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CHEMISTRY – XII

ELECTROCHEMISTRY

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WHAT IS ELECTROCHEMISTRY?
It is the study of production of electricity from the energy released during
spontaneous chemical reaction and use of electrical energy to bring about
non spontaneous transformation

Electrochemical Cell -It is a device in which chemical energy of a redox

reaction is converted into electrical energy.

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Electrode Potential
DEFINITION When an electrode is dipped into the salt solution of its own
ion then oppositely charged layers will be formed between
electrode and solution by which a potential difference is
developed. This potential difference is called electrode
potential. The electrode potential which is developed due to
the process of oxidation is called oxidation electrode
potential(O.E.P.) and electrode potential which is developed
due to the process of reduction is called reduction electrode
potential(R.E.P.).

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EXPLANATION

An electrode in contact with a solution of an electrolyte acquires

a charge as a result either of the escape of atoms into the
solution as cations, leaving behind a negative charge, or as a
result of ions becoming attached to the surface. As the
electrode becomes charged, an electrical potential difference
develops across the interface and makes that process more
difficult. For example, if the charge arises from the escape of
atoms as cations, the increasing negative charge on the
electrode makes it more unfavourable for the cations to leave.
Eventually equilibrium is reached with a characteristic potential
difference between the electrode and the solution. The charge on
the electrode affects the composition of the surrounding
electrolyte solution because it is energetically favourable
for ions with the opposite charge to cluster nearby.

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Measurements of the dynamics of electrode processes are almost

always done by using a large excess of supporting electrolyte
(e.g. a 1 mol dm−3 solution of a salt, an acid, or a base). Under
such conditions, the activity coefficients are almost constant
because the inert ions dominate the effects of local changes
caused by any reactions taking place. The use of a concentrated
solution also minimizes ion migration effects.

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The most primitive model of the boundary between

the electrode and the electrolyte solution is as an electrical
double layer, in which it is supposed that there is a sheet of
positive charge at the surface of the electrode and a sheet of
negative charge next to it in the solution (or vice versa).

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Oxidation is the removal of electrons from a species,

Reduction is the addition of electrons to a species, and a
redox reaction is a reaction in which there is a transfer of
electrons from one species to another. The electron transfer may
be accompanied by other events, such as atom or ion transfer, but
the net effect is electron transfer and hence a change in oxidation
number of an element. The reducing agent (or reductant) is the
electron donor; the oxidizing agent (or oxidant) is the electron
acceptor. It should also be familiar that any redox reaction may be
expressed as the difference of two reduction half-reactions, which
are conceptual reactions showing the gain of electrons.

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ELECTROCHEMICAL OR GALVANIC CELL

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Salt Bridge and its Functions

Salt bridge consists of a glass of U tube containing semi-
solid paste of KCl, KNO3 NH4Cl etc. as an inert electrolyte
in gelatin or agar-agar.
Functions
It maintains the charge neutrality of both half cells.
It completes the inner circuit of cell by connecting the two
solutions.

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Cell Notation

• The relevant components of each half-cell are represented by

their chemical formulas or element symbols
• All interfaces between component phases are represented by
vertical parallel lines; if two or more components are present in
the same phase, their formulas are separated by commas
• By convention, the schematic begins with the anode and
proceeds left-to-right identifying phases and interfaces
encountered within the cell, ending with the cathode
• The salt bridge which separates the two cells is represented by
two vertical parallel lines.
AnOdE CATHOdE
OXIdATIOn REduCTIOn
LEfT RIgHT
nEgATIvE ELECTROdE pOSITIvE ELECTROdE

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The galvanic cell mentioned at the beginning consists of a

solid copper anode immersed in an aqueous solution of
copper(II) nitrate that is connected via a salt bridge to an
aqueous silver(I) nitrate solution, immersed in which is a
solid silver cathode. Converting this statement to
symbolism following the above guidelines results in the
cell schematic:
Cu(s) │ 1 M Cu(NO3 )2(aq) ║ 1 M AgNO3(aq) │ Ag(s)

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The electrode potential measured in standard condition (25ºC and 1M

(for solution) or 25ºC and 1 atm (for gas)) is called standard electrode
potential (S.O.E.P. OR S.R.E.P.)
E = Electrode Potential
Eº = Standard Electrode potential
The magnitude of S.O.E.P. and S.R.E.P. is same but sign is opposite for
a particular elementFor eg. 0
E zn   5V

zn
Since Zn is oxidised to Zn2+ \ the above value is S.O.E.P. and value of
S.R.E.P. will be 0
E zn    5V
zn

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To calculate standard electrode potential of an element one reference

electrode should be used one of which is S.H.E. (Standard Hydrogen
Electrode). It includes a trough in which Pt wire is dipped in 1 M HCl
Solution and hydrogen gas is passed through solution at 1 atm pressure .

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Electrochemical Series (E.C.S.)

When elements are arranged in the increasing order of S.R.E.P. or
decreasing order of S.O.E.P. then series formed is called
electrochemical series (E.C.S.) .
Maximum value of SREP – F2
Maximum value of SOEP – Li

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Applications of E.C.S.
1. Reducing and oxidizing Nature:
The reducing property of an element depends upon the tendency to
oxidise i.e. on the value of SOEP. Greater the value of SOEP , easier
the tendency to oxidise and hence stronger will be the reducing
agent.
The oxidizing property of an element depends upon the tendency to
reduce i.e. on the value of SREP. Greater the value of SREP , easier
the tendency to reduce and stronger will be the oxidizing agent.
Therefore , Lithium will be strongest reducing agent and fluorine will
be the strongest oxidizing agent.

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Reducing power of metals:

reducing nature decreases from top to bottom
in the electrochemical series.

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Oxidising nature of non-metals

Oxidising nature increases from top to bottom
in the electrochemical series.

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2. Reactivity of Metals :
Reactivity of a metal depends upon the tendency of an element to loose
e- or the process of oxidation. Therefore , greater the value of SOEP ,
more reactive will be the metal.
Therefore , Li is most reactive metal .

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REACTION WITH WATER AND ACID

Alkali metals and alkaline earth metals having high
negative values of standard reduction potentials are
chemically active. These react with cold water and evolve
hydrogen. These readily dissolve in acids forming
corresponding salts' and combine with those substances
which accept electrons.
Metals like Fe, Pb, Sn, Ni, Co, etc., which lie a little down
in the series do not react with cold, water but react with
steam to evolve hydrogen.
Metals like Cu, Ag and Au which lie below hydrogen are
less reactive and do not evolve hydrogen from water.

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Metals lying below Hydrogen in electrochemical series do

not undergo corrosion.
To prevent rusting of iron - galvanization

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Metals with very low reduction potential are extracted by

the electrolytic method, e.g. – Na, Al, Mg, Li etc.

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3. Feasibility of the reaction :

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4. Thermal stability of metallic oxides: The thermal

stability of the metal oxide depends on its electropositive nature.
As the electropositivity decreases from top to bottom, the thermal
stability of the oxide also decreases from top to bottom. The·
oxides of metals having high positive reduction potentials are not.
stable towards heat. The metals which come below copper form
unstable oxides, i. e. , these are decomposed on heating.

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RELATIONSHIP BETWEEN EO
AND FREE ENERGY (G)

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When E O is positive, the cell reaction is spontaneous and

serves as a source of electrical energy.

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NERNST EQUATION
o
DG = DG - RTlnQ

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NERNST EQUATION

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Will Fe be oxidised to Fe2+ by reaction with

1.0 M HCI? EO for Fe / Fe2+ = + 0.44 volt.

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Relation between K(equilibrium constant) &

Eo(standard cell potential)

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Some Commercial cell (Batteries)

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ELECTROLYSIS

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PREFERENTIAL DISCHARGE
THEORY

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If an electrolytic solution consists of more than two ions and the

electrolysis is done, it is observed that all the ions are not
discharged at the electrodes simultaneously but certain ions are
liberated at the electrodes in preference to others. This is
explained by preferential discharge theory. It states that if more
than one type of ions are attracted towards a particular electrode,
then the one discharged is the ion which requires least energy.
The potential at which the ion is discharged or deposited on the
appropriate electrode is termed the discharge or deposition"
potential.

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