective film. The metal below the deposit
is exposed to lower oxygen concentration acts as anode and the metal surrounding the deposit
acts as cathode since it is exposed to higher concentration of oxygen. Corrosion starts under the
dust resulting in a pit. The pit grows and ultimately may cause failure of the metal.

Corrosion reactions:
At anode Fe Fe 2+ + 2e- (oxidation)
At cathode H2O + ½ O2 + 2e- 2OH- (reduction)

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3. Stress corrosion with example.
Stress in the metals arises during fabrication of the articles or when metal is subjected to
mechanical operations such as riveting, welding, bending, pressing, hammering and servicing.
At the stressed area, the atoms of the metal are at higher energy state as compared to metal
atoms in the stress-free part and have higher oxidation potential. The stressed areas are
attacked even by a mild corrosive environment and undergo corrosion. Metal alloys are more
susceptible to stress corrosion than pure metals. Stress corrosion decreases ductility, increases
brittleness and results in cracking of metal surface, hence this corrosion also called as stress
corrosion cracking (it can take just few minutes to several years to produce the cracks).
Stress corrosion occurs only in the presence of specific corrosive environment (It must be noted
that the presence of both stress and a specific corrosive environment are necessary for stress
corrosion to occur). The corrosive agents are highly specific and selective such are: (a) caustic
alkali and strong nitrate solution for mild steel (b) traces of ammonia for brass (seasonal
cracking of brass) (c) acid chloride solution for stainless steel (d) H2O and NaCl solution for
aluminum alloys (e) chloride ions for zirconium and magnesium alloys.

Caustic embrittlement in boilers.

It is a very dangerous form of stress corrosion, occurring in boilers at high pressure and
temperatures. Boiler-water usually contains sodium carbonate, added for water softening
purposes.

Caustic embrittlement in boiler

Sodium carbonate undergoes hydrolysis to give sodium hydroxide and carbon dioxide and
hence boiler water becomes alkaline.
Na2CO3 + H2O 2NaOH + CO2↑
The alkaline water flows into the cracks present at the inner surface of the boilers due to
capillary action. Eventually the concentration of NaOH in the cracks increases. The boiler
material is thus under two different concentrations of NaOH, higher inside the cracks and dilute
outside. The iron in the main body containing dilute NaOH acts as cathode whereas the iron of
the cracks surrounded by concentrated NaOH behaves as anode. The anodic iron is corroded by
the action of NaOH forming sodium ferroate.
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 Fe + 2NaOH → Na2FeO2 + H2 ↑
Sodium ferroate decomposes as
3Na2FeO2 + 4H2O 6NaOH + Fe3O4 + H2↑
Fe3O4 is precipitated and NaOH is regenerated causing further corrosion.

Note: Caustic embrittlement can be prevented by the addition of compounds such as sodium
sulphate, phosphates, etc., which block the cracks or crevices, thereby preventing the infiltration
of alkali.

Factors affecting the rate of corrosion.

The rate and extent of corrosion, depends the following factors:
a. Relative areas of the anode and cathode: The rate of corrosion at anodic area is directly
proportional to the ratio of cathodic to anodic area. Corrosion is more rapid, severe, and highly
localized, if the anodic area is small and cathodic area is large. Larger cathodic area will demand
for electrons from smaller anodic area. To meet the demand, anode undergoes corrosion more
rapidly. e.g. a small steel pipe fitted in a large copper tank, undergoes rapid corrosion.
b. Nature of the metal: The tendency of a metal to undergo corrosion is dependent on the
nature of the metal. The metals with lower electrode potential are more reactive than metals
with higher electrode potentials. The more reactive metals are more susceptible for corrosion.
Thus, tendency of a metal to undergo corrosion decreases with increase in electrode potential.
Example: The active metals like K, Na, Mg, Zn etc with low electrode potential values are more
susceptible to corrosion. The noble metals like gold, platinum, silver etc with higher electrode
potential are less susceptible for corrosion.
c. Nature of corrosion product and tendency to form protective film (Passivity)
If the corrosion product deposited is insoluble, stable, uniform and nonporous with low ionic
and electrical conductivity, it acts as a protective film preventing further corrosion of metal. For
example, in case of metals like aluminium, chromium, titanium etc. their oxides as corrosion
products form protective films on the metal surface, preventing further corrosion.
If the corrosion product is soluble, unstable, non-uniform and porous with high ionic and
electrical conductivity, the fresh metal surface is exposed for further attack and corrosion of the
metal surface takes place continuously. For example, metals such as iron, zinc, magnesium etc.
oxides do not form any protective film and corrosion is continued.
d. Nature of corroding medium:
* pH of the medium: In general, the rate of corrosion increases with decrease in p H. If pH is lower
than 3, severe corrosion occurs even in the absence of air. This is because in high acidic
solutions, H+ ions consume electrons from anode and liberate hydrogen gas continuously at the

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cathodic region. At pH greater than 10, corrosion of iron practically ceases due to the formation
of a protective coating of hydroxides of iron. Ex: ships submerged for hundreds of years in ocean
remain almost unaffected. Between pH 10 and 3, presence of oxygen is essential for corrosion
of iron at this pH range.
* Conductance of the medium: The rate of corrosion in dry atmosphere is less than that in wet
atmosphere since the latter is more conducting. Iron undergoes corrosion faster in clay than in
sandy soil. In the marine atmosphere, sodium and other chlorides (of sea water) increase the
conductivity of the liquid layer in contact with the metal surface, and enhance the corrosion rate.
* Temperature: In general, the rate corrosion is directly proportional to temperature. Increase
in temperature increases the conductance of the aqueous medium and results in increase in the
diffusion rate and hence corrosion progress faster at higher temperatures. In some cases, a
passive metal may become active at higher temperature, which again leads to an increase in the
corrosion rate.
Note:
a) Polarization – It is defined as “A process in which there is a variation in electrode potential
due to slow supply/insufficient supply of ions from the bulk of the solution to the electrode”.
b) Decomposition potential – It is defined as “the minimum voltage which must be applied
between the two electrodes immersed in the given electrolytic solution so as to bring about
continuous electrolytic decomposition”.
c) Over voltage/Over potential – It is defined as “the excess voltage that has to be applied above
the theoretical decomposition potential to start electrolysis”.
e. Hydrogen overvoltage: Hydrogen overvoltage is the measure of the tendency of the electrode
(cathode) to liberate hydrogen gas. A metal with low hydrogen overvoltage on its surface is
more susceptible for corrosion, when the cathodic reaction is hydrogen evolution type. With
lower hydrogen overvoltage, hydrogen gas is liberated easily and thus the cathodic reaction rate
is faster. This will make the anodic reaction also faster, thereby promoting overall corrosion
reaction. When the hydrogen overvoltage on the metal surface is high, cathodic reaction is
slower and the corrosion of the metal also becomes slower.
f. Polarization at anodic and cathodic region: During the process of corrosion, the polarization
of anode or cathode decreases the corrosion rate substantially. Metal ions liberated at anode
cannot move freely towards cathodic area because of opposing factors like lower conductivity
and higher resistance of the medium. Thus metal ions get concentrated at anodic area. This
increases the potential of anode and decreases the rate of oxidation. Similarly, due to insufficient
movement of hydroxyl ions formed at cathodic area towards anodic area, their concentration
increases. Hence, due to increase in concentration of hydroxyl ions, potential of cathode area
decreases. This decreases the rate of reduction. Thus, higher the polarization at anodic and

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cathodic area, lower will be the difference in potential between anodic and cathodic area and
hence lower will be the rate of corrosion. With increase in polarization of anode and cathode,
the rate of corrosion decreases.

Corrosion Penetrate Rate (CPR) / Corrosion rate measurement

Corrosion rate is a quantitative expression for a material’s corrosion behavior and it is defined
as speed at which any given material corrodes at a particular environment. To know the
corrosion rate is a prime importance for all kind of engineering applications so that we can
determine the life span of metal based structures and gives an idea to use different metals in
different environmental conditions for desired applications also to take necessary precautions
to avoid from getting corrosion. The corrosion rate can be expressed in different ways such as
percent weight loss, milligrams per square centimeter per day, and grams per square inch per
hour. From an engineering point of view finding the corrosion rates in terms of penetration or
thinning of a structural object is very useful. The above mentioned expressions are unable to
give corrosion rate in terms of penetration or thinning of a structural object. The most
convenient way of expressing corrosion rate is mils per year (mpy) or millimeter per year
(mm/y). The measurement ‘mil’ is used particularly in US. 1 mil is equal to 0.001inches or
approximately equal to 0.0254mm or 25.40µm. In this research work for convenience corrosion
rate is measured in mm/y.
The corrosion rate for any metal can be calculated using the formula
W
mpy or mm/y = K ×
DAT

Where
W – Weight loss of metal in mg
D – Density of a metal in g/cm3 (D or ρ)
A – Area of metal in cm2
T – Exposure time in hour

W W
mpy = 534 × DAT & mm/y = 87.6 × DAT

In industries the selection of metals based on their corrosion rates that is given in the
Table 1 below and the table is based on some ferrous and nickel based alloys
Relative corrosion resistance Corrosion rate in terms of Corrosion rate in terms of
mpy mm/y
Outstanding ˂1 ˂0.02
Excellent 1-5 0.02-0.1
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 Good 5-20 0.1-0.5
Fair 20-50 0.5-1
Poor 50-200 1-5
Unacceptable ˃200 ˃5

Corrosion control
At present number of methods are invented to control corrosion, only few are discussed
below
1) Cathodic Protection
Example: Sacrificial anodic method and Impressed current method
2) Chemical conversion coatings
Example: Anodizing (anodizing of Aluminium) & Phosphating

Cathodic protection
Definition: Cathodic protection is defined as a method of protecting a metal or alloy from
corrosion by converting it completely into cathodic. Cathodic protection can be achieved by the
following methods: (i) Sacrificial anode method (ii) Impressed current method.
Sacrificial anode method: In this corrosion control
method, the metallic structure to be protected is
connected to a more active metal with an insulated
copper wire. Thus, the metal structure acts as
cathode and more active metal acts as anode.
The more active metal itself gets corroded slowly;
while the metal structure (cathodic) is protected.
The more active metal so-employed is called sacrificial anode. The corroded sacrificial anode
block is replaced by a fresh one, when consumed completely. Metals commonly employed as
sacrificial anodes are Mg, Zn, Al and their alloys.
Important applications of sacrificial anodic method include protection of buried pipelines,
underground cables, marine structures, ship-hulls, water-tanks, etc.

Impressed current method: In this corrosion

control method, the metal to be protected is
made as cathode by connecting it to negative
terminal of a D.C battery or rectifier. Graphite,
high silicon iron, stainless steel or platinum is
used as inert anode by connecting it to positive

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terminal. The electrons supplied from the negative terminal of the D.C battery convert the
corroding metal from anode to cathode and prevents corrosion. This type of cathodic protection
has been applied to open-box coolers, water-tanks, buried water pipes, condensers, transmission
line towers etc.

Metal finishing
Definition: The term metal finishing is a process carried out in order to change the surface
properties of metal by deposition of layer of another metal or a polymer or by the formation of
an oxide film. Electroplating and Electroless plating are the important metal finishing techniques.
Technological importance of metal finishing:
 To offer corrosion resistance.
 To give decorative surface.
 To impart hardness, abrasion resistance, wear resistance, thermal resistance and impact
resistance.
 To provide electrical or thermal conduction.
 To offer the surface a thermal or optical reflectivity.
 To provide thermal insulating properties.
Some Important techniques of metal finishing are electroplating of metals/alloys, electroless
plating of metals/alloys, Immersion plating of metals, chemical conversion coatings and
electrophoretic painting etc.

Electroplating (electrodeposition) and its Mechanism.

Definition: Electroplating is the deposition of metal, by

electrolysis, over the surface of a substrate which may be another
metal, polymer, ceramic or a composite.
Electroplating is achieved by passing an electrical current through
a solution containing dissolved metal ions and the metal object to
be plated. The metal object serves as the cathode in an
electrochemical cell, attracting metal ions from the solution. Ferrous and non-ferrous metal
objects are plated with a variety of metals, including aluminium, tin, bronze, cadmium, copper,
chromium, lead, nickel, zinc etc.,
Mechanism of electroplating:
 Metal to be deposited is made as anode (except chromium, chromium is not used as
anode). Article to be coated is made as cathode.

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  Anode & cathode are connected to a battery, the positive pole of the battery is connected
to a metal to be deposited and negative pole of the battery connected to the article to be
coated.
 A metallic solution of the metal to be deposited is electrolyzed to have a uniform coating
of the metal on cathode.
 When electrolysis is carried out, the anode dissolves into electrolytic bath and metal
ions from the bath gets deposited as pure metal over the cathode (article).

The electrolyte MA ionizes as

Electrolysis
MA M+n (aq)+An- (aq)
Electrolyte

At the anode, electrode dissolves giving raise to metal ions

M → M+n+ne- (At anode)

At the cathode, metal ions get reduced and are deposited as metal atoms
M+n + ne- → M (At cathode)
Electroplating of chromium
Chromium
Decorative chromium Hard chromium
plating
Insoluble anodes- Pb-Sb or Pb- Insoluble anodes- Pb-Sb or Pb-
Anode
Sn coated with PbO2 Sn coated with PbO2
Cathode Object to be plated; pretreated Object to be plated; pretreated

Electrolyte (bath Chromic acid (CrO3 and H2O) Chromic acid (CrO3 and H2O)
composition) and H2SO4 in 100:1 proportion and H2SO4 in 100:1 proportion

Operating
45-550C 43-660C
temperature
Current density 100-200 mAcm-2 215-430 mAcm-2
Current
8-12% 10-15%
efficiency
Provides decorative, durable
and corrosion resistant finish Extensively used in industrial
Application
to automobile parts, surgical and engineering applications
instruments.
Need to reoxidise Cr(III)
Limitations Hard, wear-resistant deposit
formed. Poor throwing power

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Reactions:
At cathode: Plating bath contains chromic acid (Chromium trioxide and water) in which Cr is
present in +6 state. During electroplating of chromium, Cr(VI) is reduced to Cr(III) in the
presence of SO42- catalyst (furnished by sulphuric acid). Cr(III) is reduced to Cr(0), which gets
deposited on the article.
Formation of chromic acid by the reaction of chromium trioxide with water
CrO3 + H2O  H2CrO4 (  CrO42- + 2H+)
(+6 oxdn state) (+6 oxdn state)

Chromic acid is in equilibrium with dichromic acid

2H2CrO4 ⇄ H2Cr2O7 + H2O ( Cr2O72- + 2H+ + H2O)
(+6 oxdn state)

in presence of catalyst SO42- Cr in +6 oxidation state is reduced to +3

oxidation state
Cr2O72- + 14H+ + 6e-  2Cr3+ + 7 H2O
(+6 oxdn state) (+3 oxdn state)

Cr(III) is reduced to Cr(0), which gets deposited on the article.

Cr3+ + 3e-  Cr
Note: Chromium anodes are never used in Cr plating due to the fact that Cr metal passivates
strongly in acid sulphate medium. Moreover, chromium anode gives rise to Cr3+ ions on dissolution,
which leads to the formation of black Cr deposit.

Electroless plating and its advantages

Definition: Electro less plating is the controlled deposition of a continuous film of a metal from
its salt solution on to a catalytically active surface by a suitable reducing agent without using
electrical energy. The reducing agent brings about the reduction of the metallic ions to the metal
which gets plated over a catalytic surface.

catalyst surface
Metal ion + Reducing agent Metal + Oxidized product

Advantages:
 Use of electrical power and electrical contacts are eliminated.
 Semiconductors and insulators like plastics can also be plated.
 Electro less baths have better throwing power. Intricate parts with irregular shapes,
inside parts of tubes, recesses can be uniformly coated.
 Hydrogen gas liberated is not trapped in blind holes.
 Electro less coating is harder than that produced by conventional electroplating.
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  No levelers are required.
 Resulting deposits have unique chemical, mechanical and magnetic properties.

Electroless plating of copper. Manufacture of double-sided printed circuit board with

copper and its applications.
Pretreatment and activation of the surface: The surface to be treated is degreased, etched in
acid and activated by dipping first in stannous chloride and then in palladium chloride.
Composition and conditions of plating bath solution:
Electrolyte : Copper sulphate (12 g/dm3).
Reducing agent: : Formaldehyde (8 g/dm3).
Buffer : Sodium hydroxide (15 g/dm3) + rochelle salt
(potassium sodium tartarate, KNaC4H4O6.4H2O) (14g/dm3).
Complexing agent : EDTA (20 g/dm3).
pH : 11
Temperature : 250C
Rate of plating : 1 to 5 μm h-1.

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

catalyst surface
Overall reaction: Cu2+ +2HCHO+4OH- Cu+2HCOO- +2H2O+H2

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An important application of electro less copper plating is printed circuit boards (PCB). In double
side and multilayer boards where plating-through holes is required,
electro less technique is the best since the holes cannot be
electroplated.
The steps involved are as follows:
 Initially, the base object, plastic board is degreased and
etched in acid.
 The plastic board is then partially covered with copper foils
(copper clad board).
 The copper clad board is printed with the required pattern of
the circuit.
 On etching, copper below the printed pattern is etched
away, leaving behind the circuit pattern.
 The connection between 2 sides of PCB is made by drilling
holes, activation (treating the board with SnCl2 containing
HCl and PdCl2), followed by plating through holes by
electroless plating.
 The activated board is immersed in plating bath maintained at
25 ºC (room temperature).
 Plating is carried out at a rate of 1–5 μm/h, till a thickness
of 5–100 μm is obtained.

Applications of electroless plating

 Widely used for metalizing printed circuit boards.
 For producing through hole connections
 For plating on non-conductors
 As a base for subsequent conventional electroplating
 Applied on wave guides and decorative plating on copper

Differentiate between electroplating and electroless plating.

Parameter Electroplating Electroless plating
Driving force Passage of current Auto catalytic redox reaction
Site for Anodic A separate anode is used Catalytic surface of the
reaction substrate acts as anode
Anode reactant Pure metal (M) Reducing agent
Anode reaction M ⟶ M + ne
n+ - Reducing agent⟶Oxidation
product + ne

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 Site for Cathodic Object treated to remove Object treated to make the
reaction surface impurities surface catalytically active
Cathodic reaction Mn+ + ne- ⟶ M Mn+ + ne- ⟶ M
Throwing power Throwing power is not Throwing power is satisfactory
satisfactory for intricate parts irrespective of the shape and
with irregular shape and inside inaccessibility of the parts.
of tubes
Nature of the Pure metal or alloy Metals with reducing agents
deposit and oxidized products as
impurities
Applicability Applicable only to conductors Applicable to both conductors
and non-conductors

Chemical conversion coatings (Inorganic coatings)

Coatings in which surface of the metal is converted in to its compounds, which in turn acts as
barrier between the underlying metal and corrosive environment and protect the metal from
corrosion are called Chemical conversion coatings. Examples anodizing and phosphating.
Anodizing: It involves the electrolytic oxidation of metal surface to produce a tightly adherent
& durable oxide scale by passing electric current through an electrolyte to impart more
protection against corrosion. Anodized coating is generally produced on non-ferrous metals like
Al, Zn, Mg and their alloys.

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Anodising of Aluminium is carried out by electrolysis in a suitable acid electrolyte
(sulphuric, chromic, oxalic or phosphoric acid) at
moderate temperature (35-40 0C) and moderate
current densities (10-20 mA cm-2). Aluminium is
made as anode and a plate of lead or stainless steel is
made as cathode. The coating forms as a result of
progressive oxidation, starting at the aluminum
surface. When current is passed the oxygen liberated
at anode combines with it to form oxide which takes
the form of thick film. The outer part of the oxide film
formed may be slightly porous and it is sealed by dipping in boiling water. This treatment
converts porous alumina at the surface of coating into its monohydrate (Al 2O3.H2O),
which occupies more volume, there-by the pores are sealed.
Applications: It is used providing attractive, highly durable exteriors, roofs, ceilings,
floor, lobbies, escalators and staircases.

Phosphating
Phosphating is the process of depositing a coating of metal phosphate on metal surface.
It is obtained generally on iron, steel or zinc surface by converting the surface metal
atoms into their phosphates by chemical or electrochemical reactions. Phosphating
improves corrosion resistance and also imparts the surface a good paint adhesion quality.
The Phosphating bath contains three essential components:
 Free phosphoric acid
 A primary metal phosphate like Fe, Mn and Zn phosphates and
 An accelerator such as nitrates, nitrites, chlorates, H 2O2 etc.

The pH is usually within the range 1.8-3.2 and temperature 35 0C. The reactions include
dissolution of metal as ions, forming a phosphate with the bath solution which
subsequently gets deposited on the surface of the metal. Originally phosphate coating was
applied only on iron and steel. But now it has been extended to Zn, Al and their alloys.

Applications: Phosphate coating is the first layer applied in the production of

corrosionresistant automobile parts. It is used in steel sheet fabrications such as
refrigerators and washing machines. Phosphate coatings are used mainly as base
for paints and impart good paint adhesion quality to the surface of a metal.
Phosphating of galvanized iron eases painting on its surface.
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Additional information
Electrochemical series or
Electromotiveforce(EMF) series Galvanic Series

is an orderly listing of standard half-cell is an orderly listing of corrosion potential

electrode potential. for different metals and alloys
Electrode potentials are measured by This series was developed by studying
dipping pure metals in their salt corrosion of metals and alloys in
solution of 1M concentration, without unpolluted sea-water, without their
any oxide films on them. oxide films, if any removed.
The position of a metal in electro- The position of a given metal may shift in
chemical series is fixed. galvanic series.
It gives no information regarding Since alloys are included in galvanic
positions of alloys series, so their corrosion can be studied
from this series.
The position of a metal in this series is The position of a metal, when present
permanently fixed in the form of an alloy is different
from that of pure metal.
This series comprises of metals and non- This series comprises of metals and
metals alloys
It predicts the relative displacement It predicts the relative corrosion
tendencies tendencies
It is absolute and quantitative It is relative and qualitative
it is a series only for pure metals and It is a series for pure metals and alloys
used for theoretical calculations. also and used for practical
applications.

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Figure 1 Figure 2

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