COMMERCIAL VOLTAICCELLS

Batteries can be classified as primary and secondary. Primary batteries can not be returned to their original
state by recharging. so when the reactants are consumed, the battery is "'dead" and must be discarded.
Secondary batteries are often called storage batteries or rechargeable bateries. The reactions in these batteries
can be reversed: thus, the batteries can berecharged.
(A)Primary cells : Drycells and mercury cells Carbon rod
The most familiar type of battery is the dry cell which is (cathode)
acompact of Leclanche cell known after its discoverer Leclanche
(fia.). In this cell, the anode consists of a zinc container and the
cathode is agraphite rod surrounded bypowdered MnO, and
carbon. The space between the electrodes is filled with a moist
paste of NH,C and ZnC.,. The electrode reactions are complex,
but they can be written approximately as follows.
Anode Zn(s) ’Zn*2 + 2e
Cathode MnO, + NH, + e ’ MnO(OH) + NH,
In the cathode reaction, manganese is reduced from the Zinc cup MnO, +
4+ Oxidation state to the 3+ state. Ammonia is not liberated as Carbon black
+ NH,CI
agas but combines with Zn2* to form Zn(NH,),2+ ion. Dry cells
do not have an indenfinite life as acidic NH,Clcorrodes the zinc A commercial dry cell consists of
a graphite (carbon) cathode in a
container even when not in use. Dry cells have a potential zinc container: the latter acts as the anode
of approximately 1.25 to 1.5V.
Mercury cell, suitable for low curent devices like hearing aids, watches, etc. consists of zinc - mercury
amalgam
ZnO. The
as anode and a paste of HgOand carbon as the cathode. The electrolyte is a paste of KOH and
electrode reactions for the cell are given below:
Anode : Zn(Hg) + 20H ’ ZnO(s) + H,0+ 2e
Cathode: Anode Cathode
Hg0 +H,0+ 2e Hg) + 20H
The overal reaction is represented by
Zn(Hg) + HgOls) ’ ZnO(s) + Hgl)
The cell potential is approximately 1.35 Vand
remains constant during its life as the overall reaction
does not invove any ion in soution whose concentration
can change during its life time.
(B) SECONDARY OR RECHARGEABLE BATTERIES
The most important secondary cell is the lead storage battery. It consists of a lead anode anda grid of
lead packed with lead dioxide as cathode. A solution of sulphuric acid (38 percent by mass or having
density 1.30 gm cm) is used as an electrolyte.
Cathode
Anode

Negative plates:
lead grids filled
with spongy lead

38% Sulphuric
Positive plates:
acid solution
lead grids filled
with PbO,
ig: The Lead storage battery
When the cell discharges, it operates as a voltaic cel. The lead is oxidised to Pb+2 ion and lead plates
acquire a negative charge.
At Anode : Pb(s) ’Pb+2 + 2e ....)
Pb2 ions combine with sulphate ions of solution to form insoluble PbSO,
Pb+2 + SO, 2 4 ’ PbSO, Precipitation) ....i)

Overall reaction Pbls) + SO, ’ PbSO,(s) + 2e

The electrons given by Pb areused at cathode (PbO, electrode)
At Cathode :
PbO,s) + 4H* + 2e ’Pbe + 2H,0 ....(i)
Pb2 + SO,2 ’PbSO,(Precipitation) .....iv)

PbO,(s) + 4H' + SO, ?+ 2e ’ PbSO,(s) + 2H,0

 Therefore the overallcell reaction during discharging
Pb(s) + S0, ’ PbSO,(s) + 2e
PbO,(s) + 4H' + SO,2+ 2e ’ PbSO,(s) + 2H,0

Pbs) + PbO,(s) + 2H,S0, 2PbSO,(s) + 2H,0

When a potential slightly greater than the potential of battery is applied, the battery can be reacharged.
During recharging the cell is operated like an electrolytic cell ie. now electrical energy is supplied to it
from an external source, The electrode reactions are reverse of those that occur during discharge :
At Cathode : PbSO,(s)+ 2e Pb(s) + SO,
At Anode : PbSO,(s) + 2H,0. ’ PbO,(s) + 4H* + SO,2+ 2e

2PbSO,(s) + 2H,0 ’ Pb(s) + PbO,s) + 2H,SO,

It isclear that H,S0, is used up during the discharge & produced during reacharging reaction of cell.
The discharging process of the storage cell is based on the principles of
electrochemical cell, whereas the charging process is based upon the principles
of electrolytic cells.
n factor for H,SO, during charging and discharging is equal to one.
B +
2 2 2 2 2 2

Vg-= 12 volts

A The battery consists of

six two-volt cells connected
in series.

B Eech component cell is

Composed of several
negatiVe and p0sitive
electrodes made of pure
spongy lead and lead oxide,
Pb0, respectively; the electrodes,
connected in parallel, are
immersed in a dilute solution
of sulfuric acid.
plates in asolution
Pb (spongy)
of H,SO, 8nd H,0

(C) Nickel - Cadmium ("Ni -Cd") batteries:

They are used in variety of cordless appliances such as telephones, video camcorders, and cordless
power tools, are lightweight and rechargeable. The chemistry of the cellutilizes the oxidation of cad1mium
and the reduction of nickel (|I) Oxide under basic conditions.
At cathode: [NiO(OH) (s) + H,00+e’ Ni(OH),(s) + OH(aq)l x2
At anode: Cd(s) + 2 OH ’ Cd(OH),(s) + 2e

Net cellreaction : 2NIO(OH\s) + Cd(s) + 2H,0 (, ’ 2Ni(OH), (s) + Cd(OH), (s)

As the active masses of allreaction components are independent of their amount. The cel delivers
constant EMF throughout.
 (D) Fuel Cells
Water
It is possible to make batteries in which the reactants are
fed continuously to the electrodes. Electricalcells that are anode (’ +) cathode
designated to convert the free energy from the combustion
aqueous
of fuels such as hydrogen, carbon monoxide or methane
electrolyte
directly into electrical energy are called fuel cells.
One of the most successful fuel cells uses thereaction of H,2, E0,
hydrogen with oxygen to form water (fig.). This cell has
been used for electric power in the Appollo space
programme. The water vapours produced were condensed
and added to the drinking water supply for the astronauts. Fig. : A simple fuel cell

In the cell shown in figure hydrogen and oxygen are bubbled through a porous carbon electrode into
concentrated aqueous sodium hydroxide. Catalysts are incorporated in the electrode. The electrode
reactions are :

At anode: 2[H,(g) + 20H (aq)’ 2H,0(0) + 2e]

At cathode : O,g) + 2H,0(0) + 4e ’40H (aq)

Net cellreaction : 2H,(g) + O,g)’ 2H,O()

This cells runs continuously as long as the reactants are supplied. Since fuel cells convert the energy of
a fuel directBy to electricity, they are potentially more efficient than the conventional method of generating
electricity on a large scale by burning hydrogen, carbon fuels or by using nuclear reactor. Although
theoretically we expect 100 percent efficiency in fuel cells, so far an efficiency of only 60
70 per cent has been attained. Since fuel cels are efficient and free from pollution, efforts are being
made to produce better commercially practical fuel cells.
(AG)-x100
Efficiency of a Fuel Cell (AH)
Main features of different cells.
Name of the Anode Cathode Electrolyte
cell/Battery
(i) Drycell Zinc Graphite NH,CI + ZnCl,
MnO, + C (touching anode)
(touching cathode)
(ii) Mercury cell Zinc/Mercury Paste of HgO Paste of KOH and ZnO
Amalgum and carbon
Lead storage Lead Lead dioxide
(iii) H,SO, (38%)
battery
(iv) Ni-Cd cell Cadmium Nickel dioxide KOH sol.

() H,-0, fuel cell Porous carbon Porous carbon Conc. aq. NaOH sol.
containing catalysts containing catalysts
(H, passed) (O, passed)
CORROSION
Corrosion is basically an electrochemical phenomenon. The rusting of iron, the tarnishing of silver, development
causes enormous
ot a green coating on copper and bronze are some of the examples of corrosion. Corrosion
damage tobuikding, bridges, ships and to manyother articles made of iron.
ironfwhich is commony
In coosion, a metal is oxidised by koss of electrons to oXygen and forms metal oxide. Corrosion of
is complex but it is
known as nusting oocurs in presence of water and oxägen (air). Although the chemisty of corrosion
understood that at one spot of an iron object oxidation occurs and that spot behaves as an anode.
Anode : Fe(s) ’Fe2 (ag) + 2e;(ErFe =-0.44V)
and reduce the
Electrons released at anode move through the metal and go to another spot on the metal
dissolution of CO,
Oxygen in presence of H* ions (which is believed to be available from H,CO, formed due to
in water). This spot works as a cathode:
Cathode: 0,g) + 4H+ (aq) + 4e 2H,0 (0): (E° = 1.23 V)
it wil help more
Here Fe ions move through water on the surface of the iron object. (lf water present is saline,
corrosion). The overall reaction of the
in carrying the current in the miniature cell thus formed and will enhance
miniature cellis the sum of the cathode and anode reactions as follows:
2Fels) + O,g) + 4H(ag)’2Fe2laq) + 2H,O0); E = 1.67 V)
form
The Fe?* ionsare further oxidised byatmospheric oxygen to Fe+ (as Fe,O) and comes out as rust in the
of a hydrated iron (1l) oxide expressed as Fe,O,, xH,0.
4Fe?*laq) + 0,g) + 4H,0(0) 2Fe,0.(s) + &H
H+ ions produced in the above reaction help further in rusting.
Impurities present in iron also enhance rusting by settinga number of miniature cells. Very pure iron does not
rust quickly.
3PREVENTION FROM CORROSION Water drop
Corrosion of a metal is prevented by applying
protective coating (such as grease, paint, bisphenol O, + 2H + 2e
Zn Zn + 2e
or metal coatings) on metal surface. In case of iron ’ 2H,0
this coatingis done in two ways : i) electrolysis (Cr, Zinc anode Iron cathode
Ni and Cd coating) (i) dipping iron objects in a
molten metal (Zn and Sn coating). Use of zinc
coating to protect iron is called Galvanisation. In Fig. : Gavanised iron. Cathodic protection of iron in
contact with zinc is provided by galvanization.
galvanising iron, zinc being more reactive than iron
serves as an anode and is oxidised magnesium anode
Mg ’ Mgz + 2e
(Ez/Zn = -0.76V and E'Fe /Fe =-0.44V). 0
Here it is important to note that iron does not rust
even after zinc coating is broken which is not true
in case of tin coating Over iron

(E'sn /sSn = -0.14V). Now if the coating is

broken, iron is exposed and iron being more active
than both copper and tin, is corroded. Here iron
Iron pipe (cathode)
corrodes more rapidly than it does in the absence
of tin. But tin protects copper in the same way as O, + 2H,0 + 4e40H
Fig. :Cathodic protection by connecting a block of
zinc protects iron (E®au /Cu =0.34V). magnesium to an iron pipe burried underground.
Instead ot coating more reactivemetal on iron, the use of such metals is made as sacrificial anode. This method
of preventing iron from corrosion is called CATHODICPROTECTION.
In this method,a plate of reactive metal Zn orMa) is bumied beside the iron pipe or tank and connected to it by wires.
Here iron becomes cathode and more reactive metal becomes anode. The reactive metal anode is sacrificed
to protect the iron. Since these reactive metal plates are Oxidised quickly, they are replaced from time to time
which is easy to do.
Air
Rust Og)
(Fe,0) -
cathode
FNateranode
Therusting of iorn (Iron incontact with
water forms the anode and in contact
0, + 4H + 4e ’ 2H,0 Fe> Fe2+ + 2e with air forms the cathode. Atthe anode
iron is oxidised to Fee,andat the cathode
Iron Oxygen is reduced to water