UNIT ELECTROCHEMICAL CELL AND CORROSION

UNIT-II ELECTROCHEMICAL CELLS AND CORROSION

Electro chemical cells: Electro chemical cell is a device, which converts chemical energy into electrical
energy, and electrical energy into chemical energy.
● Oxidation and reduction reaction takes place in electrochemical cells for the generation of
electrical energy.
There are two types of electro chemical cells,
1.Galvanic (or) Voltaic cells: These are devices which convert chemical energy into Electric energy.
These reactions are spontaneous.
2.Electrolytic cells: These are the devices in which electrical energy is converted into chemical energy.
These are non-spontaneous reactions.
● Both types of cells contain electrodes where the oxidation and reduction reactions occur.
Oxidation occurs at anode (-ve) and reduction occurs at cathode (+ve).

SINGLE ELECTRODE POTENTIAL

The tendency of an electrode to gain or lose electrons when it is contact with its own ions in solution
is called electrode potential. It is denoted by ‘E’.
Electrode potential depends upon the,
1. Nature of the metal or non-metal.
2. Concentration of the electrolyte.
3. Temperature of the electrolyte solution.
4. Pressure in case of gas electrode.

The potential of an electrode measured as standard conditions of 25 0C temperature, 1 atm. Pressure and
using ions at unit concentration is known as standard electrode potential. It is denoted by “E 0”. Standard
electrode potential is also known as single electrode potential.

The tendency of an electrode to gain electrons or to get reduced is called its reduction potential.

Cu+2 + 2e- ……. Cu

The tendency of an electrode to loss electrons or to get oxidised is called oxidation potential.

Zn …….. Zn+2 + 2e-

The reduction potential of an electrode measured at 25 0C, 1 atm, 1M. electrolyte concentration is called
standard reduction potential.
For any half cell , the standard reduction potential = - ( standard oxidation potential).

Ex: Zn+2 + 2e- …… Zn, the standard reduction potential is – 0.76 v.

Zn …… Zn+2 + 2e- , the standard oxidation potential is + 0.76 v.
 UNIT ELECTROCHEMICAL CELL AND CORROSION
ELECTROCHEMICAL SERIES:
When various metals as electrodes are arranged in the order of their increasing values of standard
reduction potential on the hydrogen scale, then the arrangement is called electrochemical series.
Li+, K+, Ca+2, Na+, Mg+2, Al+3, Zn+2, Cr+3, Fe+2, Co+2, Ni+2, Sn+2, Pb+2, H+1, Cu+2, Ag+1, Hg+2, Pt+2,
Au+3.

Reaction
0
Electrode Electrode Reaction Potential (E
Values)
Volts
+ - -3.01
Li /Li Li+ e  Li
2+ 2+ - -2.37
Mg /Mg Mg + 2e  Mg
2+ 2+ - -1.12
Pb /Pb Pb + 2e  Pb
2+ 2+ - -0.76
Zn /Zn Zn + 2e  Zn
2+ 2+ - -0.44
Fe /Fe Fe + 2e  Fe
2+ 2+ - -0.13
Sn /Sn Sn + 2e  Sn
+ + - 0.00
H /H H +e H
Cu+2/Cu Cu+2 + 2e- -🡪 Cu + 0.34
+ + - +0.80
Ag /Ag Ag + 2e  Ag
+ + - +1.50
Au /Au Au + e  Au

Electrochemical series
Significance and applications of electrochemical series
1. Calculation of standard EMFof a cell
Standard electrode potential of any cell can be calculated using this series.
2. Relative ease of oxidation and reduction
Higher the value of standard reduction potential (+ve value) greater is the tendency to get reduced.
Thus, metals on the top having more negative (–ve) values are more easily ionized (oxidized).
3. Displacement of one element by another
Metals which lie higher in the series can displace those elements which lie below them in the
series.
4. Determination of equilibrium constant for the reaction
 UNIT ELECTROCHEMICAL CELL AND CORROSION
The equilibrium constant for the cell can be calculated from the standard electrode potential.
5. Hydrogen displacement behaviour
Metals having more –ve potential in the series will displace hydrogen from acid solutions.

6. Predicting spontaneity of redox reactions

Spontaneity of redox reaction can be predicted from the standard electrode potential values of the
complete cell reaction.

STANDARD HYDROGEN ELECTRODE .

An electrode whose electrode potential is known is called standard electrode. These are also called
as Reference electrodes.
To determine the electrode potential of Zn electrode, zinc rod is dipped in ZnSO 4 solution, it will
combine with standard hydrogen electrode. Then the following reactions,

At anode (- ve): Zn …….. Zn+2 + 2e- ( Oxidation )

At cathode (+ ve) 2H+ + 2e- ……. H2 ( Reduction )

Cell reaction: Zn + 2H+ ……. Zn+2 + H2.

Cell representation: Zn/ Zn+2 (aq) // H+ (1M) / H2 (1 atm),Pt.

So, E cell = E cathode – E anode.

E cell = E H+/H2 – E Zn+2/Zn
E cell = – E Zn+2/Zn (E H+/H2 = 0)

Therefore, when standard hydrogen electrode is connected with another electrode, the voltage of the cell
thus formed will evidently be equal to the potential of electrode connected.
The best reference electrode is standard hydrogen electrode. Important reference electrodes are,

1.HYDROGEN ELECTRODE ( Gas electrode):

Construction: It consists of a small platinum foil coated with platinum black which absorbs hydrogen gas.
A platinum wire welded to the electrode. The electrode is sealed with a glass tube. The platinum foil is
surrounded by an outer glass tube having an inlet at the top to H2 gas, and the number of holes at the base,
the electrode is placed in 1M. solution of HCl. Pure H2
 UNIT ELECTROCHEMICAL CELL AND CORROSION

gas is passed at 1 atm. Pressure through the inlet of the glass tube.
A small amount of the gas is absorbed by the Platonized electrode, while the remaining escapes through
the lower holes provided at the base of the glass tube.
Working: when this hydrogen electrode acts as anode following reactions takes place.
H2 ……. 2H+ + 2e- (Oxidation)
That means, hydrogen gas is converted into H+ ions and discharged into the solution. On the other hand,
When this hydrogen electrode act as cathode following reaction takes place.
2H+ + 2e- ……… H2 (Reduction)
That means some H+ ions from the solution are converted into H2 gas.Thus hydrogen electrode is
reversible with respect to H+ ions. This Electrode is represented as, Pt, H2 (1 atm) / H+ (1M).

Limitations: 1. It is readily affected by compounds of Hg, As,S and oxidizing agents (Fe+3, KMnO4-).
2. It can’t be used in the presence of ions of many metals.

2. CALOMEL ELECTRODE (metal-metal salt ion electrode):

Construction: It consists of mercury, solid mercurous chloride and KCl solution. Hg is placed at the
bottom of a glass tube with a side tube on both the sides.it is connected to the outer circuit by means of a
Pt wire sealed in a glass tube. The surface of mercury is coveredwith a past of Hg 2Cl2 (calomel). A
saturated normal and deci-normal KCl solution is introduced through the side tube present in the right
side.
 UNIT ELECTROCHEMICAL CELL AND CORROSION

Working: when this electrode acts as anode the following reactions takes place.
2 Hg (s) ……… Hg2+2 + 2e- (Oxidation)

Then these ions combine with chloride ions (KCl) to form

Sparingly soluble mercurous chloride.

Hg2+2 + 2Cl- …….. Hg2Cl2 (s)

When this electrode acts as cathode the following reaction takes place.

Hg2Cl2 (s) ……… Hg2+2 + 2Cl- (Reduction)

Then these mercurous ions discharges at the electrode as mercury.

Hg2+2 + 2e- ……… 2 Hg (l).

Thus calomel electrode is reversible with respect to ions. this electrode is represented as,
Hg, Hg2Cl2 (s) ; KCl (solution).

The potential of the calomel electrode depends upon the concentration of the KCl solution. It can be
determined accurately by connecting the electrode to standard hydrogen electrode.
Electrode potential of calomel electrode at different concentration of KCl at 24 0C. are,

For 0.1 N. KCl solution E = -0.3338 v.

For saturated KCl solution E = -0.2415 v.

CONCENTRATION CELLS:

It is a galvanic cell in which electrical energy is produced by the transfer of substance from the one
electrode having higher concentrated solution to other electrode having lower concentration solution. It
 UNIT ELECTROCHEMICAL CELL AND CORROSION
is made up of two half cells having identical electrodes, identical electrolyte, except that the
concentration of the reactive ions at the two electrodes are different. The two half-cells are joined by a
salt bridge or a semi-permeable membrane.

Cell representation for a concentration:

M / Mn+ (C1) // Mn+ (C2) / M.
Where C1 and C2 are the concentration of the active metal ions in contact with the two electrodes
respectively,
Concentration cells are of two types, 1. Concentration cell with out transfer.
2. Concentration cell with transfer.
1. Concentration cell with out transfer: when two hydrogen electrodes of different gas pressures P 1 and
P2 (P1 > P2) are immersed in the same solution of hydrogen ions, oxidation of H takes place at left hand
electrode and reduction of hydrogen ions at the right hand electrode as shown below,
Cell representation: Pt, H2 (P1) : H+ // H+ : H2 (P2), Pt.
Left side right side
Electrode reactions:
H2 (P1) ……. 2H+ + 2e- (Oxidation)

2H+ + 2e- …… H2 (P2) (Reduction)

H2 (P1) ……. H2 (P2) (net reaction)

From the above net reaction it is known that, there is no overall chemical change and there is only a
transfer of hydrogen gas from the electrode with pressure P1 to the electrode with pressure P2. In this case
the emf of electrode depends only on the two pressures and is independent of the concentration of
hydrogen ions in which electrodes are immersed.

E cell = RT /nF log P1 / P2 ( since E0 = 0 )

2. Concentration cell with transfer: In this electrodes are identical but electrolyte solution has different
concentrations. Due to difference in the concentration of electrolyte there occurs corresponding change in
the potential of the electrodes dipping in them. The electrical energy in the concentration cell arises from
the transference of substance from the solution of the higher concentration to the solution of lower
concentration the two half cells are joined by salt bridge.
When a metal or electrode is immersed in a solution of its own ions, then a potential is generated in
the cell. But the potential value varies with the concentration of ions (C).

The Nernst equation E = E0 + 0.0592 / n log C

When the two electrodes of same metal (M) with different concentration of C1 and C2 (C2 > C1) of its own
ion solution are dipped and connected with a salt bridge, the following reactions takes place.

M …….. M n+ (C1) + ne- ( Oxidation )

M n+ (C2) + ne- ……… M ( Reduction )

M n+ (C2) ……… M n+ (C1) ( Net reaction )

 UNIT ELECTROCHEMICAL CELL AND CORROSION

Cell representation: M : M n+ (C1) // M n+ (C2) : M

Left side right side

Nernst equation for electrodes are,

E right = E0 + 0.0592 / n log C2 and E left = E0 + 0.0592 / n log C1

E cell = E right - E left

= (E0 + 0.0592 / n log C2 ) - ( E0 + 0.0592 / n log C1)

= (E0 - E0) + 0.0592 / n log C2 / C1

= 0.0592 / n log C2 / C1

From the above equation it is clear that, the emf of the cell developed is mainly due to the transfer of
metal ions from the solution of higher concentration (C2) to the solution of lower concentration (C1).

GLASS ELECTRODE:
A glass electrode is a type of ion selective electrode consists of a thin walled glass bulb attached to a
glass tube. A very low melting point and high electrical conductivity glass is used for the construction
of this bulb. The glass tube contains a dilute solution of constant pH of HCl (0.1 N) solution. A silver-
silver chloride electrode or platinum wire is immersed as reference electrode in the HCl solution. The
working of glass electrode is based upon the observation that when a glass surface is in contact with a
solution, there exists a potential difference between the glass surface and the solution, the magnitude of
+
which depends upon the H ion concentration of the solution and the nature of glass. The glass
electrode may be represented as
≈
Ag, AgCl(s) | 0.1 N HCl | glass | H = unknown
The electrode potential of the glass electrode depends upon the
≈
concentration of H ions contained in the experimental solution and is given
by
E0 g is the standard electrode potential i.e. the potential of the glass electrode when the
g
≈ 0
solution contains unit concentration of H ions. The value of E depends on the nature of
the glass used in the construction of the glass bulb.

The pH of the solution can be determined if the potential of the glass electrode is known. To
determine the value of glass electrode (Eg), the glass electrode is combined with a reference electrode
such as calomel electrode. The EMF of this
 UNIT ELECTROCHEMICAL CELL AND CORROSION

cell will be given by

EC is the electrode potential of calomel electrode and is constant for a particular concentration of HCl
solution. Thus, measuring the EMF of the cell using experimental solution, the pH of the solution can
be calculated.
The commercial pH meters are based on potentiometric circuits capable of measuring the EMF of
cell consisting of the glass electrode and reference electrode and indicate the pH of solution directly
in a digital display.
There are different type of pH glass electrode and almost all electrodes are working in the most
popular pH range from pH = 1 to pH = 12.

BATTERIES:

Battery is a device consisting of one or more electrochemical cells. That convert stored chemical
energy into electrical energy. These batteries are used as source of DC power.

Batteries are classified as follows,

I) Primary battery
ii) Secondary battery
iii) Fuel battery or Flow battery
Primary battery:
Primary battery is a cell in which the cell reaction is not reversible. Thus, once the
chemical reaction takes place to release the electrical energy, the cell gets exhausted. They
are use and throw type.
Example: Dry cell (Laclanche cell) etc.
Secondary battery:
Secondary battery is a cell in which the cell reaction is reversible. They are rechargeable
 UNIT ELECTROCHEMICAL CELL AND CORROSION
cells. Once the battery gets exhausted, it can be recharged.
Example: Nickel-Cadmium cell, Lead-acid cell (storage cell), etc.
Fuel battery or Flow battery:
Flow battery is an electrochemical cell that converts the chemical reaction into electrical
energy. When the reactants are exhausted, new chemicals replace them.
Example: Hydrogen-oxygen cell, Mthyl alcohol-oxygen cell, etc.

DRY CELL: A cell without fluid component is called as dry cell.

Construction and working:
The anode of the cell is zinc container containing an electrolyte consisting of NH4Cl,
ZnCl2 and MnO2 to which starch is added to make it thick paste-like so that is less likely to
leak. A graphite rod serves as the cathode, which is immersed in the electrolyte in the centre
of the cell.
The electrode reactions are given below.
2+ -
Anodic reaction: Zn (s) ———> Zn (aq) + 2e (Oxidation)
- –
Cathodic reaction:
2 2
2MnO2 (s) + H2 O2 + 2e ———> MnO (s) + 2OH (aq) (Reduction)
Overall reaction: Zn(s) + 2MnO2 (s) + H2O ———> Zn+2 + Mn2O3 + 2OH-
+ -
Reaction between NH 4
4 (from NH4Cl) and OH formed at cathode evolves NH3 gas which disturbs the
2 2
current flow. This is prevented by the reaction of NH3 with Zn+2 to form complex [Zn(NH3)2 Cl2]
+ -
NH4
4 (aq) + OH ———> NH3 (g) + H2O (l)
3

Zn+2 + 2 NH3 + 2 Cl- ———> [Zn(NH3)2 Cl2] (s)

The reaction involved in the dry cell can not be reversed by passing electricity back through the
cell.hence dry cell is a primary cell.

Matal cap (positive) Insulating washer

Collar to keep rod in

Zinc cup (negative)

Mixture of manganese (iv) oxide. graphite,
ammonium chloride and zinc chloride Carbon rod

Metal cover (negative)

Advantages: Low price, gives voltage of about 1.5v. and non-toxic.

Applications: Dry cell is used in consumer electronic devices like calculators, Transistor radios, Flash
 UNIT ELECTROCHEMICAL CELL AND CORROSION
lights, Quartz wall clocks, Walkmans etc.

NICKEL – CADMIUM CELL:

A nickel – cadmium storage cell consists of Cadmium as anode and NiO2 paste as
cathode and KOH as the electrolyte.
The cell is represented as: Cd | Cd(OH)2 || KOH (aq) | NiO2 | Ni
Construction and Working:
2+
When the nickel battery operates, Cd is oxidized to Cd ions at anode and the insoluble
2+ -
Cd(OH) is formed. NiO is reduced
2
to Ni ions which further combines with OH ions to form Ni(OH) .
2
It produces about 1.4 V. The following cell reactions occur.
- -
Anodic reaction: Cd (s) + 2OH
2
———> Cd(OH) (s) + 2e
- -
Cathodic
2
reaction:
2
NiO (s) + 2H O + 2e ———> Ni(OH) (s) + 2OH
Overall cell reaction during discharging:
Cd (s) + NiO2 (s) + 2H2O ———> Cd(OH)2 (s) + Ni(OH)2 (s) + Energy
From the above cell reactions, it is clear that Cd(OH)2 and Ni(OH)2 are deposited at
both the anodes and cathodes respectively. So, this can be reversed by recharging the cell.
Overall cell reaction during recharging:
The cell can be charged by passing electric current in the opposite direction. The
electrode reactions get reversed. As a result, Cd is deposited on the anode and NiO2 on the
cathode.
Cd(OH)2 (s) + Ni(OH)2 (s) + Energy ———> Cd (s) + NiO2 (s) + 2H2O

Advantages of Ni-Cd battery:

1. It is portable and rechargeable cell.
2. It has longer life than lead – acid battery.
3. It can be easily packed like dry cell since it is smaller and lighter.

Uses:
1. It is used in calculators.
2. It is used in gas electronics flash units.
3. It is used in transistors, cordless electronic appliances, etc.

NICKEL METAL HYDRIDE BATTERIES (NiMH):

The NiMH batteries are related to sealed Ni-Cd batteries and the only difference is instead of
cadmium hydrogen is used as the active element at the anode. The components of NiMH batteries include
 UNIT ELECTROCHEMICAL CELL AND CORROSION
a cathode of nickel hydroxide, an anode of hydrogen absorbing alloys of Lanthanum and rare earths that
serves as solid source of reduced hydrogen and the electrolyte is alkaline KOH. The cell voltage is 1.2v.
Anode reaction: M + H2O + e- …….. MH + OH-
Cathode reaction: Ni(OH)2 + OH- ……. NiOOH + H2O + e-
Net reaction: M + Ni(OH)2 ……… MH + NiOOH
Advantages:
1. These are 50% more energy density then Ni-Cd battery.
2. More cycle life.
3. Environmentally friendly.
4. Wide operating temperature range.
Disadvantages: low cell voltage only 1.2 v, high self discharge and
deterioration of battery during long time storage.
Applications: NiMH batteries are in low cost consumer appliances,
Electric razors, tooth brushes, cameras, mobile phones, medical instruments
And automotive batteries.

LITHIUM BATTERIES: Lithium batteries are two types.

a). Solid lithium batteries. b). Lithium ion batteries (Re-chargeable)

a). Solid lithium batteries: One of the most common lithium primary batteries is Lithium-manganese
dioxide (Li-MnO2) battery. In this battery solid lithium act as anode and MnO 2 acts as cathode. The
mixture of propylene carbonate and 1.2-dimethoxy ethane containing dissolve salt such as LiClO 4 acts as
electrolyte. The cell reactions are as follows.

At Anode: Li ……. Li+ + e-

At cathode: MnO2 + Li+ + e- …… MnO2 (Li)
Net reaction: Li + MnO2 ……… MnO2 (Li).
Applications:
1. Cylindrical Li-batteries are used in automatic cameras.
2. Coin type cells are used in electronic devises like calculators and watches.

b). Lithium ion batteries (Re-chargeable):

These cells do not contain metallic lithium hence they are called lithium ion cells and use lithium
ions instead. In these cells actually oxidation and reduction reactions does not takes place, but transport of
Li+ ions through the electrolyte from one electrode to other electrode takes place through the external
circuit to maintain charge balance.
In this battery, lithium ions inter change between two layers of graphite and LiCoO 2. When the cell
is charging, lithium ions leave LiCoO2 and travel through the electrolyte to the graphite (C6).
 UNIT ELECTROCHEMICAL CELL AND CORROSION
Charging: LiCoO2 + Graphite (C6) …….. Li 1-x CoO2 + Li x C6.
When the cell discharges to provide power, Li+ ions move back through the electrolyte to the cobalt oxide
while the electrons move through the external circuit from the graphite electrode to the cobalt oxide
electrode.
Discharging: Li 1-x CoO2 + Li x C6 …….. Li 1-x+y CoO2 + Li x-y C6.
Thus charging and discharging cycle is simply migration of Li+ ions from one electrode to another
electrode with flow of electrons through the external circuit.
Applications: these are used in electronic circuit boards, military and space applications, medical devices
such as neuro- simulators, drug delivery systems etc.

ZINC AIR CELLS (Zn-Air):

Metal air batteries like Zinc-air batteries have powerful potential for use as alternative storage device,
low cost, abundance, low equilibrium potential. The important merit of Zinc-air batteries is that non-noble
metal catalyst is used for reduction reaction.
Zinc-air cells are composed of three parts zinc metal as anode, an air electrode as cathode which is
divided into a gas diffusion layer and a catalytic active layer and a separator. Because the solubility of
oxygen very low at atmospheric pressure it is necessary to use oxygen in the gas phase not liquid. Oxygen
from atmosphere diffuses into the porous carbon electrode by difference in pressure of oxygen between
the out side and the inside of the cell. the catalyst facilitates the reduction of oxygen to hydroxyl ions in
the alkaline electrolyte by using the electrons generated by the zinc metal as anode reaction. This way we
call the process a three phase reaction, catalyst (solid), electrolyte (liquid), and Oxygen (gas). The
hydroxyl ions migrate from the air cathode to zinc anode to complete the cell reaction, which is given
below,

Anode: Zn …… Zn+2 + 2e-

Zn+2 + 4 OH- …… Zn(OH)4-2
Zn(OH)4-2 …….. ZnO+ H2O + 2 OH- ( E0 = -1.25v)
 UNIT ELECTROCHEMICAL CELL AND CORROSION
Cathode: O2 + 2H2O + 4e- ……. 4 OH- ( E0 = + 0.4 v)
Net reaction: 2 Zn + O2 ……… 2 ZnO ( E0 = + 1.65 v)
Drawback: The working voltage of battery is much lower due to internal losses.

FUEL CELLS:
A Fuel cell is a electrochemical cell which converts chemical energy contained in an easily
available fuel oxidant system into electrical energy. The basic principles of fuel cells are identical to those
of the well known electrochemical cells, the only difference is that in fuel cell the chemical energy is
provided by a fuel and an oxidant stored outside the cell.
The fuel and the oxidizing agents are continuously and separately supplied to the electrodes of the
cell, at which they undergo reactions. Fuel cells are capable of supplying current as long as the reactants
are supplied .
Fuel cells are characterized by,
1. High efficiency.
2. Low noise levels.
3. Free from vibration, heat transfer and thermal pollution.

1. H2-O2 Fuel cell (Green fuel cell)

A typical example of pollution free cell is H2-O2 fuel cell in which the fuel is hydrogen
and the oxidizer is oxygen.
A full cell converts the chemical energy of the fuels directly to electricity. The essential
process in a fuel cell is
Fuel + Oxygen ———> Oxidation products + Electricity
Construction and working:
Hydrogen – oxygen fuel cell consists of two porous electrodes made
up of compressed carbon coated with small amount of catalysts (Pt, Pd, Ag) and KOH or NaOH solution
as the electrolyte
 UNIT ELECTROCHEMICAL CELL AND CORROSION

During working, Hydrogen (the fuel) is bubbled though the anode compartment, where
it is oxidized. The oxygen (oxidizer) is bubbled though the cathode compartment, where it is
reduced. The following cell reactions occur.
- -
Anodic
2
reaction: 2H2 + 4OH ———> 4H2 O + 4e
- -
Cathodic
2
reaction: O2 + 4H2 O + 4e ———> 4OH
Overall cell reaction: 2H2 (g) + O2 (g)———> 4H2O (l)
From the above cell reactions, hydrogen molecules are oxidized to water. When a large
number of fuel cells are connected in series, it is called fuel battery.
Advantages of fuel cells:
1. Fuel cells are efficient and take less time for operation.
2. No harmful chemicals are produced in fuel cells.

Uses:
1. It is used as auxiliary energy source in space vehicles, submarines etc.
2. It is used in producing drinking water for astronauts in the space.

3.Methyl Alcohol – Fuel cell:

In this fuel cell, CH3OH is used as a fuel and O2 as oxidant to generate electrical energy.
The methyl alcohol – oxygen fuel cell has two electrodes. The anode consists of porous nickel electrode
impregnated with Pt/Pd catalyst. Porous nickel electrode coated with silver catalyst constitute a cathode of
the cell. The electrolyte, KOH, is taken in between the two electrodes. CH3OH and O2 are sent
continuously into their respective electrodes. And the electrical energy is produced with the continuous
replenishment of the fuel, CH3OH at the anode.
 UNIT ELECTROCHEMICAL CELL AND CORROSION

At anode: CH3OH + 6 OH- ……. CO2 + 5 H2O + 6e-

At cathode: 3/2 O2 + 3 H2O + 6e- …… 6OH-
Overall reaction: CH3OH + 3/2 O2 …… CO2 + 2 H2O
Advantages:
1. These are stable at all environmental conditions.
2. Easy to transport.
3. Because of high H2 concentration in methanol it is an excellent fuel.
4. There is zero emission by the cells hence it is ecofriendly.
Application: The major application of methyl alcohol-oxygen fuel cells is a fuel for fuel cell motor
vehicles like NECAR-5 in Japan, USA etc.

3. Phosphoric Acid Fuel cells (PAFC):

The electrolyte is highly concentrated, pure phosphoric acid (H3PO4) in silicon carbide matrix.
The electrodes are made of carbon paper coated with a finely dispersed platinum catalyst.
The electrode reactions are,
 UNIT ELECTROCHEMICAL CELL AND CORROSION

Anode reaction: 2 H2 ……… 4 H+ + 4e-

Cathode reaction: O2 + 4 H+ + 4e- ….. 2 H2O
Overall reaction: : 2 H2 + O2 ……. 2 H2O
Applications:
1. These are used for stationary power generations
With output 100 kw to 400 kw.
2. Used for large vehicles such bas buses.
3. In India DRDO has developed PAFC for air independent propulsion for integration into
submarines.

4.Molten carbonate fuel cell (MCFC):

The utilization of electricity in natural gas, bio gas and coal based power plants is by molten
carbonate fuel cells.
The anode consists of porous Ni based alloy with 2% of either chromium or aluminum. The
materials are crepe resistant and prevents sintering of anode at high temperature. The cathode consists of
porous Ni. That is converted lithinated nickel oxide. The electrolyte consists of sodium potassium
carbonate, supported by a ceramic (LiAlO2) matrix to maintain liquid between cathode and anode.
Cell reactions:
Anode: H2 + CO3-2 ……. H2O + CO2 + 2e-
Cathode: ½ O2 + CO2 + 2e- ……. CO3-2
Overall reaction: H2 + ½ O2 + CO2 ……. H2O + CO2.
 UNIT ELECTROCHEMICAL CELL AND CORROSION

Applications:
1. Molten carbonate fuel cells are used in many industrial purposes.
2. To produce electric power via steam turbines.

CORROSION

Corrosion is defined as the decay of a metal or alloy by chemical or electrochemical reactions with its
surrounding environment. Due to corrosion the useful properties of metal like malleability, ductility,
electrical conductivity and also the surface appearance are lost.
● Metals undergo corrosion and convert to their oxides, hydroxide, carbonates, sulphates etc.
● Most familiar examples of corrosion are,
Corrosion of Iron- reddish brown colour rust (Fe2O3.3H2O)
Corrosion of copper – green film of basic carbonate [CuCO3 +Cu(OH)2 ].

Theories of corrosion: There are three theories of corrosion,

1.Acid theory
2.Dry or chemical corrosion
3.Galvanic or electrochemical or wet corrosion

Dry or chemical corrosion:

The direct chemical action of atmospheric gases like oxygen, halogen, H2S etc. in a dry environment
on metals a solid film of the corrosion produced is formed on the surface of the metal. This is known as
chemical corrosion. A solid film of the corrosion product is formed on the surface of the metal which
protects the metal from further corrosion. Oxygen is mainly responsible for the corrosion of most metallic
substances when compared to other gases and liquid metals.

1).Oxidation corrosion (reaction with oxygen)

some of the metals directly react with oxygen in the absence of moisture. Alkali and alkaline earth
 UNIT ELECTROCHEMICAL CELL AND CORROSION
metals react with oxygen at room temperature and form corresponding oxides,while almost all metals
react with oxygen at high temperature. Metals like Au, Ag and Pt are not oxidized as they are noble
metals. During oxidation of a metal, metal oxide is formed as a thin film on the metallic surface which
protects the metal from further corrosion. The nature of oxide film plays an important role in the process
of corrosion.
Nature of oxide film:
i).Stable oxide film: the oxides of Pb, Al and Sn are stable and non-porous. As the oxides are stable
tightly adhering and form non-porous oxide film they inhibit further corrosion.
Through the oxides of alkali and alkaline earth metals are stable, the oxide film is porous. Hence
the atmospheric gases pass through the pores and react with the metal and the process of corrosion
continues till the entire metal is converted into oxide.
ii).Unstable oxide film: Au, Ag, Pt form unstable oxide layer which decomposes soon after the formation.
There by preventing further corrosion.
iii).Volatile oxide film: Molybdenum forms a volatile oxide film of MoO3, which accelerates corrosion.

2.Corrosion by other gases: If the corrosion of metal is due to other gases like Cl2, SO2, H2S, NOx in dry
atmosphere, it is called corrosion by other gases. The corrosion products may be protective or non-
protective. Dry Cl2 reacts with Ag and forms AgCl, which is stable and forms a protective layer, where as
SnCl4 as volatile.

3.Liquid metal corrosion: this type of corrosion takes place, when molten metal passes through metallic
pipes due to dissolution of solid metal by liquid molten metal or due to internal penetration of solid metal
into liquid metal.
Ex: Liquid metal mercury most metals by forming amalgams, there by corroding them. And coolant (Na)
leads to corrosion of Cd in nuclear reactors.

Wet (or) Electrochemical theory of corrosion:

It is a common type of corrosion of metal in aqueous corrosive environment. This type of

corrosion occurs when the metal comes in contact with a conducting liquid or when two dissimilar
metals are immersed or dipped partly in a solution. According to this theory, there is the formation
of a galvanic cell on the surface of metals. Some parts of the metal surface act as anode and rest act
as cathode.
The chemical in the environment and humidity acts as an electrolyte. Oxidation of anodic part
takes place and it results in corrosion at anode, while reduction takes place at cathode. The
corrosion product is formed on the surface of the metal between anode and cathode.
To understand the wet theory, let us take the example of corrosion of iron. Oxida- tion of metal
takes place at anode while the reduction process takes place at cathode. By taking rusting of iron as
an example, the reaction can be explained as that it may occur in two ways: (i) evolution of
hydrogen and (ii) absorption of oxygen.
At anode: oxidation occurs.
Fe ……. Fe+2 + 2e- (oxidation)

At cathode:
Case I: Evolution of H2: In acidic medium and in the adsence of oxygen, hydrogen ions are
 UNIT ELECTROCHEMICAL CELL AND CORROSION

reduced to H2 gas.

2H+ + 2e- …… H2 (Reduction)

The overall reaction is: Fe + 2H+ ……. Fe+2 + H2

In this case, metals react in the acidic environment and are dissolved (undergo corrosion) to release H2
gas. All metals above hydrogen in electrochemical series can show this type of corrosion. In hydrogen
evolution type of corrosion, anodic area is large as compared to its cathodic area.
 UNIT ELECTROCHEMICAL CELL AND CORROSION

Mechanism of wet corrosion by (a) hydrogen evolution and (b) oxygen absorption
Case II: Absorption of O2:
This type of corrosion takes place in neutral or basic medium in the presence of oxygen. The
oxide of iron covers the surface of the iron. The small scratch on the surface creates small anodic area
and rest of the surface acts as cathodic area. The following chemical reactions occur at anode and
cathode.

++
At anode Fe …….. Fe + 2e- (oxidation)

4 Fe(OH)2 + 2 H2O + O2 …… 2 (Fe2O3.3H2O)

Ferric hydroxide is actually hydrated ferric oxide, (Fe2 O3.3H2 O), which is a yellowish rust.
232
Anhydrous magnetite, Fe3O4 [a mixture of (FeO + Fe2O3)], is also formed, which is brown-black in
colour. It is markable that the corrosion occurs at anode but the corrosion product is formed near cathode.
++ –
It is because of the rapid diffusion of Fe as compared to OH. Hence corrosion occurs at anode, but
rust is deposited at or near cathode.

Different types corrosion:

1. Galvanic corrosion: This type of electrochemical corrosion is also called bimetallic corrosion. When
two dissimilar metals are connected and exposed to an electrolyte, they will form a galvanic cell. The
anodic metal will be oxidised and it will undergo corrosion. Zinc and copper metals connected with each
other in an electrolyte medium form a galvanic cell. Zinc acts as anode and undergoes corrosion while
cathode will be unaffected.

At anode: Zn Zn+2 + 2e- [Oxidation] corrosion

 UNIT ELECTROCHEMICAL CELL AND CORROSION
++ –
At cathode: Cu + 2e Cu [Reduction] unaffected

1. Galvanic corrosion can be avoided by coupling metals close to the electrochemical series.
2. Fixing insulating material between two metals.
3. By using larger anodic metal and smaller cathodic metal.
Example of galvanic corrosion:
1. Steel screws in brass marine hardware.
2. steel pipe connected to copper plumbing.
3. steel propeller shaft in bronze bearing.
4. zinc coating on mild steel.
5. lead–tin solder around copper wires.

2.Differential aeration corrosion: If a metal rod is dipped in an electrolyte, the portion dipped in water
is poor in oxygen concentration and works as anode which gets corroded and the portion above water
acts as cath- ode which is protected. The system will act as a concentration cell and the chemical
reactions for zinc dipped in water are given as:
 UNIT ELECTROCHEMICAL CELL AND CORROSION
Mechanism of differential aeration attack caused by partial immersion of a metal .

3.Stress corrosion: In a metallic structure, if there is a portion under stress, it will act as anode and rest
part of the structure will act as cathode. It is now a galvanic system and hence anodic part which is
small in area will corrode more. Stress corrosions are observed in the following systems:

i).Caustic embrittlement is a type of stress corrosion occurring in steel tank (Boiler) at high temperature
and in alkaline medium. Boiler water has Na 2CO3; it will be hydrolyzed at high temperature to give
NaOH. It flows into hair cracks and crevices. There it reacts with iron and forms Na2FeO2 (sodium
ferroate) which decomposes to give Fe3O4 ( Ferroferric oxide) and NaOH.
Reaction:

3Na2FeO2 + 3H2O Fe3O4 + H2 + 6NaOH

NaOH thus formed further reacts with iron to cause corrosion. It is called caustic embrittlement.
Addition of Na2SO4 to boiler water in addition to tannin and lignin to boiler water prevents caustic
cracking. By neutralization of excess of alkali with dilute acid (or) control of pH value caustic
embrittlement can be controlled.
ii).Season cracking: It is applied to stress corrosion of copper alloys bronze. Pure copper metal is less
sensitive to stress corrosion. However, presence of alloying impurities like P, Zn, Al, etc. results in
marked sensitivity for corrosion. Some of the alloys like brass are made of zinc and copper. In the
presence of ammonia or amines, zinc and copper undergo inter-granular cracking. These metals form
complexes [Cu(NH3)4]++[Zn(NH3)4]++ which appear as corrosion products. Stress corrosion may be
reduces:
1. By applying protective coatings
2. Using corrosion inhibitors
3. By stress relief heat treatments

4.Waterline corrosion: It has been observed in the case of an iron tank contain- ing water, that the
portion of iron tank just below the water level undergoes corrosion. It is due to the difference in oxygen
concentration. Corroding portion is poor in oxygen and acts as anode.

Reactions:
 UNIT ELECTROCHEMICAL CELL AND CORROSION

Waterline corrosion occurs just underneath the meniscus and the water level
PASSIVITY OF METALS:

The process in which a metal exhibits higher corrosion resistance is called passivity. When a very
thin, invisible and highly protective film is formed on the surface of a metal or an alloy, it is called
passivity. This film is insoluble and non-passive. A metal is passive in a certain environment if its
corrosion rate is very low. By the change of the environment, the passivity of a metal may change and
may become active towards corrosion. The formation of a passive film on the metal surface in
determined by the Pourbaix diagram, which depends on the electrode potential and pH of the medium.
Low carbon steel does not corrode in conc. HNO 3 due to protection effect of passive film. However, in
dil. HN3 does not form a stable passive film and therefore dissolves steel. Passive film is formed on the
surface of aluminum, Cr, Si, Ti in air, water and dilute acids. There is a good corrosion and oxidation
resistance of stainless oxide passive layer.
A damage of passive film may cause intensive localized corrosion (pitting corrosion). Passive
–2
oxide layers are dissolved in electrolytes containing SO and chloride. Phosphate and chromate ions
stabilize passive films, promoting the regain of its defects.

GALVANIC SERIES:

Electrochemical reactions are predicted by electrochemical series. A metal having higher

position can replace (reduce) other metals that have lower position in the series. For example,

Zn + CuSO4 ………. ZnSO4 + Cu

++ ……………… ++
i.e, Zn + Cu Zn + Cu

Or in other words, zinc will corrode faster than copper.

Some exceptions have been observed in this generalization. For example, Ti is less reactive than Ag.
Galvanic series is the series of metals that is made keeping in view the process of corrosion of a metal
in a particular atmosphere, i.e. sea water. In galvanic series, oxidation potential of metals is arranged in
the decreasing order of activity of a series of metals. The series is towards the increasing noble nature.

More anodic: Mg, Mg alloys, Zn, Al, Cd, Fe, Pb, Sn, Ni–Mo–Fe alloys) Brasses, Cu, Ni,
 UNIT ELECTROCHEMICAL CELL AND CORROSION
Cr–steel alloy, Ag, Ti, Au, Pt towards noble nature.
Comparison between Galvanic Series Vs Electrochemical Series:
Galvanic Series Electrochemical Series

It predicts the relative displacement tendencies

1. It predicts the corrosive tendencies of metal alloys

2. Calomel electrode is used as a reference electrode Standard hydrogen electrode is used as reference
Electrode.
3.Positioning of metal or alloy may change. Position of metal is fixed. That cannot be
Changed.

4.The metals and alloys are immersed in the sea Concentration of salts of the same metal that was
water for study. Being used.
5.Electrode potentials are measured for both Electrode potentials are measured only for metals
metals and alloys. And non-metals.

FACTORS INFLUENCING CORROSION:

Since corrosion is a process of destruction of metal surface by its environment, the two factors that
govern the corrosion process are:
(i) Metallic and (ii) Environmental.

(i) Nature of metal: Different properties of a metal are responsible for corrosion. These properties are
given here.
(a) Position of metal in galvanic series: It decides the corrosion rate. A metal having higher position in
galvanic series undergoes corrosion when connected to another metal below it. Also, more
difference in the position of galvanic series will cause faster corrosion at anodic metal.
(b) Purity of metal: Pure metal resists corrosion, while impurities in a metal form a local galvanic cell
(metal as anode and impurity as cathode) and result in the corrosion of metal. Rate of corrosion
increases due to more exposure of impurities. For alloys the system is a homogeneous solid solution,
hence no local action and no corrosion.
(c) Relative areas of anode and cathode: Smaller the area of anode com- pared to cathode will lead to
faster corrosion of anode. It is because the corrosion current at anode and at cathode will be 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 (oxidation), i.e. rapid
corrosion.
(d) Physical state of the metal: Small granular metal will corrode faster than the larger one. Also the
type of structure formed by a metal will have effect on the corrosion rate. A bent metal (stress) is
rapidly corroded due to stress.
(e) Nature of oxide film: An oxide film is formed by the reaction between metal and oxygen. If this
oxide film is porous and oxygen can be diffused through it, more corrosion is expected (already
shown in dry or chemical corrosion). Also, if volume of metal oxide is more than the volume of
 UNIT ELECTROCHEMICAL CELL AND CORROSION
metal (The specific volume ratios of Ni, Cl, W are 1.6, 2.0 and 3.6) least corrosion or no further
corrosion occurs.

ii).Effect of environment:
The role of environment in the corrosion of a metal is very important. Environmental parameters like
temperature, humidity, pH, etc. play important role. The effect is discussed here.

(a) Temperature: The rate of diffusion increases by rise in temperature, hence the rate of
corrosion is also increased. At higher temperature, passive metals also become active and
undergo corrosion. But higher temperature reduces the concentration of oxygen and hence
corrosion is reduced (in case of water where oxygen is dissolved).
(b) Humidity: In humidity, gases like CO2, SO2, NOx are dissolved which form electrolytes. It
will cause galvanic corrosion. Some oxides are water soluble, humidity washes away the
corrosion products and metal surface is further corroded. Other soluble corrosion products can
also be washed away by humidity, causing further corrosion.
(c) Impurity of atmosphere: Pollutants like H2S, SO2, CO2 and acid vapors cause more pollution
where they dissolve. In sea water (salty in nature which acts as an electrolyte) corrosion rate
increases. Some suspended particles are dissolved in humidity and form electrolyte which
helps in corrosion.
+
(d) pH value: pH value means concentration of H (acidic nature). In acidic medium (pH
less than 7), corrosion is faster. Also, in basic medium pH > 7, some metals such as Pb, Zn,
Al, etc. form complexes and hence they corrode. Pourbiax relation between pH of medium
and potential of metal deals with the corrosion process and it gives idea how to reduce
corrosion.
Example: Zn corrodes minimum at pH 11, but at higher pH (more than
11) it corrodes faster. At pH 5.5, Al corrodes minimum.

(e) conductance effect: Due to presence of salts and water in earth, it is of con- ducting nature.
More conductance leads to more stray current and hence fast corrosion. Dry sandy soil is less
conducting and hence less corrosion, while mineralized clay soil is more conducting hence
more corrosion occurs.

CORROSION CONTROL:

1.Proper designing:
Due to corrosion, there is a great loss of material and money. Therefore, it is essential to protect
metals from corrosion. Since, there are two components involved in corrosion—the metal and
environment—both are considered in corrosion protection. Following methods have been adopted for
the protection of metal from corrosion.

Proper designing of an object helps in prevention of corrosion.

(i)
(ii) Contact of two dissimilar metals must be avoided. If it is unavoidable, anodic area should
be very large compared to cathodic area.
 UNIT ELECTROCHEMICAL CELL AND CORROSION
(iii) Two different metals used in the structure should be such that they are occupying near
positions in galvanic series.
(iv) Putting an insulator between two metals resists corrosion.
(v) As far as possible, metal used in a structure should be extremely pure. Small amount of
impurity causes corrosion.
(vi) While using an alloy, it should be completely homogeneous.
(vii) Design or fabricate equipment or metal parts in such a manner that they have minimized
sharp edges and corners and also avoid, as for as possible, the crevices in joints, etc.
(viii) The modification of environment also helps in protection from corrosion. It includes:
(a) De-aeration removes oxygen by adjusting temperature and mechanical ageing.

(b) Deactivation involves addition of chemicals such as Na2SO3, NH2 – NH2◊H2O

which absorb oxygen.
(c).Dehumidification of environment is done by adding alumina or silica gel. These chemicals
absorb humidity from metallic surface.
In humidity, gases such as CO2, H2S, SO2 and HCl give acidic medium responsible for
corrosion. They are neutralized by NH3 or NaOH or lime.
(ix) There are some chemicals which reduce the rate of corrosion. These chemicals are called
corrosion inhibitors. They are of two types, anodic and cathodic. Phosphate, chromate,
tungstate protect anode. They form sparingly soluble products which are adsorbed on the
surface of metal and hence check corrosion. Cathodic protection is done by organic amines,
mercap- tans, thiourea and substituted urea. The above chemicals retard reduction reaction
taking place at cathode.
Also, by the use of salts of Mg, Zn or Ni, the insoluble hydroxides of
Mg, Zn, Ni are deposited preventing corrosion.

2.Cathodic protection or Electrochemical method:

The principle involved in this method is that the metal is forced to behave like cathode, thereby
preventing corrosion. For protecting corrosion–electrochemically, there are two methods for the
protection from corrosion.
1. Sacrificial anodic protection: Underground steel pipes are protected from corrosion by this method.
A magnesium rod is fixed near the metal under protection and both are connected with a conducting
wire. Magnesium is more positive than iron and, hence, in electrochemical cell it acts as anode and the
iron acts as cathode. According to the principle of galvanic cell, it is anode that undergoes oxidation,
and, hence, corrosion occurs at anode saving cathode (iron) from corrosion. Thus, magnesium scarifies
 UNIT ELECTROCHEMICAL CELL AND CORROSION
itself for saving the iron.

Sacrificial anodic protection.

2. Impressed current cathodic protection: The object to be protected is made cathode and it is
connected to the negative terminal of a DC (direct current) source. The positive terminal of the
source is connected to the other electrode made of graphite or platinum, lead or nickel. The impressed
current opposes the galvanic current (corrosion current) and, hence, protection from corrosion takes
place.

Impressed current cathodic protection

Recent developments have given paints that automatically fill the gap if scratches are there and, thus,
protect the metal from corrosion.

PROTECTIVE COATINGS:

The oldest common methods of protection of a metal from its surroundings is applying a protective
coating on the surface of the metal. The coated surface isolates the metal from its corroding environment.
The requirements of this type of protection are,
a). The coating applied must be chemically inert to the environment under particular conditions of
temperature and pressure.
b). Coatings must prevent the penetration of the environment to the material, which they protect.
 UNIT ELECTROCHEMICAL CELL AND CORROSION

Functions of the protective coatings:

1. To protect the metal from corrosion.
2. To impart beautiful appearance or decoration to the metal surface.
3. To impart specific mechanical and physical properties like hardness, wear resistance.
4. To give oxidation resistance and thermal insulating properties.

Surface preparation:

Before applying any protective coating the metal surface must be thoroughly cleaned to remove dirt.
Old protective coatings like paints, greases, corrosion products etc. the following are some of the methods
adopted for metal cleaning.

1.Solvent cleaning: This method is used to remove oils, greases, buffing compounds and fatty substances.
This method involves the cleaning of metal surface by the applications of organic solvents like Naptha,
Chlorinated hydrocarbons like CCl4, Toulene, Xylene or Acetone. Then the metal surface is cleaned with
steam and hot water containing wetting reagents and alkalis.
● This treatment is specially adopted for electroplating where the metal surface requires wetting.

2.Alkali cleaning: The metal surface is cleaned with alkali cleaning agents like trisodium phosphate along
with soaps and wetting agents like caustic soda. This method removes old paint coating from metal
surfaces. Alkali treatment is followed by through rinsing with water and then immersion in 0.1% chromic
acid, to remove the last traces of alkalis.
A more effective cleaning with alkali is made by the application electric current by making the metal
to be coated as cathode. This removes effectively the grease or oily substances attached to the metal
surface.

3.Mechanical cleaning: This method removes loose rust, scales, dirt etc. from the metal surface different
methods are adopted for cleaning.
⮚ Cleaning of the metal surface is done by using bristle brusher and metal brushes to remove the
loosely adhering impurities.
⮚ Sand paper are also used to remove strongly adhering scales and rust.
⮚ Detergents like soap are adopted for cleaning the metal surface.
This method is followed by steam or hot water treatment.

4.Flame cleaning: This method involves heating the metal surface with a hot flame to removes loosely
adhering scales, followed by wire brushing.

5.Sand blasting: The oxides scales, particularly when a slightly roughen surface is desired are removed by
this method.

METALLIC COATINGS:
 UNIT ELECTROCHEMICAL CELL AND CORROSION

Metallic coatings are produced by coating one metal on the surface of another metal. The metal which
is protected is called base metal and the metal which is coated on the surface of the base metal is called
coating metal. Broadly we can classify the metallic coatings into two categories.
1. Anodic coatings
2. Cathodic coatings.

1.Anodic coatings:
This type of coatings are produced by coating an anodic coating metal on the surface of base metal.
For example coating of Zn, Al and Cd on iron are anodic, because their reduction potentials are lower
than that of base metal iron.
If any pores, breaks or discontinuation in metallic coating, exposing the base metal, a galvanic cell
is formed between coating metal and base metal, where the coating metal dissolves anodically and the
base metal is protected. Hence no corrosion occurs to the base metal until all the coating metal corrodes
and disappear from vicinity of the exposed base metal spot.

2.Cathodic coatings:

Cathodic coatings are obtained by coating a more noble metal than the base metal. The coating metal
has higher reduction potential than the base metal and protect the base metal due to higher corrosion
resistant than the base metal. For example coating of tin on the surface of iron. Cathodic coatings provide
effective protection to the base metal only when the coating is completely continuous and free from pores,
breaks and discontinuities.
When a break pore or discontinuity occurs in the cathodic coating more corrosion damage is done
to the base metal. When the base metal which is anodic to the coating metal is exposed to environment , a
galvanic cell is set up and an intense localized attack at the small exposed part occurs resulting severe
pitting and perforation in the base metal because of a small anode and large cathode area.
 UNIT ELECTROCHEMICAL CELL AND CORROSION

Methods of application on metals:

ELECTROPLATING: The process of depositing the coating metal on the surface of base metal or non-
metal by electrolysis is called electroplating.
The base metals are inferior or anodic to the coating metal and electrolyte is the solution containing the
metal ions to be deposited on the base metal. The base metal is made cathode and the coating metal is

made anode or an inert material of good electrical conductivity is also used as an anode. A direct current
is passed through the electrolytic solution. If anode is made of graphite, the electrolytic salt is added
continuously to maintain the proper coating metal ion concentration in the electrolyte bath.
The article to be electroplated is subjected to solvent cleaning by trichloroethylene to remove oil,
grease etc. then it is subjected to acid pickling with dil. HCl or dil. H2SO4 to remove any scales, oxides
etc. the cleaned article is made cathode of the electrolytic cell and the anode can be made of the pure
coating metal or graphite. The electrodes were dipped in the salt solution of the coating metal, which acts
as an electrolyte. When direct current is passed, the coating metal ions migrate to the cathode and
deposition the base metal article in the form of a thin layer. For brighter and smooth deposits conditions
like low temperature, medium current density, low metal ion concentration are used.
For example electroplating of copper on iron Article, the following are maintained.
 UNIT ELECTROCHEMICAL CELL AND CORROSION

● Electrolytic bath solution: CuSO4

● Temperature maintained: 40-700 C.
● Current density: 20-30 m.A / cm2.
● Anode: Graphite.
● Cathode: Base metal article.
Applications:
● In metals the electroplating increase resistance to corrosion, chemical attack, hardness were
resistance and surface properties.
● In non-metals electroplating increases strength and decorates the surface of non-metals like
plastics, wood, glass etc.

ELECTROLESS PLATING:

The method of deposition of a metal from its salt solution on a catalytically, active surface by a
suitable reducing agent without using electrical energy is called electro less plating. This process is also
called chemical plating or autocatalytic plating.
Electroless plating of Nickel:
The base object, a plastic material like acrylonitrile-butadiene styrene (ABS) can be coated with
Nickel.
The base metal surface is activated by stannous chloride followed by palladium chloride to get a layer
of Pd and the surface is dried and dipped in a solution of nickel chloride, sodium hyposulphite (reducing
agent), sodium acetate buffer, sodium succinate (complexing agent) PH of the bath maintained is 4.5 and
temperature maintained is 930 C. the following reactions take place and Ni get plated electrolessly on the
surface of the base object.

Ni+2 + H2PO2- + H2O ………. Ni + H2PO3 + 2H+

 UNIT ELECTROCHEMICAL CELL AND CORROSION
Properties: Electroless plated Ni object has better corrosion resistance, deposits are pore free, hard and
wear resistant.

Applications:
● Electroless plated Ni coating are used extensively in electronic application providing a non-
magnetic underlay in magnetic components.
● ABS plastics coated objects are used for decorative applications automotive, electronic and
domestic of industry like knobs in hi-fi equipment, tops on perfume bottles costume jewellery and
car decorative. They are also used in digital and electronic instruments for electromagnetic
interference shielding.

PAINTS:

Paint is a dispersion of a pigment in medium oil (vehicle). When paint is applied on a surface, the
medium oil saves the surface from corrosion. The pigment saves the medium oil from the ultra violet
light given by the sun.
Components of paints and their functions
The important constituents of paint are as follows.
1. Pigment
2. Drying oil or medium oil or vehicle
3. Thinner
4. Drier
5. Filler or extender
6. Plasticizer
7. Anti-skinning agent
1. Pigment:
A pigment is a solid and colour producing substance in the paint.
Functions:
a) A pigment gives opacity and colour to the film.
b) A pigment gives strength to the film.
c) It protects the film by reflecting the destructive ultraviolet rays.
2. Drying oil or medium oil or vehicle.
The liquid portion of the which the pigment is dispersed is called a medium or vehicle. E.g. linsed
oil, dehydrated castor oil, soyabean oil and fish oil.
Functions:
(a) Vehicles hold the pigment particles together on the surface.
(b) They form the protective film by evaporation or by oxidation and polymerization of the unsaturated
constituents of the oil.
(c) Vehicles give better adhesion to the surface.
 UNIT ELECTROCHEMICAL CELL AND CORROSION
(d) They impart water repellency, durability and toughness to the film.
3. Thinner:
Thinners are added to paints to reduce the viscosity of the paints so that they can be easily applied
to the surface. E.g. turpentine and petroleum sprit.
Functions:
(a) Thinners reduce the viscosity of the paint to render it easy to handle and apply to the surface.
(b) They dissolve the oil, pigments etc. and produce a homogeneous mixture.
(c) Thinners evaporate rapidly and help the drying of the film.
(d) They increase the elasticity of the film.
(e) Thinners increase the penetrating power of the vehicle.
4. Drier:
Driers are used to accelerate the drying of the oil film.
Eg: Naphthenates of lead and cobalt, Resonates of lead and cobalt.
Functions:
Driers act as oxygen carrier catalysts which help the absorption of oxygen and catalyze the drying
of the oil film by oxidation, polymerization and condensation.
5. Filler or extender:
Fillers are added to reduce the cost and increase the durability of the paint, E.g. talc, Gypsum,
mica, asbestos etc.
Functions:
(a) Fillers serve to fill the voids in the film.
(b) They reduce the cracking of the paints.
(c) Fillers increase the durability of the paints.
(d) They reduce the cost of the paint.
6.Plasticizers:
Plasticizers are chemicals added to paints to give elasticity to the film and to prevent cracking of
the film, e.g. triphenyl phosphate, tertiary amyl alchol, Tributyl Phthalate.
7.Antiskinning agent:
They are chemicals added to the paint to prevent skinning of the paint, E.g. polyhydroxy phenols.

SPECIAL PAINTS:
In addition to the normal ingredients some special chemicals are incorporated to paints for some
specific purposes. They are commonly known as special paints.
1. Luminescent paints:
Luminescent paints contains luminophor pigments are used for visibility in the dark. They find
application in inks, advertising signboards, road marks, number plates of vehicles, watch dials, etc. The
active components in luminous paint are specially prepared phosphorescent materials like CaS, ZnS, etc.
They absorb light radiations and emit them in the dark. For colour effect in luminous paints, certain
 UNIT ELECTROCHEMICAL CELL AND CORROSION
chemicals like copper salts (green), silver salts (blue), cerium and uranium salts (yellow), etc. are used.
2. Heat Resistance paints:
When the surfaces are exposed to high temperatures such as in chimneys, exhaust pipes, furnaces,
oil stills, etc. Oil paints tend to decompose or get charred, they being organic in nature. Then the
surfaces become liable for corrosion. To overcome this problem, a suspension of graphite or lamp
black in small amounts of drying oils and more thinners can be used. But more recently, silicone paints
are used for heat resistance.
3. Fire-retardant paints:
These are paints containing chemicals which are fire-resistant in nature. In other words, they produce gases
like CO2, NH3 , HCl,HBr on heating which are themselves non-combustible and do not support combustion, there
by minimizing the rate of burning or extinguishing the fire.
4. Antifouling paints:
Oil paints are liable for attack by living organisms because of the organic content in them. So, in places
where living organisms are handled or are present, such paints cannot be used. For use in breweries and
biochemical laboratories, the paint is mixed with compounds having fungicidal properties. The active
ingredients employed are HgO, Cu2O, Hg2Cl2, DDT, pentachlorophenol, etc.
Such paints are called Antifouling paints.
5. Cement Paint:
Cement paint is the coating, which is applied on plastered brickwork, concrete work, etc. The ingredients
are
1. White cement (about 70%)
2. Hydrated lime [Ca(OH)2 ]
3. Pigment ( a colouring agent)
4. Very fine sand (an inert filler) and
5. Water- repellent compound
Such paints of different colors are marked in powder form (eg Snowcem, Smocem). The powder is mixed
with a suitable quantity of water to get a thin slurry, and applied on surfaces. For good results, a 1.5% to 2%
aqueous solution of sodium silicate and Zinc sulphate is applied as primer coat.
6.Aluminum Paint:
The base material in aluminium paint is a fine powder of aluminium.
The finely ground powder of aluminium is suspended in either spirit
varnish or in an oil-varnish depending on the requirement. When paints is applied, the thinner evaporates and
oil, if any, undergoes oxidation and polymerization. A bright adhering film of aluminium is obtained on the
painted surface.
Advantages of aluminum paint:
1. It possesses a good covering power.
2. It imparts very attractive appearance to the surface.
3. It has fairly good heat-resistance.
4. It has very good electrical resistance
5. The painted film is waterproof.
6. The electrical surface is visible even darkness.
 UNIT ELECTROCHEMICAL CELL AND CORROSION
7. Corrosion protection for iron and steel surface is better than all other paints.

**************