Electrochemistry

Electrochemistry: It deals with the phenomenon of

interconversion of electrical and chemical energy, the
mechanism of such transformations and other
phenomena associated with this.

Electrolysis: The phenomenon of decomposition of

compounds by electricity is called electrolysis. The
arrangement in which this electrical energy is converted
into chemical energy is known as electrolytic cell. e.g.
when electricity is passed through acidified water, water
decomposes into hydrogen and oxygen.

2H2O(l) → 2H2(g) + O2(g)

Electrolyte: An electrolyte is a substance which

dissociates into ions when dissolved in water. Or the
solutes which conduct electricity in solutions are known
as electrolytes. e.g. NaCl, CH3-COOH, NaOH etc.

Strong electrolyte: These are those electrolytes which

are good conductor of electricity in solution or ionize
completely in aqueous solution. e. g. NaCl, HNO3,
NaOH etc.
Weak electrolyte: These are those electrolytes which
are poor conductors of electricity in solution or
dissociate partially is aqueous solution. e.g. CH3-
COOH, NH4OH, HCOOH etc.

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Insulator: These are the substances which do not
conduct electricity at all. e.g. plastic,

Electrodes: The poles, usually wires or plates through

which electricity is supposed to enter or leave the
solution are termed as electrodes.

Anode: The pole, usually wires or plates through which

electricity is supposed to enter the solution is termed as
anode. Or, the pole at which oxidation reaction occurs is
termed as anode.

Cathode: The pole, usually wires or plates through

which electricity is supposed to leave the solution is
termed as cathode. Or, the pole at which reduction
reaction occurs is termed as cathode.

Cation: The species carrying a positive charge and

moving towards the cathode are referred as cations.

Anion: The species carrying a negative charge and

moving towards the anode are referred as anions.

Coulometer: It is a cell in which measurements can be

made of quantity of electricity passed and the masses of
substances liberated at or dissolved from the electrodes.

Voltameter: The part of the coulometer which is

constructed to allow any gases evolved to be collected.

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Faradays laws of electricity:

1st law: The mass of substance liberated at or dissolved

from an electrode is proportional to the quantity of
electricity passed. The quantity of electricity passed is
measured as the product of current (in ampere) and time
(in second) .i. e. Q = It.

2nd law: When same quantity of electricity passes

through different electrolytes, equivalent masses of
elements are formed at electrode. Mathematically,

w = Itz

w-mass of the substance in gram dissolved by a current

I ampere for t seconds. z- is a constant for a particular
element, termed as electrochemical equivalent.

Electrochemical equivalent: It is the mass of the

substance in gram liberated at or dissolved from the
electrode when one ampere current flows through the
electrode for one second

Faraday: It is the quantity of electrical charge

associated with Avogadro’s number of electrons (or any
mono-valent ion) and equal to 96,500
(6.02x1023x1.6x10-19) coulombs.

Electrochemical or galvanic cell: An arrangement in

which transformation of chemical energy into electrical

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energy takes place is known electrochemical, or
galvanic, or voltaic cell. Or a cell in which electricity is
produced by means of a spontaneous redox reaction.
Common example of such a call is the Daniel cell,
which consists of a zinc rod dipped into a solution of
ZnSO4 and a copper rod dipped into a solution of
CuSO4, the two solutions being separated by a porous
partition which permits the solutions to come in contact
with one another.
V

. . ..………………

Porous partition

ZnSO4 solution CuSO4 solution

Half-cell or electrode: It is the portion of an

electrochemical cell in which a half reaction (oxidation
or reduction) takes place.

Reversible and irreversible cell: A reversible cell is one

which does not give any current when it is connected in
opposite sense to an outside source of emf exactly equal
to that of the cell. If the emf of the external source is
infinitesimally higher then that of the cell then the
current will in opposite direction, i.e. the cell reaction
will be reversed; on the other hand, if the value is
slightly lower current will flow from the cell. e. g.
Daniel cell.

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When in a cell reaction a gas is evolved or a precipitate
is formed the cell is irreversible because the cell cannot
be brought back to its original condition by reversing
the current. e.g. when a cell is prepared by dipping a Zn
and a Cu electrode is a solution of H2SO4. Cell reaction
is
Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g)

When the current is reversed, following reaction occurs,

Cu(s) + 2H+(aq) → Cu2+(aq) + H2(g)

Which is not the reverse of earlier one.

Different types of half-cell or electrode:

(i) Metal-metal ion electrode: In this type of electrode
a metal is dipped into a solution of its ions. e.g.

Ag│Ag+(aq), Zn2+(aq)│Zn, Cu│Cu2+(aq);

the electrode reactions are;

Ag(s) → Ag+(aq) + e- , Zn2+(aq) + 2e- → Zn(s)
Cu(s) → Cu2+(aq) + 2e-

The vertical line, │, represents the direct contact of

metal with its ions in solution, it’s also represented by
“,” as: Ag,Ag+(aq), Zn2+(aq),Zn, Cu,Cu2+(aq)

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(ii) Amalgam electrode: In this type of electrode an
amalgam i.e. a solution of metal in mercury is used
instead of metal and the electrical contact is made by
a platinum wire immersed in the amalgam. Amalgam
electrode is used in Weston standard cell. e.g.

Pt,Cd-Hg(c1),CdSO4(s) Cd2+(c2)(aq)

Pt,Na-Hg(c1) Na+(c2)(aq)

(iii) Metal-metal-insoluble salt electrode: It consists

of a metal in contact with an insoluble salt in contact
with a solution containing the anion of the salt. e.g.

Ag, AgCl(s) Cl-(ci)(aq),

Cl-(ci)(aq) , Hg2Cl2(s) ,Hg,Pt

The electrode reactions of these electrodes considered

to be as taking place in two steps,

Ag(s) → Ag+(aq) + e-
Ag+(aq) + Cl- (aq) → AgCl(s)
Ag (s) + Cl- (aq) → AgCl(s) + e-

Hg2Cl2(s) + 2e- → 2Hg(l) + 2Cl-(aq)

(vi) Oxidation-reduction electrode: In this type of

electrode an inert metal (Pt) dips in a solution
containing ions in two different oxidation states. e. g.

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 Pt , Fe2+(aq),Fe3+(aq) MnO4-(aq),Mn2+(aq),Pt

The electrode reactions are,

Fe2+(aq) → Fe3+(aq) + e- and

MnO4-(aq) + 8H+(aq) + 5e- → 4H2O(l)+ Mn2+(aq)

(iv) Gas electrodes: These electrodes are prepared by

bubbling the gas over the surface inert metal (Pt or
Au) dipped in a solution containing the ions of that
gas. e. g. Pt,H2(g) (P atm) H+(ci)(aq)

The reaction at the electrode,

½H2(g) → H+(aq) + e-
Standard Hydrogen Electrode (SHE): The standard
hydrogen electrode is the reference electrode with
which other electrodes are compared. It consists of a
platinized platinum electrode immersed in a solution of
1mol dm-3 hydrogen ions and hydrogen gas is bubbled
over the platinum electrode at pressure of 1 atm.
Following equilibrium is established on the surface of
the platinum,

H2(g) + 2H2O(l) ⇋ 2H3O+(aq) + 2e-

A potential develops on the surface of the platinum and

assigned a value zero. The standard electrode potentials
of other systems or any electrode potential can be found

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by combining them with a standard hydrogen electrode
and measuring the emf of the cell formed.
Pt

H2 gas at 1 atm pressure

Temperature 250C
Solution of 1M H+ ions

Platinized platinum electrode

Standard hydrogen electrode

Disadvantages of SHE: It is not a convenient reference

electrode to use in measurement for the following
reasons:
(i) Its preparation procedure is very cumbersome.
(ii) Very careful arrangement is required to maintain H2
gas flow on Pt surface at 1 atm.
(iii) Preparation of a soln. of [H+] 1 moldm-3 is difficult.
(iv) Preparation of pure H2 gas is difficult.
(v) Careful handling of H2 gas is needed as it is
inflammable.

Secondary Standard electrode: The hydrogen

electrode is not convenient reference electrode to use in
measurement as maintaining a stream of hydrogen at 1
atm takes careful arrangement. This can be avoided by
using other electrodes those can be prepared easily and
their electrode potentials are constant under certain

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conditions. These electrodes are known as secondary
standard electrodes. e.g.
calomel electrode, Pt,Hg,Hg2Cl2(s)KCl(std.)(aq) and
Pt,Hg,Hg2Cl2(s) KCl(0.1M)(aq),
silver-silverchloride electrode, Ag,AgCl(s) KCl(ci)(aq).
Calomel electrode: Calomel is the most frequently
used secondary standard electrode. It consists of
mercury in contact with mercurous chloride (calomel)
as paste over which is placed a solution containing Cl-
ion, usually KCl. The cell is usually made with 0.1M or
saturated KCl solution. The potential of saturated
calomel electrode is 0.244 volt. The electrode is
represented as Pt,Hg,Hg2Cl2(s) KCl(std.) (aq)

Pt

Hg
Hg2Cl2
Sintered glass disc
Saturated KCl solution

KCl(s)
Sintered glass disc

Saturated Calomel Electrode

The electrode reaction is Hg2Cl2(s)+2e-→2Hg(l)+2Cl-(aq)

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Salt bridge: A salt bridge is a U tube of an electrolyte
in a gel that connects the two half cells of a voltaic cell.
It allows the flow of ions but prevents the mixing of the
different solutions that would allow direct reaction of
the cell reactants. It minimizes the liquid junction
potential. A salt bridge is prepared by filling a doubly
bent tube with agar jelly containing a saturated of
solution of KCl or NH4NO3 or KNO3 (salts having same
transport number ions). The two ends of the tube being
placed in two electrode vessels.
Zn Cu
Salt bridge
saturated of soln. of KCl
in agar gel
Cotton

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