Chapter 3

Electrochemistry

Electrochemistry
 introduction

• Electrochemistry is the study of

production of electricity from energy
released during spontaneous chemical
reactions and the use of electrical
energy to bring about non-spontaneous
chemical transformations

Electrochemistry
 Electrochemical cells
The cell that converts chemical energy
to electrical energy is called daniell’s
•
cell. and has an electrical potential
equal to 1.1 V .

If an external opposite potential is

applied in the galvanic cell then the
• reaction continues to take place till the
opposing voltage reaches the value
1.1 V

Any further increase in the external

potential again starts the reaction but
•
in the opposite direction .

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

Electrochemistry
Functioning of Daniell cell when
external voltage Eext opposing Electrochemistry
the cell potential is applied.
 Oxidation and Reduction

• What is reduced is the oxidizing agent.

➢H+oxidizes Zn by taking electrons from it.
• What is oxidized is the reducing agent.
➢Zn reduces H+by giving it electrons.
Electrochemistry
 Galvanic cells
In this device the Gibbs energy of the spontaneous redox reaction is
• converted into electrical work.(CHEMICAL ENERGY TO ELECTRICAL
ENERGY)

•
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s)
This reaction is a combination of two half reactions whose addition gives the
• overall cell reaction:
•
(i) Zn(s) → Zn2+ + 2e– (oxidation half reaction)
• (ii) Cu2++ 2e– → Cu(s) (reduction half reaction)
•
• The reduction half reaction occurs on the copper electrode while the
oxidation half reaction occurs on the zinc electrode.

These two portions of the cell are also called half-cells or redox couples.
The copper electrode is called the reduction half cell Electrochemistry
The zinc electrode, the oxidation half-cell.
•
Standard electrode potential.
• A potential difference develops between
the electrode and the electrolyte which is
•
called electrode potential. When the
concentrations of all the species involved
in a half-cell is unity then the electrode
potential is known as standard electrode
potential.
•

• In a galvanic cell, 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 Electrochemistry
potential with respect to the solution.
.
•

• The potential difference between the two electrodes of a

galvanic cell is called the cell potential and is measured in
volts. The cell potential is the difference between the
electrode potentials (reduction potentials) of the cathode and
anode.

It is called the cell electromotive force (emf) of the cell when

no current is drawn through the cell.

Ecell = Eright – Eleft

Electrochemistry
•
 Cell reaction:
Cu(s) + 2Ag+(aq) → Cu2+ (aq) + 2 Ag(s)

Half-cell reactions:

Anode (oxidation): Cu(s) → Cu2+(aq) + 2e–

Cathode (reduction): 2Ag+(aq) + 2e– → 2Ag(s)

• silver electrode acts as a cathode .

• copper electrode acts as anode.

The cell can be represented as:

Cu(s) | Cu2+(aq) || Ag+(aq) | Ag(s)

Ecell = Eright – Eleft

= EAg+ // Ag – ECu2+ Cu
Measurement of electrode potential
The potential of individual half-cell cannot be
measured. We can measure only the
•
difference between the two half-cell potentials
that gives the emf of the cell..
Standard hydrogen electrode
• H+(aq)+e– → 1/2H2.
•The standard hydrogen electrode consists of a
platinum electrode coated with platinum black.
The electrode is dipped in an acidic solution.
• •Pure hydrogen gas is bubbled through it.
•The concentration of both the reduced and
oxidised forms of hydrogen is maintained at
unity .
• The pressure of hydrogen gas is one bar and
the concentration of hydrogen ion in the
Electrochemistry
solution is one molar.
Electrochemistry
• Sometimes metals like platinum or gold are used as inert
electrodes. They do not participate in the reaction but provide
their surface for oxidation or reduction reactions and for the
conduction of electrons.

• For example,
• Pt is used in the following half-cells:

Hydrogen electrode: Pt(s)|H2(g)| H+(aq)

•
With half-cell reaction:
• H+(aq)+ e–→ 1⁄2 H2 (g)

Electrochemistry
Standard Reduction Potentials

Lithium has the lowest

electrode potential
indicating that lithium ion is
the weakest oxidising
agent

fluorine has the highest electrode potential

Electrochemistry
indicating that fluoride ion is the weakest reducing
agent.
Oxidizing and Reducing Agents

• The strongest
oxidizers have the
most positive
reduction potentials.
• The strongest
reducers have the
most negative
reduction potentials.

Electrochemistry
 Standard Cell Potentials

The cell potential at standard conditions

can be found through this equation:

E cell = E  red(cathode) − E red (anode)

Electrochemistry
Cell Potentials
• For the oxidation in this cell,
Ered= −0.76 V

• For the reduction,

Ered= +0.34 V

Electrochemistry
 Cell Potentials

Ecell = Ered (cathode) − Ered (anode)

= +0.34 V − (−0.76 V)
= +1.10 V

Electrochemistry
Voltaic Cells

• A typical cell looks

like this.
• The oxidation occurs
at the anode.
• The reduction
occurs at the
cathode.

Electrochemistry
 Nernst’s equation

• We have assumed that the

concentration of all the species
involved in the electrode reaction is
unity. This need not be always true.
Nernst showed that for the electrode
reaction:
• Mn+(aq) + ne–→ M(s)
Electrochemistry
R = gas constant (8.314 JK–1 mol–1)
F = Faraday constant (96487 C mol–1)
T = temperature in kelvin
[Mn+] = concentration of the species.
Calculate the emf of the following cell at 298 K:
Fe(s) | Fe2+ (0.001 M) || H+ (1M) | H2(g) (1 bar), Pt(s)
(Given E°cell = +0.44V
Fe + 2H+ → Fe2+ + H2 (n = 2)
A zinc rod is dipped in 0.1 M solution of ZnSO4. The salt is 95%
dissociated at this dilution at 298 K. Calculate the electrode
potential. [ E°Zn2+ /Zn = – 0.76 V] (log 95= 1.977)

The electode reaction is given as

Zn+2 + 2e → Zn
A copper-silver cell is set up. The copper ion concentration in it is
0.10 M. The concentration of silver ion is not known. The cell
potential is measured 0.422 V.
Determine the concentration of silver ion in the cell.
Given : E°Ag+/Ag = + 0.80 V, E° Cu2+/Cu = + 0.34 V.

At anode (oxidation) :
Cu(s) → Cu2+(aq) + 2e–
At cathode (reduction) :
2Ag+(aq)+ 2e– → 2Ag(s)
At anode (oxidation) :
Cu(s) → Cu2+(aq) + 2e–
At cathode (reduction) :
2Ag+(aq)+ 2e– → 2Ag(s)
 Equilibrium Constant from Nernst Equation
Zn(s) + Cu2+(aq) Zn2+ (aq) + Cu(s)
As time passes, the concentration of Zn2+ keeps on increasing while the
concentration of Cu2+ keeps on decreasing.
. After some time, there is no change in the concentration of Cu2+ and Zn2+ ions
and voltmeter gives zero reading.
This indicates that equilibrium has been attained. In this situation the Nernst
equation may be written as:
Electrochemical Cell and Gibbs Energy of the Reaction
If the emf of the cell is E and nF is the amount of charge passed and ∆rG is the Gibbs
energy of the reaction, then
The standard electrode potential (E°) for Daniel cell is +1.1 V.
Calculate the ΔG° for the reaction
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
(1 F = 96500 C mol-1)

ΔG° = -nF E°cell

E°cell = 1.1 volt

ΔG° = -2 × 96500 × 1.1

= -212300 J mol-1
= -212.3 KJ mol-1
Conductance of electrolytic cells
• The inverse of resistance (R) is called conductance
(G)

• l= length
• A= area of cross section

Unit of conductance = siemens(SI),ohm–1 , mho,

.
Ω–1.

Electrochemistry
Specific conductance(κ)
• The inverse of resistivity (ρ) is called conductivity (specific
conductance) .
• It is represented by the symbol, κ.
• Units of conductivity = S m–1 OR S cm–1.
• Conductivity of a material in S m–1 is its conductance when it
is 1 m long and its area of cross section is 1m2.

ρ=RA/l
Κ=1/ ρ
K= l
A×R
Specific conductance = Cell Constant
Resistance
 Cell constant

• The quantity l/A is called cell constant denoted by the symbol,

•
G*.

• It depends on the distance between the electrodes and their

• area of cross-section.

• The cell constant, G*, is then given by the equation:

G*= llA

Electrochemistry
 MOLAR CONDUCTIVITY
Molar conductivity is defined as the conductivity (K)of
an electrolytic solution divided by the molar
concentration (M) of electrolyte.

Molar conductivity denoted by the symbol Λm (Greek,

lambda).

Unit of Λm = S m2 mol–1 / S cm2 mol–1

Λm= kV.
Equivalent conductance

Equivalent conductance is the conductance of a volume (V) of

solution containing one equivalent of an electrolyte.

Equivalent conductance is denoted by the symbol Λeq (Greek,

lambda).

Λeq = K. V
Volume = in ml

Unit of Λeq = S m2 gm eq–1

The electrical resistance of a column of 0.05 M NaOH solution of
diameter 1 cm and length 50 cm is 5.55 × 103 ohm. Calculate its
resistivity, conductivity and molar conductivity.

A = πr2 = 3.14 × (0.5)2 = 0.785 cm2, l = 50 cm

 Variation of conductivity and molar
conductivity with concentration
• Both conductivity and molar conductivity change with the
concentration of the electrolyte.

Conductivity/MOLAR CONDUCTANCE always decreases with

• decrease in concentration both, for weak and strong
electrolytes.

• This can be explained by the fact that the number of ions per
unit volume that carry the current in a solution decreases on
dilution.

• Electrochemistry
• Molar conductivity of a solution at a given concentration is the
conductance of the volume V of solution containing one mole of
electrolyte

• Λm= k V

Electrochemistry
 • Molar conductivity increases with
•
decrease in concentration. This is
because the total volume, V, of solution
containing one mole of electrolyte also
increases.
Λm= k V

• When concentration approaches zero, the

molar conductivity is known as limiting molar
conductivity and is represented by the symbol
Λ° m.

Electrochemistry
 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.
• Thus, if λ ° Na + and λ ° Cl – are limiting molar conductivity of the
sodium and chloride ions respectively –

Electrochemistry
•
In general, if an electrolyte on dissociation gives ν+
cations and ν–-
anions then its limiting molar
conductivity is given by:

Λ°m= ν + λ° + + –
ν λ ° –
Here, λ ° + and λ ° – are the limiting molar conductivities
of the cation and anion respectively.

Electrochemistry
 Weak electrolytes
•
At infinite dilution i.e., concentration c → zero
the conductivity of the solution is so low that
it cannot be measured accurately.
• o

α is the degree of dissociation

Electrochemistry
•
What is meant by ‘limiting molar conductivity’?
( 2010)
Answer:
The molar conductivity of a solution at infinite
dilution is called limiting molar conductivity and is
represented by the symbol Λ 0. m

Question 2.
Express the relation between conductivity and
molar conductivity of a solution held in a cell.
(2011)
:
Λ = K/C
m
The molar conductivity of a 1.5 M solution of an
electrolyte is found to be 138.9 S cm2 mol-1.
Calculate the conductivity of this solution. (2012)
Answer:
C = 1.5 M, Λ = 138.9 S cm mol
m
2 -1

Λ = K×1000/C
m

∴K = Λm×C/1000
=138.9×1.5/1000
= 0.20835 S cm -1
Calculate the degree of dissociation (a) of acetic acid if its molar
conductivity (Λm) is 39.05 S cm2 mol-1.
Given: λ°(H+) = 349.6 S cm2 mol-1 and λ°(CH3COO–) = 40.9 S cm2 mol-
1 2017)

Answer:
λ° CH3COOH = λ° + λ°
H
+
CH3COO
–

= 349.6 S cm2 mol-1 + 40.9 S cm2 mol-1

= 390.5 S cm2 mol-1
summary

Electrochemistry
 Electrolytic cells and electrolysis
• In an electrolytic cell external source of voltage is used to bring about a chemical
reaction.
• One of the simplest electrolytic cell consists of two copper strips dipping in an
aqueous solution of copper sulphate.
• If a DC voltage is applied to the two electrodes, then Cu2+ions discharge at the
cathode (negatively charged) and the following reaction takes place:
• Cu2+(aq) + 2e– → Cu (s) Copper metal is deposited on the cathode. At the anode,
copper is
• converted into Cu2+ions by the reaction:
Cu(s) → Cu2+(s) + 2e–
• Thus copper is dissolved (oxidised) at anode and deposited (reduced) at cathode.
This is the basis for an industrial process in which impure copper is converted into
copper of high purity. The impure copper is made an anode that dissolves on passing
current and pure copper is deposited at the cathode.
• Sodium and magnesium metals are produced by the electrolysis of their fused
chlorides and aluminium is produced by electrolysis of aluminium oxide in presence
of cryolite. Electrochemistry
 Faraday’s law of electrolysis
Faraday’s two laws of electrolysis are:
•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).
According to faraday Q=It

Electrochemistry
DELETED SYLLABUS
 Batteries
Any battery (actually it may have one or more
than one cell connected in series) or cell that we
use as a source of electrical energy is basically a
galvanic cell where the chemical energy of the
redox reaction is converted into electrical
energy .
There are 2 types of batteries
a)Primary batteries
b)Secondary batteries
Electrochemistry
Batteries

Electrochemistry
 Primary batteries
• In the primary batteries, the reaction occurs only once and after
use over a period of time battery becomes dead and cannot be
reused again.
The most familiar example of this type is the dry cell is also known
as Leclanche cell after its discoverer which is used commonly
in our transistors and clocks.
• The cell consists of a zinc container that also acts as anode
and the cathode is a carbon (graphite) rod surrounded by
powdered manganese dioxide and carbon . The space between
the electrodes is filled by a moist paste of ammonium chloride
(NH4Cl) and zinc chloride (ZnCl2). The electrode reactions are
complex, but they can be written approximately as follows :
• Anode: Zn(s) → Zn2++ 2e–
• Cathode: MnO2 + NH4++ e- → MnO(OH)+NH3 Electrochemistry
• In the reaction at cathode, manganese is reduced from the + 4 oxidation
state to the +3 state. Ammonia produced in the reaction forms a complex
with Zn2+to give [Zn (NH3)4]2+. The cell has a potential of nearly 1.5 V.
• Mercury cell, suitable for low current devices like hearing aids, watches, etc.
consists of zinc – mercury amalgam as anode and a paste of HgO and
carbon as the cathode. The electrolyte is a paste of KOH and ZnO. The
electrode reactions for the cell are given below:
Anode:
Zn(Hg)+ 2OH → ZnO(s) + H2O + 2e–
Cathode:
• HgO + H2O + 2e → Hg(l ) + 2OH–
• The overall reaction is represented by
• Zn(Hg) + HgO(s) → ZnO(s) + Hg(l)
• The cell potential is approximately 1.35 V and remains constant during its
life as the overall reaction does not involve any ion in solution whose
concentration can change during its life time.

Electrochemistry
Alkaline Batteries

Electrochemistry
 Secondary batteries
• A secondary cell after use can be recharged by passing current through it in the
opposite direction so that it can be used again. A good secondary cell can undergo a
large number of discharging and charging cycles.
• The most important secondary cell is the lead storage battery commonly used in
automobiles and invertors. It consists of a lead anode and a grid of lead packed with
lead dioxide (PbO2 ) as cathode. A 38% solution of sulphuric acid is used as an
electrolyte.
• The cell reactions when the battery is in use are given below:
Anode: Pb(s) + SO42(aq)
–
→ PbSO4 (s) + 2e –
Cathode: PbO(s)+SO42-(aq)+4H +(aq)+2e –→PbSO4 (s)+2H2O(l)

• i.e., overall cell reaction consisting of cathode and anode reactions is: Pb(s) +
PbO2(s) + 2H2SO4(aq) → 2PbSO4(s) + 2H2O(l)
• On charging the battery the reaction is reversed and PbSO4(s) on anode and cathode

is converted into Pb and PbO2, respectively .

Electrochemistry
A lead storage battery (secondary
battery)

Electrochemistry
• Another important secondary cell is the nickel-cadmium cell
which has longer life than the lead storage cell but more
expensive to manufacture.
• The overall reaction during discharge is:
• Cd (s) + 2Ni(OH)3 (s) → CdO (s) + 2Ni(OH)2 (s) + H2O (l)

Electrochemistry
 Fuel cells
• Galvanic cells that are designed to convert the energy of combustion of fuels
like hydrogen, methane, methanol, etc. directly into electrical energy are
called fuel cells.
• One of the most successful fuel cells uses the reaction of hydrogen with
oxygen to form water.
• In the cell, hydrogen and oxygen are bubbled through porous carbon
electrodes into concentrated aqueous sodium hydroxide solution. Catalysts
like finely divided platinum or palladium metal are incorporated into the
electrodes for increasing the rate of electrode reactions. The electrode
reactions are given below:
• Cathode: O2(g) + 2H2O(l) + 4e– → 4OH–(aq)
• Anode: 2H2 (g) + 4OH–(aq) → 4H2O(l) + 4e–
• Overall reaction being:
2H2(g) + O2(g) → 2 H2O(l)
• The cell runs continuously as long as the reactants are supplied. Fuel cells
produce electricity with an efficiency of about 70 % compared to thEelercmtroachlemistry
plants whose efficiency is about 40%.
Hydrogen Fuel Cells

Electrochemistry
 corrosion
• Corrosion slowly coats the surfaces of metallic objects with oxides or other salts of
the metal.
• Corrosion of iron (commonly known as rusting) occurs in presence of water and air.
The chemistry of corrosion is quite Complex but it may be considered essentially as
an electrochemical phenomenon. At a particular spot of an object made of iron,
oxidation takes place and that spot behaves as anode and we can write the reaction
• E 0(Fe2+/Fe)= – 0.44 V
• Anode: 2 Fe (s) → 2 Fe2++ 4 e–
• Electrons released at anodic spot move through the metal and go to another spot on
the metal and reduce oxygen in presence of H+(which is believed to be available from
H2CO3 formed due to dissolution of carbon dioxide from air into water. Hydrogen ion in
water may also be available due to dissolution of other acidic oxides from the
atmosphere). This spot behaves as cathode with the reaction
Cathode: O2(g)+4H+(aq)+4e- →2H2O(l)
• The overall reaction being:
2Fe(s) + O2(g) + 4H+(aq) → 2Fe2+(aq) + 2 H2O (l) E(H2O)=1.23V Electrochemistry
• E0=1.67 V
cell
• The ferrous ions are further oxidised by atmospheric oxygen to ferric ions
which come out as rust in the form of hydrated ferric oxide (Fe2O3. xH2O) and
with further production of hydrogen ions.
• Prevention of corrosion is of prime importance. It not only saves money but
also helps in preventing accidents such as a bridge collapse or failure of a
key component due to corrosion.
• One of the simplest methods of preventing corrosion is to prevent the
surface of the metallic object to come in contact with atmosphere. This can
be done by covering the surface with paint or by some chemicals (e.g.
bisphenol).
• Another simple method is to cover the surface by other metals (Sn, Zn, etc.)
that are inert or react to save the object. An electrochemical method is to
provide a sacrificial electrode of another metal (like Mg, Zn, etc.) which
corrodes itself but saves the object.

Electrochemistry
How to Prevent Corrosion ?

Electrochemistry