Electrochemistry

Electrochemistry
Electrochemistry is the study of production of electricity from the energy
released during a spontaneous chemical reaction and the use of
electrical energy to bring about non-spontaneous chemical reactions.

Electrochemical Cells
Galvanic cells or voltaic cell: It is a device used to convert the
chemical energy of a spontaneous redox reaction in to electric energy.
e.g. Daniell cell
Electrolytic cell: In Electrolytic cell, electrical energy is used to carry
out a non-spontaneous redox reaction.
 Daniell Cells
anode cathode
oxidation reduction

spontaneous
redox reaction
• The half-cell in which oxidation takes place is called anode and
it has a negative potential with respect to the solution.

• The other half-cell in which reduction takes place is called

cathode and it has a positive potential with respect to the
solution.

• The electrons flow from anode to cathode in external circuit

• However conventionally the current is said to flow from

cathode to anode
Salt Bridge
It is a U- shaped tube filled with concentrated solution of an
strong electrolyte like KCl / KNO3 solidified in agar agar
/gelatin.
Functions:
1.It completes the internal circuit by facilitating the flow of
ions through it. Negative ions flow to the anode and positive
ions flow to the cathode through the salt bridge .
2. It helps maintain electrical neutrality of two solutions
without mixing of the two.
 For Daniell cell , E cell = 1.1V

 When Eext,opp = 1.1 V , no flow of electrons ,no chemical reaction.

 When Eext ,opp< 1.1 V , electrons flow from Zn to Cu rod

Hence current flows from Cu to Zn , Zn dissolves at anode and copper
deposits at cathode.

 When Eext ,opp> 1.1 V, electrons flow from Cu to Zn rod

Hence current flows from Zn to Cu ,i.e. reaction occurs in backward
direction
Electrode Potential
It may be defined as the tendency of an electrode to either lose or
gain electrons when present in contact with solution of its own ions.
It is called oxidation potential if oxidation takes place at given
electrode .
It is called reduction potential if reduction occurs at given electrode.

Standard electrode potential:

The potential difference developed between metal electrode and solution of ions of
unit molarity (1M) at 1 atm pressure and 25°C (298 K) is called standard electrode
potential. It is denoted by E°.

E°reduction = – E°oxidation

According to IUPAC convention, standard reduction potential alone be

called as the electrode potential unless it is specifically mentioned.
Electromotive Force (emf ) of cell
It is the difference between the electrode potential of
two half cells which causes the current to flow from an
electrode at high potential to electrode at low
potential .
Standard emf of cell is
E°cell = E°cathode – E°anode
Or E°cell = E°right – E°left
Or E°cell = E°reduction + E°oxidation
.
.
 1 2

1 2

Representation of an electrochemical cell:

Left
(s)
|| Right
Anode salt bridge Cathode
Oxidation Reduction
Negative Positive
e.g. The Daniel cell is represented as follows :
Zn(s) | Zn2+ (1 M) || Cu2+ (1M ) | Cu (s)
 Measurement of Electrode potential of an
electrode
Absolute value of electrode potential of an electrode
cannot be calculated because neither oxidation nor
reduction takes place independently at an electrode.

 But we can calculate difference of electrode potential

of two half cells called emf by using use some standard
reference electrode Thus we can find relative electrode
potential only.

Standard hydrogen electrode is used as standard

reference electrode
Standard Hydrogen Electrode ( SHE) /Normal hydrogen electrode
(NHE),
• It consist of a platinum electrode carrying platinum foil coated with finely
divided platinum black. It is immersed in 1 M HCl. The H2 gas at 1 atm pressure
is bubbled through the solution at 25°C.
• SHE is assigned an arbitrary value of exactly 0.00 V at all temperatures.

• It is represented as Pt(s) / H2 (g) / H+ (aq)

• At the surface of platinum, either of the following

reaction can take place :

2H+ (aq) + 2e-  H2 (g), E°= 0.00 V

H2 (g)  2H+ (aq) + 2e- , E°= 0.00 V

• Its main drawbacks are:
1. It is difficult to maintain 1 atm pressure of H 2 gas.
2. It is difficult to maintain H+ ion concentration 1 M.
3. The platinum electrode is easily poisoned by traces of impurities
 Electrode potential of Zinc electrode
Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

 Oxidation half reaction

Zn (s) → Zn2+ (1 M) + 2e-

 Reduction half reaction

2H+ (1 M) + 2e- → H2 (1 atm)

 Overall reaction : Zn (s) + 2H+ (1 M) → Zn2+ + H2 (1 atm)

 E0cell = E0 H +/H 2 - E0 Zn 2 + /Zn

0.76 V = 0 - E0 Zn 2 + /Zn
E0 Zn 2 + /Zn = -0.76 V
 Zn2+ (1 M) + 2e- → Zn , E0 = -0.76 V
Electrode potential of Copper electrode
 Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)

 Oxidation half reaction :

H2 (1 atm) → 2H+ (1 M) + 2e-

 Reduction half reaction

Cu2+ (1 M) + 2e- → Cu (s)

 Overall reaction : H2 (1 atm) + Cu2+ (1 M) → Cu (s) + 2H+ (1 M)

 E0 cell = E0 Cu 2+ /Cu – E0 H +/H 2

0.34 = E0 Cu 2+ /Cu – 0
E0 Cu 2+ /Cu = 0.34 V
 Cu2+ (1 M) + 2e- → Cu , E0 = 0.34 V
 Electrochemical Series
The arrangement of elements in order of increasing standard reduction potential
values .
 Applications of Electrochemical Series (ECS)
*Standard reduction potential decreases → Reducing power increases
Oxidising power decreases
* Anode: Oxidation → Electrode higher up ion the series
Cathode : Reduction → Lower in series wrt anode.
* Metals higher in series can displace metals lower in series from their salt
solution
Zn + CuSO4 → Cu + ZnSO4 E0Zn 2+ / Zn = - 0.76 V
ZnSO4 + Cu → No reaction E 0Cu 2+ / Cu = 0.34 V

*
Metals placed above hydrogen in ECS can release hydrogen gas from
dil. acids but metals placed below hydrogen cannot replace hydrogen from dil. acids.
e.g. Ca does but Cu doesn’t.

* Oxides of metals placed below hydrogen are reduced by H 2 but oxides of metals
placed above hydrogen are not reduced by H2·
SnO, PbO, CuO are reduced by H2
CaO, K2O are not reduced by H2·
Applications of Electrochemical Series (ECS)
* emf is the difference of reduction potentials of two half-cells.
Eemf = ERHS – ELHS

Consider the reaction between zinc and silver:

Ag+(aq) + e–  Ag(s) (E° = 0.80 V )
Zn2+(aq) + 2 e–  Zn(s) ( E° = – 0.76 V)
Therefore, zinc forms the oxidation half-cell and silver reduction half
cell.
If emf comes out to be positive ,cell reaction is feasible and if it is negative, it is
not feasible.

Q: What is the standard emf of an electrochemical cell made

of a Mg electrode in a 1.0 M Mg(NO3)2 solution and a Ag
electrode in a 1.0 M AgNO3 solution?

Q: Can you store copper sulphate solution in a zinc pot?

 NERNST EQUATION
Helps to calculate electrode potential of an electrode or EMF cell
Mn+(aq) + ne- → M(s)

E(Mn+/M) = E°(Mn+/M) - (2.303RT) log [ M]

nF [Mn+]
 Concentration of solid taken as unity.
 E°(Mn+/M) is standard electrode potential
 R is gas constant (8.314JK–1 mol–1) ,
 F is Faraday constant (96487 C mol–1)
 n is number of electrons gained or lost.
 T is temperature in Kelvin

or E(Mn+/M) = E°(Mn+/M) - 0.059 log (1/[Mn+])

n
Q.The 0.1M copper sulphate solution in which copper electrode is dipped at 25°C.

Calculate the electrode potential of copper electrode [Given E ° = 0.34V]

Cu+2 / Cu
 NERNST EQUATION
Ecell = E°cell - 2.303RT log [Product]
nF [Reactant]
or Ecell = E°cell - 0.059 log [Product]
n [Reactant]
e.g. Galvanic cell - Zn(s) | Zn2+ (1 M) || Cu2+ (1M ) | Cu (s)
Cell reaction is – Zn + Cu2+ → Zn2+ + Cu
Ecell = E0cell – 0.059 log [Zn2+]
n [Cu2+]
 Ecell increases with increase in concentration of Cu 2+ and decreases with
increase in concentration of Zn2+

Q .Calculate the EMF of the cell

- Cr / Cr 3+ (0.1M) // Fe+2 (0.01M) / Fe
(Given E° Cr+3 / Cr = – 0.75V E° Fe+2 / Fe = – 0.45 V)
Electrochemical cell and Gibbs Energy of Reaction
Work obtained from electrochemical cell = –
free energy of cell ΔG = –n F Ecell
If the concentration of all the reacting species is unity
ΔG° = –nFE°cell
 As E°cell = 2.303RT log Kc , ΔG° = –nF 2.303RT log Kc
nF nF
or ΔG° = – 2.303 RT log Kc
Cell reaction is spontaneous, if ΔG = – ve or Ecell= +ve
 Cell reaction will be in equilibrium ifΔ G = 0 , Ecell = 0
Cell reaction is non- spontaneous, if ΔG = + ve or Ecell= -ve
Ecell is an intensive property &
does not depend on stoichiometry of half reactions.
 Equilibrium constant from Nernst Equation
In nernst equation
Ecell = E°cell - 2.303RT log [Product]
nF [Reactant]

At equilibrium, concentration of ions involved becomes constant

and voltmeter gives zero reading.

Ecell = 0 and [Product] = Kc (equilibrium constant)

[Reactant]

E°cell = 2.303RT log Kc = 0.059 log Kc at 298 K

nF n
Answer the following:
 Electrolytic Conductance
Conductance. ( G)The ease with which current flows through a conducter.
It is the reciprocal of resistance, i.e. G = 1/ R. Its units are ohm -1 or Ω-1 or mho
or Siemen(S).
 Specific resistance or Resistivity (ρ) If 'I' is the length of a
conductor and 'A' is its area of cross section,
Resistance R α l /A
or R = ρ l /A ,
So ρ = RA / l
The units of resistivity are Ω cm or Ω m.
Specific conductance or Conductivity (κ) It is the reciprocal of
specific resistance, i.e. κ = G l /A
If I = 1 cm and a = 1 cm2, κ = G.
Conductivity of a solution is defined as the conductance of one centimeter cub
e of solution of the electrolyte.
Units of κ = ohm -1 cm -1 , SI units are Ω -1 m -1 or S m -1 .
Differences b/w metallic and electrolytic conductors
Matallic / electronic Conductor
· Flow of electricity due to movement of electrons
· No chemical change as there is no transfer of matter.
· Conduction decreases with temperature because kernels start vibrating which
interfere in the flow of electrons
· Depends upon nature, structure of metal and number of valence electrons per
atom.
Electrolytic conductor
Flow of electricity due to movement of ions
Ions are oxidised or reduced at the electrodes, hence involve transfer of matter .
Conduction increases with temperature because dissociation increases and
viscosity decreases
Depends upon nature of electrolyte (weak or strong), size of ions and their
solvation, nature of solvent and viscosity.

Superconducters
Substances that have zero resistivity or infinite conductivity.
e.g. Hg at 4.15 K , Zn at 0.88K , some mixed oxides and ceramic materials are
superconductors at high temperatures.
 Conductance of Electrolytic Solutions
Substances which conduct electricity in fused state or in aqueous solution are called
electrolytes .Conductance of electrolytic solutions depend on
Nature of electrolyte : weaker the solute solute interactions, greater will be the freedom of movement of
ions and higher will be the conductance.

Solvation of Ions : greater the solute solvent interactions, lower will be the electrical conductance

The nature of solvent and its viscosity : Larger the solvent- solvent interactions, more will be the
resistance offered by the solvent to flow of ions and hence lesser will be the electrical conductance.

Temperature : As the temperature of electrolytic solution rises, solute-solute, solute-solvent and solvent-
solvent interactions decreases, this results in the increase of electrolytic conductance.


 Measurement of the conductivity of ionic
solutions
Two main problem we face in the measurement of
resistance of ionic solution are
1. passing of DC changes the composition of the
solution.
2.solution is difficult to connect to a wires.
These problems are solved by
passing AC instead of DC and using specially designed
cell called conductivity cell.
 CONDUCTIVITY CELLS
It consists of two platinum electrodes coated with platinum black. The area of cross section is
‘A’ and are separated by a distance ‘l’.The resistance of column of solution taken inside is
given by:
R = ρ.l/A , ρ is resistivity
= l/κ A κ is conductivity
The quantity l/A = cell constant (G*)
The measurement of l / A is inconvenient
and unreliable.
The cell constant is usually determined by measuring the resistance of the cell
containing a KCl solution whose conductivity is known accurately at various
concentrations and at different temperatures. The cell constant, G*, is then given by the
equation:
G* = l / A = R κ
Once the cell constant is determined, we can use it for measuring the resistance or
conductivity of any solution.
 Wheatstone Bridge
It consists of two resistances R3 and R4 , a variable resistance R1
and the conductivity cell having the unknown resistance R2 .
At null point ,Unknown resistance R2 = R1 R4
R3
Once the cell constant and the resistance of the solution in the
cell is determined, the conductivity of the solution is given by the
equation:
κ = cell constant = G*
R R
Molar conductivity (ᴧm) The conductivity of all the ions
produced when 1 mole of an electrolyte is dissolved in V mL of solution is
known as molar conductivity.
It is related to specific conductance as Λm = κ x V
or Λm = κ x 1000
M where. M = molarity.

It units are Ω-1cm2mol-1 or Scm2mol-1 .

Equivalent conductivity(Λeq) The conducting power of

all the ions produced when 1 g-equivalent of an electrolyte is dissolved in
V mL of solution, is called equivalent conductivity.
Λeq = = κ x 1000
N where N = normality.

Its units are Ω-1cm2geq-1 or Scm2geq-1 .

Answer the following:
Variation of Conductivity with Concentration
Conductivity always decreases with decrease in
concentration or on dilution ,both for weak and strong
electrolytes.
•This is due to the fact that the conductivity is the
conductance of one cm3 of solution of electrolyte and on
dilution, number of ions per unit volume decreases.

Limiting Molar Conductivity (ᴧ 0m)

When concentration of solution approaches zero, molar
conductivity is called limiting molar conductivity/
molar conductivity at infinite dilution.
Variation of Molar Conductivity with Concentration
Debye-Huckel Onsagar equation gives a relation between molar
conductivity, Λm at a particular concentration and molar conductivity at
infinite dilution.
Λm = Λ0 m – b√C
where, b is a constant. It depends upon the nature of solvent and temperature.

Factors Affecting Conductivity

i)Nature of electrolyte: The strong electrolytes like KNO 3 ,KCl, NaOH.
etc. are completely ionised in aqueous solution and have high values of
molar conductivity. The weak electrolytes are ionised to a lesser extent in
aqueous solution and have lower values of conductivity.
ii) Concentration of the solution: The concentrated solutions of strong
electrolytes have significant interionic attractions. which reduce the speed
of ions and lower the value of Λm. The dilution decreases such attractions
and increase the value of Λm.
The limiting value, Λ0 m (the molar conductivity at zero concentration or
at infinite dilution) can be obtained by extrapolating the graph.

In case of weak electrolytes, the degree of ionisation increases on dilution

which increases the value of Λm. The limiting value Λ 0 m can’t be
obtained by extrapolating the graph as dissociation is never 100 %
complete. limiting value, Λ0 m, for weak electrolytes is obtained by
Kohlrausch law.

( Temperature The increase of temperature decreases inter-ionic

attractions and increases kinetic energy of ions and their speed. Thus, Λm
increase with temperature)
 Kohlrausch law of independent migration of
ions
The law states that limiting molar conductivity of an
electrolyte can be represented as the sum of the individual
contributions of the anion and cation of the electrolyte.
if λ°Na+ and λ°Cl – are limiting molar conductivity of the sodium
and chloride ions respectively, then the limiting molar
conductivity for sodium chloride is given by the equation:
Em°(NaCl) = λ0Na+ + λ0Cl–
In general, if an electrolyte on dissociation gives v+ cations and
v– anions then its limiting molar conductivity is given by:
Em° = ν+ λ0+ + ν– λ0–
Here,λ +0 andλ−0 are the limiting molar conductivities of the
cation and anion respectively
 Applications of Kohlrausch law
(i) Determination of molar conductivities of weak electrolytes at infinite
dilution, e.g.
Λom for NaCl, HCl and NaAc are 126.4, 425.9 and 91.0 S cm 2 mol–1
respectively. Calculate Λom for HAc.
Λ om(HAc) = λο mH+ + λο mAc–
= λο mH++ λο mCl– + λο mAc–+ λο mNa+ - λο mNa+- λο mCl–
= Λ om (HCl)+Λ om(NaAc)- Λ om(NaCl)
= (425.9 + 91.0 – 126.4 ) S cm2 mol –1
= 390.5 S cm2 mol –1
(ii) Determination of degree of dissociation (α) of an electrolyte at a given
dilution.

The dissociation constant (K) of the weak electrolyte at concentration C of

the solution can be calculated by using the formula
Ka = (Cα2 /1 – α) where, α is the degree of dissociation of the electrolyte.
Answer the following:
.
 Electrolytic cells
 The device used to convert electrical energy into chemical energy .
 It consists of a vessel for electrolytic solution or molten electrolyte in which
two metallic electrodes connected to a source of electric current are immersed.
 Anode is positively charged and cathode is negatively charged.
 When an electric potential is applied between the electrodes, the cation moves
towards the cathode and reduction occurs .Anion moves towards the anode
and oxidation occurs.
 If an electrolytic solution consists of more than two ions then during
electrolysis, all the ions are not discharged simultaneously but certain ions are
liberated at the electrode in preference to the others. This is based on the
principle of preferential discharge theory which states that the ion which
requires least energy is discharged first.
 e.g. The discharge potential of H+ ions is lower than Na + ions.
ORDER OF DISCHARGE POTENTIAL :
The decreasing order of discharge potential or increasing order of deposition of
some of ions are given below :
For cations : K+, Na+, Ca2+ , Mg2+ , Al3+ , Zn2+ , H+, Cu+, Ag2+ , Ag+
For anions : SO42–, NO3– , OH– , Cl– , Br – , l–
 Electrolysis of Water

Courtesy Stephen Frisch

Fig 18-25 A photograph and schematic diagram of a cell for the

electrolysis of water. The reaction generates hydrogen and
Pg 898 oxygen in a 2:1 ratio.
 Products of Electrolysis
molten/ fused NaCl NaCl (l) → Na+ + Cl–
The products of electrolysis are sodium metal and Cl2 gas.
at cathode - Na+ + e– → Na
at anode - Cl–→ ½Cl2+e–
Electrolysis of aqueous NaCl solution
the products are NaOH, Cl2 and H2.
NaCl (aq) → Na+ (aq) + Cl– (aq) *
H2O → H+ + OH–
At cathode – discharge potential of H+ is lower than Na+ ,so H+ is preferably discharged.
H+ (aq) + e– → ½ H2 (g)
but H+ (aq) is produced by the dissociation of H2O, i.e.,H2O (l ) → H+ (aq) + OH– (aq)
Therefore, the net reaction at the cathode may be written as the sum of the above two and we
have H2O (l ) + e– → ½H2(g) + OH–
At anode - discharge potential of OH- is lower than Cl - ,however due to overpotential of
oxygen , Cl2 is preferably discharged.
Cl– (aq) → ½ Cl2 (g) + e–
Net reaction:
NaCl(aq) + H2O(l) → Na+(aq) + OH–(aq) + ½H2(g) + ½Cl2(g)

when Hg electrodes are used instead of Pt, +

Na (aq) further reacts with Hg to form sodium
- amalgam
Solve the following:
 Faraday’s Laws of Electrolysis
First Law: The amount of a substance deposited or liberated at any
electrode is directly proportional to the quantity of electricity passed
through the electrolyte.
If a current of I amperes is passed for t seconds, to give charge Q in
coulombs and
If W gram of substances is deposited by Q coulombs of electricity,
then W α Q α It

or W = z It = E It
96500
z = constant of proportionality called electrochemical equivalent

Electrochemical equivalent ( z ) : if I = 1 A and t = I s , w = z

It is the mass of substance deposited when a current of one ampere is
passed for one second.
second law:
When same quantity of electricity is passed through solutions of different
electrolytes connected is series, amounts of substances deposited at electrodes
are directly proportional to their equivalent weights.
w1 = E1
w2 E2 Faraday (F)
is the quantity of charge in coulombs required to deposit
one g equivalent of any substance.
Faraday (F) is also the quantity of charge carried by one mole of
electrons . 1F = 96500 Coulombs.
Ex :The same current if passed through solution of silver nitrate and cupric salt
connected in series. If the weight ofsilver deposited is 1.08 g. Calculate the weight o
f copper deposited.
 Batteries and Fuel Cells
Batteries are classified as two types:

Primary: use oxidation-reduction reactions that

cannot
be reversed very easily. Over a period of time
battery becomes dead and cannot be reused.

Secondary : reactions of these batteries can be

reversed (rechargeable batteries
 LACLANCHE CELL/ DRY CELL
Dry Cell

NH4Cl
 Laclanche cell
 Zinc container as anode.
 Graphite rod surrounded by paste of MnO2 and carbon as
cathode.
 A paste of NH4Cl and ZnCl2 as electrolyte.

Anode- Zn(S) —› Zn2+ + 2e-

Cathode - MnO2(s) + NH4+ + e- —› MnO(OH) + NH3

 The emf of the cell is 1.5V

 The cell is used in transisters and clocks.
Mercury Battery
 Mercury cell
 Anode – Zinc amalgam.
 Cathode – A paste of HgO and carbon.
 Electrolyte - A paste of KOH and ZnO

Anode – Zn(Hg) + 2OH- —› ZnO + H2O + 2e-

Cathode – HgO + H2O + 2e- —› Hg + 2OH-
Overall reaction – Zn + HgO —› ZnO + Hg

The cell potential is approximately 1.35 V

• Cell potential remains constant throughout as overall reaction does
not involve any ion whose concentration can change with time.
• Used in low current devices like hearing aids ,watches etc.
 Secondary Batteries

The primary batteries no longer produce a current when

the chemicals inside have reached equilibrium conditions

Secondary batteries can be recharged.

How ? The original reactant concentration can be

restored by reversing the net cell reaction
using an external source of electric energy
 Lead Storage Batteries:
The battery is recharged by current from the car’s alternator
 Lead storage battery
Anode: lead grid filled with spongy lead.
 Cathode: lead grid coated with lead dioxide.
Electrolyte :A 38 % solution of H2SO4

Anode - Pb(s) + SO42- —› PbSO4 + 2e-

Cathode – PbO2(s) + 4H++ SO42- + 2e- —› PbSO4 +2H2O
Cell reaction- Pb(s) + PbO2(s) + 2H2SO4 —› 2PbSO4 +2 H2O

 On recharging cell reaction is reversed.

i.e. 2PbSO4 +2 H2O —› Pb(s) + PbO2(s) + 2H2SO4
 Cell Potential: 1.924 V
.
Ni-Cad Battery
 Nickel – Cadmium cell.
 Cadmium metal act as anode.
 Nickel grid containing Ni(III) compound act as cathode.
 KOH solution act as electrolyte.

Anode - Cd + 2 OH- ---> Cd(OH)2 + 2e-

Cathode - NiO(OH) + H2O + e- ---> Ni(OH)2 + OH-
overall reaction – Cd(S) + 2Ni(OH)3(s) —›CdO(S) + 2Ni(OH)2(s) + H2O

Cell reaction is reversed on recharging.

 emf of cell is approximately 1.4 V . Also called Ni-cad cell.

 FUEL CELLS
It is an electrochemical device used to convert energy of
combustion of fuels directly into electrical energy. Fuel used in
gaseous state are H2,CH4 , CO or methanol.

 H2 – O2 fuel cell.
It consists of porous carbon electrodes.
NaOH or KOH is used as electrolyte
Reactions are:
Anode – 2H2(g) + 4OH-(aq) —› 4H2O(l) + 4e-
Cathode – O2 + 2 H2O + 4e- —› 4OH-(aq)
overall reaction -2 H2(g) + O2 —› 2 H2O(aq)
Cell works as long as H2 and O2 are supplied .
 H2 – O2 fuel cell

H2 – O2 fuel cell was used for providing electric power in the Apollo
space programme .The water vapours produced during the reaction were
condensed and added to the drinking water supply for the astronauts.

Advantages
1)More efficient( abt 75%)
than any conventional source.
2)Pollution free ,no harmful
products formed
3) Continuous source of energy
if the supply of gases is
maintained.
 CORROSION
 It involves the slow destruction of a metal as a result of
its reaction with moisture and gases present in
atmosphere.

More reactive metals corrode more easily. Corrosion of

Iron is called rusting.
Chemically rust is Fe2O3 .xH2O
Mechanism of Rusting-
(Electrochemical theory of rusting)
 Pure Iron act as anode and impure iron surface as
cathode. Moisture having dissolved carbon dioxide or
oxygen acts as the electrolyte.
Oxidation:Fe(s)  Fe2+(aq) + 2 e–
Reduction: O2(g) + 4 H+(aq) + 4 e–  2 H2O(l)
Overall: 2 Fe(s) + O2(g) + 4 H+(aq)  2 Fe2+(aq) + 2 H2O(l)

Fe2+ ions so formed are further oxidised by atmospheric

oxygen to form Fe3+ ions which on hydration give rust
Fe2O3 .x H2O.
2+
4 Fe (aq) + O2 (g) + 4H2O( l)  2Fe 2 O 3(s) + 8H
+
Salt speeds up rusting by increasing conductivity

Prevention of corrosion
1)Barrier protection – By coating with a suitable material –
paints, oil or grease etc.

2) Galvanization – The process of coating the surface of

iron with Zinc is called Galvanization. . Zinc is more
easily oxidized than iron, which protects and
reverses oxidation of the iron.

3)Alloying with metals that form oxide coats.

4) Cathodic / Sacrificial protection - a plate
of reactive metal (Zn or Mg) is burried beside
the iron pipe or tank and connected to it by wires.
Here iron becomes cathode and more reactive
metal becomes anode. The anode is sacrificed
to protect the iron. Since these reactive metal plates are
oxidised quickly, they are replaced from time to time
which is easy to do.
5) Antirust solutions – Alkaline phosphate or
chromate solutions are applied on iron surface to
form a heat resistant iron phosphate or chromate
coating which prevent corrosion.