Electrochemistry

Corrosion is a process involving the conversion of a

metal into an undesirable compound (usually oxide)
on exposure to atmospheric conditions. i.e., moisture
and oxygen. Corrosion may also be called weeping
of metals.
Tarnishing silver, development of a green coating on
copper and bronze and rusting of iron are some
important examples of corrosion.
In case
H of iron, corrosion is known as rusting. Rusting
is catalysed by
ions. Chemically, theFe
rust
is
2 O3 .nH 2 O
hydrated ferric oxide

 Several workers have carefully investigated the

conditions under which rusting takes place. It has
been observed that
i) Pure iron does not rust if it is kept in contact with
pure water .
ii) Impure iron gets rusted if water contains some
dissolved impurities.
iii) The presence of carbon dioxide (or) acidity in water
helps in rusting.
iv) The presence of metals like chromium and
nickel slows down the rusting.
v) The presence of alkalis also retards rusting.

Tarnishing .silver

Devalopment.green.
coating .on.copper

Mechanism of rusting:
Commercial form of iron behaves like small electric
cells in presence of water containing dissolved
oxygen, carbon dioxide (or) sulphur dioxide.
At anode oxidation reaction occurs as
2 Fe 2 Fe 2 4e ; E ( Fe 2 / Fe ) 0.44v
At cathode, these electrons form hydroxyl ions,
H 2O O 2e 2OH

The Fe 2ions
and
then diffuse under
OH
ions
the influence of dissolved
Fe 2ions oxygen and Fe 3ions
are oxidized
.
Fe 3ionsto
OH ions
These
then combine with
to
form hydrated ferric oxide. i.e., rust

2 Fe H 2O O 2 Fe 2OH
3

2 Fe 6OH Fe2O3 .3H 2O

 Rusting of iron is quicker in saline water than in

ordinary water. It is because the saline water contains

Na (and )Cl
ions which furnishes
the electrolyte,
NaCl
. These ions help in the flow of current in the
miniature cell set up on the iron surface. As a result
corrosion process increases.
CO2
Rusting of iron
H 2CO3
CO2 also increases in water containing
2

)CO3 ions
H ions
dissolved
.HIt(and
is because
dissolves in
water to give carbonic acid
Fe 2
which ionizes to give
.
Are unstable
gain electrons and forms
.
CO2and
Hcan
2 O H 2 CO3

H 2CO3 2 H CO3
Fe Fe

2e ;2 H 2e H 2

Methods to prevent Corrosion:

1. Barrier protection
2. By using anti rust solution
3. Electrical protection

Batteries
1.Primary batteries: The battery after their
use over a period of time, becomes dead and cell
reaction is completed and this cannot be reused
again called primary battery.
Eg: Dry cell
2. Secondary batteries: The battery after its use can
be recharged and can be used again is called
secondary battery.
Eg: lead storage battery

Lead storage battery

 It is a secondary battery.
It consists of two lead electrodes. Sponge lead acts as
PbO
anode and lead
coated
with
acts as cathode.
2
The electrolyteHis2 SO4
.
The charged cell represented as

Pb / PbSO4 ( s) / H 2 SO4 (aq) / PbSO4 ( s) / PbO2 ( s ), Pb

Anode(-)
Cathode(+)

20%

At.LHE :
Pb( s ) Pb 2 2e
Pb 2 ( aq ) SO4

( aq ) PbSO4 ( s )

the.net.recation :
Pb SO4

PbSO4 ( s ) 2e

At.RHE.net.reaction :
2

PbO2 ( s ) 4 H SO4 2e PbSO4 ( s ) 2 H 2O

total.net.reaction :
Desch arg ing
Pb( s ) PbO2 ( s ) 2 H 2 SO4 (l ) 2 PbSO4 ( s ) 2 H 2O(l )
ch arg ing

 During the discharging step, both the electrodes of

and ) H 2 SO4 of
lead get coated with PbSO
white4 (precipitate
gets diluted due to the formation of
water. The reaction stops and the cell has to be
charged by connecting external source of current of
higher voltage.
The
electrode reactions are reversed.
H 2 SO
4
During charging
is regenerated to its original
concentration and water is consumed.
The lead storage battery acts as a voltaic cell as well
as an electrolytic cell. Eg: when the storage battery is
used to start the engine of an automobile, it acts like
a voltaic cell and generates an electric current. When
it is recharged, it acts like an electrolytic cell.

Fuel cells