ELECTROCHEMISTRY

PREPARED
BY
GEETHA K
PGT CHEMISTRY, JNV KANNUR , KERALA
 Why Study Electrochemistry?
It is important because
• Many of devices that we
use every day that are
battery powered.
• A big problem called corrosion
is an electrochemical phenomenon.
• Many chemicals and elements
such as Cl2, NaOH, Al etc.
are produced electrolytically.

 DEFINITION

It is the study of the inter-conversion
between chemical energy and
electrical energy.


 ELECTROCHEMICAL CELLS
GALVANIC CELL

What is an Electrochemical Cell?

An electrochemical cell is a device
that can generate electrical energy from the
chemical reactions occurring in it, or use the
electrical energy supplied to it to facilitate
chemical reactions in it. These devices are
capable of converting chemical energy into
electrical energy, or vice versa.
Such cells capable of generating an
electric current from the chemical reactions
occurring in them care called Galvanic cells 
or Voltaic cells. Alternatively, the cells which
cause chemical reactions to occur in them
when an electric current is passed through
them are called electrolytic cells.

 ELECTRO CHEMICAL CELLS

A COMPARISON
GALVANIC CELL ELECTROLYTIC CELL
Chemical energy is transformed into Electrical energy is transformed into
electrical energy in these electrochemical chemical energy in these cells.
cells.
The redox reactions that take place in An input of energy is required for the redox
these cells are spontaneous in nature. reactions to proceed in these cells, i.e. the
reactions are non-spontaneous.
In these electrochemical cells, the anode is These cells feature a positively charged
negatively charged and the cathode is anode and a negatively charged cathode.
positively charged.
The electrons originate from the species Electrons originate from an external source
that undergoes oxidation. (such as a battery).
 DANIEL CELL
In Daniel’s cell, copper ions are reduced at the cathode while
zinc is oxidized at the anode.
Reactions of Daniel cell at cathode and anode are:

At cathode: Cu 2+ + 2e– → Cu

At anode: Zn → Zn2+ + 2e–

 ELECTRODE POTENTIAL
Following two changes occur when a metal rod is dipped in its
 
salt solution, 
(a) Oxidation: Metal ions pass from the electrode into solution
leaving an excess of electrons and thus a negative charge on
the electrode.
The conversion of metal atoms into metal ions by the attractive
force of polar water molecules.
M →  Mn + ne-
(b) Reduction: Metal ions in solution gain electrons from the
electrode leaving a positive charge on the electrode. Metal ions
start depositing on the metal surface leading to a positive charge
on the metal.
Mn+ +  ne- →  M

In the beginning, both these changes
occur with different speeds but soon an
equilibrium is established.

M Mn+ + ne-
In practice, one effect is greater than the
other,
If f irst effect is greater than the second,
the metal acquires a negative charge
with respect to solution and
If the second is greater than the f irst, it
acquires positive charge with respect to
sol ut i on, t h us i n bot h t h e ca se s a
potential difference is set up.
 REFERENCE ELECTRODE
• A reference electrode is an electrode which
has a stable and well-known electrode
potential.
• There are many ways reference electrodes
are used. The simplest is when the reference
electrode is used as a half-cell to build an 
electrochemical cell. This allows the potential 
of the other half cell to be determined. An
accurate and practical method to measure an
electrode's potential in isolation (absolute
electrode potential) has yet to be developed.

 STANDARD HYDROGEN ELECTRODE
(SHE)
 It is reference electrode consists
of a platinum electrode in contact
with H gas (1 atm) and aqueous
H+ions (1 M).
 It is assigned 0.0 V electrode
potential.
 I t may b e h ave as an o d i c o r
cathodic half cell.
 It is represented as
Pt(s)|H2 (g)(aH2 (aq)(aH+
= 1)|H+ = 1).
 When SHE is coupled with an
other half cell then cell potential
is th e valu e of th e electrode
potential of half cell.

 Determination of Standard Electrode
Potential of Zn/Zn  Electrode

2+

•A zinc rod is dipped in 1 M zinc sulphate solution. This
half-cell is combined with a standard hydrogen electrode
through a salt bridge.
•Both the electrodes are connected with a voltmeter.
•The deflection of the voltmeter indicates that current is
flowing from hydrogen electrode to metal electrode or the
electrons are moving from zinc rod to hydrogen electrode.
•The zinc electrode acts as an anode and the hydrogen
electrode as cathodeOxidation
and thehalf
cell can be
reaction
represented
Reduction half
as     
reaction
Cell Representation

Zn|Zn2+ (aq)/Anode(-) || Zn →  Zn2+ + 2e- 2H+ + 2e- →  H2↑
2H(aq)| H2 (g)/Cathode (+)

•The EMF of the cell is 0.76 volt
E0CELL =E0CATHODE - E0ANODE

0.76 =  EoAnode + 0
EoAnode = +0.76 V
 NERNST EQUATION
Reduction Potential under Non-standard Conditions is
determined using Nernst Equation when Concentrations not
-equal to 1M.

where:
E = actual ½ cell reduction potential
Eo = standard ½ cell reduction potential
2 . 303 RT [M ]
E E 
o
log  n = number of electrons in reaction
nF [M ]

0.059 [ 1] T = temperature (K)

E E  o
log 
n [M ] R = ideal gas constant (8.314J/(K-mol)
F = Faraday’s constant (96500 C/mol)
 Nernst Equation for a cell
Reduction Potential under Non-standard Conditions is determined using
Nernst Equation when Concentrations not-equal to 1M. Thus For the cell,
Cu(s)I Cu2+(aq)IIZn2+ (aq)IZn(s)
With cell reaction. Cu2+ (aq) + Zn(s) Zn2+ (aq) +Cu(s)

2
2 . 303 RT [ Zn ]
E  E
o
 log 2
nF [ Cu ]
2
0.059 [ Zn ]
 E  E
o
 log 2
2 [ Cu ]
 NERNST EQUATION......
c d
0 . 05916 [C ] [ D ]
E cell Eo log a b
n [ A] [ B ]

At equilibrium Ecell =0:

0 . 05916
E
o
cell  log K
n

The value of E˚cell is related to Gibbs free energy, ΔG˚ by:

ΔG˚ = –nFE˚cell

The value of Equilibrium constant, K is related to ΔG˚ by:
ΔG˚ = –2.303RT logK
 EQUILIBRIUM CONSTANT
AND GIBB’S
FREE ENERGY FROM NERNST
AtEQUATION
equilibrium Ecell = 0

There fore E0cell = 0.059/n log Kc

log Kc= E0cellX n/0.059


0rG = – nFE0(cell)

Where 0rG is standard Gibb’s free energy of
reaction and E0(cell) is standard emf of the cell

 RESISTENCE & CONDUCTIVITY
• Resistance, R, is proportional to the distance, l, between the electrodes and is
inversely proportional to the cross-sectional area of the sample, A (noted S on
the Figure above). Writing ρ (rho) for the specific resistance (or resistivity),
R =l/Aρ
• In practice the conductivity cell is calibrated by using solutions of known
specific resistance, ρ*, so the quantities l and A need not be known precisely. If
the resistance of the calibration solution is R*, a cell-constant, C, is derived
R*= C X ρ*
• The specific conductance (conductivity), κ (kappa) is the reciprocal of the
specific resistance.
κ = 1/ρ = C/R
• Conductivity is also temperature-dependent. Sometimes the ratio of l and A is
called as the cell constant, denoted as G*, and conductance is denoted as G.
Then the specific conductance κ (kappa), can be more conveniently written as
κ = G* X G

 MOLAR CONDUCTIVITY
• The conductivity is defined as the conductivity
of an electrolyte solution divided by molar
concentration
• Molar conductivity = λ = κ/c m

• if k is expressed in Sm and the concentration, c

–1

in mol m then the unit of λ will be Sm mol .

–3
m
2 –1

• If we use Scm as the units for k and mol cm ,

–1 –3

the units of concentration, then the units for λ m

are Scm mol . It can be calculated by using the

2 –1

equation:
• λ (Scm mol ) = κ(S cm ) × 1000
m
2 –1 –1

(cm /L)/molarity (mol/L).

3

• OR, 1 Sm mol = 10 Scm mol

2 –1 4 2 –1
 CONDUCTIVITY CELL
 While measuring the
resistance (DC)
c h a n g e s t h e
c omp osit ion of t he
solution. So we use an
alternating current (AC)
source.

 A solution cannot be
connected to the bridge
like a metallic wire, so
we use a specially
designed vessel called
conductivity cell.

 VARIATION OF CONDUCTIVITY &
MOLAR CONDUCTIVITY WITH
DILUTION
• Conductivity
decreases with
dilution
• Molar conductivity
increases with
dilution
For strong
electrolytes
Λm=Λ0m-AC1/2


 KOHLRAUSCH’S LAW
 It states that limiting molar conductivity of an
electrolyte is the sum of the individual
contributions of the anion and cation of the
electrolyte.

 Thus, if λ° + and λ° are limiting molar
N a C l -

conductivity of the sodium and chloride ions ,

then the limiting molar conductivity for sodium
chloride is given by the equation:
Ë° = λ° + λ°
m(NaCl) Na+ Cl - .

APPLICATION OF KOHLRAUSCH’S
LAW
• This law may be used to determine the
limiting molar conductivity, ‘λ°m’ degree of
dissociation ‘α’ and dissociation constant
‘Ka’ of a weak electrolyte.

 ELECTROLYTIC CELL AND
ELECTROLYSIS
 Electrolysis: It is the process in which electrical energy is
used to drive a non-spontaneous chemical reaction.

 An electrolytic cell is an apparatus for carrying out
electrolysis.

 Processes in an electrolytic cell are the reverse of those in
a galvanic cell.
 Electrolysis process is used in Manufacture of Cl and
NaOH, Electro-ref ining and Electroplating, Electrolysis of
water etc.

 FARADAY’S LAW OF
ELECTROLYSIS
 (i) First Law: The amount of chemical reaction which
occurs at any electrode during electrolysis by a current is
proportional to the quantity of electricity passed through
the electrolyte (solution or melt).
 (ii)Second Law: The amounts of different substances
liberated by the same quantity of electricity passing
through the electrolytic solution are proportional to their
chemical equivalent weights (Atomic Mass of Metal ÷
Number of electrons required to reduce the cation).

 BATTERIES
 Batteries are the most important practical
application of galvanic cells.
 Single-cell batteries consist of one galvanic
cell.
 Multi-cell batteries consist of several galvanic
cells linked in series to obtain the desired
voltage.

 Types of batteries

PRIMARY BATTERY SECONDARY BATTERY

 A secondary battery after
 In these batteries, the
u se ca n be reu sed by
reaction occurs only
recharging by passing
once and after use over current through it in the
a time period battery opposite direction
becomes dead and  Example: Lead storage
cannot be reused again. cell

 Example: Dry Cell

 DRY CELL
A dry cell is a type of electric battery, commonly used for
portable electrical devices. It was developed in 1886 by
the German scientist Carl Gassner, after development of
wet zinc-carbon batteries by Georges Leclanché in 1866.
The modern version was developed by Japanese Yai
Sakizo in 1887.
A dry cell uses a paste electrolyte, with only
enough moisture to allow current to flow
A common dry cell is the zinc-carbon cell, sometimes
called the dry Leclanché cell, with a nominal voltage of
1.5 volts, the same as the alkaline cell.
It is also called Leclanche cell

Anode: Zinc metal can

Cathode: MnO2 and carbon paste

Electrolyte: NH4Cl and ZnCl2 paste.

Cell Potential: 1.5 V but decreases

to 0.8 V with use.

Anode: Zn(s)  Zn2+ (aq) + 2e-

Cathode: 2NH+4 (aq) + 2MnO2 (s) + 2e-  Mn2O3 (s) + 2NH3 (aq) + H2O
(l)
Overall: Zn(s) + 2NH+4(aq) + 2MnO2(s)  Zn2+ (aq) + 2NH3(aq) + H2O(l) +
Mn2O3(s)
 MERCURY CELL/ BUTTON CELL
A mercury battery (also called mercuric oxide battery, 
mercury cell, button cell, or Ruben-Mallory) is a non-
rechargeable electrochemical battery, a primary cell.

Mercury batteries use a reaction between mercuric
oxide and zinc electrodes in an alkaline electrolyte.

The voltage during discharge remains practically
constant at 1.35 volts, and the capacity is much greater
than that of a similarly sized zinc carbon battery.
Mercury batteries were used in the shape of button
cells for watches, hearing aids, cameras and
calculators, and in larger forms for other applications
Anode: Zn(Hg) + 2OH- (aq)  ZnO(s) + H2O (l) + 2e-

Cathode: HgO(s) + H2O (l) + 2e-  Hg(l) + 2OH- (aq)

Overall: Zn(Hg) + HgO(s)  ZnO(s) + Hg (l)
 LEAD STORAGE CELL

Anode : Pb(s) + SO2- (aq) PbSO4(s) + 2e-

Cathode:
PbO2(s) + 4H+ (aq) + SO42- (aq) + 2e- PbSO4(s) + 2H2O(l)
Overall reaction:
Pb(s) + PbO2(s) + 4H+(aq) + 2SO42-(aq) 2PbSO4 (s) + 2H2O (l)
 NICKEL CADMIUM BATTERY
• The nickel–cadmium battery (Ni-Cd battery or NiCad battery) is a type
of rechargeable battery using nickel oxide hydroxide and metallic 
cadmium as electrodes.
A fully charged Ni-Cd cell contains:
• a nickel(III) oxide-hydroxide positive electrode plate
• a cadmium negative electrode plate
• an alkaline electrolyte (potassium hydroxide).
• anode reaction
• (i) Cd  + 2OH-  ==> Cd(OH)  + 2e-
(s) (aq) 2(s)

cathode reaction
• C




• It is rechargeable
• Cell Potential :1.30 V
• Electrolyte: NiO(OH).

Anode: Cd(s) + 2OH–(aq)  Cd(OH)2(s) + 2e–

cathode reaction
(ii) NiO2(s) + 2e-  + 2H2O ==> Ni(OH)2(s) + 2OH-(aq)
overall cell reaction
(iii) Cd(s) + NiO2(s) + 2H2O ==> Cd(OH)2(s) + Ni(OH)2(s)
 FUEL CELL
 It’s a type of galvanic cell that requires a continuous supply of
reactants to keep functioning.
 Fuel cells are not batteries because they are not self-contained.
 It uses externally fed CH , CHOH or H, which react to form
water.
 Electrolyte: Hot aqueous KOH solution.
 Cell Potential: 1.23 V and have about 40% conversion to
electricity; the remainder is lost as heat. Excess heat can be
used to drive turbine generators.

Anode : 2H2 (g) + 4OH- (aq) 4H2O (l) + 4e-
Cathode: O2 (g) + 2H2O (l) + 4e- 4OH- (aq)
Overall: 2H2 (g) + O2 (g) 2H2O (l)
 CORROSION
 Corrosion is the oxidative deterioration of
metal.

 25% of steel produced goes to replace steel
structures and products destroyed by corrosion.

 Rusting of iron requires the presence of both
oxygen and water.

 Rusting results from tiny galvanic cells formed
by water droplets.

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)
 Prevention of corrosion
 Galvanizing: is the coating of iron with zinc. Zinc is
more easily oxidized than iron, which protects and
reverses oxidation of the iron.
 Cathodic Protection: is the protection of a metal from
corrosion by connecting it to a metal ( a sacrif ic ial
anode e.g. Mg or Zn) that is more easily oxidized.
 Electroplating.
 By applying paint, grease, rubber to prevent contact of
metal surface from air.