UNIT – II – Part A

REDOX REACTIONS AND ELECTROCHEMISTRY

Important key points in Unit II are discussed in this document. Students can use this
document to revise the already learned concepts in this unit
Electrochemistry is the study of chemical processes involving redox reactions that cause the
movement of the electrons
Example of a redox reaction

Electrode potential
When a metal is placed in a solution of its ions, the metal tends to undergo either
reduction or oxidation and acquires either a positive or negative charge. On account of this, a
definite potential difference is developed between the metal and the solution. This potential
difference is called 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
M → Mn + ne-
The Mn+ goes into the solution and the electrons remain on the metal making it negatively
charged.
(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 at different speeds but soon equilibrium is
established.
In practice, one effect is greater than the other,

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  If the first effect is greater than the second, the metal acquires a negative charge
with respect to solution and
 If the second is greater than the first, it acquires a positive charge with respect to the
solution, thus in both cases, a potential difference is set up.
Example:
i. Zn in ZnSO4

When Zn is placed in a solution of its salt solution, the

electrons are liberated in the process and accumulated over
the metal. Hence the metal is negatively charged with respect
to solution and thus a potential difference is set up between
zinc plate and the solution. This potential difference is termed
the electrode potential of zinc. Now the negatively charged
metal attracts the positive ions from the salt solution and
hence the formation of a double layer takes place near the
surface of the metal.
ii. Cu in CuSO4
When Cu is placed in the solution of CuSO4, the Cu2+ in the
solution gets deposited over the metal. Hence the metal becomes
positively charged with respect to solution. A potential difference
is set up between the copper plate and the solution. The potential
difference thus developed is termed as electrode potential of
copper. The positively charged metal attracts the negatively
charged sulphate ions in the solution and hence a doubly charged
layer (Helmholtz electrical double layer) is formed near the metal

Thus the electrode potential of a metal is a measure of its relative tendency to lose or gain
electrons, i.e., it is a measure of the relative tendency to undergo oxidation (loss of electrons)
or reduction (gain of electrons).

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 Depending on the nature of the metal electrode to lose or gain electrons, the electrode
potential may be of two types:
 Oxidation potential: The measure of the tendency of a chemical species to act as
an anode. (ie) tend to undergo oxidation readily.
M → Mn+ + ne-
 Reduction potential: The measure of the tendency of a chemical species to act as
an cathode. (ie) tend to undergo reduction readily.
Mn+ + ne- → M
 It is not possible to measure the absolute value of the single electrode potential
directly. The difference in potential between two electrodes can be measured
experimentally. It is, therefore, necessary to couple the electrode with another electrode
whose potential is known. This electrode is termed as a reference electrode. The EMF of
the resulting cell is measured experimentally.
Reference electrode.
 It is an electrode whose potential is arbitrarily taken as zero or is exactly known.
 Examples:
Primary reference electrode: Standard Hydrogen Electrode (SHE)
Secondary reference electrode: Calomel electrode, silver-silver
chloride electrode and glass electrode.

Single electrode potential

 It is a measure of the tendency of a metallic electrode to lose or gain electrons when it
is in contact with its salt solution
Standard electrode potential

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  It is a measure of the tendency of a metallic electrode to lose or gain electrons when it
is in contact with its salt solution of 1 Molar concentration at 25°C
 According to the IUPAC convention, the reduction potential alone be called as the
electrode potential (EO), i.e., the given value of electrode potential can be regarded as
reduction potential unless it is specifically mentioned that it is oxidation potential.
 The standard reduction potential of an electrode means that the reduction reaction is
taking place at the electrode. If the reaction is reversed, then the potential associated
with that reaction is referred to as oxidation potential. The numerical value of the
electrode potential (oxidation) will remain the same as the standard potential but the
sign will be reversed. Thus
Standard reduction potential = - (Standard oxidation potential)
or
Standard oxidation potential = - (Standard reduction potential)
 The EMF of the cell is equal to the sum of potentials on the two electrodes.
 Emf of the cell = EAnode + ECathode = Oxidation potential of anode + Reduction
potential of the cathode
 Knowing the value of the reference electrode, the value of other electrodes can be
determined.
Example: Determination of Standard Electrode Potential of Zn/Zn 2+ Electrode
To determine the electrode potential of zinc, a galvanic cell is constructed connecting the
half-cell consisting of the zinc rod dipped in 1 M zinc sulfate solution with a standard
hydrogen electrode through a salt bridge and measured the EMFof the cell. In this cell, the
zinc electrode acts as an anode and the hydrogen electrode as a cathode and the cell can be
represented as
Zn|Zn2+ (aq)/Anode(-) || 2H(aq)| H2 (g)/Cathode (+)
The half-ceactions are given in the table:

Anode: Oxidation half-reaction Cathode: Reduction half reaction

Zn → Zn2+ + 2e- 2H+ + 2e- → H2↑
The EMF of the cell is 0.76 volt
 ECell = EoAnode + EoCathode 0.76 = Eocathode + EoAnode = 0+ EoAnode

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 EoAnode = + 0.76 V
Similarly, copper electrode potential can be determined by constructing the galvanic cell and
measuring its EMF. The cell representation and the half-cell reactions are as follows
Cell Representation Oxidation half-reaction Reduction half-reaction
H2 (g)|2H+ (aq) ||Cu2+ (aq) |Cu H2 → 2H+ + 2e- Cu2+ 2e- → Cu
 From the measured EMF (ie) +0.34 V, copper electrode potentials can be calculated
using the formula ECell = EoAnode + EoCathode +0.34 V= Eocathode + EoAnode == Eocathode + 0
Eocathode = + 0.34 V
Electrochemical Cell
The cell can convert electrical energy using a chemical process and vice versa is known as
Electrochemical cell
Types of Electrochemical Cells
 Electrolytic Cells
 Galvanic Cells

Electrolytic Cells
 Electrolytic Cells: In these cells, electrical energy is used to carry out a non-spontaneous
reaction. In an electrolytic cell, electrical energy is converted into chemical energy. In
this, as electricity is conducted through an electrolytic solution or its molten form or fused
form generates free ions, so that electrical energy is converted to chemical energy in
electrolytic cells.
 Eg. Electrolysis of molten or fused NaCl.

Galvanic Cells
A galvanic cell is an electrochemical cell in which the electrons are transferred due to redox
reaction to generate electrical energy (i.e. conversion of chemical energy into electrical
energy). In a galvanic cell, two different electrodes are kept immersed in their respective salt
solutions. This cell consists of two half cells and it is connected using a salt bridge.

Example: Voltaic cell or Daniel cell which is represented as

Zn (s)| Zn2+ (1.0M)|| Cu 2+ (1.0 M) | Cu (s)

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 Cell reaction
At anode
Zn Zn2+ + 2e- (Oxidation half cell reaction) E° = -0.76V
At cathode
Cu2+ + 2e- Cu (Reduction half cell reaction) E° = 0.34V
Net cell reaction:
Zn + Cu2+ Zn2+ + Cu (Redox reaction) E° = 1.1V

Electrolytic Cell Vs Galvanic Cell

Electrolytic Cell (s) Galvanic Cell (s)
Electrical energy is transformed Chemical energy is transformed into electrical
into chemical energy. energy.
Non-spontaneous reaction occurs Spontaneous reaction occurs
Anode is a positive electrode & An anode is a negative electrode & Cathode is a
Cathode is a negative electrode. positive electrode.
Ions are discharged on both anode Ions are discharged only on the cathode.
and cathode.
If the electrodes are non-reactive Concentration on the side of anodic half-cell
or inert, the concentration of the increases while that of cathodic half-cell decreases
electrolyte decreases when the when the two electrodes are joined by a wire.
electric current is circulated due
to electrolysis.
Both the electrodes can be fitted The electrodes are fitted in a different cell.
in the same cell.

Salt bridge
 It is usually an inverted U-tube filled with a concentrated solution of inert
electrolytes (ie) ions of inert electrolytes like KCl, KNO 3, NH4NO3, etc., that do not
react with the electrolytes in the two half cells.

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  Salt bridge is prepared by dissolving the gelatin or agar-agar in a hot concentrated
aqueous of an inert electrolyte.

Importance of Salt Bridge

The following are the functions of the salt bridge:

 It helps to complete the connection of both half cells.
 It prevents diffusion of the solutions in both the half cells.
 It helps to build electrical neutrality.
 It avoids liquid-liquid junction potential. (The potential difference arising when two
liquids are in contact with each other.)
Note:
 Salt bridge can be replaced by a porous partition that allows the migration of ions
without allowing the solution to intermix.
EMF of a Galvanic Cell
Every galvanic or voltaic cell is made up of two half-cells, the oxidation half-cell
(anode) and the reduction half-cell (cathode). The potentials of these half-cells are always dif-
ferent. On account of this difference in electrode potentials, the electric current moves from
the electrode at the higher potential to the electrode at a lower potential, i.e., from cathode to
anode. The direction of the flow of electrons is from anode to cathode

 The difference in potentials of the two half-cells is known as the electromotive

force (EMF) of the cell or cell potential and can be calculated from the values of
electrode potentials of the two half-cells constituting the cell

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  When oxidation potential of anode and reduction potential of the cathode are taken
into account:
ECello = Oxidation potential of anode + Reduction potential of cathode
ECello = Eoxo (anode) + Eredo (cathode)
 When reduction potentials of both electrodes are taken into account:
ECello = Reduction potential of cathode - Reduction potential of the anode
ECello = ECathodeo - EAnodeo = Erighto - Elefto
 When oxidation potentials of both electrodes are taken into account:
ECello = Oxidation potential of anode - Oxidation potential of the cathode
ECello = Eoxo (anode) - Eredo (cathode)
Difference between EMF and Potential Difference
The potential difference is the difference between the electrode potentials of the two
electrodes of the cell under any condition while emf is the potential generated by a cell when
there is zero electron flow, i.e., it draws no current.
Nernst equation - Dependence of cell EMF on Concentration
The electrode potential and the emf of the cell depend upon the nature of the
electrode, temperature and the activities (concentrations) of the ions in solution. The variation
of electrode and cell potentials with the concentration of ions in solution can be obtained
from thermodynamic considerations.
Consider an electrochemical reaction,
aA + bB cA + dB

The free energy change of the reaction is given by

ΔG = ΔGo + RTlnK ------- (i)
ΔGo is the free energy change of the reaction under standard conditions and “K” is the
equilibrium constant.
ΔG = - nFE
Substituting this in the equation (i) we get,
- nFE = - nFEo + RT lnK
- nFE = - nFEo + 2.303 RT logK
2.303 RT
E = Eo log K
nF

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 Substituting the values of
R=8.314 JK-1 mol-1; T = 298 K; F=96500 C,
0.0592
E = Eo log K
n
Potential of Single Electrode (Anode)
Consider the general oxidation reaction,
M → Mn+ + ne-
Applying Nernst equation,
E = Eox° - 0.0592/n log [Mn+]/[M]
where Eox is the oxidation potential of the electrode (anode), is the standard oxidation
potential of the electrode.
Note: The concentration of pure solids and liquids are taken as unity
E = Eox° - 0.0592/n log [Mn+] i.e. [M] = 1
Now, let us consider a Daniell cell, concentrations of the electrolytes are not 1 M.
Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s)
Potential at zinc electrode (Anode)
Eox = Eox° - 0.0592/n log [Zn2+]
Potential at Copper Electrode (Cathode)
Ered = Ered° + 0.0592/n log [Cu2+]
Emf of the cell
Ecell = Eox + Ered
Ecell = Eox° + Ered° + 0.0592/n log [Cu2+]/[ Zn2+]
The value of n = 2 for both zinc and copper.
Hence,
 E0 of a cell is known. We can calculate the cell EMF under different concentrations of
CuSO4 and ZnSO4 solutions.
 Thus, Nernst equation helps us to calculate the EMF of various cells under the given
conditions.

Concept of Equilibrium in Electrochemical Cell

In an electrochemical cell a reversible redox process takes place, e.g., in Daniell cell:

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 Zn(s)+Cu2+(aq) Zn2+(aq)+Cu(s)
At equilibrium mass action ratio becomes equal to equilibrium constant, K = Ke
Oxidation potential of anode = -Reaction potential of cathode
i.e., EMF = oxidation potential of anode + Reduction potential of cathode = 0
Cell is fully discharged
According to Nernst equation:
E = Eo - 0.0591/n log10 K at 25o C
At equilibrium, E = 0, K = K
0 = Eo - 0.0591/n log10 K
K = Antilog [(nEo)/0.0591]
Let n faraday charge be taken out of a cell of emf E; then work done by the cell will be
calculated as:
Work = Charge x Potential = nFE°
Work done by the cell is equal to the decrease in free energy.
ΔG = - nFE°
where, Eo = standard emf or standard cell potential.
Electrochemical series
 Electrochemical series also sometimes referred to as activity series is a list that
describes the arrangement of elements in order of their increasing electrode potential
values.
 The series has been established by measuring the potential of various electrodes
versus the standard hydrogen electrode (SHE).
 In the electrochemical series, the electrodes (metals and non-metals) in contact with
their ions are arranged based on the values of their standard reduction or oxidation
potentials.
 This standard reduction or oxidation potentials is obtained by measuring the voltage
when the half cell is connected to the standard hydrogen electrode under standard
conditions.

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 Electrochemical Series
Element Electrode Reaction (Reduction) Standard Electrode
Reduction potential Eo, volt
Li Li+ + e- → Li -3.05
K K+ + e- → K -2.925
Ca Ca2+ + 2e- → Ca -2.87
Na Na+ + e- → Na -2.714
Mg Mg2+ + 2e- → Mg -2.37
Al Al3+ + 3e- → Al -1.66
Zn Zn2+ + 2e- → Zn -0.7628
Cr Cr3+ + 3e- → Cr -0.74
Fe Fe2+ + 2e- → Fe -0.44
Cd Cd2+ + 2e- → Cd -0.403
Ni Ni2+ + 2e- → Ni -0.25
Sn Sn2+ + 2e- → Sn -0.14
H2 2H+ + 2e- → H2 0.00
Cu Cu2+ + 2e- → Cu +0.337
I2 I2 + 2e- → 2I- +0.535
Ag Ag+ + e- → Ag +0.799
Hg Hg2+ + 2e- → Hg +0.885
Br2 Br2 + 2e- → 2Br- +1.08
Cl2 Cl2 + 2e- → 2Cl- +1.36

Au Au3+ + 3e- → Au +1.50

F2 F2 + 2e- → 2F- +2.87

Note:
 When zinc is coupled with SHE, it acts as the anode (-ve electrode) i.e., oxidation
occurs on this electrode.
 Similarly, the +ve sign of standard reduction potential indicates that the electrode,
when coupled with SHE, acts as cathode and reduction occurs on this electrode.

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 Characteristics of Electrochemical Series
 In the electrochemical series, the reduction potential of an element is taken about the
hydrogen scale where Eo = zero. As per the definition, the standard reduction
potential of an element is described as the measure of the tendency of an element to
undergo reduction.
 The substances which have a greater tendency to undergo oxidation are placed above
the hydrogen
 The substances which have a greater tendency to undergo reduction are placed above
the hydrogen
 The substances which are weaker reducing agents or stronger oxidizing agent than
hydrogen placed below hydrogen in the series and have positive values of reduction
potentials.
 The metals on the top (having high negative values of standard reduction potentials)
tend to lose electrons readily. These are active metals.
 The activity of metals decreases from top to bottom.
 The non-metals on the bottom (having high positive values of standard reduction
potentials) tend to accept electrons readily. These are active non-metals.
 The activity of non-metals increases from top to bottom..
Applications of Electrochemical Series
Reactivity of Metals
 The activity of the metal depends on its tendency to lose electron or electrons, i.e.,
tendency to form cation (M"+). This tendency depends on the magnitude of standard
reduction potential.
 The metal which has a high negative value (or smaller positive value) of standard
reduction potential readily loses the electron and is converted into a cation. Such a
metal is said to be chemically active.
 The chemical reactivity of metals decreases from top to bottom in the series. The
metal higher in the series is more active than the metal lower in the series.
For example,
 Alkali metals and alkaline earth metals having high negative values of
standard reduction potentials are chemically active. These react with cold water

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 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
Electropositive Character of Metals
 The electropositive character also depends on the tendency to lose electrons.
 Like reactivity, the electropositive character of metals decreases from top to bottom in the
electrochemical series.
Displacement Reactions
 To predict whether a given metal will displace another, from its salt solution:
 A metal higher in the series will displace the metal from its solution which is lower in
the series, i.e., the metal having low standard reduction potential will displace the
metal from its salt's solution which has a higher value of standard reduction potential.
 A metal higher in the series has a greater tendency to provide electrons to the cations
of the metal to be precipitated.
 Displacement of one nonmetal from its salt solution by another nonmetal:
 A nonmetal higher in the series (towards the bottom side), i.e., having a high value of
reduction potential will displace another nonmetal with lower reduction potential i.e.,
occupying position above in the series.
 The nonmetals which possess high positive reduction potentials tend to accept
electrons readily. These electrons are provided by the ions of the nonmetal having a
low value of reduction potential. Thus, Cl2 can displace bromine and iodine from
bromides and iodides.
Oxidation Half Reduction half-reaction Cell reaction
reaction
2I- → I2 + 2e- Cl2 + 2e- → 2Cl- Cl2 + 2KI → 2KCl + I2
 The activity or electronegative character of the nonmetal increases as the value of
reduction potential increases.
 Displacement of hydrogen from dilute acids by metals:

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  The metal which can provide electrons to H+ ions present in dilute acids for reduction
evolve hydrogen from dilute acids.
Oxidation Half reaction Reduction half-reaction
Mn → Mnn+ + ne- 2H+ + 2e- → H2
 The metal having negative values of reduction potential possess the
property of losing electrons.
 Thus, the metals occupying top positions in the electrochemical series readily
liberate hydrogen from dilute acids and descending in the series tendency to
liberate hydrogen gas from dilute acids decreases.
 The metals which are below hydrogen in electrochemical series like Cu, Hg, Au, Pt,
etc., do not evolve hydrogen from dilute acids.

 Displacement of hydrogen from water:

 Iron and the metals above iron are capable of liberating hydrogen from water.
 The tendency decreases from top to bottom in electrochemical series.
 Alkali and alkaline earth metals liberate hydrogen from cold water but Mg, Zn and Fe
liberate hydrogen from hot water or steam.

 Reducing Power of Metals

 Reducing nature depends on the tendency of losing electron or electrons.
 The more the negative reduction potential more is the tendency to lose electron. Thus,
reducing nature decreases from top to bottom in the electrochemical series.
 The power of the reducing agent increases as the standard reduction potential
becomes more and more negative.
 Sodium is a stronger reducing agent than zinc and zinc is a stronger reducing agent
than iron.
Element Na Zn Fe
Reduction Potential -2.71 -0.76 -0.44
 Alkali and alkaline earth metals are strong reducing agents.

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  Oxidising Nature of Nonmetals
 Oxidising nature depends on the tendency to accept electron or electrons. More the
value of reduction potential, higher is the tendency to accept electron or
electrons. Thus, oxidising nature increases from top to bottom in the electrochemical
series.
 The strength of an oxidising agent increases as the value of reduction potential
becomes more and more positive.
 F2 (Fluorine) is a stronger oxidant than Cl2, Br2 and I2.
 Cl2 (Chlorine) is a stronger oxidant than Br2 and I2.
Element I2 Br2 Cl2 F2
Reduction Potential +0.53 +1.06 +1.3 +2.85
 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.
 Products of Electrolysis
 In case two or more types of positive and negative ions are present in solution,
during electrolysis certain ions are discharged or liberated at the electrodes in
preference to others.
 In general, in such a competition, the ion which is a stronger oxidizing agent (high
value of standard reduction potential) is discharged first at the cathode.
The increasing order of deposition of few cations is:
K+, Ca2+, Na+, Mg2+, Al3+, Zn2+, Fe2+, H+, Cu2+, Ag+, Au3+
 Increasing Order of Deposition
Similarly, the anion which is a stronger reducing agent (low value of standard reduction
potential) is liberated first at the anode.
The increasing order of discharge of few anions is:
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 SO42-, NO3-, OH-, Cl-, Br-, I-
 Increasing Order of Discharge
Thus, when an aqueous solution of NaCl containing Na+, Cl-, H+ and OH- ions is
electrolyzed, H+ ions are discharged at cathode and Cl- ions at the anode, i.e., H2 is
liberated at cathode and chlorine at the anode.
When an aqueous solution of CuSO4 containing Cu2+, H+ and OH- ions is
electrolyzed, Cu2+ ions are discharged at cathode and OH- ions at the anode.
Cathodic reaction Anodic reaction
Cu2+ + 2e- → Cu- 4OH- → O2 + 2H2O + 4e-
Cu is deposited on cathode while O2 is liberated at anode.
 Extraction of Metals
A more electropositive metal can displace a less electropositive metal from its salt's
solution. This principle is applied for the extraction of Ag and Au by cyanide process.
Silver from the solution containing sodium argento cyanide, NaAg(CN)2, can be obtained
by the addition of zinc as it is more electro-positive than Ag.
2NaAg(CN)2 + Zn → Na2Zn(CN)4 + 2Ag
 Predicting the Feasibility of Redox Reaction
Any redox reaction would occur spontaneously if the free energy change (ΔG) is
negative. The free energy is related to cell emf in the following manner:
ΔGo = nFEo
Batteries
 A device that converts chemical to electrical energy.
 They are the collection of one or more electrochemical cells whose chemical reactions
create a flow of electrons in a circuit.
 Basic components are
o Anode (the '-' side) where oxidation occurs
o Cathode (the '+' side) where reduction occurs
o Electrolyte (a substance that chemically reacts with the anode and cathode) –
provides ionic conductivity between anode and cathode.
o Separator –a physical barrier between anode and cathode to avoid direct short
circuiting of the electrodes

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 Battery discharge mechanism

 The most preferable energy storage technology for portable and mobile applications
owing to their low cost, high conversion efficiency, and user-friendly shape, size and
design

Primary batteries Secondary batteries

Irreversible redox reactions occurs
They are mostly used for low drain
applications. On exhaustion of the stored
energy, the batteries can’t be used
again.
Examples: Dry cell, silver oxide battery,
alkaline battery etc
Reversible redox reactions occur
They can withstand high energy drain. On
exhaustion of the stored energy, they can be
charged and the redox reactions are reversed by
passing current through them in the opposite
direction to that of the discharge current
Examples: nickel-cadmium battery, lithium-ion
battery, lead-acid battery

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 Primary Battery –Alkaline Battery/ Heavy Duty Battery
Anode – Zinc; Cathode – MnO2; Electrolyte – KOH ; Cell voltage 1.5 V
Cell reactions are as follows:

 KOH is used in the form of a paste or gel rather than dissolving in water
 MnO2 is mixed with graphite to increase the conductivity
 Anode is a paste containing powdered zinc and this powdered zinc increases the surface
area and improves performance.
 Compared to lechlanche cell, alkaline batteries can sustain heavy use and offers better
performance with very low replacement rate for low-drain applications like flashlights,
portable radios, alarm clocks, remote controls, toys etc

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 Secondary Battery
Lead-acid battery
The lead-acid battery was the first known rechargeable battery.
Anode – Pb; Cathode – PbO2; Electrolyte –H2SO4 (28-30% )
Consists of six galvanic cells connected in series
Each cell generates 2 V; Total cell voltage 12 V

During discharging

Recharging is carried out by applying an external negative voltage to the negative pole and
positive voltage to the positive pole of the cell. On applying voltage higher than the output
voltage obtained during discharge, the reverse of the discharging redox reactions occur and
the electrolyte consumed during discharging is regenerated during charging.
During charging

Advantages: Low cost, high power, and easy recyclability.

Owing to the ability to deliver high current in a very short time, lead-acid battery is ideally
suited as car engine starter. Both the power and energy capacities of lead-acid batteries
depend on the size and geometry of the electrodes. Main drawback of lead-acid batteries is
the decrease in usable capacity when high power is discharged.

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 Nickel-Cadmium Battery
Anode – Cd; Cathode – NiO(OH); Electrolyte – KOH; Cell voltage 1.4 V
In Ni-Cd battery, the two electrodes are separated by using nonwoven fabric immersed in
potassium hydroxide electrolyte.

Advantage: Low maintenance cost, long shelf life than lead-acid battery, high performance
and usable over a wide range of temperature. It is used in calculators, rechargeable flash
lights and electronic camera flashes.
Limitation: Ni-cad batteries are susceptible to a performance decreasing memory effect
resulting in successive recharging in shorter time.
Lithium-ion battery
 Possess high energy density
In commercial lithium-ion battery, graphite act as anode, layered compound such as layered
oxide (LiCoO2) or spinel oxide (LiM2O4) or polyanions (LiFePO4) act as cathode and the
electrolyte is made up of a complex compound of lithium such as LiPF6, LiAsF6.H2O,
LiClO4, etc., dissolved in an organic solvent.
Lithium-ions migrate from anode to the cathode through the electrolyte and get intercalated
into the layered structure of the cathode during discharging where as on applying voltage
during charging, the intercalated lithium-ions move back forcibly to the anode.

Advantage: Minimal memory effect, low toxicity, low self-discharge, longer cycling stability,
excellent efficiency, high theoretical cell potential, and high theoretical energy density.
Hence they are widely used in portable electronic industries.
Limitations: Low earth reserve, instability on exposure to the aqueous environment, high
cost, safety, etc.

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 Capacitors are used to store electrical energy and the stored energy is measured as
capacitance. SI unit is farad (F). Based on electrical parameters, size, functionality,
composition, etc., the capacitors are classified into
(i) electrostatic capacitors (ii) electrolytic capacitors (iii) electrochemical capacitors
Electrostatic capacitors Electrolytic capacitors
Store electrical energy by accumulating Store electrical energy by accumulating
charges on the surface of the electrodes and charges on the surface of the electrodes and
there is no redox reaction occurring in them there is no redox reaction occurring in them
Consists of dielectric spacer such as paper, Uses aluminum or tantalum with an oxide
plastic, ceramic, mica, etc., sandwiched layer as a dielectric, and the electrolyte is
between two conducting electrodes connected to the circuit by another foil
Capacitance range from picofarads to Capacitance range from microfarads to
millifarads millifarads
 The electrochemical capacitor or supercapacitor is an energy storage device that stores
energy electrostatically by polarising an electrolytic solution. Supercapacitor, utilizes
higher surface area electrodes and thinner dielectrics to achieve greater capacitances.
They contain moving ions.
 Supercapacitors are classified into two types, namely, (i) electric double layer capacitor
(EDLC) and (ii) pseudocapacitor

Electric Double Layer Capacitor (EDLC) Pseudocapacitor

In EDLCs, electrical energy is stored by Pseudocapacitors store electrical energy
reversible adsorption and desorption of by reversible Faradaic reactions in
electrolyte ions onto/from the surface of the addition to adsorption and desorption of
electrode material electrolyte ions onto/from the surface of
the electroactive material
High surface area carbonaceous materials are Functionalized high surface area
mostly used as electrode materials carbonaceous materials, metal oxides and
conducting polymers are extensively
studied as electrode materials

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  Supercapacitors are used in electric vehicles, hybrid electric vehicles, digital cameras,
digital communication devices, pacemakers, uninterruptible power supplies, laser
techniques, tramways, starting of diesel engines, and etc.

Fuel Cells
A fuel cell is an energy conversion device that converts the chemical energy of a [fuel
(hydrogen, methanol, etc.) and an oxidant (oxygen or air) into electrical energy. Fuel cell
offers the opportunity to create eco-friendly portable power supplies capable of generating
enough energy to run devices and vehicles. Like a battery, it generates electrical energy by
the electrochemical oxidation of fuel using the oxidant. But unlike a battery, it operates with
the continuous replenishment of the fuel at the electrodes and therefore does not require any
recharging. Since the fuel supplied at the anode does not undergo combustion, the process is
clean, efficient and noise free. Unlike batteries, fuel cells do not run down as they produce
electrical energy as long as fuel and oxidant are supplied at anode and cathode, respectively.
Based on the choice of electrolyte and fuel, fuel cells are classified into
(i) Proton exchange membrane fuel cell (ii) Alkaline fuel cell (iii) Phosphoric acid fuel cell
(iv) Direct methanol fuel cell (v) Molten carbonate fuel cell (vi) Solid oxide fuel cell, etc.
The most common fuel cells are based on the reaction of hydrogen and oxygen to produce
water. The fuel fed at the anode undergoes oxidation into cations and electrons. The cations
flow from anode to cathode through the electrolyte, whereas, the electrons are drawn from
anode to cathode through an external circuit, resulting in the generation of electricity. Oxygen
supplied at the cathode undergoes reduction, combines with positive ions and form water.

Alkaline Fuel Cell

Anode – Fuel (H2); Cathode – Oxidant (O2); Electrolyte – NaOH or KOH
Electrodes - Porous carbon or graphite
Electrocatalysts - Metals, such as Ni, Pt, Pd
Operating Temperature - 60-80oC
Efficiency 40-45%
Output range 10-100 KW

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 Uses: Alkaline fuel cell is used as source of electricity and water in the U.S. space programs

Proton exchange membrane fuel cell

Anode – Fuel (H2); Cathode – Oxidant (O2);
Electrolyte – Nafion, a perfluorinated cation exchange membrane
Electrodes - Porous carbon
Electrocatalysts - Pt
Operating Temperature – 80 °C
Efficiency - 60%
Output range 5 - 200 KW

The protons formed by the oxidation of hydrogen are transported through the membrane to
the cathode side, while the released electron travels through the external circuit powering the
load before reaching the cathode side. Concurrently, the stream of air (oxygen) at the cathode
reacts with the protons to form water molecules.
Uses: This is most suitable for electric and hybrid vehicles owing to its capability to deliver
high energy and power, and low operational temperature.

Solid oxide fuel cell

Solid oxide fuel cell offers several advantages, such as high efficiency, low level of
pollution, high fuel adaptability, high oxygen ion conductivity etc.
Electrolyte – solid-oxide (Yettria stabilized zirconia)
Electrodes - Porous carbon
Electrocatalysts - ceramic
Operating Temperature – 1000 to 1100 °C
Efficiency - 50 to 60%

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 Most commonly anode is constructed using Ni/yettria-stabilized zirconia cermets and cathode
is lanthanum strontium manganite (LSM). The oxygen at the cathode reacts with the electrons
released from the anode to form oxide–ion which then migrate through the oxide-ion
conducting electrolyte to the anode side. The migrated oxide ions subsequently react with the
fuel (hydrogen) to form water
Uses: Owing to its electrolytic resistance to catalytic poisoning, the solid oxide fuel cells can
be used for industrial applications and for the large power plants.

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School of Chemical & Biotechnology