You are on page 1of 48


Electrochemistry & Battery Technology 3

Unit-2:Three sub divisions are as
a)Electrode potential and cells
c)Fuel cells
Elcctrochcmistr)' is an important area of physical chemistry. It plays a dominant role in a vast
number of fundamental and appl icd science such as energy storage, energy conversion, biochemistry,
solid state chemistry, materials science and microelectronics. It is basically a consequence of unique
combination or different feature:-> of electrochemical reactions.
In the academic trad il j, !JL electrochemistry deals with interaction between matter and electricity.
In other words, it is the study of relationship that exists between chemical reactions and the now of
electricity. lt involves spontaneous redox reactions that would supply electrical energy and non-
spontaneous changes which are forced to occur by the passage of electricity.

History of Electrochemistry
It was in the sixteenth century when the new phenomenon of electricity was growing, the
electrochemistry took a birth by the Italian physician and anatomist Luigi Galvani ( 1737-
1798). In 1791 Galvani proposed animal electricity. He demonstrated that animal tissue
contained an unknown vital force, which activated nerves and muscles when touched with
metal probes.
Later in the nineteenth century the foundation stone of modern electrochemistry goes to
Alessandro Volta (1745-1827), a professor of natural philosophy at the University of Pavia,
who showed in the early 1800s that the frog legs used in Galvani' s experiments served only
as an electroscope and suggested that the true source of stimulation was the contact
between dissimilar metals. He effectively demonstrated the first electrochemical battery.
Michae.l Faraday ( 1791-1867) is considered to be one of the greatest scientists in history.
Some refer to him as the greatest experimentalist ever, especially because his work on
electricity found expression in day-today technology. Farad, the Sl unit of capacitance, and
the Faraday constant, are named after him.
The momentous period for the growth of electrochemistry was marked by the American
Scientist Josiah Willard Gibbs (1839-1903) in the latter half of the nineteenth century. In
fact he was the first awardees of doctoral degree for an engineering thesis by Yale University.
In 1836, John Frederic Daniell ( 1790-1845) unveiled a two-fluid battery, which was the
l first battery to provided constant and reliable source of current over a long period of time.
\ In 1888, Walther Hermann Nernst (1864-1941) came out with a theory connecting the
i electromotive force (EMF) in an electrochemical cell to the free energy of the chemical

l reaction that produces the current. He formulated the well known Nernst equation. He also
I demonstrated that solvents with high dielectric constants promoted the ionization of

~ ... A
4 Engineering Chemistr

Electrochemistry today has matured into a multidisciplinary branch of study. It is now used
in much fundamental research, such as the study of new organic and inorganic compounds
and biological systems. In more applied research areas, such as used to shape materials
from the macroscopic to the microscopic scale, to understand and prevent the corrosion of
materials at low and extremely high temperatures, to probe the function of living cells, and
to convert chemical energy into electricity. More recently the introduction of in-situ scanning
probe t~chniques has allowed us to follow electrochemical reactions on an atomic or molecular

Electrocheinical cells
Electrochemical cells are the devices which converts chemical energy into electrical ener
or electrical energy into chemical energy by means of electrochemical redox reactions. These ce
consist of two electrodes immersed in a suitable electrolyte. They are broadly classified as follov

Electrochemical cells

Galvanic cells Electrolytic cells

(Voltaic cells) (Conductance cells)

Primary cells Secondary cells

Galvanic cell or voltaic cell is a device which converts chemical energy into elect
energy. The free energy change of the redox reaction at the electrodes is transformed into elect
energy. Eg: Daniel cell, Batteries.
Galvanic cells are further classified into two types.
a. Primary Cell (Irreversible): In this, the cell reaction is not reversible. They ar
rechargeable. Eg: Dry cell, Zn- Ag 20 cell and Zn-air battery and Li-Mn0 2 battery.
b. Secondary Cell (reversible): In this, cell reaction is completely reversible and recharg1
Therefore we use over and over again. These are also called as storage cells. Eg: Lead
storage battery. Ni-Cd battery. Ni- Metal hydride battery & lithium ion battery.

Electrochemistry & Battery Technology - 5

Electrolytic Cell is a device which converts electrical energy into chemical energy.
Eg: Electroplating of metals, electrolysis of water.

Single electrode potential: Single electrode potential is the potential developed at the interface
between metal and its solution when it is in contact with a solution of its own ions and the two
are in equilibrium with each other. It is denoted by 'E'.
Standard electrode potential: Standard electrode potential is the potentittl developed when
the pure metal electrode is in contact with a solution of its ions of unit concentration at 298 K.
If the electrode involves gas, then the gas is at 1 atmo~pheric pressure. It is denoted by E0 •
Emf of a cell: The potential difference between the two electrodes of a cell which causes the
flow of current from one electrode (high reduction potential) to the other (lower reduction
electrode) is called electromotive force of the cell. It is denoted by Eccll'
Emf of cell = Reduction potential of cathode- Reduction potential of anode

Ecell = E<:<Hhoue - Eanode

F Emf of a cell depends upon the

1) Nature of the metals which constitutes the two half cells.
2) Concentrations of solutions of 2 half cells.
3) Temperature.
but, Emf of cell does not depend on the size and area of the electrode.

Construction and working of a Galvanic cell (Daniel cell)

Daniel cell (fig. 1) consists of a Zn rod dipped in 1M solution of ZnSO4 forms a half cell and
Cu rod dipped in l M solution of CuSO 4 forms another half cell. The two half cells are internally
connected by a salt bridge (an inverted U-shaped glass tube filled with saturated KCl solution) and
the two ends of the salt bridge are plugged with a porous material. The two electrodes are connected
externally by a wire through voltmeter.
The two half cell reactions are represented as follows:
At Anode : Zn oxidizes to Zn2+ liberating two electrons.

At Cathode: Cu 2+ ions reduces to Cu by accepting two electr<?ns.

Thus the Net cell reaction Zn + Cu 2+( 1M) -----.• Zn2+ (1M) + Cu
Engineering Chemist~

Volt meter
e- ... e- ...

Salt Bridge

Zn (anode) - - - •

CuSO~ (I M)
ZnS04 OM)
Solution Porous

Figure I : Daniel cell

The electron liberated at the zinc half cell builds up an electrical potential difference. i.e ..
electrons move from the zinc electrode (Anode) to the copper electrode (Cathode) producing a
current in the circuit which is indicated by voltmeter. In the gaLvanic cell, the electrode where
oxidation takes place is referred as anode which is assigned with a negative sign and the electrode
where reduction takes place referred as cathode which is assigned with a positive s1gn.

Functions of salt bridge

A salt bridge helps to,
• Bring about internal contact between the electrodes.
• To minimize liquid junction potential.
• To maintain electrical neutrality
• To minimize polarization.

Electrochemical conventions
1. There arc two electrodes in galvanic cell. Each of these electrodes is referred to as half cell.
2. If reduction occurs at an electrode, it is called a reduction (positive) electrode or cathode. lf
oxidation occurs at an electrode. it is called an oxidation (negative) electrode or anode.
'· :
3. The potential of an electrode is always expressed as reduction potential and is represented as

4. The electrode at which oxidation occurs (anode) is written on the LHS and the electrode at
which reduction occurs (cathode) is written on the RHS.

Electrochemistry & Battery Technology

5. The electrode on the lcfl (anode) is written by writing the metal first and then the electrolytic
solution. For example. ZniZnSO.l
6. The electrode on the right (cathode} is written by writing the electrolytic solution first and then
the metal. For example. CuSO ~!Cu.
7. The single vertical line indicates the phase boundary between the metal and the electrolytic
so!wion and double vertical line indicates the salt bridge
... .
8. The concentration of corresponding electrolytic solutions is represented in the parenthesis.
The arrow mark indicates the directiPn of flow of electrons i.e., from anode to cathode.
For example. a Daniel celi can be represented as:
.. II cu~+ (1M) !Cu
Zn!ZnSO-' ( l M} II CuSO-' (I M) !Cu or Zn!Zn~+ (1M)

<J. The EMF of a cell is given by

FJcl'll =E C011hnde
- E;\nod,· or Eeel! = EC - EJ:\
where Ec and E,\ are the reduction electrode potentials of Cathode and Anode respectively.

Derivation of Ncrnst c<tuation for single electrode potential NOT IN THE SYLLABUS

Ncrnst clcrivccl a thermodynamic equation which relates the change in free energy (~G), electrode
potential <E) and the concentration of metal ions (M +). He considered a reduction reaction or the


M(aq) + ne

The change in the free energy for spontaneous reaction is related to equilibrium constant (K) by
Van 't Hoff equation:
L1G = L1G 0 + RT ln K
Where L1G is the free energy change, L1G0 is the std. free energy change
R is the Universal gas constant, Tis the absolute temperature and K is the equilibrium constant.
Equilibrium constant for the reduction reaction of the type, Mn+ + ne- --7 Misgiven by,

[M] ----- (~)


For a spontaneous reaction, decrease in the free enngy (- L\G) is the maximum amount or work
and is given by
- L1G = W max ----- fl)
But the maximum amount of work done for an electrochemical reaction depends on the number of
coulombs of electricity that flow and the energy available per coulomb.
8 Engineering Chemistry

i.e., W = nFE ----- ( 4)


Where, n =number of moles of electrons involved in the reaction.

F = Faraday's constant E = Electrode potential

Then, The relationship between free energy change (ilG) and electrode potential (E) is given by
ilG = -nFE ----- (5)
Under standard conditions, NOT IN THE SYLLABUS
ilGu = -nFEu ----- (6)
On substituting (2), (5), (6) in (1 ), we get

-nFE = -nFE" + RT ln ----- (7)

Divide equation (7) by -nF, on both sides and converting natural logarithm to the base 10,
We get

E = E" _ 2.303RT log [[M] ] ----- (8)

nF M'l+

Under standard conditions [M] = I, hence the above equation reduces to

E = Eo_ 2.303 RT log [l]


E = Eo+ - - - log [Mn+] ----- (9)
On substituting the values for
R = 8.314 1/K/mol
T = 298 K
F = 96500 C/mol, the above equation reduces to
E =Eo+--- log [M"+] ----- ( 10)

The above equation (10) is known as the Nernst equation for single electrode potential.

Electrochemistry & Battery Technology 9

Application of Nernst equation

• The potential of an electrode and EMF of a cell can be calculated at any temperature
and concentration.
• Knowing potemial of an electrode, the concentration of the electrolyte can be calculated.

NOTE : Nernst equation for a cell

Let us consider a celL
M, I M,n+ I M~n+ I M2

\Vhich is obtained by connecting two half cells

The net cell reaction is given as
M I + M 2n+
The emf of the cell is

Eo 2.303 RT [Metal ion concentration at cathod]

Ecell = . . cell + nF log [Metal ion concentration at anode]

Eo 2.303 RT
Ecell = cell+ nF

Ecdl =

where, [M 111+] =The metal ion concentration at Anode

[M/+] = The metal ion concentration at Cathode
For Daniel eel I,

. 0.0591 [ Cu 2+]
Ecell = Eo cell +
log [
Zn 2
J Where ' E0 CC ll -_ E0 Cu 2+ _ E0 Zn2+

10 Engineering Chemistry


I. Calculate the standard electrode potential of Cu 2+/Cu if its electrode potential at

25°C is 0.296V when [Cu 1+] ().015 = [VTU, June, 200S]

Solution :
" 0.0591
E = E + log [M 11 +]

(l 0.0591
E = E- log [Cu 2+]

l 0.0591
E' = 0.296 - log (0.0 15)

E 0 = 0.349V

2. Calculate the voltage generated in the following cell lVln/i\tln 2+ II· Fc2+fFe when
iron rod is immersed in l.OM FeS04 solution and i\tln rod is immersed in O.llVl

1\:fnSO,.. solution. Given E".1- c-'+II'.c =- 0.40 V and E'l\'1n z+1 '', 111 =- 1.18 volt. [Feb, 2001]

Solution :
(i) Cell representation:
Mn!Mn 2+ (0.1 M) II Fc 2+ ( 1.0 M)IFe
( ii) Electrode reactions :
At anode: Mn ~ Mn 2+ + 2e-
At cathode: Fe2+ + 2e- ~ Fe
Net cell reaction: Mn + Fe 2+ ~ Mrl~+ + Fe

(iii) The emf of the cell is

E = E'
0.0591 [Fe 2+ J
log -=-[M'------ +::;.]
cdl cdl 2
11 11

0 059 1
E = (E" '+ .. -Eo .,+ ) + - · - - loll _l.O
cdl Fe- /l·c Mn- /Mn 2 ° 0.1

= = [-0.40-(-1.18)] + 0.02lJ55 x log (10) = 0.78 + ().02955 xI

Ecetl = 0.8095 V

Electrochemistry & Battery Technology 11

3. Calculate the potential of Ag-Zn cell at 29HK if the concentration of Ag+ and Zn 2+are
5.2 x w-6 J\1 and 1.3 x 1()·-' l\'1 respectively. E0 of the cell at 298K is 1.56 V. Calculate
the change in free cnerg)' L1G for the reduction of lmole of Ag+. [July, 2006]
Solution :
\Ve know from electrochemical series that, E(,); g+ 1"g
, > E • .,
Zn - /Zn
so Zn becomes anode and A2:'-
become cathode.
At anode:
At cathode:
Net cell reaction:

.. Ecell = E0 .. 11 +
[ Ag+
[ zn-,,
,, n lY

= 1.56 + 2 log '-

= 1.56 + 0.02955 log [20.8 X Io-lJ]

= 1.56 + (0.02955 X -7 .6819]
= 1.56- 0.2270
Ecdl = 1.3329 V
L1G =- nEF
= -1 x 1.3329 x 96,500 for 1 mole of Ag+

~G = -128.62 kJ/mol
4. Calculate the potential of Ag-Cu cell at 298K if the concentration of Ag+ and Cul+ arc
4.2 x l0-1' M and 1.3 x 10·3 J\11 respectively. Given E"Ag + /Ag = 0.80V, E"cu 2+ 1cu = 0.34V of
the cell at 298K. Calculate the change in free energy L1G for the reduction of I mole
of Ag+.
[Jan, 2004]
Solution :
At anode: Cu -7 Cu:!+ + 2c-
At cathode: [Ag++ e- -7 Ag] x 2

Net cell reaction: Cu + 2Ag+ -7 2Ag + Cu 2+


12 Engineering Chemistry

o 0.0591 (Ag+]
Ecdl = Eccll + lol!..., [ C ,,<.+ ]
n ,u

0 0591 [ 4 2 X 10-(, ]
= (0.80-0.34) + · log -:::--·---
2 [ t.3 x 1o-3 J
= 0.46 + 0.02955 log [ 13.56 x tO-'~]

= 0.46 + [0.02955 X- 7.867]

= 0.46- 0.2324
£cell = 0.2275 V
~G =- nEF
= - 1 x 0.2275 x 96.5 for l mole of Ag+
~G = - 21.95 kJ I mol

5. The E11 values of Jj+/Li , Zn 2+/Zn, Cu 2+/Cu and Ag+/ Ag are - 3.0V, -0.76V, + 0.34V,
and +0.80 Volts respectively. \Vhich combination of the electrodes you usc to construct
a cell ot' highest emf, if the ionic concentrations nrc O.lM, l.Ol\1, 101\'1 and ().() lM in
the same order. .Justify your answer. [July, 2005]
Solution :
The potential of a half cell is

E = E" + 0.0591 log [Mn+]

i) For Li+ /Li, the electrode potential is
E = - 3.0 + log (0.1)
= -3.0 + (0.0591 X- 1] =- 3.0591 V
ii) For Zn ~+ /Zn, the electrode potential is
E = -0.76 + log (1.0)
= - 0.76 v
iii) For Cu- /Cu, the electrode potential is

E = 0.34 + log (1 0.0) =0.34 + 0.02955 x 1
= 0.3695 v
Electrochemistry & Battery Technology 13

iv) For Ag+ lAg, the electrode potential is

E = 0.80 + log (0.0 I)

= 0.80 + (0.0591 X -2]

= 0.80- 0.1182
= 0.6818 v
From the above E values, if we couple Ag.,./Ag (as cathode) and Li+fLi (as an anode) the cell
(rencrates highest emf.

E cell =E cathode -E a11<•<.k

= 0.6818 + 3.0591

Ecell = 3.7409 V

6. Calculate the emf of the cell Fe /Fe 2+(0.011\tf) II Ag+ (O.lM)/Ag at 298K, if SRP of Fe and
Ag are- 0.42 and 0.8V respectively. [VTU, Jan 2008]

, Solution :
'~ At anode: Fe ---7 Fe2+ + 2e-

At cathode: [Ag++ e- ---7 Ag] x 2

Net cell reaction: Fe+ 2Ag+
---7 ,.,
Fe 2+

(l 0.0591
Eccll = Eccll + log


E _ (E -E ) 0.0591 l (0.1r
cell - Ag+/Ag
Fc +/Fc + 2 og [0.01]

= [0.8- (-0:42)] + 0.02955 log (I)= 1.22 + 0

Eccll = 1.22 V
7. Calculate the voltage of a cell which consists of a iron rod immersed in a 1M solution
of FeS04 and manganese rod immersed in a O.lM solution of MnS04 at 25°C.Write
the cell reaction. Given E~.d' 2+ 11•c• =- 0.44 V and E0Mn 2+ /Mn =- 1.18V.
[VTU, July 2011]
14 Engineering Chemistry

Solution :
(i) Cell rcpresentalion :
MniMn~+ (().I M) II Fe 2 + ( 1.0 tv{) ! Fe
(ii) Electrode reactions :
At anode: Mn -7 Mn 2+ + 2e-
At cathode: Fe 2+ + 2e- -7 Fe
Net cell reaction:
(iii) The em!' of the cell is :

[Fe _,_ J
( 0.0591
E' + - - - loo -="----=
= ccll n c [Mn2+ J

I Ecdl log-
! ~ 0.1
= [-0.44-(-1.1 X)j + 0.02955 = 0.74 + 0.02955
E cell = 0.7696 V

8. An electrochemical cell consists of an iron electrode, dipped in O.lM FeS0-1 and

silver electrode dipped in O.OSlVI AgN0 3 solution. "Vrite cell representation, cell
reaction and calculate the emf of the cell at 29XK. Given SRP of Fe and Ag arc -0.44
and +0.8V rcspcctively.[VTU, Jan 2011]
(i) Cell representation:
FeiFeS0 4 (0.1 M) I AgN0 1 (0.05 M) I Ag
(ii) Electrode reactions:
At anode: Fe -7 Fe 2+ + 2e-
At cathode:
Net cell reaction: Fe + 2At!+
.... -7 2Ag + Fe2+

(iii) The emf of the cell is

o 0.0591 [Ag+]
Ecell = Ecell +
n log [ Fe-+
, J

II II ) o.o59t [o;osr
Ecell = ( E Ag + /Ag - E Fe-'+ /Fe + 2 tooo [ 0.1 ]

Electrochemistry & Battery Technology 1'5

= [0.8-(-0.44)] + 0.02955 log (0.025) = 1.24-0.0473

Eccll = 1.1927 V

9. A galvanic cell is constructed by coupling Ag and Cd electrodes dipped in 0.51\'1

AgN0 3 and 0.251\'1 CdSO.t respectively at 25uc. \Vrite the cell scheme, cell reaction
and calculate emf of the cell. Given SRP of Ag and Cd are 0.80 and -0.40V respectively.
[VTU, june 2010]
(i) Cell representation:
CdiCdS04 (0.25 M) II AgNOJ (0.5 M) I Ag
(ii) Electrode reactions:
At anode: Cd ~ Cd~+ + 2e-
At cathode: [Ag+ + e- Ag] x 2
Net cell reaction: Cd + 2Ag+ ~ 2Ag + Cd:!+
(iii) The emf of the cell is

- Eo + 0.0591 loo [ Ag+
- cell n o [ Cd 2+

_(Eo+ -Eo J+ ) o.059I [

Eccll - Ag /Ag cct- /Cu + 2 log (0.25]

= [0.8- (-0.40)] + 0.02955 x log 1 = 1.2 + 0

E ccII = 1.2 v
10. An electro chemical cell is formed from Ni and Pb electrodes having 0.01 M NiS04
and 0.5M PbSO 4 electrolytes. The standard electrode potentials of Ni and Pb
electrodes are -0.24V and -0.13V respectively. Write the cell scheme, cell reaction
and calculate emf of the cell at 298K. [VTU, Jan 2012]
(i) Cell representation :
Ni I NiS04 (O.Ot M) II PbS04 (0.5 M) I Pb
(ii) Electrode reactions:
At anode: Ni ~ 2
Ni ++ 2e-
At cathode: Pb 2+ + 2e- ~ Pb
Net cell reaction: Ni + Pb 2+ ~ Pb + NF+

16 Engineering Chemistry

(iii)The emf of the cell is,

[ Pb +]

Ecell = Eo 0.0591 log -=--------=-

cell + n . [ Ne+ J
0 0 ) 0.0591 [05]
Ecell = ( EPb2T tPb- ENi2+ tNi + 2 log [0.01]

=:= [- 0.13 - (-0.24)] + 0.02955 log 50 =0.11 +0.050

Ecell = 0.16 V
Types of electrodes
The following are the six important types of electrode:

1) Metal-Metal ion electrodes: These are the electrodes where a metal is dipped in a solution
containing its own ions. Eg: CuiCuSO 4, ZniZnSO 4

2) Gas electrodes: These are the electrodes where a gas is in contact with an inert metal like
Pt foil which is dipped in an ionic solution of gas molecules. Eg: Hydrogen electrode.

3) Metal-Metal Insoluble salt electrodes: These are the electrodes where a metal will be in
contact with a insoluble salt of the same metal dipped in a solution containing anions of the
Eg: Calomel (HgiHg 2 Cl~lcn, Silver-silver chloride electrode (AgiAgCliCn.

4) Ion selective electrodes: These are the electrodes which are sensitive to particular ionic
species and will develop a potential when a membrane is in contact with an ionic solution. Eg:
Glass membrane electrode

5) Redox electrodes: These are the electrodes, where the inert metal like Pt will be in contact
with oxidized and reduced forms of the same metal in solution. The electrode potential arises
due to the presence of both oxidized and reduced species of the same metal at an inert
electrode like Pt. Eg: Pt/Fe2+;Fe3+, Pt/Cr3+;Cr6+, Pt/Sn~+;Sn4 +

6) Amalgum electrode: An amalgum electrode is a modification of metal-metal ion electrode.

Amalgum is the alloy of any me~al with mercury. In place of a metal, its solution in mercury is
used. Eg. Zinc amalgam electrode Zn (Hg)/ ZnS04 •

Reference electrodes
Reference electrodes are those electrodes which have constant reduction potential and
which are used to determine the electrode potential of other electrodes. There are two types of
reference electrodes.

Electrochemistry & Battery Technology 17

I. Primary reference electrode. Eg: Standard hydrogen electrode (SHE).

2. Secondary reference electrode. Eg: Calomel electrode, Silver-Silver Chloride electrode.

Limitation of prin1ary reference electrode

I. It is difficult to construct hydrogen electrode.
2. It is difficult to maintain H+ ion concentration at IM.
3. It is difficult to maintain constant pressure (1 atm) of the~ gas.
4. H2 gas should be pure. If any impurities present in the H2 gas, the Pt electrode becomes
5. It cannot be used in the presence of strong oxidising and reducing agents.
6. Presence of arsenic compounds would poison the Pt foil.

Secondary reference electrodes : These are the type of electrodes whose reduction potential
remains constant and their potential is measured w.r.t SHE and can be used as reference
electrode for measuring potential of other electrodes and for various analytical analysis.

Requirement of seconda~y reference electrodes

I. It should be portable.
2. It should not be bulky.
3. It should not be easily poisoned by the impurities.
4. Its electrode potential should not change even with change in pH of the solution.

Construction and working of calmnel electrode

Construction: Calomel electrode is a
metal-metal insoluble salt electrode. ,-----External contact
Dipping type calomel electrode is shown
in figure 2. It consists of a two glass
tubes. A -..;·•all amount of graphite is
placed at the bottom of the inner glass
tube covered with paste of Hg and
mercurous chloride (calomel) and above _:t.t.ol!":!":!t---=-Saturated KCl
which mercury is placed. The remaining
portion of both inner and outer tube is Paste of Hg + Hg2Cl 2 (Calomel)
filled with saturated KCI solution. A
platinum wire is dipped in the inner tube ~--Graphite
and is used to provide external electrical
contact. The porous plug at the bottom
of the outer tube acts as a salt bridge.
--Porous plug (Salt bridge)
Figure 2 : Dipping type calomel electrode
18 Engineering Chemistry

The calomel electrode is represented as :

PtiHgiHg:!Cl 2IKCl (sat)
Working : Calomel Electrode can act as anode or cathode depending on the nature of the other
a) When it act as anode the electrode reaction is
2Hg + 2Cl
b) When it act as cathode the electrode reaction is
Hg 2Cl 2 + 2e- - - • • 2Hg + 2Cl-

The overall electrode reaction: Hg 2CL2(s) + 2e- -;===~ 2Hgw + 2Cl

The electrode potential is given by

IEcalomcl = Eo- 0.0591 log [Cf]l

From the above equation it is clear that as the concentration of Cf ion increases, the electrode
potential decreases. The electrode potential depends on the concentration of chloride ions and the
electrode is reversible with respect to chloride ions. At 298K, the electrode potentials are as follows.

KCl concentration 0.1N 1N Saturated

Electrode potential (V) 0.3334 0.2810 0.2422

1) Calomel electrode is easy to construct and portable
2) Cell potential is reproducible.
3) Potential is stable over a long period.
4) It can be used in the presence of strong oxidizing agent.
1) It is used as a secondary reference electrode in the measurement of electrode potential of
other electrodes.
2) It is used as reference electrode in all potentiometric titnitions.
3) It is used as reference electrode with· glass membrane electrode in pH determination.

Construction and working of silver - silver chloride electrode

Construction: Silver- silver chloride electrode is a metal-metal insoluble salt electrode. It consists
of a silver wire partially coated with AgCl, dipped in saturated KCl solution. The porous plug at
the bottom acts as a salt bridge (fig. 3).

Electrochemistry & Battery Technology 19

.-----External contact

Saturated KCl

Ag coated with AgCl

--Porous plug (Salt bridge)

Figure 3 : Dipping type silver-silver chloride electrode.

The silver-silver chloride electrode is represented as:
Ag jAgCljKCl (sat)
Working: Silver-silver chloride electrode can act as anode or cathode depending on the nature of
the other electrode.
a) When it act as anode the electrode reaction is
Ag+Cl _ _._., AgCI +e-
b) When it act as cathode the electrode reaction is
AgCl + e- _ __,.._., Ag + Cl

~ Ag (s) +
The overall electrode reaction: AgCl(',lll) + e- ,..,.r=:::=:::.. cr .(<lljJ

The electrode potential is given by

I EAgiAgCI = E"- 0.05911og [Cr] I

From the above equation it is clear that as the concentration of CI- ion increases, the electrode
potential decreases. The electrode potential depends on the concentration of chloride ions and the
electrode is reversible with respect to chloride ions. At 298K, the electrode potentials are as follows.

KCI concentration O.IN IN Saturated

Electrode potential (V) 0.2901 0.2230 0.1999


20 Engineering Chemjstry

1) It is easy to construct and portable.
2) Its superior tempera~ure stability makes it usable even above 130°C.
3) The potential remains constant as long as the chloride concentration remains constant.
4) The potential is stable over a long period.

1. It is used as an internal reference electrode in glass membrane electrode.
2. It is used in determining the potential distribution on the ship's hulls and oil pipelines.
3. It is used in corrosion studies.

Measurement of standard electrode potential using calontel electrode

Eg: Determination of std. electrode potential of zinc electrode
To measure the standard electrode potential of Zn electrode it has to be coupled with calomel
electrode. The emf of the cell is determined using an electronic voltmeter (figure 4 ).

Zinc electrode Calomel electrode

Lr-rn-~ Pt wire

:::J-U!¥,......_-=- KCI( 1M)

:.:=::~..---.- Paste of Hg
+ Hg 2 CI 2 [calomel}


Porous Plug [salt bridge]

------- ZnS0 4 (1 Ml ------

Figure 4. Zinc-calomel electrode cell.

Cell representation
Zn I Zn2+ (1M) II KCl (lN) IHg2Cl 2 IHgiPt
The electrode reactions are:
At anode: _ ____..;,.~ Zn 2+ + 2e- (Oxidation)
At cathode: _ _.,..,.. 2Hg + 2Cl (Reduction)

Net cell reaction: Zn + H~Cl 2 --•)11 Zn 2+ + 2Hg + 2Cl


E:lectrochemistry & Battery Technology 21

b) Assigning sign on electrode

When the two electrodes are connected to voltmeter direction of the current indicates sign ofu

he electrode. In case of Zn electrode it takes negative sign and is assigned as anode. Calomel
~lectrode takes positive sign and assigned as cathode.

c) Calculation

Ecell =Ecalomel -E,


The emf of the cell was found to be 1.040 V.

Ecalorncl is 0.2810 V for IN KCl solution.

Therefore, 1.040 = 0.2810- Eznl+tzn

E,~ 2+1,~ =-0.759V ::: -0.76V = E~ n

2+tzn [because [Zn 2+] = lM]

on selective electrodes
Ion selective electrodes are tlze electrodes which are sensitive to certain specific ions
resent in the solution and they develop the potential with respect to that species. Eg: Glass
1embrane electrode.
Glass membrane electrode is an ion selective electrode in which a thin membrane present is
ermeable only to H+ ions and not to other ions in the solution. It develops the potential if any
hange in the H+ ion concentration.

~onstruction and working of a glass membrane electrode

~onstruction: A typical glass membrane electrode is shown in the figure 5. It consists of a long
lass tube with a thin walled (0.01-0.03 mm) bulb at the bottom. This is made up of special corning
lass of relatively high electrical conductivity, low melting point and high hygroscopic in nature. The
pproximate composition of glass membrane is 72% Si0 2 , 22%Na20 ancl6% CaO. It specifically
!lows only H+ ions up to a pH range from 1 to 9. The bulb is filled with 0.1 M HCl in which a silver
;ilver chloride electrode is clipped as an internal reference electrode and is connected for external
lectrical contact.

22 Engineering Chemistry

,-----External Contact

-~---+-<~1M HCI (C,)

____________ -_-_-_-_+--Test solution (C 2 )

Figure 5. Glass membrane electrode.

The glass membrane electrode is represented as:
AgjAgCll HCl (O.lM) lglass membrane.
Working: When the glass membrane electrode is dipped in the test solution, the Na+ ions of the
glass membrane is exchanged with H+ ions of the test solution.

Na+Gl + H+Gl + Na+

membrane Solution membrane Solution

It can be represented as follows:

Test solution
Unknown [H+] =C2
0 Internal Ref. solution
C1 = 0.1 M HCl
~ ~

(Internal Reference electrode)

Glass membrane
Test solution whose concentration is C2 and correspondingly it exhibit electrode potential, E2
and internal reference solution whose concentration is C 1 and correspondingly it exhibit electrode
potential E1• The exchange of ions by the inner and outer membrane gives rise to a boundary
potential (Eh).

Electrochemistry & Battery Technology 23

Determination of boundary potential (Eb) & electrode potential of glass membrane

electrode (E()
When a thin walled glass tube containing 0.1 M HCl solution is immersed in test solution,
potential developed across the glass membrane at the interface is called boundary potential.
Eh= E2 - E 1
E11 is related to difference in the H+ ion concentration of two solutions.

= 2.303RT I C 2.303RT
Eh nF og 2- nF log C1

E = L + 2.303RT log CJ 2303

where L = RT 1 C
h nF - nF og '
Since C2 is the unknown hydrogen ion concentration we can write

E = L + 2.303RT Iog [H+]

h nF
On substituting the values for R, T & F
Eb = L+ 0.059llog [H+] since n = I
IE., = L- 0.0591 pHI since pH = - log [H+]
It is found that the potential of the glass membrane electrode EG has three components:
i) Eh, boundary potential.
ii) Potential of the internal reference electrode (Ag/AgCl) i.e, EAgtAgCI
iii) Asymmetric potential E.,tssy
. (This potential arises due to the difference in response of the
inner and outer surface of the glass bulb to the change in H+ ion activity and strain in the
inside and outside the electrode bulb)
Therefore, E G =E+E +E assy ----- (1)

Substitute for Eh in equation (I) becomes,

EG = (L- 0.0591 pH) + EAg/AgCI+ Eassy

jEG = E"G- 0.059lpHj ----- (2)

Where 0
E G = L + EAg/AgCI + Eassy· E0G is the combination of 3 constant terms.

Advantages and disadvantages of glass membrane electrode

a) Accurate results are obtained between pH range 1 - 9.
24 Engineering Chemistry

·b) The glass membrane electrode does not get poisoned.

c) It can be used in the presence of oxidizing and reducing agents.
d) Glass electrodes are portable and easy to operate.
e) Equilibrium is attained rapidly.
t) It can be used for colored, turbid and colloidal solutions.
g) It does not require the use of salt bridge.

a) Glass electrode cannot be used in presence of fluoride ions.
b) Glass electrodes are very thin and fragile, should be handled with care.
c) It requires special glass membrane for solutions of pH less than 0.5 and more than 10.
d) Glass membrane has high internal resistance; ordinary potentiometer is not employed and
hence requires vacuum tube voltmeter (VTVM) .This is relatively costlier when compared to
ordinary potentiometers.

Method to measure pH of unknown solution using glass membrane electrode

To determine the pH of the given unknown solution, the glass membrane electrode is combined
with saturated calomel electrode (SCE) and both the electrodes should be immersed in the test
solution (figure 6). The emf of the cell is measured using electronic voltmeter-VTVM (vacuum
tube voltmeter). By convention glass membrane electrode is taken as cathode and SCE as the

Glass membrane
SCE (Anode) electrode (Cathode)

Solution of unknown pH

Figure 6. Calomel-glass membrane electrode cell.


Electrochemistry & Battery Technology 25

The cell assembly is represented as:
PtiHgiHg,CL, ICI-IIsolution of unknown pHI glass membraneiHCl (0.1 M) IAgCIIAg
The emf of the cell is given by
Ece II = Ecathode - Eanode
Eccll = EG - ESCE
Eccll = (E0G-0.0591 pH)-ESCE (WhereEc;=E0G-0.0591 pH)

H _ E~ -ESCE -Ecdl
p - 0.0591
E0G value is calculated by dipping the glass membrane electrode in a solution of known pH
and measuring the emf of the cell when combined with a calomel electrode.
Concentration cells
A concentration cell is a galvanic cell which generates electrical energy at the expense
of chemical energy. In concentration cells, electrode and electrolyte present in both half
cells are same but the concentration of electrode or electrolyte is different. Concentration calls
are classified into two types: ·
1. Electrode concentration cells and 2. Electrolyte concentration cells
Electrode concentration cells: In these cells, the concentration of electrolyte is same.
The two electrodes contain the same material but with different concentrations.
Ex: (1) Two hydrogen electrodes having hydrogen gas at different pressures, dipped in the same
electrolytic solution. It is represented as: Pt/H 2 (P 1)1HCI (x M)/H 2 (P:)!Pt
Where, P, and P2 are the pressure at which H2 gas is maintained at anode and cathode
respectively. P1 > Pr
The half cell reactions are
At Anode: H (P,) _ _ ___. 2H+ + 2e-

At Cathode: 2H+ + 2e- - - - - - + H2 (P2)

Net cell reaction

According to Nernst's equation

2.303RT l P1
Eccu -- F
x og-
[E~n = 0, since both electrodes are hydrogen electrodes]

(2) Pb(O.SM)(Hg)/PbSO /Pb(O.lM)(Hg) : The electrode with higher concentration of metal

will have lower potential and it is taken as anode, whereas electrode containing lower concentration
of metal will have higher potential and it taken as cathode. These type of cells are generally
obtained by dissolving different amount of metal in liquid mercury. They are called as amalgum

26 Engineering Chemistry

Electrolyte concentration cells

(i) Electrolyte concentration cells with transference
In these cells, same electrode material as anode and cathode are dipped iu different
concentration of the same electrolyte. The two electrodes are connected directly through a
diffusion membrane. These types of cells are called electrolyte concentration cells with
transference. Ex: Pt/H 2 (1 atm)/HCI (a 1 M) !I HCl (a 2 M)/H 2 (I atm)/Pt
The dashed line indicates the direct contact between the electrodes through a membrane.
As there is a direct contact between the electrodes, ions are free to move. H+ ions move from
oxidation electrode to reduction electrode, while Cl- ions move in the opposite direction. After the
diffusion, the dilute solution ofHCI contain excess ofH+ ions which are highly mobile and acquire
net positive charge at the junction of the membrane. On the other hand, the concentrated solution
will contain an excess of CI- ions which are less mobile and acquire negative charge_ As a result,
potential difference is developed at the junction of the solution, which is called liquid junction
potential. Liquid junction potential complicates the measurement of the EMF of the cell. The liquid
junction potential can be reduced using salt bridge.
(ii) Electrolyte concentration cells without transference
In these cells, two same electrode materials are dipped in the two solutions containing
the same electrolyte of different concentrations_ The electrodes are connected through a salt
bridge (fig. 7). This minimizes the junction potential and the cell works without transference of ions
from the electrodes.
Ex: Znl ZnS04 (C 1) II ZnSOq(C2)1 Zn
Where C2 > C 1

Expression for emf (Ecen) of aelectrolyte concentration cell


Zn (Anode) Salt Bridge Zn (Cathode)

Figure 7. Zinc concentration cell.

· Electrochemistry & Battery Technology 27
Zinc concentration cell can be represented as
Znl Zn2+ (C 1) II Zn 2+ (C)I Zn
The half cell reactions arc
At anode:
At cathode:

C, and C2 are concentrations of Zn2+ in the two half cells respectively and C:? C,.
Emf of a concentration cell can be calculated using Nernst Equation as follows:

2.303 RT
E annJc = E anotlc + nF

2.303 RT
Ecathode = E cathode + nF log C2

Ecell = Ecathode - E anode

2.303 RT 2 303 RT
= [E0cathode + nF loob C2] - [E0anode + · nF log C 1]

2.303RT (C2]
Eccll = nF log [C1]
By substituting the values of R, T and F we get,

0.0591 [Metal ion concentration at cathode]

Eccll = n · log [Metal ion concentration at anode]

1. A concentration cell was constructed by immersing two silver electrodes in 0.011\1 and
10M AgNO~ solutions. Write the cell reactions and calculate the emf of the concentration
cell. [VTU, July 2005]
An electrode of higher concentration of Ag+ (1OM) acts as cathode, while the other silver
electrode with Ag+ ion concentration (O.OlM) acts as anode.
(i) Cell representation:
Agl Ag+ (0.01 M) II Ag+ (10M) I Ag

28 Engineering Chemistry

(ii) Electrode reactions:

At anode: Ag1s 1 --~~ Ag+(O.OIM) + e-
At cathode: Ag .. (1OM) + e- ----1~ Ag1s)
Net cell reaction: Ag+ (10M) ---+• Ag+ (O.OlM)
(iii) The emf of the concentration cell,

0.0591 (C2]
Eccii = n log [C,]

0.0591 [10]
E.:cll = 1 log [0.01]

= 0.0591 log 1000

= 0.0591 X 3
Eccll = 0.1773V
2. Represent the cell formed by the coupling of two Cu electrodes immersed in CuS04
solutions. Concentration of cupric ions in one electrode system in 100 times more
concentrated than other. Write the cell reaction and calculate the potential at 300K.
[July 2007]
(i) Cell representation:
CuiCuSO4 (I M) I CuSO 4 (I 00 M) I Cu
(ii) Electrode reactions:
At anode: Cu1s, • Cu 2+(1M) + 2e-
At cathode: Cu2+ ( 100 M) + 2e- )lo Cu s

Net cell reaction: Cu 2+ (100M) ---+)lo Cu 2+ (1M)

(iii) The emf of the concentration cell,

2.303 RT I (C2]
Eccu = nF og (C,]

E = 2.303 8.314 X 300

X [100]
2 X 96500 log-[1]

= 0.02976log 100
= 0.02976 x2
Eccll = 0.05952 V

Electrochemistry & Battery Technology 29

3. A concentration cell was constructed by immersing two silver electrodes in 0.05 M

and 1 lVI AgN0 3 solutions. Write the cell reactions and calculate the emf of the
concentration cell. (VTU, July 2006)
(i) Cell representation:

Agl Ag+ (0.05 M) II Ag+ ( 1 M) I Ag

(ii) Electrode reactions:

At anode: Agrs> .._ Ag+ (0.05M) + e-
At cathode: Ag+ (1M) + e- .._ Ag<sJ
Net cell reaction: Ag+ (1M) ._ Ag+ (0.05M)

(iii) The emf of the concentration cell,

0.0591 (C2]
Eccll = n log (Ct]

0.0591 [1]
Eccll = 1 log [0.05]

= 0.0591log20
= 0.0591 X 1.3010
Ecell = 0.07689 V
4. The emf of the cell Cd/CdSO i0.0093 M) II CdSOix M) /Cd is 0.086V at 25°C. Find
the value of x. [Jan 2010]

0.0591 (C2]
Eccll. = n log (Ct]

0.0591 [x]
0.086 = log [ ]
1 0.0093

l og [0.0093] = 2.910

log x -log 0.0093 = 2.910

log x- (- 1.0315) = 2.910
logx = 2.910-1.0315 =0.8785
x = antilog (0.8785) =7.55 M


5. The emf of the cell Ag/AgN03(0.0083 M) ~/ AgN0 3()( 1\tr

at 298K. Calculate the value of x and wnte cell react' ) I I\~ t)Qi 11
Cell reactions:

"'a~ f() ~~r1
11Q Q
At anode: Ag
• Abu+ (0.0083M) + e- Qll.()_ t
() b ~~"'·
At cathode: Ag+ (x M) + e- • AgrsJ [-. ~ ()
a• ·0)<l
l ~() v
Net cell reaction: Ag+ (x M) -~• Ag+ (0.0083M)
The emf of the concentration cell,

0.0591 [C2]
Eccll = n log [C1]

0.074 = 0.0591 log [x]


l ( x] = 1.252
og [0.0083]

log x -log 0.0083 = 1.252

log x - (- 2.0809) = 1.252
log x = 1.252- 2.0809 = 0.8289
x = antilog (0.8289) = 0.1483 1\t

6. A spontaneous galvanic cell tin/tin ion (0.024M//ti11 •

emf of 0.0126V at 2511 C. Calculate the valency of th1 l()ll (() n
. '"6
The emf of the concentration cell, <ll\t)
0.0591 [C2] ''tlt1 {\~v
Eccll = n log (C1] ~lCJ\l~

O.O 126 = 0.0591 log [0.064]

n [0.024]

0.0591 [0.064]
n = 0.0126 log [0.024]

= 4.690 x log (2.6666)

= 4.690 X 0.4259
n = 1.9972-2
Valency of tin is 2

Electrochemistry & Battery Technology 31



1. What are electrochemical cells? Give the classification with examples?

2. Define (i) single electrode potential and (ii) standard electrode potential?
(Jan 2013) (Dec 2011)

3. Derive Nernst equation for a single electrode potential? (Jan 2013) (July 2013) (Jan2015)

4. State the different types of electrodes with examples?

5. What are reference electrodes? List the limitations of primary reference electrode?

6. What are secondary reference electrodes? Mention the requirements of secondary reference

7. What are the advantages of secondary reference electrodes over primary reference electrodes?

8. Explain the construction, working and applications of calomel electrode?

(Jan 2011) (Jan 2013) (July 2013) (Jan 2015)

9. What are secondary reference electrodes? Explain the construction, working and applications
of Ag/ AgCl electrode?

10. What are reference electrodes? Explain the determination of electrode potential of an unknown
electrode using calomel electrode? (Jan 2014) (Jan 2015)

11. What are ion selective electrodes?

12. Explain the construction, working and applications of Glass membrane electrode? (Jan 2011)

13. What are the advantages and limitations of glass membrane electrode?

14. Explain how glass membrane electrode can be used in determination of pH of unknown
(Jan 2011)

15. What are concentration cells? Give its classification with examples?

16. What are electrolyte concentration cells? Deduce an expression for the EMF of a concentration
cell? (Dec 2011) (Jan 2014)
32 Engineering Chemistry

A battery is an electrochemical device which produces electricity by means of redox
chemical reactions. It consists of one or more galvanic cells connected in series or parallel
or both. It stores chemical energy in the form of electro active materials and on demand converts
it into electrical energy through redox reactions. Thus, a battery acts as portable source of electrical
Batteries are widely used as sources of D.C electrical energy in automobiles, boats, aircraft,
ships, portable electric/electronic equipment and lighting equipment. In some instances, they are
used as the only source of power; while in others, they are used as a secondary or standby power
The working principle of a battery is the electrochemical conversion of free energy of redox
reactions of the electrode active materials into electrical energy.

Basic components of a battery

The basic components in a battery are anode, cathode, electrolyte, separator and container.
(fig. 1)

Anode active Cathode active

material material

Figure 1. Schematic representation of a battery.

1) The anode [-ve electrode] is oxidised during the electrochemical redox reaction and liberates
electrons to the external circuit.

The materials ~aving the following properties are preferred as anodic material. It should be
an efficient reducing agent; it should have low reduction potential, good conductivity, good
stability in contact with electrolyte, ease of fabrication and low cost. The following metals can
be used as anode: zinc (cheap metal), lead, cadmium and lithium (lightest metal) etc.

Electrochemistry & Battery Technology 33

2) At cathode [+ve electrode] reduction takes place during the electrochemical redox reaction.
The reduction of the active materials at cathode takes place by accepting the electrons from
the external circuit.
Mn+ + ne- • M
Thus, cathode must be efficient oxidizing agent, it should have high reduction potential, exhibit
good conductivity, stable when in contact with the electrolyte. It should facilitate the reduction
of active material in the medium and have useful working voltage.
3) The electrolyte, which provides medium for transfer of ions, inside the cell between the
anode and cathode. The electrolyte must have good ionic conductivity but poor electrical
conductivity. It should be non-reactive with the electrode material and safe to handle. Electrolytes
are typically either acids or bases (alkaline), Lithium batteries use organic solvent in which
lithium salts are dissolved.
4) Separator permits ions to pass through easily from anode to cathode compartment and vice
versa during discharging or charging reaction. It should not allow mixing of the active materials
in the two compartments. It should be ionically conducting but electrically insulating material.
It should be strong, flexible and non reactive with the active materials. Cellulose, vinyl
polymers and Nafion membranes are used as separators.
5) Container provides a means of holding (containing) the electrolyte. The container is also
used to mount the electrodes. It should not react with the electrolyte. It must be resistance to
corrosion from both inside and outside the battery. Eg. Ebonite, Polypropylene (PP) etc.
Classification of batteries
Batteries are classified into three categories. They are primary [Non-rechargeable], secondary
[rechargeable] and reserve batteries.
(i) Primary battery (Non-rechargeable battery)
A primary battery is the one in which electrical energy can be obtained at the expense of
chemical energy as long as the active materials are present. The primary cell acts only as a
galvanic cell.
A primary battery cannot be recharged since the net cell reaction is irreversible and discarded
when the battery has delivered all its chemical energy. In other words, the electro inactive materials
cannot be converted into electro active materials on the passage of electricity in the opposite
Example: Zn- Mn0 2 (dry cell), Modern batteries: Zinc/Air, Lithium-Mn0 2 primary cell,
(ii) Secondary (rechargeable battery)
A secondary battery is a type of galvanic cell, which after discharge, may be restored to
tlze fully charged state by tlze passage of an external electric current through the cell in the
opposite direction to that of tlze discharge current, wlziclz is higher than the emf of battery.
The electro inactive materials which are formed during discharge are converted into electro active
materials when electricity is passed in the reverse direction.
In other words, the net cell reactions of a secondary battery are reversible. They are also
called storage batteries because during recharging the externally applied current to the battery
will be stored in the form of chemicalenergy and utilized for supplying the current when needed.

34 Engineering Chemistry -

The secondary battery can act both as galvanic cell and electrolytic cell. During discharging
[fig. 2(a)] it acts as a galvanic cell, converting chemical energy to electrical energy and during
charging [fig. 2(b)] it acts as an electrolytic cell converting electrical energy to chemical energy.

- +

(a) Discharge Separator

Figure 2. Schematic representation of battery during discharge and charging

Examples: Conventional batteries: Lead-acid battery, Ni-Cd battery, Modern batteries:
Nickel-metal hydride battery, Lithium-ion battery etc.
The secondary batteries have better cycle life and capacity, so that it can be used over and
over again. The secondary batteries are further classified into two types based on type of electrolyte
1) Acid storage battery- They use acid as the electrolyte eg. Lead acid battery.
2) Alkaline storage battery: They use alkali as the electrolyte eg. Ni-Cd battery, Ni-Metal hydride
Lithium based batteries use organic solvent as electrolyte in which lithium salts are dissolved.
Eg. LiCl or LiBr dissolved in propylene carbonate.
(iii) Reserve battery
In this type of batteries, the vital component is separated from the rest of the battery
prior to activation. Usually the electrolyte is the component that is isolated. When one of the key
components is separated from the remaining parts of the cell self-discharge is essentially prevented
and the battery is capable of long-term storage.
Example lithium-vanadium pentoxide (Li-V20 ~)battery, Magnesium- water activated battery.
These batteries are used for delivering high power for relatively short period of time. They are
used in missiles, torpedoes and other weapon systems.

Important characteristics properties of a battery

The battery can be built in many shapes and configurations - cylindrical, button and flat. But
the L,lse of battery for a particular application depends on certain characteristic properties of the
battery. The few important characteristic properties of batteries are

Electrochemistry & Battery Technology 35

i) Emf of a battery
The voltage of the battery depends on the total number of cells. which constitute a battery.
The overall reaction of a battery is given as,
M I+ Mn+
+ M2
Then, the emf of a cell

E =Eo _ 2.303 RT lo Q = E(' _ 2.303 RT log

cell ..:ell nF g cell nF -

Where E<' cell = Eocathode - Eoanode

and Q is the Reaction Quotient for the cell reaction at any stage of the reaction which is
the ratio of the ionic concentrations of M~+ and M~+ :
It is evident from the above relation that, the emf of a battery dependents on.
(i) Eocell (Difference in the standard reduction potential between the cathode and anode). Higher
the difference higher is the emf of a battery.
(ii) Emf of the battery decreases with increase in the ratio of the ionic concentration of M~+ and
M~+ and
(iii) With increase in temperature emf of a battery decreases marginally.
ii) Current
It is the· rate of discharge reactions of the cell and is measured in amperes. One ampere
of current is said to flow when one coulomb of electrons pass through a point in one second. It
depends on the amount of active materials. Higher the amount of active materials stored emf is
generated for longer time.
iii) Capacity
The capacity of~ battery is expressed as the total quantity of electricity that can be
obtained from the battery. lt_is expressed in ampere-hours (A-h) or Watt-hours (W -h)
The total number of ampere-hour or watt-hours that can be withdrawn from a fully charged
battery under specified conditions of discharge is termed as the capacity of a battery.
The theoretical capacity of a battery is the quantity of electricity involved in the electro-
chemical reaction. It is denoted by C and is given by:
Where, W = Weight of active material, n = number of electrons transferred per mole of
reaction, F =Faraday's constant and M =Molar mass of the active materiaL The ability of the cell
to continue to ddiver the expected capacity at increased discharge rates is an important battery
36 Engineering Chemistry

The variation of voltage v/s time during discharge of battery is given below.


The length of horizontal portion of the curve is the direct measure of the capacity of battery.
Higher the length of the horizontal portion better is the capacity of the battery.
Eg. A battery rated at 100 Ah will deliver 5 A over 20 hours period at room temperature.
However, if it is discharged at 50 A, it will come only for 2 hours that means it will have a lower
apparent capacity.
iv) Electricity storage density
This is a measure of the total current which can be withdrawn from the unit weight of
a substance when it widergoes an electrochemical redox reaction. In other words it is the
capacity per unit weight i.e. electricity storage density is the amount of electricity per unit weight
which the battery can hold.
Eg. 7g of lithium is required at anode to give 96500 Coulombs whereas for the same charge,
65g of zinc is required. To get high storage density the mass of subsidiary elements should be
v) Energy efficiency
It is applicable to a rechargeable battery. Energy efficiency for the storage batteries is given
energy released on discharge x 100
% energy efficiency =
energy required for charge

Higher the energy efficiency, better is the battery.

vi) Cycle life
It is applicable only for secondary batteries. The cycle life is the number of charge/discharge
cycles that are possible before failure occurs. For rechargeable batteries, the duration of
satisfactory performance measured in years. The cycle life should be higher for secondary battery.
In practice, end of life is usually considered to be reached when the battery delivers
approximately 80% of rated ampere-hour capacity.
vii) Shelf Life
The duration of storage under specified conditions at the end of which ,a cell or battery
still retains the ability to give a specified performance. It is essential for most batteries to be
stored, sometimes for many years, without self discharge.

Electrochemistry & Battery Technology 37

For a dry celL the period of time (measured from date of manufacture), at a storage temperature
of 21 °C, after which the cell retains a specified percentage (usually 90%) of its original energy
Tolerance to service conditions: Apart from the above characteristic properties the battery has
to be tolerant to different service conditions such as variation in temperature, vibration andshock.

Construction, working and applications of modern batteries

1. Zinc- Air battery
Zinc- air battery is a metal-air primary modern battery. It uses oxygen directly from the
atmosphere to produce electrochemical energy. The diffused oxygen acts as a cathode reactant in
the battery. The air at cathode catalytically promotes the reaction of oxygen with an aqueous
alkaline electrolyte and is not consumed during the discharge reaction. As the cathode can be very
compact, high energy densities can be achieved.


.. ·..... ..
. ..
. ·.. ·.. · .· .·· .· .· .· .·
. .· .· .· .· .· .· . .· . .. ·. .· .·.· ....
.. .. .. ... ..· .......... .
• • 0 • • • • • • • • • •

..· ..·· ..··..· .·.· .·.· .·.· .·.· ...

• • • • • • • • • • • t ••••

..·· .·.· .·.· .·.·· ....· ·.· .·...... .· .·· .. ·

.· .· .· .· .· .· .· .· ..... · .· ·.·.· .· .· .· .· .· .· Powdered Zn +
Seperator--+--+--'-\' ·· .. · ·.· .·· .·· .·· .· · .··.. · .·· .·· .·· .·· .· .· .· Electrolyte + gelling agent

Carbon, Mn0 2 on Ni mesh

. . . ~.............-Teflon layer (hydrophobic)

Cathode end

Figure. 3. Zinc - Air button cell.

A schematic representation of a typical Zn/ air cell is shown in Figure. 3. It consists of an
anode, made up of granulated powder of zinc mixed with an aqueous alkaline electrolyte (6M
KOH) and a gelling agent to immobilize the composite and to ensure adequate contact with zinc
granules. Cathode is a carbon/catalyst (Mn0 2) mixture with a wet proofing agent coated on a
nickel plated steel mesh support and with an outer layer of hydrophobic gas permeable Teflon thin
layer to steady the air entry. The two electrodes are separated by an electrolyte absorbent separator.
The two containers are provided with a plastic gasket as insulation material.

38 Engineering Chemistry

Anode - granulated Zn powder mixed with aqueous electrolyte and gelling agent.
Cathode - Carbon!catalyst (MnO) mixture coated on nickel plated steel mesh.
Electrolyte- KOH 6M
Seperator - Polypropylene (PP)
It is represented as : Zn/6M KOH/ Air/C

Working of Zinc-Air battery

The electrode reactions taking place in zinc - air battery are as follows:
At anode,
Zn • Zn2+ + 2e-
Zn2+ + 20H- • ZnO + H,O

Zn + 20H- --•~ ZnO + H,O + 2e-

At cathode,

The overall reaction of Zn - air battery,


1) Light weight and provide high energy density.
2) Flat discharge voltage of 1.3 V.
3) Long shelf life (sealed)
4) Eco-friendly
5) Low cost
6) Capacity independent on load and temperature.
Zn-air batteries have been successfully employed as a power source for hearing aids. Other
applications include electronic pagers, voice transmitters, portable battery chargers, military radio
receivers, rail road signaling, medical devices and so on.
2. Nickel - Metal hydride battery
A relatively new technology is adopted in the case of the chargeable nickel - metal hydride
battery with characteristics similar to those of the Ni-Cd batteries. The Ni ~M~ battery uses
hydrogen absorbing metal alloy (M~) as the active negative material whereas cadmium is used in
the Ni-Cd battery and that makes the noticeable difference between the two.
Smaller amount of the negative electrode is sufficient in the Ni-metal hydride battery. Hence
higher energy density can be achieved in the case of metal hydride battery than the Ni-Cdbattery.

Electrochemistry & Battery Technology 39

This allows for a larger volume for the +ve electrode, which results in a higher capacity of the Ni-
metal hydride battery. Moreover, the metal hydride battery is free from Cd, hence it is environmentally
friendly than the Ni-Cd battery and may reduce the problems associated with the disposal and
recycling of batteries.


Cell cap

Contact spring

Sealing washer

Seperator - - - - - - .

Cathode -------...1

Cell can -----....._.

Figure 4. Nickel-Metal hydride button type battery.

The button type Nickel-Metal hydride battery is shown in figure 4.
Anode - Highly porous nickel wire gauze into which the plastic bonded active hydrogen storage
alloy like LaNi 5 and TiNi is coated. The electro active material at anode is a transition metal
hydride (MH 2) like V~, ZrH2 and Ti~. Hydrogen atoms generated during charging diffuse into
lattice of the alloy to form metal hydride.
Cathode- Nickel ox y hydroxide on highly porous sintered nickel substrate impregnated with nickel
hydroxide as its active material
Electrolyte - 6M KOH
Separator- A synthetic non-woven material (PP) separates the two electrodes, which serves as a
medium for absorbing the electrolyte
It can be represented as follows:
Ni/MH/KOH (6M) II NiOOH, Ni(OH)2/ Ni

Working ofNi-metal hydride battery

In the charged state of the Ni-MH2 battery, hydrogen is stored in a hydrogen absorbing alloy
as 'metal hydride'. This metal alloy is capable of undergoing reversible reaction with hydrogen.
That is absorbing of hydrogen as the battery is charged and discharged.

40 Engineering Chemistry

The discharge electrode reactions of the Ni- MH2 battery are as follows:
At anode

At cathode
2Ni0(0H) + 2H20 + 2e- _......,.. 2Ni(OH) 2 + 20H-
The overall reaction during discharge is,

MH2 + 2Ni0(0H) ,.. M + 2Ni(OH) 2
The process is reversed during charge

M + 2Ni(OH\ ,.. MH2 + 2Ni0(0H)
The net cell reaction during discharging and charging can be represented as

MH 2 + 2Ni0(0H) discharging M+ 2Ni (0H) 2

• chargmg

As can be seen from the overall reaction above, that the hydrogen moves from the +veto -ve
electrode during charge and reverses during the discharge. The electrolyte does not directly take
part in the overall reaction, which means that there is no decrease or increase in electrolyte
concentration. It produces an emf of 1.35 volts.

1) High capacity (30- 40 %) compare to Ni-Cd battery.
2) Environmentally friendly- contains only mild toxins; profitable for recycling.
3) Rapid recharging capability
4) Long cycle life and shelf life in charged state
5) Less prone to memory effect than the Ni-Cd battery
6) Simple storage and transportation

1) Performance degrades if stored at elevated temperatures.
2) Battery requires regular full discharge to prevent crystal formation.
3) About 20 % more expensive than Ni-Cd battery.

The nickel-metal hydride batteries are 1.1Sed in lap top computers, cellular phones and camcorders.
It is also used in electrically driven vehicles. It has high potential for 2 and 3 wheelers in Asian

Electrochemistry & Battery Technology 41

3. Lithium Batteries
Lithium metal is the excellent choice as anode material because of light weight (0.534 g/cm 3
at 2SO C), has low reduction potential (-3.0V) and provides the largest specific energy per weight.
Lithium batteries are available as primary and secondary batteries. In primary batteries Li metal is
used as anode electrode. But in rechargeable batteries because of the inherent instability of lithium
metal, especially during charging it is not used as an anode electrode but a carbon matrix material
is used instead of it as the negative electrode which during charging, takes up lithium ions by
cathodic intercalation.
Pioneer work with the lithium battery began in 1912 under G.N. Lewis, but it was not until the
early 1970s that the first non-rechargeable lithium batteries became commercially available. Attempts
to develop rechargeable lithium batteries started in the 1980s.
(i) Lithium-Manganese dioxide (Li-Mn0 2) primary battery
The most commercially used modern primary battery is the lithium-manganese dioxide solid
cathode battery. It is available in many configurations [coin, bobbin, prismatic] and is designed for
low, moderate and high capacity applications.

Anode Can

Cathode Separator
Figure 5. Litlzium-Mn02 primary battery
The schematic representation of lithium primary battery is shown in figure 5. It uses lithium as
the anode and heat treated manganese dioxide as the cathode active material and an electrolyte
containing lithium salts mixed in organic solvent [propylene carbonate and 1, 2 dimethoxy-ethane J.
Anode Lithium metal
Cathode heat treated Mn0 2
Electrolyte Lithium salts like LiCl, LiBr mixed in organic solvents like propylene carbonate
and 1, 2 dimethoxy- ethane
Separator Non woven PP immersed in the electrolyte

42 Engineering Chemistry

It can be represented as:

Li/LiCl in a mixture of organic solvents/ Mn0 2

Working ofLi-Mn02 battery

The cell reactions are
At anode,

At cathode,

Mn0 2 + Li+ + e- • LiMn0 2 (Mn 3+0 2 Li+)

Overall cell reaction
Li + Mn0 2 • LiMn0 2
Mn4+ state is reduced to Mn 3+state by the interstitially occupied lithium ions in the 'Mn0 2
intercalation compound'. Mn3+Q 2Li+ signify the interstitial Li+ ion in the host Mn0 2 lattice. The
voltage of the cell is 3.0-3.5 Volts.

1) High volumetric and gravimetric energy density due to low weight ofLi.
2) Wide operating temperature range [-40 to 70°C],
3) Performance at high discharge rates,
4) Superior shelf life,
5) Relatively low cost.

The lithium-manganese cell is used in a wide variety of application such as long term memory
back up, safety and security devices, lighting equipments and many consumer electronic devices
such as watches, calculators etc.
(ii) Lithium-ion rechargeable batteries NOT IN THE SYLLABUS
It was thought that rechargeable batteries with lithium metal as the anode (negative electrodes)
could provide extraordinarily high energy densities; however, it was discovered in the mid 1980s
that discharging and charging produced unwanted dendrites on the anode. These dendrite particles
penetrate the separator and cause an electrical short. Due to this, the cell temperature rises quickly
and approaches the melting point of lithium, causing thermal runaway, also known as "venting with
flame." [Also the poor reversibility of the lithium electrode. During hattery charging, spongy lithium
is deposited from the solution. This deposit rapidly loses contact with the bulk of the lithium electrode.
(due to rapid oxidation) Hence, with every discharge-charge cycle of a battery, the amount of
lithium participating in the electrode reaction decreases and the battery's discharge cag(lcity drops
The design of lithium ion batteries has been a great achievement toward overcoming this
defect. In 1991, Sony commercialized the first Li- ion battery, and today this battery has become the
most promising and fastest growing on the market.


Electrochemistry & Battery Technology 43

The schematic representation of lithium ion rechargeable battery is shown in figure. 6. The
carbon matrix material (graphite) is used as the negative electrode (anode) which during charging,
takes up lithium ions from cathodic electrode. Materials for the positive electrode (cathode) are
selected among those which, unlike carbon, will intercalate lithium ions during discharge while
retaining a sufficiently highly positive value of potential. During charging of these electrodes, lithium
ions undergo deintercalation. Common cathode materials are Lithium Cobalt Oxide (or Lithium
:obaltate, LirCo0 2), Lithium Manganese Oxide (or Lithium Manganate, LirMn 20), Lithium
·1ickel oxide (LirNi02), Lithium Iron Phosphate (LiFeP04). The electrolyte is typically a combination
)f lithium salts·, such as LiPF6 , LiBF4, or LiC104, in an organic solvent, such as ether.

Discharge Load or



Anode Membrane Cathode

Graphite Electrolyte LiCo0 2

Figure.6. Schematic representation of a Lithium-ion battery,

during charge discharge cycle
Representation of Lithium-ion battery ; Graphite I Li Salt in organic solvent I LiCo0 2

'orking of lithium ion battery

1ring discharging
At Anode, LiC 6 ,.. 6C + Li+ +e-
At Cathode, Li05Co02 + Li+ + e- ,.. LiCo02

Cell reaction, - - - - . . 6C + LiCo0 2
Engineering Chemistry
During discharge, lithium ions spontaneously move from the anode (graphite) to cathode
(LiCo0 2) and the e- flow through the external circuit.

During charging~ 6C + LiCo0 2 • LiC 6 + Li 05Co0 2
During charging an external power supply forces thee- to flow through the external circuit
and allows lithium ions to travel from LiCo0 2 electrode to graphite electrode.
The net cell reaction during discharge and charging can be given as

·c _ . C discharging
L1 6 + L105 o0 2 ----• 6C + LiCoO..,

In summary, during discharge, the lithium ions t1ow from the anode to the cathode through the
electrolyte and separator~ charge reverses the direction and the Li ions flow from the cathode to
the anode. For this reason the term rocking-chair batteries was coined for batteries of this type.
Figure 7 illustrates the process.


\ \


Cathode (Li
Metal Oxide)

Figure 7: lithium ion flow in lithium-ion battery.

1) Lighter than other rechargeable batteries for a given capacity \
2) Li-ion chemistry delivers a high open-circuit voltage
~) Low self-discharge rate (about 1.5% per month) NOT IN THE SYLLABUS
n Do not suffer from battery memory effect
i) Environmental benefits: rechargeable and reduced toxic landfill.
i) Low maintenance - no periodic discharge is needed.
') Long cycle life.

Electrochemistry & Battery Technology 45

I) Safety concerns if overheated or overcharged NOT IN THE SYLLABUS
2) Poor cycle life, particularly in high current applications
3) Rising internal resistance with cycling and age
4) Shipment of larger quantities of Li-ion batteries may be subject to regulatory controL
5) About 40 % higher in cost compare to Ni-Cd battery.

1) For portable applications such as laptop, cellular telephones, video cameras, digital cameras,
DVD players, MP3 players, portable games machines etc.
2) Medical applications include emergency lighting, defibrillator machines and pacemaker devices.
3) In heavy industry, including electric power trains for vehicles
4) All forms of sustainable energy, such as wind turbines or photovoltaics, require excellent
energy storage systems. The lithium ion batteries are the potential of energy storage systems
compared to other carbon anode based batteries.


Fuel cells are electrochemical devices in which chemical energy of a fuel is directly
converted into electrical energy by means of redox reactions involving fuels and oxidants.
Fuel cell does not store energy but converts the chemical energy available in the fuels into electrical
energy directly.
Fuel cell also has two electrodes and an electrolyte. The fuel and the oxidant are continuously
and separately fed into anode and cathode electrodes respectively, at which they undergo oxidation
and reduction generating electrical energy.
Fuel cell may be generally represented as

Fuel I electrode I electrolyte I electrode I oxidant

Fuel cell reactions

At anode, fuel undergoes oxidation

Fuel ._ oxidized product+ ne-

At cathode, the oxidant get reduced

Oxidant + ne- --»-~ reduced product

The overall reaction

Fuel + Oxidant --»-• oxidized product+ reduced product

46 Engineering Chemistry

The fuel cell differs from batteries in the following aspects

Fuel Cells Batteries

Do not store chemical energy Stores chemical energy
Reactants are fed from outside continuously The reactants form an integral part of it
Need expensive noble metal catalysts Not required
No need of charging Gets discharged when stored-energy lS
Never become dead Limited life span in use
Useful for long-term serv1ces for electricity Useful as portable power

Fuel cell has the following advantages

i) Fuel cells have high energy density and high conversion efficiency (60-70%)
ii) Fuel cells never become dead as long as fuel is supplied continuously
iii) They operate with inexpensive fuels
iv) Silent operation
v) They are ceo-friendly since the products formed are non toxic
vi) Recharging of fuel cells is not required
vii) They can produce electricity for long periods at a low cost
Limitations of fuel cells are
i) The cost of the catalyst used is high
ii) Fuel and oxidant are needed to be stored in containers under high pressure
iii) It is difficult to provide contact between three phases namely, gaseous fuel, liquid electrolyte
and solid catalyst
iv) They are sensitive to fuel contaminants such as CO, H2S, NH 3 and halides.

Classification of Fuel cells

I) Based on the operation temperature as
a) Low temperature fuel cells (less than 100 °C)
b) Moderate temperature fuel cells (100-500 °C)
c) High temperature fuel cells (> 500 °C)
II) Based on the type/nature of electrolyte used
a) Alkaline fuel cells (AFCs)
Aqueous solution of alkali is used as the electrolyte. These are low temperature fuel cells
which operates around 80 °C. e.g. hydrogen-oxy-gen and methanol-oxygen fuel cells
b) Phosphoric acid fuel cells (PAFCs)

Electrochemistry & Battery Technology 47

c) Molten carbonate fuel cells (MCFCs)

d) Polymer electrolyte membrane fuel cells (PEMFCs)
e) Solid oxide fuel cells (SOFCs)
III) Based on the physical state of fuels
a) Gaseous fuel cells: e.g. H2 , NH 3
b) Liquid fuel cells: e.g. Alcohols, hydrocarbons
c) Solid fuel cells: e.g. Coal, metal hydrides

lVIethanol-Oxygen Fuel cell

In methanol-oxygen fuel cell, methanol is used as a fuel and oxygen as oxidant to generate
electrical energy.
Construction: The schematic diagram of methanol-oxygen fuel cell is shown in the figure.S.

e e

A(-) C(+)

Porous nickel electrode Porous nickel electrode

impregnated with Pt/Pd impregnated with Ag

Figure.8. Methanol-Oxygen fuel cell.

It consists of two electrodes; Anode is made of porous nickel electrode impregnated with Pt/
Pel catalyst. Whereas, the cathode is also made of porous nickel electrode coated with silver
catalyst. The electrolyte (3M) H2S04 is taken in between the electrodes. Methanol and oxygen are
sent continuously into their respective electrodes and electrical energy is produced.

Methanol-oxygen fuel cell can be represented as

Methanol/Pt or Pd/H 2S0/3M)/Ag/0 2
The electrode reactions are

At Anode
CH~OH + H20
At Cathode
(Yz 0 2 + 2H· + 2e- --~Jio H20) x 3

Net cell reaction

(i) Like hydrogen, methanol does not have storage problems.
(ii) It has higher energy density than H2 , though lesser than gasoline or diesel.
(iii) Easy to transport and supply to the customer.

Methanol-oxygen fuel cell is used in wireless head sets for mobile phones [8.5 gram weight],
in laptops, military applications and in large scale power production.
Electrochemistry & Battery Technology 49



1. What are batteries? Give the classification of batteries with examples.

2. What are primary batteries? Give example.
3. What are secondary batteries? Give example.
4. What are reserve batteries? Give examples
5. What are the principle components of a battery?
6. Explain the following battery characteristics:
a) Voltage,
b) Capacity [Jan 2015]
c) Cycle life [Jan 2011] [June 2013] [Jan 2015]
d) Shelf life [Jan 2011]
e) Current,
f) Electricity storage density and
g) Energy efficiency [June 2013] [Jan 2015]
7. Explain the construction and working Zn-air battery? Mention its applications? [Jan 2011]
8. Give the construction, working and applications ofNi-Metal hydride battery?
[Dec 20ll][Jan 2014] [Jan 2015]
9. What arc the special properties of Li that make it advantageous to use as an anode electrode
material in primary battery?
10. Explain the construction and working ofLi-Mn0 2 battery? Mention the advantages and uses.
11. Explain the construction, working and applications of ofLi ion battery? Why lithium metal is
not used as anode? [Jan 2013][Jan 2015]
12. What are Fuel cells? Give the classification. [Jan 2014]
13. What are the differences between batteries and fuel cells? [Jan 20141
14. What are the advantages and disadvantages of fuel cells? [Jan 20 13]
15. Give the construction and working of Methanol-0 2 Fuel cell? List the advantages and uses.
[Jan/Dec 2011][June 2013] [Jan 2014][Jan 15]

11+11+11 + 11+11+11