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+2

t4 t2

MioM
t3

(all reachen,
Slacihelgni Soluton_

A Soluton Way Contais maße thay

bt
pattapatii elathayur
enaau

Nacl ag

Oxelab? (at anode SRP

Peducon

Na

SRPi

Na Na t,
at ahode

Ouilie at aodla

þtascnt
evapctzat
 lu electrode

at cohode
0.34

Anodo Culs)

Pectiola
Ineht

Sane

Cathode (educhit) Ato dle Cacdatien)

:

+ne, M huyehontt ohtet

M

No,
 Esl.ly Ext= l.1V
(a) (b)

anode current çathode I=0

Zn salt Cu Zn -Cu
-Ve
bridge +ve
When E ext
=1.1 V
(i) No flow of
electrons or
Currernt.
(i1) No chemical
Znso, CuSO. ZnSO, CuSO4 reaction.

When E.t < l.1 V Eext >1.1

(1) Electrons flow from Zn rod to (c)
Cu rod hence current flows
from Cu to Zn. When E > 1.1 V
(11) Zn dissolves at anode and e
(i) Electrons flow
copper deposits at cathode. Cathode Current Anode from Cu to Zn
+ve -ve
and current flows
Zn -Cu from Zn to Cu.
Fig. 3.2 (ii) Zinc is deposited
Functioning of Daniell at the zinc
cell when external electrode and
voltage Et oppostng the copper dissolves at
cell potertial is applied. copper electrode.
+Strictly speaking activity should be used instead of concentration. It is drectly proportional to concentration. In dlute
solutions, it is equal to concentration. You will study more about it n higher classes.

Chemistry 66
 2ho te,
Table 3.1: Standard Electrode Potentials at 298 K

Ions are present as aqueous species and H,0 as liquid; gases and solids are shown by g and s.
neReduced form)
F(g) + 2e ’2F 2.87

mas Cost + e ’ Co2* 1.81

H,0, + 2H + 2e ’2H,0 1.78
MnO, + 8H + 5e ’Mn? + 4H,0 1.51
Au* +3e ’Au(s) 1.40
Clíg) + 2e ’2C1 1.36

Cr,0,+ 14H* + 6e 2Cr* + 7H,0 1.33

O,lg) + 4H + 4e ’2H,0 1.23

MnO,(s) + 4H* + 2e -Mn* + 2H,0 1.23

Br, + 2e ’2Br 1.09

agent NO, + 4H* + 3e ’NOg) + 2H,0 agent 0.97

2Hg + 2e ’Hg,* 0.92

oxidising Agt + e ’Agls) reducing 0.80
Fe + e ’Fet 0.77
Olg) + 2H + 2e ’H,0, 0.68
of I, +2e ’21 of 0.54
strength Cu + e ’ Cu(s) strength 0.52
Cu?+ 2e ’Cu(s) 0.34

AgCl(s) +e ’Agls) + CI 0.22

Increasing AgBr(s) + e Increasing 0.10
’Ag(s) + Br
2H + 2e ’H,(g) 0.00

Pb* + 2e ’Pb(s) -0.13

Sn2* + 2e ’Sn(s) -0.14
N* + 2e ’ Ni(s) -0.25

Fe+ 2e ’Fe(s) -0.44

Cr + 3e ’ Cr(s) -0.74

Zn+ 2e Zn(s) -0.76

2H,0 + 2e Hlg 20H(aq) -0.83
AISt + 3e ’Al(s) -1.66

Mg* + 2e ’ Mgls) -2.36

Na* + e ’Na(s) -2.71
’ Ca(s) -2.87
Ca+ 2e
K*+ e ’ K(s) -2.93
Eo? Li +e ’Li(s) 3.05

couple is stronger reducing agent than the H/H, couple.

1. A negative E means that the redox
2. Apositive E means that the redox couple is a weaker reducing agent than the H/H, couple.
71
Electrochemistry
 Calculate the equilibrium constant of the reaction:
Cxample 3.2 + 2Ag(s)
Culs) + 2Ag (aq) ’Cu*ag)
= 0.46 V
E(cel)
0.059 V
log K =0.46 V or
Solution Egc)
0.46 Vx2
= 15.6
log Ke= 0.059 V

K, = 3.92 × 1o!5

to electrical potential
3.3.2 Electro Electrical work done in one second is equal obtain maximum work
to
chemical mitiplied by total charge passed, If we want
passed reversibly The
Cell and from a galvanic cell then charge has to be in its Gibbs
Gibbs reversible work done by agalvanic cell is equal to decrease the amount
nF is
Energy of energy and therefore, if the emf of the cell is E and
the reaction, then
the Reaction of charge passed and A,G is the Gibbs energy of
(3.15)
AG=- nFcel)
It may be remembered that E,n is an intensive parameter but AG
is an extensive thermodynamic property and the value depends on n.
Thus, if we write the reaction
Zn(s) + Cu(ag) ’ Zn*(aq) + Cu(s) (3.1)
AG =- 2FEicel)
but when we write the reaction
2 Zn (s)+2 Cuaq)2Zn*(aq) + 2Cu(s)
AG= 4FEceli
If the concentration of all the reacting species is unity, then
Eicel) Eroel) and we have
4,G° = - nFE(cell) (3.16)
Thus, from the measurement of E we can obtain an important
thermodynamic quantity. AG, standard Gibbs energy of the reaction.
From the latter we can calculate equilibrium constant by the
equation:
AG =-RT ln K.

Cxample 3.3 The standard electrode potential for Daniell cell is 1.1V.
the standard Gibbs energy for the Calculate
reaction:
Zn(s) + Cu(aq) ’ Zn"(aq) + Cu(s)
Solution 4,G =- nFEgel)
nin the above equation is 2, F=
96487 C mol and E= 1.1 V
Therefore, A,G =-2 × 1.1V ×96487 C mol-1
= - 21227 J mol!
=- 212.27 kJ mol
 = 1.96 V (3.39)
2S04 (aq) ’S,0 (aq) + 2e
Ercel)
For dilute sulphuric acid, reaction (3.38) is preferred but at higher
Concentrations of H,SO, , reaction (3.39) is preferred.

Intext Questions
3.10 If a current of 0.5 ampere fows through a metallic wire for 2 hours,
then how many electrons would flow through the wire?
3.11 Suggest a list of metals that are extracted electrolytically.
3.12 Consider the reaction: Cr,0, + 14H" + 6e 2Cr* + 7H,0
What is the quantity of electricity in coulombs needed to reduce 1 mol
of Cr,0,

3.6 Batteries Any battery (actually it may have one or more than one cell connected
in series) or cell that we use as a source of electrical energy is basically
a galvanic cell where the chemical energy of the redox reaction is
converted into electrical energy. However, for a battery to be of practical
use it should be reasonably light, compact and its voltage should not
vary appreciably during its use. There are mainly two types of batteries.
3.6.1 Primary In the primary batteries, the reaction occurs only once and after use
Batteries over a period of time battery becomes dead and cannot be reused
again. The most familiar example of this type is the dry
Carbon rod cell(known as Leclanche cell after its discoverer) which is
(cathode)
used commonly in our transistors and clocks. The cell
consists of a zinc container that also acts as anode and
the cathode is a carbon (graphite) rod surrounded by
powdered manganese dioxide and carbon (Fig.3.8). The
space between the electrodes is filled by a moist paste of
ammonium chloride (NH,CI) and zinc chloride (ZnCl,). The
electrode reactions are complex, but they can be written
approximately as Jilows :
Anode: Zn(s) Zn* + 2e
Cathode: Mno,+ NH,+ e MnO(OH) + NH,
In the reaction at cathode, manganese is reduced
from the + 4 oxidation state to the +3 state. Ammonia
produced in the reaction forms a complex with Zn to give
(Zn (NH), )". The cell has a potential of nearly 1.5 V.
Zinc cup MnO, +! Mercury cell, (Fig. 3.9) suitable for low current devices
(anode) carbon black like hearing aids, watches, etc. consists of zinc -
+ NH,Cl paste
amalgam as anode and a paste of HgO and carbon mercury
as the
Fig. 3.8: A commercial dry cell cathode.The electrolyte is apaste of KÖH and ZnO. The
consists of a graphite electrode reactions for the cell are given below:
(carbon) cathode in a Anode:
zinc corntainer: the latter ZnHg) + 20H ’ ZnO(s) + H,O + 2e
acts as the anode. Cathode: HgO + H,0 + 2e Hg(l) + 2OHS
Chemistry 88
 Anode Anode cap The overall reaction is represented by
ZnHg) + HgO(s)’ ZnO(s) + Hgl)
The cell potential is approximately
its
I.35 Vand remains constant during
does not
Fig. 3.9 life as the overall reaction
solution whose
Comnonly used involve any ion in
mercury cell. The concentration can change during its life
reducing agent is time.
zic and the
Gasket Cell can
oxidising agent is
mercury (u) oxide. Separator Cathode

3.6.2 Secondary A secondary cell after use can be recharged by passing current
Batteries through it in the opposite direction so that it can be used again. A
good secondary cell can undergo a large number of discharging
and charging cycles. The most important secondary cell is the lead
Storage battery (Fig. 3.10) commonly used in automobiles and
invertors. It consists of a lead anode and a grid of lead packed with
lead dioxide (PbO,) as cathode. A 38% solution of sulphuric acid
is used as an electrolyte.
The cell reactions when the battery is in use are given below:
Anode: Pb(s) + So (aq) PbSO,(s) + 2e
Cathode: PbO,(9) + SO, lag) +4H*ag) +2ePbSO, (s) +2H,0 Q)/
i.e., overall cell reaction consisting of cathode and anode reactions is:

Pb(s) + Pb0,(s) + 2H,so, aq) ’2PbSO s) + 2H,00)

On charging the battery the reaction is reversed and PbSO,(s) on
anode and cathode is converted into Pb and PbO,. respectively.

Anode -Cathode

Negative plates:
lead grids filled
with spongy
lead.

Positive plates:
38% sulphuric lead grids filled
acid solution
with Pb0,

Fig. 3.10: The Lead storage battery.

89 Electrochemistry
 Another inmportant secondary
cell is the nickel-cadmium cel
(Fig. 3.11)which has longer life
than the lead storage cell but
Fig. 3.11 more expensive to manufacture.
A rechargeable We shall not go into details of
nickel-cadmium cell working of the cell and the
n a jelly roll Positive plate electrode reactions during
arrangement and -Separator charging and discharging.
separated by a layer The overall reaction during
Soaked in moist Negative plate
discharge is:
sodium or potassum
hydroxide.
Cd (s) + 2Ni(OH), (S) ’ CdO (s) + 2Ni(OH), (s) + H,01)
3.7fuel ells Production of electricity by thermal plants is not a very efficient method
and is a major source of pollution. In such plants, the chemical energy
(heat of combustion) of fossil fuels (coal, gas or oil) is first used for
Converting water into high pressure steam. This is then used to run
a turbine toproduce electricity. We know that a galvanic cell directly
converts chemical energy into electricity and is highly efficient. It is
now possible to make such cells in which reactants are fed continuously
to the electrodes and products are removed continuously from the
electrolyte compartment. Galvanic cells that are designed to convert
the energy of combustion of fuels like hydrogen, methane, methanol,.
etc. directly into electrical energy are called fuel cells
One of the most successful fuel cells
H,0 uses the reaction of hydrogen with
Anode +Cathode Oxygen to form water (Fig. 3.12). The
cell was used for providing electrical
-Aqueous electrolyte power in the Apollo space programme.
Thewater vapours produced during the
reaction were condensed and added to
the drinking water supply for the
H,’ astronauts. In the cell, hydrogen and
OXygen are bubbled through porous
carbon electrodes into concentrated
aqueous sodium hydroxide solution.
Catalysts like finely divided platinum or
palladium metal are incorporated into
the electrodes for increasing the rate of.
Fig. 3.12: Fuel cell using H, and O, produces electricitu. electrode reactions. The electrode
reactions are given below:
Cathode: 0,(g) + 2H,01) + 4e’4OH(aq)
Anode: 2H, (g) + 40H(aq) ’ 4H,00) + 4e
Overall reaction being:
2H,(g) + 0,g)’ 2H,O1)
The cell runs continuously as long as the
Fuel cells produce electricity with an efficiency reactants are supplied,
of about 70% compared
Chemistry 90
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