ELECTROCHEMICAL CELLS

Structure
13.1 Introduction
Objective8
13.2 Electrochemical or Galvanic Cells
13.2 1 A Convenient Notation for UIC Representationof El& and Ceb
13.3 Types of Electrodes
13.4 Electromotive Force and its Measurement
13.5 Free Energy Change and Electrical Work
13.6 The Nernst Equation
13.7 Standard Electrode Potentials
13.8 Using the Table of Standard Electrode Potentials
13.8.1 SigniT~canceof Positive and Negative Values
13.8.2 Elearode Potential and Stoichimetry
13.8.3 Displacement Reacriom
13.9 Calculation of the EMF of Galvanic Cells
13.10 Applications of EMF Measurements
13.1 1 Corrosion and its Prevention
13.12 Protective Measures Against Corrosion
13.13 Eectrochemical Energy Sources
13.3.1 Dry Cells
13.3.2 Nickel-CadmiumBatteries
13.3.3 Fuel Cells
13.14 Summary
13.15 Glossary
13.17 Answers to SAQs

13.1 INTRODUCTION
Electrical energy can be used to bring about chemical reactions in electrolytic cells.
The passage of electricity through aqueous solutions of electrolytes or molten
electrolytes provides sufficient energy to cause an otherwise non-spontaneous
reduction-oxidation or redox reaction to take place. This process, called electrolysis is
widely used in electroplating, extractive metallurgy, electrochemical machining, etc.
The converse process of conversion of the chemical energy of a spontaneous redox
reaction into electrical energy takes palce in electrochemical or galvanic cells. These
are also called voltaic cells in honour of Volta. He demostrated that by interposing
sheets of paper soaked in salt water between different metals and connecting the
metals, electricity could be produced. Batteries and fuel cells are such devices. The
phenomenon of corrosion also belongs to this category. Both in electrolytic and
galvanic cells, the redox reactions involve the transfer of charge between the
electrode and the electrolyte. Thus, electrochemisuy can be broadly defined as the
science that deals with the consequences of transfer of electric charges from one
phase to another.
Application of electrochemistry such as the extraction and refining of metals,
manufacture of important chemicals like chlorine, caustic soda etc., are quite well
known. The increasing awareness to minimise the pollution by automobile exhausts
and thermal power plants has rekindled an intrest in batteries and fuel cells.
Non-conventional energy sources like the solar energy or wind power can be used to
generate electricity which can be used to charge the batteries. The batteries can be
used during periods of break down of power and also in running automobiles and
mopeds.
0 bjectives
After studying this unit, you should be able to :
* understand how a redox reaction can be made to produce electric current in
a galvanic cell,
* represent such a galvanic cell and to explain by means of electrode reactions
how the cell produces an electric current,
* identify the anode, cathode, psitive electrode and negative electrode of a'
galvanic cell,
* know how the standard electrode potentials are determined and how to use
these to calculate the standard E.M.F. of a cell,
* know how to use the relationship between free energy change and E.M.F.
and to calculate the equilibrium constant from the standard E.M.F. of a cell,
* use Nernst equation to calculate the electrode potential of half cells or the
E.M.F. of cells in which the reactants and products are not in their standard
states.
* Explain the working of a pH meter and use EMF measurements for
measuring pH and solubility products,
* appreciate the usefulness of potentiometric titrations,
* Analyse the advantages and limitations of various electrochemical energy
sources, and
* explain what galvanic corrosion is and how it may be minimized.

These are devices in which the free energy change accompanying a redox reaction is
converted into electrical energy. If a zinc rod is dipped into a solution of copper
sulphate, a brownish-red deposit of copjgr is formed on the surface of zinc and the
bluish-green colour of the copper sulphate solution disappears. The redox reactions
that occur can be represented as
oxidation :
~n(s)-2e+~x?+(aq) (13.1)
reduction :
cu2+(aq) + 2 e + C u ( s ) (13.2)
The overall reaction is represented as (13.3)
Z n ( s ) +C$+(aq) + ~ x ? + ( a q ) +Cu(s) (13.3)
In reaction (13.3), only the active constituents taking part in the reaction are
indicated. The sulphate ions do not take part in the reaction. At 298 K and 101.3 kPa
(i.e., lam) the standard free energy change ( AGO ) corresponding to this
spontaneous reaction is -212.9 kJ. Though AGO is a measure of the electrical work
that can be derived from this reaction i.e., Eq.(13.3), the electron transfer from zinc to
Cu2+( aq ) can be demonstrated only when the oxidation and reduction reaction are
allowed to take place separately as in the Daniel1 cell, which is a Galvanic cell.
[Figure 13.11. This cell consists of a zinc rod (electrode) dipping into a solution of
zinc sulphate (one can use an aqueous solution of sodium chloride also) and a copper
rod (a platinum electrode can also be used ) dipping into a solution Of capper
sulphate. A porous barrier prevents the mixing of the two electrolytes [
Figurel3.l(a)] but allows the passage of the ions. The two electrolytes may also be
kept in separate beakers and a salt bridge enables the passage of ions from one
compartment to another [Figure13.1(b)].
When the two electrodes are connected by means ~f a wire (electronic conductor),
oxidation (reaction-1) takes palce at the zinc electrode. The zinc ions dissolve in the
 Elwetron flow EMr~&emlerlCdls

Porous b o r r l r r

!(a) Solutlow equated by a porous b a d =

so$-

-
(b) Sdutlons separated by a salt brldge
Flpre 13.1 :Laboratory Verdons of the Daniell Cell

electrolyte and the electrons left behind on the electrode push other electrons via the
connecting wire to the copper electrode. These electrons are used by cu2+ions in
solution and reduction (reaction-2) occurs. The electron flow from the zinc electrode
to the copper electrode provides a source of electricity. The direction of the current
flow, as measured by a current measuring device, is opposite to that of electron flow.
Sirice oxidation takes place at the zinc electrode it is called the anode. In this galvanic
cell, this electrode, being a source of a negative charge, is the negative electrode. The
copper electrode at which reduction occurs is the cathode and since it is a sink for
electrons (accepts electrons), it is the positive electrode. As the cell continues to
produce current, the zn2+ ions entering the electrically neutral solution make the
solution positively charged. The zinc electrode acquires a nagative charge with
respect to the solution. As a result of the build up of charges, an electrical double
layer is established at the electrode-electrolyte interface. The resultant potential
difference between the electrode and electrolyte is called the electrode potential. The
negative electrode potential on the zinc electrode will prevent the zinc ions from the
metal lattice leaving the electrode. At the other electrode, the cuZ+ions in solution
are used up in the reduction (reaction-2). The remaining sulphate ions tend to make
the solution Acquire a negative charge. Since electrons are removed from the copper
electrode it acquires a positive potential and so prevents the approach of cu2+ions to
the electrode (cathode). A continuous flow of current can be maintained if electrical
neutrality is maintained at both the compartments A and C. The excess of sulphate
ions from C move through the barrier into A so as to neutralize the excess positive
charge of the solution in A. The sulphate ions do not undergo any chemical change.
Instead of a porous partition, a salt bridge is often used. This consists of a glass tube
containing a concentrated solution of KC1 or NH,NO, gelled by adding gelatin or
Equilibria & Electroehmlstry
agar. The gel confines the electrolyte to the tube, prevents the mixing of the
electrolytes and allows the passage of ions. Here, K+or N e ions move to C and the
anions ( Cl- or NO; ) to A so as to maintain electrical neutrality. The high
concentration ensures that most of the current is carried by the ions of the electrolyte
used in the salt bridge. These ions also carry equal shares of the current and do not
undergo any reaction with the electrode.
13.2.1 A Convenient Notation for the Representation of
Electrodes and Cells
Any electrochemical cell like the Daniell cell consists of two electrodeelectrolyte
assemblies and each of these is called a half cell or simply an electrode. Oxidation
occurs at one half cell and reduction at the other. The cell reaction is simply the sum
of the two half cell or electrode reactions.
A convenient notation is generally followed to represent on paper the electrodes and
cells. A single vertical line denotes the boundary between two phases. In the case of
aqueous solutions, the concentrations of the ionic species are indicated in parenthesis.
The Daniell cell [Fig.13.1] can be represented on paper as
~n 1 w+( 1 . 0 ~ 1II cu2+ ( 1 . 0 ~ I ) cu
The double vertical line between the electrolyte solutions indicates that a barrier
[Figure 13.l(a)] or a salt bridge [Figure13.1(b)] has been used. The half cell or
electrode at which oxidation occurs, i.e., anode, is written on the left hand side, and
the cathode on the right hand side. An easy way of remembering all that has been said
about galvanic cells is given below, using the Daniell cell as an example.

L H S electrode B H S electrode
Qxidation occurs Reduction occurs
Anode Cathode
Uega tive Electrode Positive Electrode
It is simpler to remember the letters "LOAN" which summarizes the conventions. It
will be noticed that the underlined alphabets on the LHS appear earlier than the
corresponding ones on the RHS in alphabetical order. In general, irrespective of how
the electrodes are represented, a galvanic cell should be represented on paper as
Anode 1 Anode solltion 1 1 Cathode solution 1 Cathode
(C, (GI
Thecell reaction in the case of the Daniell cell can be written as
Cathode : cu2++2 e = cu
Anode : a'-2 e = ~ n 2 +
Therefore, Zn(s) + c u 2 + = Z n 2 + + ~ ( s )
You ought to try and think of alternative conventions of representing cells, which
may help you to remember the conventions better.
13.3 TYPES OF ELECTRODES
There are three categories of electrodes (half cells). The electrodes of the first kind
iqclude a metal electrode in contact with its ions or a gas (G) bubbled over the
surface of an inert electrode like R,dipping in a solution containing G or G+ions. In
the case of gases, the pressure of the gas should be specified.
The hydrogen electrode can be represented as

since the gas at a pressure of 1 atm and W = 1.OM conform to standard conditions,
the hydrogen electrode is called the Standard Hydrogen Electrode (S.H.E.)
[Figurel3.2]. More examples are given in Table 13.1
 Table 13.1 : Representation and Electrode reactions in the case of Gas Electrodes

All electrode reactions have

Electrodes of the second kind consist of a metal coated with layer of an insoluble salt
of the metal dipping in a solution containing the common anion. Some of these are
given i0 Table 13.2
Table 13.2 :Representation of Electrodes of the Second Kind

Electrodes of the third kind are called redox electrodes. In these electrodes, an inert

-
electronic conductor like Pt dips into a solution containing two different oxidation
states of a species.

Glass t u b e
Hydrogen C 1 a t n >

P t electrode coated wi-

Finely divided P t

*
Figure 13.2 :A diagrammatic representation of a Standard Hydrogen Elecvode (SHE)

Pt I Fe2+(c,) ,Fe3+(c2)
~t I sn4+(c',),sn2+(C',)
The order of writing the two species is immaterial.
Equlllbria & Electrochemistry SAQ 1
In the following reactions, identify the reactants that undergo oxidation.
a) Z n ( s ) + 2 A g C l ( s ) ->ZnC&+2Ag(s)
b) Fe(s) + 2 ~ + - > ~ e ~ + + ~ , ( g )
c) 2cuZ++4r->~cuI+&
d) I,+s~+--->s~~++~I-

SAQ 2
Study the cell diagram of a galvanic cell and also the electrochemical terms
arranged in an alphabetical order below the LHS compartment. Can you
suggest a suitable alternative mnemonic (easy way of remembering) by
concentrating on the underlined alphabets.
Zn I ~ 2(1.0+M) II cu2+(1.0 M) 1 CU
Anode Cathode
LHS electrode RHS electrode
Negatively charged Eositively charged
Qxidation occurs Reduction occurs
If it is an electrolytic cell will the same hold good ?

13.4 ELECTROMOTIVE FORCE AND ITS

MEASUREMENT
A flow of charge occurs only if there is a difference in the electrical potential. In the
case of the Daniel1 cell, a flow of electric charge from anode (Zn) to the cathode (Cu)
occurs, since the negative potential at the anode is more negative than that at the
cathode. The potential difference which is respnsible for forcing the electrons to
flow from the negative electrode to the positive electrode is called the electromotive
force (EMF). Potential is energy per unit charge. If energy is expressed in joule (J)
and charge in coulomb (C), both potential and potential difference are to be expressed
in J/C or volt (V). A voltmeter connected across the terminals of the two electrodes
will give the voltage of the cell. This depends on the current drawn from the cell by
the voltmeter. As the cell reaction progresses, the voltage will be found to decrease.
The voltage will be a maximum only when the current drawn is zero. The voltage
under zero current conditions is the EMF of the cell. For this purpose, a
potentiometer lFigure13.31 is used. In this instrument, the EMF of the cell is balanced
by an opposing EMF from within the potentiometer. When the two EMF'S are equal,
no current flows, and thus the EMF is measured when the current drawn is nil.
A storage battery is connected across the potentiometer wire NP Lhrough a variable
resistance R. Both the standard cell (S) having a known and constant EMF ( E, ) and
 El~rtrochcmicalCells

F l p r e 1 3 3 :Measurement of EMF using a Patentlometer

the cell X whose EMF ( Ex ) has to be determined are connected as shown in Figure
13.3. The negative pole of each cell is c o ~ e c t e dto the negative end N of the
potentiometer. The positive and of each cell is to be connected through a
galvanometer (G) to the sliding contact, C. The EMF of the cell is measured by
comparing its EMF with that of a standard. The standard cell used for this purpose is
the Weston cadmium cell which can be represented as :
Cd ( Hg ) 1 3 Cd SO, . 8H20( s ) 1 Cd SO, ( saturated solution) I Hg2S0, ( s ) I Hg
It has an EMF of 1.0146V at 298 K and does not vary much with temperature. With
the Weston cell (S) included in the circuit by the DPDT switch and the sliding contact
is moved along the wire till there is null deflection in G. If NC is the length of the
potentiometer wire at which no deflection is observed in G, the potential drop across
NC is balanced by the EMF,E,, of the cell S. The purpose of R is to adjust the
resistance in such a way that the balance point occurs when NC is equal to 1014.6
cm. The potential drop will thus be 1 millivolt/cm of the potentiometer wire. Now the
cell is brought into the circuit using the DPDT switch and without disturbing R, the
sliding contact is moved till the galvanometer reads nil deflection. Let ND be the
length of the potentiometer wire when there is nil deflection. The EMF of the
unknown cell is given by Eqn. 13.1

EMF measurements using a potentiometer are also useful in hawing the polarity of
the electrodes. In the case of the Daniel1 cell, only when the zinc electrode (negative
electrode, anode) is connected to N and the copper electrode (positive electrode,
cathode) to the sliding contact it will be possible to find a balance point. U the
connections are reversed no balance point will be found. In a balanced potentiometer
circuit, the electrode connected to N is the negative electrode (anode) and the other
one is the positive electrode (cathode) of the galvanic cell. U the external EMF is
decreased slightly, the cell reaction in the galvanic cell occurs in the forward
direction so as to force a current through the potentiometer circuit. However if the
external EMF is increased slightly, a current is forced through the galvanic cell and
the reverse reaction will be favoured. Such a cell is said to be thermodynamically
reversible.

13.5 FREE ENERGY CHANGE AND ELECTRICAL

.WORK
At constant temperature and pressure, the Gibbs free energy change accompanying a
process is equal to the reversible work, other than the work of expansion,(Unit 7).
This is the electrical work in galvanic cells. When a charge of q coulomb is
transported under the influence of a potential difference of E volt, the electrical work
 S I~:lcc~rtrhernlstry
I.q~~ilil)ri.~
done on the surroundings is qE volt- coulomb or qE joules. If a redox reaction
involves n mol of electrons, q = nF coulombs where F is the Faraday. Hence the
electrical work done by the cell on the surroundings ,W"
WSur= n F E Joules (13.2)
Since the cell is thermodynamically reversible, this is also the maximum electrical
work, which is equal to -AG. Thus Eqn. 13.2 becomes
AG-W"=-nFE (13.3)
In Eqn. 13.3, n is the number of moles of electrons involved in the cell reaction, F is
the Faraday and E is the EMF of the cell. The EMF of any galvanic cell depends on
(i) the nature of half cells used to form the cell, (ii) the concentrations of the species
involved in the redox reaction, and (iii) temperature. For the sake of comparison, rhe
temperature is usually 298 K and the reactants and products are assumed to be in the
respective standard states (Unit 6 and 7). All solids and liquids must be pure and in
their stable forms. The gases should be at a pressure of 101.3 kPa (1 a m ) and the
activities of all the species in solution must be unity. However, as an approximation,
a concentration of 1.0 M can be used instead of unit activity. The EMF and the
corresponding free energy change under the standard conditions are E0 and AGO
respectively. Thus for standard conditions
AGO=-nFEO (13.4)
Eqn. 13.4 provides the link between thermodynamics and electrochemistry.
Example 13.1 :
For the galvanic cell,
z n I zn2+ ( 1 . 0 ~ 1) I C I - ( 1 . 0 ~ 1I ~ g ~ l ( Is ~g
)
the EMF at 298 K is 0.985 V. (a) identify (i) the anode, (ii) the cathode
(iii) the positive electrode (iv) the negative electrode. (b) Write down (i) the
electrode reactions and (ii) the cell reactions and (c) calculate AGO at 298 for
the cell reaction.
Solution:
(a) (i) LHS elecuode viz., Zn is the anode
(ii) RHS electrode viz., Ag is the cathode
(iii) The Ag electrode is the positive elecuode
(iv) The Zn electrode is the negative electrode
(b) (i) cathode :
AgCl(s)+e'=Ag(s) +Cl- 1
anode:
Zn - 2 e- = zn2+ 2
(ii) For the purpose of making the number of electrons gained equal to the
number lost, eqn(1) is multiplied by 2 and added to Eqn (2) to get the
cell reaction
Zn(s) +2AgCl(s) = z ~ * + + ~ c T + ~ A ~ ( s )

(c) AGO=-nFEO
Here n = 2, F = 96500 C and E0 = 0.985V

AGO=-2mole-~96500- C (0.985V)
mol e'
= -190105 J or -190.1 1 kJ
 Electrochemical Cclb
13.6 THE NERNST EQUATION
The free energy change of a reaction depends on the concentrations (activities) of reactants
and products. If the same reaction occurs reversibly in a galvanic cell, the EMF of the cell
will also depend on the concentrations of the reactants and products. For a cell reaction
aA+dBzmM+nN
the free energy change is related to the standard free energy change as ( Eqn. 7 of Unit 7)

h Eqn 13.5, Q, the reaction quotient, has the same form as the expression for the
equilibrium constant K. However, the concentration terms used in the expression for Q are
arbitrary and do not correspond to those in the equilibrium state. From equations 13.3, 13.4
and 13.5,

Here EOis the standard EMF and E is the EMF under non-standard conditions. The
standard EMF ( E0 ) is a constant for a given cell and at a pressure of 101.3 kPa, varies
only with temperature. Substituting for R,T and F in Eqn. 13.7 we get Eqn. 13.8

Equations 13.6 to 13.8 are different forms of the Nernst equation. All forms of the
Nernst equation are applicable not only to cell reactions but also to electrode reactions.
When the concentrations of all the species are unity, Q=1, log 1 = 0 and so E = EO.When
the concentrations are not unity (non-standard conditions) E is not equal to EOand the
Nernst equation (Eqn. 13.6 to 13.8) should be used to calculate E. If all the species are
at their equilibrium concentrations, Q = K, AG = 0 and E = 0. Eqn 13.6 can then be
written as

In a similar fashion, Eqn. 13.8 can be written as

K = 10(nlf/0.0591)

For example, the reduction reaction.cu2++ 2e+

given by
-
Thus, it is possible to calculate the equilibrium constant of a reaction if it is allowed to
take place in a galvanic cell under standard conditions.
Cu, the Nernst's equation is

El = E: +9
2
log [cu2+]

for the reduction reaction zn2++ 2e- --+ Zn

huiiibri8 EicctdclnYq The cell potential for the cell reaction
a+cu2++ZnZ+ + cu,
is given by the difference of the two reduction potentials expressed by Eqns (1) and (2) ,
0.0591
-
Ed = (E! - @ + 2 [log (&+) log (2h2+)] -

For any cell reaction it is easy to write the Nernst eqn by keeping in mind that the Q term
is similar to the expression for the equilibrium constant but set at actual concentrations and
not equilibrium concentrations.
Example f 3.2
Calculate the half cell potential at 298 K for
cu2+(aq) + 2e- ----+ Cu (s), if ( ~ $ 9= 10.0 M and E0 = + 0.336 V.
Solution:

E = E O - - 0.0591 [Cu]
2 log [Cd+]

-
= 0.336 V + 0.0591 log 10
2
= 0.3655 V
Example 133
Calculate the equilibrium constant of the cell reaction given in Example 1.
Solution:
Cell reaction : Z n ( s ) +2AgCl(s) = Z n 2 + + 2 ~ g ( s+2CT
)
K = [zn2+] [ C I - ] ~ = ~ X ~ ( ~ F E O / R T )
- exp [ 2
- 965m x 0q985
8.314 x 298
)= up ( 76-731

= 2.14 x l d 3
Example 13.4
For the galvanic cell
~d I C ~ ~ + ( O . O S1)MC) T ( O . ~ O MI )C b ( l a t m ) I ~t
calculate the EMF at 298 K, if E0= 1.76 V
Solution:
The concentrations are arbitrary and also nonstandard. The Nernst Eqn. (Eqn. 13.8)
can be applied.

The cell reaction can be written as

~ d ( s +) c I , ( ~ ) = ~ d + + 2 ~ 1 - ( n = 2 )
 Note that C%gas at 1 a m pressure and Cd(s) are in their standard states and so their ~ o e h e m k Cdb
d

activities are unity.

SAQ 3
1. If the EMF of a cell under standard conditions is 1.00 volt, what will be the
values of AGO and K if the cell reaction involves 2 moles electrons ?

2 Given that EzeI,is + 1.10 V. Calculate the EMF of the cell in which the cell
reactionisZn(s) + c u 2 + ( 0 . 0 2 ~-+Cu(s)
) +zn2+(0.40~)

13.7 STANDARD ELECTRODE POTENTIALS

It is not possible to measure the potential of a single electrode since the solution can not
be directly connected to the potential measuring device (electrode) in the solution. What
is measured as EMF is the potential difference between the two electrodes. If single
electrode potentials are available, it would be possible to predict the EMF of any
combination of two half cells. In order to assign values to single electrode potentials
we can use the approach that enabled us to evaluate AG and AH without knowing the
absolute values of G and H respectively (using standard states as in Units 6 and 7). It is
assumed that the electrode potential of a standard Hydrogen Electrode (SHE) (Sec 13.3) is
exactly 0.000 V at all temperatures. What one has to do is to construct a cell consisting
of a SHE and another half cell, whose electrode potential is required, and measure the
EMF of the cell. The measured EMF (E) is a difference between the two electrode
potentials (E) i.e.,

It follows that EhalPcell

is equal to E in this case since EsM is zero. While determining the
EMF, the SHE may have to be connected either to the negative end N or to the positive
end P of the potentiometer circuit. For example, two cells in which SHE is a half cell, are
given below and the polarities of each electrode are also indicated.

At 298 K, the EMFs of cell - 1 and cell - 2 are found to be 0.763V and 0.340V
mpectively. The cell reactions are spontaneous in both cases. The electrode potentials of
the zinc electrode and copper electrode should thus be 0.763 and +0.340V respectively.
Since the electrode potential is related to the free energy change, the sign and magnitude of
the electrode potential should reflect the tendency of the electrode reaction to proceed
spontaneously. For example in cell-1, at the zinc electrode the oxidation of Zn to @i is
spontaneous whereas at the copper electrode of cell-2, it is the reduction of cu2+to Cu that
is spontaneous. This has led to the adoption of two sign conventions. In the American
convention, all electrode reactions are written as oxidations and if the oxidation is
spontaneous, a positive value is assigned to the electrode potential. If the oxidation is not
spontaneous, a negative value is assigned to the electrode potential. For example,
Z n ( s ) - 2 e - = & + ; ~ ~=0.763V
~
&Dox
C U ( S ) - ~ ~ - = C I ? + ; =-0.340V
Thus, electrode potentials, according to the American convention, are oxidation
potentials.
In the European convention, all electrode reactions are written as reductions. If the
reduction is spontaneous, a positive value is assigned to the electrode potential and if it is
not, a negative value is assigned. For example,
zn2++2e-=Zn(s) ;cod =-0.763V
Cu2++2e-=Cu(s) ;cod =+0.340V
According to the IUPAC (The International Union of Pure and Applied Chemists)
recommendation, half cell potentials corresponding to reduction potentials are to be called
Standard Elecuode Potentials. A table of standard electrode potentials is given below
(Table 13.3). I

Table 13.3 :Standard Electrode Potentials at 25" C

Equiiibria&EwochmMrg 13.8.1 Significance of Positive and Negative Values
A positive value for E0 in this table indicates that the reaction Ox + ne = red, is
spontaneous. Since oxidising agents undergo reduction (electronation), this would mean
that the species "Ox" having a higher oxidation state than the " red " is an oxidising agent.
Greater the positive value, greater is the strength of the oxidant. Thus among halogens, the
oxidising ability decreases as
F2(+2.870)>C12(+ 1.358)>Br2(+ 1.065)>$(+0.540)
The E0 values are indicated in parenthesis. Another way of stating the same thing is that, in
the half cell with a more positive potential, reduction occurs.
Similarly a negative value for E0 indicates that the reduction reaction, Ox + ne = red is not
spontaneous but the reverse reaction is. The species " red " in a lower oxidation state is a
reducing agent. More negative the value of EO,greater is the strength of the reducing agent.
Thus the reducing ability decreases as
Na(-2.711) >Zn(-0.763) >Fe(-0.441) >H2(0.000)

13.8.2 Electrode Potential and Stoichiometry

The potential of a half cell or an electrode is not related to the stoichiometric coefficients
in the electrode reaction, since it is an intensive property. This means that the following
half cell reactions
cu2++2e- SCU
(s)

have the same E0 value of +0.340V, at 298 K (refer to Example 13.4). If the half cell
reaction is written in the Teverse direction, the sign of E0 changes. Thus
z$++ 2e- Zn: EO = -0.763 V
but Zn = Zn2++ 2e-: EO = +0.763 V
i.e., reduction potential = - oxidation potential.
13.8.3 Displacement Reactions
Metals like Mg, Al, Zn. Fe etc., tend to lose electrons readily to become the corresponding
cations. Ions like c u 2 + ,Ag+,~ g etc.~exhibit
+ a tendency to accept electrons. It is
because of these opposing tendencies that the familiar displacement reactions such as .
zn+cu2+ z n 2 + + C u

occur spontaneously. In general, a metal X having a more negative E0 value (higher up in

the EMF series) will displace another metal Y having a positive or less negative E0 value
from a solution of its salt. In fact, reaction of metals like Zn, Mg, Fe etc. with dilute acids
to give hydrogen from acids can be considered as a displacement reaction. One can
understand why metals like Cu and Ag do not liberate hydrogen from acids. These
displacement reactions can also be made to take place in suitable galvanic cells and we
shall now see how to calculate the EMF of such cells.

13.9 CALCULATION OF THE EMF OF GALVANIC CELLS

As indicated earlier (13.2). the galvanic cell is always written as,
electrode 1 ion I 1 ion 1 electrode, whatever be the manner in which the half cell is
 represented in Table 13.3. For such a galvanic cell, the EMF under standard conditions is Eleebochemkid Cells
given by Eqn 13.11
E0= qHS - E b S= E L e- Eonnode (13.1 1)
In Eqn. 13.11, the E0 values are reduct ion potentials.
Examples:
Cells :E0 = E b s - GS

(ii) Pt 1 s$+,sn4+11 Fe3+,FC?' I Pt EO= -770- ,150

i The cell reactions are spontaneous if the E0 values are positive and non-spontaneous
i if the E0 values are negative. For writing the cell reaction, the reaction at the M S
electrode is written as reduction and that at the LHS electrode as oxidation. The
number of electrons gained is made equal to the number of electrons lost (see
example 1). taking care to see that the corresponding electrode potential values are
not multiplied or divided. The two half cell reactions are then added to give the cell
reaction (Vide. example 1)

Example 13.5 :
The standard electrode potential of Ag-AgC1 electrode on the hydrogen scale is
+0.222 at 298 K. For the cell
Fe 1 ~ g ' ( l . 0 ~ I )I Cl-(1.OM) I AgCl(s) 1 Ag
the EMF was found to be +0.663V at 298 K. What is the standard electrode
potential of F$+/F~on the hydrogen scale'?
Solution:
EO=E;- EL
+ 0.663 V = 0.222 -
Therefore
et=-0.441 V
Example 13.6 :
I Forthecell Zn 1 Z n 2 + ( 1 . 0 ~ )( 1 6 ? + ( 1 . 0 ~ )I Cr
I (i) Calculate the EMF under standard conditions
(ii) Write down the cell reaction and calculate the AGO value corresponding to the
cell reaction. The standard electrode potentials of zn2+ 1 Zn and c?+I Cr are
-0.763 and -0.740 V respectively.
Solution :
i. EO=Ehs-Gs
= - 0.740 - ( - 0.763 ) = + 0.023 V
ii. (i) RHS electrode :
cPi+3e-=~r;
 (ii) LHS electrode :
zn=zn2++2c;

Let AG: and AG; be the standard free energy changes for reactions 1 and 2 respectively.
In order to balance the number of electrons, Eqn. (1) is multiplied by 2 and Eqn. 2 by 3

Adding,
3Zn(s)+2~?+$ 3 Z n 2 + + 2 2 ( s ); AGO =- ~ F E O
Since
AGO = AG; + AG;
-6FE0=- 6F(-0.740+0.763)
= - 6F (-0.740 + 0.763)
EO = + 0.023 V
A GO = - 6 x 96500 x 0.023 v
=- 13317 J or - 13.32kJ
It must be realised that the predictions regarding the spontaneity of a cell reaction are
based on thermodynamic considerations. However, the rates at which the cell reactions
take place can not be easily predicted.
SAQ 4
Consider the cell
I zn2+(l.0M) II c u 2 + ( 1 . 0 ~I)cu
The standard reduction potentials ate + 0.35V for cu2++ 2,- +Cu and
- 0.763 V for zn2+ + 2e- --+ Zn
Write down the cell reaction. Calculate the E.M.F. of the cell.

SAQ 5
Oxidationpotential ~f Zn (s) / ~ n is +0.76~ volts and the oxidation potential of
Ag(s) / is -0.80 volts. What will be the emf of the Zn-Ag cell ? Predict
whether the cell is feasible or not.
SAQ 6
For the cell, Ag 1 Ag' 1 1 1 CU,find out the emf of the cell and state
whether copper will displace silver from a solution containing silver ions.

SAQ 7
1. a) Will Cu react with dilute H2S04to give H2? Justify your answer.
b) Mention the three metals which liberate Ag from AgNQ.
c) . The oxidation potential of the redox couple M I M~+ is + 1.50 V. Is M
an oxidant or a reductant ?
2. The standard electrode potential of C& I Cd on the hydrogen scale is - 0.403
+

V. If instead of SHE, SCE ( EO = 0.242) is used in combination with the

Cd 1 C6L + couple, what will be the EG,, ?

13.10- APPLICATIONSOF EMF MEASUREMENTS

B y measuring the EMF of suitable galvanic cells, it is possible to calculate the
changes in the thermodynamic functions like AH and AS and the solubility product
and the pH of a solution. EMF measurements are also useful in analytical chemistry.
13.10.1 Evaluation of Thermodynamic Functions
In this method both AG and AS are determined from EMF measurements and AH is .
evaluated from the Gibbs - Helmohltz equation. EMF measurements are normally .
made at constant temperature. Since EMF is affected by changes in temperature, the
dE
temperature coefficient of EMF viz., -can be determined by measuring the EMF at
dT
2 or 3 different temperatures. It is related to AS as shown below. Differentiating Eqn.
13.3 w.r.t. temperature

since d(AG)/dT 7 -AS (Unit 7) we have

\ /

AH at any given temperature can be calculated from the'aibbs-~elrnholtzequation

AG=AH-TAS (13.12)
Example 13.7:
f i e galvanic cell
~ p ' ( s )I AgCl(s) I KCI(l.OM) I H&c~(s)I HgO)
 is an example of cell without a liquid junction since the two electrodes dip into
the same electrolyte. The EMF of the cell is 0.058V at 298 K and 0.0614V at
308 K. (a) Write down the cell reaction. (b) Calculate (i) ASo (ii) AGO and
(iii) AHoat 298 K.
Solution:
( 1 RHS electrode :Hg2 C12 + 2e' ;f 2 Hg ( 1 ) + 2 Cl-
LHSelectrode:2Ag(s)+2Cl' 2 2AgCl+2e
The cell reaction is 2 Ag ( s ) + Hg2C12(s ) 2 2 Hg ( 1 ) + 2 AgCl ( s )
dE -
(b) (i) - AE
dT AT
-- 0.0614 - 0.058
10
= 3.40 x 10-4 VK-'
From Eqn. 13.11,
dE
AS0 = nF -
dT
=2x965000C ~ 3 . 10-4
4 ~VK-'
= 57.9 JK-'m o ~ '
(ii) AGO = -nFEO
= -2 x 96500 C x 0.058 V = -1 1194J mol-'
(iii) AGO= A* - T ASO
AHO = AGO + T AS0
=-1 l194+ 298 x 57.9
= 6060 J mol-'
Note : Had the cell reaction been written as
A ~ ( s ) + ~ H ~ ~ c I2 , (Hs g) ( l ) + A g C l ( s )
2
the values of AS', AGO and AW will-be 28.95 JK-I mol-1 - 5597 J mol-I and
3030 J moT1 respectively. In this case, the values are per mol of AgCl formed. In the
former case, the values are per mol of Hg2CI, ( s ) reacted.

13.10.2 Determination of Solubility Products of Sparingly Soluble

Salts
The solubility product K,, (Sec. 14.15) is also an equilibrium constant and its
magnitude can be predicted from a knowledge of the standard electrode potentials, so
chosen, that the overall cell reaction is the solubility product equilibrium. One can
also form a suitable galvanic cell and determine its EMF experimentally. Even if
measurements @n not be made, it is possible to arrive at an approximate value of KBp
from the appropriate half cell reaction potentials as shown below.
Example 13.8:
Calculate K, for Hg2C12( s ) at 298 K from data in Table 13.3
Solution :
H&Cl,(s) 2 H&++~cI-;
K,=[H&+] [ ~ l2 r
One should look for a reaction in which Hg2C1, takes part and another reaction
in which H$ takes part. These are
 EloctradtemlcalCells

Reaction (1) - Reaction (2) gives

From Eqn. 13.9 or 13.10, K, can be calculated

13.10.3 Determination of the pH of a Solution

The electrode reaction in the case of a hydrogen electrode is H++ e = - 1 H,. Nernst
2
eqn. (Eqn. 13.8) can be used to calculate the electrode potential of a hydrogen
electrode.

1
Since PH2= 1 atm and %,, = 0 ,this equation can be written as
EH=O-0.0591 (-log[H+])=-0.0591pH (13.13)
A hydrogen electrode dipping into a solution of unknown pH is combined with a
reference electrode like the saturated calomel electrode (SCE) and its EMF is
measured.
Pt I H 2 ( l aun) 1 [ H t ] = x 1 IKCI I Hg2C12(s) 1 Hg
E=ER-EL=0.242-E, (13.14)
In Eqn. 13.14, since E is known and the EE ,,
being + 0.242 V, E, can be calculated.
This value is substituted in Eqn. 13.13 to obtain the pH of the solution.
The commercial pH meters make use of a glass electrode-SCE assembly to measure
the pH. The glass electrode consists of a thin glass bulb of a special quality glass
containing a solution of a constant pH into which a reference electrode dips. The cell
assembly can be represented as
Ag 1 AgCl (s) I 0.1NHCl 1 Glass I experimentalsoln I I SatdKCI I Hg2CI,(s ) I Hg
glass electrode SCE
The potential of a glass electrode depends on the difference in pH on either side of
the glass electrode. Since the solution in the glass electrode has a constant pH, the
potential depends on the pH of the experimental solution. First of all, the glass
electrode is immersed in a buffer solution and the pH meter adjusted so as to read the
pH of this buffer solution. After washing, rinsing etc.. it is then immersed in the
experimental solution and the pH of the solution is read off from the instrument dial.
The glass electrode is an example of an ion- selective electrode. By making suitable
changes in the composition of glass, a glass electrode can be made selective to other
cations like Nat , K t , NH, +,etc. Compacted discs of AgCl, AgBr, AgI, Ag2S or L q
are found to be selective to the respective anions.
13.10.4 Potentiometric Titra tions
One of the widely used applications of EMF measurements is to detect the end point
of a titration by measuring the EMF of a cell consisting of an indicator electrode
(electrode, whose potential depends on the concentration of the reactant ions) and a
reference electrode (SCE) as the titration progresses. This is called a potentiometric
titration. Since the electrode potential of the reference elecuode is constant, the
observed change in EMF as the reaction progresses is due to the change in the
electrode potential of the indicator electrode.
During acid-base titfatiom, the pH of the solution changes and by monitoring the
change in pH as the titration progresses. it is possible to detect the end point in
acid-base titrations using a pH meter. Very near the equivalence point, the change in
pH is quite%ge.
In a redox titration between Fe?' and ~ ethe ~overall . reaction
ce'+ + ~ 2 3
' Ce* + F$+
can be discussed interns of the two half cell reactions
cect+e- 2 Ce?' ; E&=+1.610 V and
~ 2 + + e2 - Fez+ ; &=+0.77lV
Initially when no Cect is added to the system, the potential of the electrode.
characteristic of the Fe?, Fe?+couple. is given by Eqn. 13.15

is added, the potential is

When all the Fez+has reacted. if a slight excess of ~ e *
characteristic of the ce4+,~2'.system and is given by Eqn. 13.16

E& = E& - 0.059 log u

ce"
[ a*+
I
The variations in the reduction potential when 100 ml of 0.1N Fe?+is titrated against
de4+of the same normality are tabulated on next page :
By plotting the potential against volume of &+ added, Rgure 13.4 is obtained. Tim
equivalence point corresponds to the point of inflection of the curve. A better
procedure to obtain the equivalence point is to make use of the fact that W A V is
large in the vicinity of the equivalance point. If AWAV is plotted against V
(Figure 13.5). the sharp maximum corresponds to the equivalence point.

T i t r a n t added (V)
Piprre 13.4: ApotentiawYic-anrn

v
Fipn 135 :Dasmrinrbnof Uw squivhm point ia r p o m b n d e rilnrlm
 Vol of ce4' added . Excess ml of
E in volt
~ e ~ ' ce4'

100.0 - - - - equivalence point 1.19

It will be seen that the change in potentid within s . l ml of the equivalence point is quite high, i.e., 0.485V (1.433- 0.948)
Equilibria& Elcet~ahemMry
13.11 CORROSION AND ITS PREVENTION
Metals like iron are widely used as structural materials. Metals vary in their reactivity
to oxygen, moisture and other substances in the environment. Metals like Au and Pt
are not affected by the substances present in the environment and are called noble
metals. It is partly because of this resistance to environmental attack that these metals
are so sought after, and therefore expensive. On the other hand, when exposed to
atmosphere, a piece of iron rusts, objects made of copper are covered with a green
deposit and zinc becomes coated with a white deposit. These are the products
resulting from their reaction with the environment. The term corrosion is generally
used to describe the deterioration of a metal as a result of its interaction with the
environment. The corrosion of iron is called rusting. Rust is hydrated ferric oxide and
as such provides little protection to the metal and makes it useless as a structural
material. It has been estimated that nearly 15% of the annual production of iron is
mainly used to replace the rusted iron. The problem of rusting of iron has assumed
serious proportions in view of the increasing pollution of the environment. The
corrosion of iron will be discussed in this section.
In order to combat the problem of corrosion, one should understand the factors that
promote corrosion so that steps can be taken to avoid or minimise these. The factors
that promote corrosion are (1) oxygen and moisture. (2) electrolytes dissolved in
water, and (3) contact with metals like copper. The recognition of the redox nature of
corrosion led to the electrochemical theory of corrosion. According to this theory, a
potential difference exists on the surface of a metal because of small differences in
the composition of the metal, such as lattice defects, impurities etc. This potential
difference is responsible for the corrosion process, resembling the operation of a
galvanic cell, to take place on the metal surface. At the anode of these galvanic cells,
~ +and the ~ 2 goes
the oxidation reaction, Fe -2 e- = ~ e occurs, ' into solution in the
water formed by the condensation of water vapour from the air condensing on the
surface. The electrons left behind at the anode flow to the cathode of the galvanic
cell, the metal surface acting as the electronic conductor. At the cathode, a number of
reactions are possible. Some of the important reduction half- reactions are
1) H* e- + 2 2 H~ ( ) ( acid solution) ( EO = 0.00v )

2) 0 2 + 4 H++4 e- 2 2 H20 ( acid solution) ( ='E 1.23 V ),

3) O2 + 2 H20 + 4 e- 2 4 O H (neutral or alkaline solutions) ( EO = 0.40 V )
In the galvanic cell, the circuit is completed by the ionic conduction through the
aqueous solution af an electrolyte. This explains role of an electrolyte in promoting
corrosion.
The formation of anodic/and cathodic areas or sites on the surface of a metal may
arise as a result of the following :
(1) roughness on the metal surface
(2) presence of impurities in the bulk metal, and
(3) differences in the availability of oxygen along the metal surface
(1) The head and the pointed end of a nail are rough surfaces. These uneven surfaces
have crests and troughs. Since the metal atoms at the crest are more weakly bound
compared to those at the trough, these are oxidised more readily. Thus trough areas
act as anodic sites and the body of the nail acts as the cathodic sites. The formation of
~ e at ~the +anodic sites and O H at cathodic sites can be demonstrated using the
ferroxyl indicator (a mixure of phenolphthelein and potassium ferricyanide.) If the
iron nail (free from rust) is placed in a Petri dish containing a dilute solution of NaCl
(3%) containing 1 or 2 drops of ferroxyl indicator, it will -be noticed i;i,t~ aker some
time the solution near thc pointed end and the had regions of the nail would have
become blue whereas that near the body pink. The blue colour is due to the formation
of prussian blue, resulting from the reaction between ~ e and ~ ferrocyanide
+ ions. The
reduction of 0, at the cathode gives O K ions, which react with phenolphthelein to
n ; . ~ nn Anb ~.rrln.lr
 (2) A galvanic cell is formed when two metals of different electrode potentials are in Eledro&embl Cdls
contact with an electrolyte. This is exactly what happens when steel containing
alloying elements or steel-copper combinations are in contact with an electrolyte. In a
galvanic cell of this type, iron acting as the anode gets corroded. The alloying
element or Cu acts as the cathode. The corrosion of a less noble member of a pair of
metals is called galvanic corrosion. Graphite in grey cast iron and cementite in carbon
steel are cathodic compared to iron, and so, it is iron that corrodes. It is therefore
clear that if iron is made to act as a cathode in a galvanic cell, the oxidation of iron
leading to corrosion can be avoided. Iron pipes are coated with zinc (galvanized iron
or GI) or aluminium for this purpose. Even in a corrosive atmosphere, it is zinc.
I acting as the anode of the galvanic cell. that corrodes. Thus zinc is called the
sacrificial anode and iron is said to be cathodically protected from getting corroded.
/I Steel structures in marine environments and pipes buried under ground are
cathodically protected by connecting it to zinc rods.
r (3) The standard reduction potentials of the half reactions, in which oxygen is
, reduced, are more positive than that of ~ e ~ + /and ~ eso,
, when there is an uneven
supply of oxygen on the metal surface in contact with an electrolyte. corrosion of iron
becomes possible. The area exposed to higher concentration of oxygen acts as the
cathode and at the region where the oxygen concentration is low, the oxidation of Fe
leading to its corrosion occurs. This is referred to as the differential aeration
corrosion. The corrosion of an automobile and of GI pipes buried in sand are familiar
examples of this type of corrosion. When some. of the protective layer of paint or zinc
peels off, corrosion does not occur at the site of the broken film but at a site nearby
where the concentration of oxygen is less.

13.12 PROTECTIVE MEASURES AGAINST

CORROSION
Since water and oxygen are essential for rusting of iron, the best way would be to
protect the metal surface from these two. The most widely used method is to protect
the surface of iron with a metallic or a non-metallic coating.
The metallic coating should be capable of forming a self- protecting layer (e.g.) Zn.
Ni, Sn. Al, Cd, Cr etc. These coatings may act as physical barriers against moisture
and oxygen. In the case of iron coated with zinc (galvanised iron), even if there are a
few scratches on the surface, rusting does not take place since compounds of zinc
resulting from the oxidation of zinc plug these scratches. The same thing can not be
said about metals like tin and nickel, having less negative Eo values compared iron,
I used for the protection of iron. In these case. these metals are able to protect iron
because of their ability to form oxide layers on their surfaces. Once the protective
oxide layer is exposed, Sn or Ni acts as the cathode and iron as the anode in the
galvanic cell and corrosion occurs. This is in a way advantageous since tin plated iron
vessels can be thrown off after use. The cans get rusted and are converted to ferric
oxide powder.
The non-metallic coatings may be inorganic or organic. Metals like A1 ,Ti and Zr
have a thin film of protective oxide layers. The oxide layer can thickened
electrolytically by anodising (metal used as anode in electrolysis). Iron is protected
.
by forming a coating of phosphates of Fe Zn and Mn on its surface (phosphatizing).
These phosphate films serve as excellent bases for paints.
Paints are dispersions of finely ground inorganic or organic pigments in film-forming
materials like linseed oil (medium) dissolved in suitable solvents (thinners). The paint
may protect the iron surface by acting as a barrier against the attack by oxygen and
moisture. There may also be a chemical interaction between the constituents of paint
with the surface to prevent the anodic oxidation of iron.
Another way of protection is to add corrosion inhibitors t~ the medium with which
the iron objects are in contact. The corrosion reaction may be stifled if the anodic
oxidation and / or cathodic reaction processes are not allowed to take place. Anodic
inhibitors like sodium chromate, sodium nitrite, etc. ililiibit the anode reaction. These
are believed to act by setting right the defects in oxide films, responsible for the
reaction, Fe - 2 e- +J~ e ~ to' ,occur. In neutral or slightly alkaline media, the cathode
reaction, viz. ,the reduction of oxygen to hydroxide ion occurs. Certain salts like zinc
sulphate and magnesium sulphate act as cathodic inhibitors by forming insoluble
hydroxides on the metal surface, and thereby, preventing the occurrence of the
cathode reaction. Organic inhibitors containing N or S (e.g.) are believed to be
absorbed all over the metal surface and retard or suppress the corrosion processes.
Organic inhibitors like dicyclohexyl ammonium nitrite (DCHAN) are called vapour
phase inhibitors (VPI) and are largely used to protect iron and steel machine from
corrosion during transit by sea or air.
SAQ 8
1. Explain the following :
a) Galvanic corrosion is more facile in salt water than in fresh water.
b) When Ni and Zn form a galvanic couple, zinc is likely to corrode.
C) Electrode potential data cannot be used to predict the rate at which cell
reactions take place.

2. In order to protect steel structures from corrosion, which of the following will be
useful? Ni ,Na, Pb .Cd .Zn ,Mg ,Al.

13.13 ELECTROCHEMICAL ENERGY SOURCES -

Commercial cells which are used as a source of electrical energy are of three types:
Primary cells, Secondary cells and Fuel cells. Primary cells are based on cell
reactions which are not reversible. Once the cell reaction is complete, the cell is
discharged and cannot be charged again.
Examples: Weston Cd Cell. Leclanche' cell (dry cell) etc. Secondary cells (storage
cells or Accumulators) are galvanic cells in which the cell reactions that produce
current can be reversed by applying an extemal source of current. These can be
discharged and recharged many times until the electrode materials last. Examples:
Lead-acid battery, Nickel-Cadmium battery, NiFe cells, etc. The term 'battery' is
normally used to denote a number of galvanic cells connected in series. Fuel cells are
also galvanic cells in which the reactants, to be oxidised at the anode (fuels) and
reduced at the cathode (oxidants), are provided continuously from an external source
and the products removed as they are formed. In a conventional cell, the reactants
form a part of the cell. These are not replenished in primary cells but replenished in
secondary cells.
13.13.1 Dry Cells
These are modified Leclanchc's Cells in which an aqueous solution of the electrolyte
is mixed with enough flour or starch to prevent spillage of the electrolyte. It can be
represented as
- ' +
Zn 1 NH,CI ( 25% ).ZnC12( 10% ) + MnO, ( s ) + C ( s ) 1 Graphite
 Figure 13.6 :SchematicRep~sentaLionof a Dry C d
1. Outer Cardboard Cover
2. Zinc Cup mode (Negative Eldmde)
3. Plastic or Pitch seal
4. Gra- rod (Positive Elearode)
5. Electmlyte (20 % NH4 CI + lOaD Zn (32 +M
na (s) + carbon .thickened with starch :

The dry cell is capable of delivering 1.5 V and the cell reactions can be represented as
Anode : Zn - 2e- = zn2+
Cathode : 2Mn02+2H,0+2e-=2MnO(OH)+2OH
Cell reaction: z~+~M~o~+~H~o=z~~++~M~o(OH)+~OH
Mn02 is called the 'depolariser' since it prevents the formation of H2 at the cathode
by preferentially getting reduced at the cathode. A secondary reaction (local action)
results in the consumption of anode material and the electrolyte during the
discharging of the cell. Once discharged the dry cell cannot be charged for reuse. Dry
cells deteriorate on storage due to local action and also due to the evaporation of
water from the electrolyte.

Miniature flat and round cells, capable of delivering 1.5 V, are used in calculators,
I
hearing aids etc. In the alkaline manganese cell, zinc is the anode, a mixture of Mn$
and graphite is the cathode and the elecuolyte is a solution of KOH contained in an
absorbent material. The overall cell reaction is

The silver oxide-Zn cell, though costlier, lasts for a longer time. Here the n ~ d ise Zn,
cathode is Ag20 and the electrolyte is the KOH aq. The cell reaction is,
Zn + Ago + H20 --> ZnO + H20 + Ag
Secondary Cells
The widely used automobile battery is a storage battery capable of delivering either 6
V or 12 V depending on the number of cells connected in series. They are used as
stationary power sources in telephone exchanges, switching systems, emergency
lighting etc. The cell can be represented as

Electrode reacrhns
Anode :
Equilibria & Electrochemistry To thpr TO other
0noJes

Figuie 13.7 :Schematic reprerentationof r lead accumulator

1. Glass a Plastic antainer
2. G d l eleamdes made of Pb - Sb day
3. Spargy h d Padred in Mode
4. Pb& padred in cathode
5. Poms non-conductive Plastic Separator
6. Elecmlyce (38% by weight of H s ) sp. p v i t y = 1.30

Cathode :

Cell reaction for the passage of 2F

discharging
Pb02 + Pb + 2 H2S04 2 Pb SO4+ 2 H20 (1)
charging
The normal voltage of a single lead storage cell is about 2.OV. As the cell discharges
electricity, PbS04 is deposited on both the electrodes and sulphuric acid is consumed,
resulting in a decrease in the specific gravity of the electrolyte. With the aid of a
hydrometer, the specific gravity can be checked and if it is equal to or below 1.20
(approx 28% by weight of &SO4), the battery is charged. The charging operation is
performed in such a way that the negative pole of the battery is connected to the
negative pole and the positive pole to the positive pole of the external charging
device. The charging is done in an automobile by its electrical generator or alternator.
During the charging operation, water is converted into sulphuric acid (refer Eqn.l).
The charging is done till the specific gravity increases to the required value.
13.13.2 Nickel-Cadmium Batteries
The electrolyte is 21% by weight aqueous solution of KOH. The cell can be
represented as .

anode cathode
discharge
Cd+2NiO(OH)+2H20 2 Cd(OH),+2Ni(OH),
charging
The voltage of single Ni-Cd cell is 1.3 to 1.4 V. Compared ta a lead storage battery, it
has a longer life. It is also available as a sealed unit for use in electronic flash units
(photography) and in calculators.
The search is on for more efficient batteries for (i) storing electric power generated
during the hours of low consumption for use during the periods of peak consumption
(ii! storing electricity form solar and wind-powered generators, and (iii) use in
developing quiet-running, non-polluting electric automobiles and mopeds. Though
the lead-acid and the Ni-Cd batteries have been used to replace the internal
combustion engines of automobiles, their performance is not as good as the
gasoline-powered vehicles. Lithium or sodium-sulphur batteries have been developed
for this purpose. Their drawbacks are (i) higher temperatures required for efficient
operation, (ii) use of metals capable of violently reacting with water, and (iii) the
necessity of using corrosion resistant materials.
13.13.3 Fuel Cells
A fuel cell can be represented as
- +
Fuel 1 Electrode 1 Electrolyte I Electrode I Oxidant
.
Fuel can be eg. H2. N2H4 Hydrocarbons.
Oxidants can be eg. O2 ,H202,HN03 etc.
A fuel cell is a galvanic cell in which the chemical energy associated with the
oxidation of reducing agents (fuel) is directly converted into electrical energy. The
conventional method of utilising the chemical energy of the fuel to produce electrical
energy and the direct conversion process can be represented as given below.
(dl
Chemical energy --+ Electrical energy

I 1 (c)
(b)
Thermal energy -----., Mechanical energy
Any losses in energy in steps (a) and (c) can be minimised. However the efficiency of
the process (b) is limited by the second law of thermodynamics. Hence the process
(d) might be expected to have a higher efficiency. If AH is the enthalpy change of the
reaction, the amount of useful work that can be obtained out of this is AG.The rest of
it, i.e., AH - AG = T AS is unavailable for work.
Work obtainedfrom the cell reaction A G
Efficiency = e =
Heat change accompanyingthereaction - A PI

Thus & depends on AS and AH

The combustion (oxidation) reaction
2 H2 ( g ) + O2 ( g ) = 2 H,O, can be made tcr occur in a galvanic cell of the type
(Fig. 13.8)
- +
Inert electrode I H, ( g ) 1 H+ I O2 ( g ) 1 Inert electrode
Anode: 2%+4~,0=4~,0++4e(~O=0)
Cathode: 02+4H,0++4e=6H,0(E0=1.23V)
In the H2-02 fuel cell, the electrodes are Ti coated with porous R,and a
water-soaked cation exchange resin in the acid form is used as the electrolyte. If the
pressure of the gases are 1 aan, and water in the resin is pure, the EMF of this cell
should be + 1.23 V, corresponding to the cathode reaction O2+ 4 H,O+ + 4e = 6 %O.
This is because the potential of the hydrogen electrode under these conditions is zero.
In practice the EMF is about 0.8 to 1.0 V.
The only product discharged by the cell is water. The electrolyte in a % - O2 fuel cell
may also be.alkaline.
The electrode reactions in this case are
 Figurn 13.8 :Schematic reprearnuion of a H2 - 9 fuel cell using H3O+u electrolyta
1. Ti electrodcr canted with pomus Pt
2. Fuel (Hz) inlet
3. Oxidiser (02) inlet
4. Cation exchange membrane in acid form
~rourccofH3

Figure 13.9 :Schematic representation of a fuel cell ( H2 - 0 2 ) using an alkaline elemlyce

1. Pomus Ni anode
2. Pow Ni - NiO cathode
3. Hz inla
4. 02 mlet
s.n-mlyte. KOH ( 4.)

In spite of higher efficiencies, fuel cells are rather expensive. However they are used
in space-crafts because of their light weight and also because the product of
oxidation, water, can be used by astronauts.
SAQ 9
1. Distinguish between primary and secondary cells.
 2. Write down the electrode reactions and the cell reactions when a
lead-acid battery is discharged.

13.14 SUMMARY
Many reduction-oxidation (redox) reactions involve electron transfers from
reductants to oxidants. If the electron transfer is allowed to take place through an
external circuit of a galvanic cell, rather than directly, electrical energy can be
produced. The electromotive force (EMF) of the galvanic cell is a direct measure of
free energy change of the cell reaction. One can therefore calculate the equilibrium
constants bf redox reactions. The standard electrode potentials ( E' ) of the redox
couples, derived on the basis of the assumption that the potential of a standard
hydrogen electrode (SHE) is zero, are useful in predicting whether a redox reaction is
I feasible or not, under standard conditions. The Nernst equation is used to calculate
1 the electrode potential or EMF under non-standard conditions.
Galvanic cells in which the electrode potential of an electrode depends on [ H+]
form the basis of pH measurements. Commercial pH meters make use of a glass
electrode and a reference electrode like the saturated calomel electrode (SCE) to
measure the pH. Potentiometrically, acid-base and redox titrations can be carried out
more accurately than by using indicators.
Corrosion, which is an electrochemical reaction, can take place when i) two metals of
different electrode potentials are in contact with an electrolyte (Galvanic corrosion)
or ii) the metal is exposed to different concentrations of oxygen. Iron can be protected
from corroding using Zn or Mg as sacrificial anodes and also with the help of
metallic or non-metallic coatings.
Primary cells, secondary cells and fuel cells are the sources of electrical energy. In
the case of secondary cells the cell reaction producing electrical energy (discharge
process) can be reversed by applying an external source of current ( the charging
process). In the case of primary cells, the discharge process cannot be reversed. In
fuel cells, the chemical energy associated with the oxidation of fuels (reducing
agents) is directly converted into electrical energy more efficiently than in other
conventional processes.

13.15 GLOSSARY
Gslvanic cells : A device in which the free energy of a redox reaction is
converted into electrical energy.
Anode : In a galvanic cell, it is the negative electrpe wherein
oxidation is occuring and which is placed on the left in
the cell representation.
Equilibria & Electroehemlstrg Cathode In a galvanic cell, it is the positive electrode wherein
reduction is occuring and which is placed'on the right in
the cell representation.
electromotive force : the driving force arising due to the difference in the
chemical potential between the electrode and the
solution.
standard electrode The potential resulting when the electrode is placed in a
potential , solution of unit concentration (activity), with the
electrode potential of the standard hydrogen electrode
taken to be zero.

Nernst equation : E=EO-ElnB=EO-RTlnQ

nF [Reactants]
Potentiometric Titrations in which the EMF is measured as a function
Titration of the volume of the titrant added.
Batteries and fuel Devices for converting chemical energy in a redox
cells reaction or a combustion reaction into electrical energy.

Galvanic Corrosion : The electrochemical reaction occuring when two metals

of different electrode potentials come in contact with an
electrolyte.
Sacrificial anodes : Electrodes (such as those of Zn or Mg) used for
protecting a metal (iron) wherein they act as the anode
in the place of iron, since they have a move negative E0
value than that of Fe.

13.16 ANSWERS TO SAQs

SAQ 1
a) Z n ( s )
b). Fe (s)
c) r

SAQ 2
a The underlined letkrs on the left hand side are alphabetically arranged
(A. L, N,0)
b. Each alphabet on the LHS (with a single underline) comes earlier in the
alphabetical order compared to the corresponding underlined alphabet on the
RHS.
Note that when the opposite electrochemical terms are arranged alphabetically,
this mnemonic works. You may remember the word LOAN for left, oxidation
anode, negative or you can not think of something better, e.g., the set RRCP for
the right hand side electrode.
c. In the case of an electrolytic cell, anode is positively charged electrode. The rest
of the electrochemical terms are applicable to electrolyte cells also.

SAQ 3
1) AGO = -193KJ;K = 6.72x]d3
2) E,, = 1.062 V
 SAQ 4
Cell reaction :
zn+ZnZ++W
cu2+ + 2e- -+ Cu
Zn + cu2+-+ Cu + ZI?+
E.M.F. of the cell
Eo (oxidatiori) - EO(oxidation)
Left (Right),
or E0 (Reductiod - E0 (Reduction)
Right (Left)
1
I
= +0.35 - (-0.763)
= 1.113V

i SAQ 5
Zn (s) -+ + X, Oxidation, E0 = + 0.76 volts
2Ag++ 2e- +2Ag (s), Oxidation, E0 = - 0.80 volt
3 e cell is Zn I ~ n I +Ag+
~ I Ag
E.M.F. of the cell = E& - Ei,
= 0.76 - (- 0.80)
= 1.56 volts
Since the value of emf is positive, the cell is feasible
Rewrite the solutions of SAQ 5 and SAQ 6 using the reduction on potentials. Using
reduction potentials has become the common practice and should be adopted. Of
course, both conventions lead to the same result.
SAQ 6
j. The oxidation potentials of the electrodes :
EO Cu 1 C U += ~ - 0.337 volts
Eo Ag I Ag+ = - 0.799volts
The cell reaction :
2Ag + 2Ag+ + 2e-, oxidation, EO = -0.799volt

I + 2e- +Cu, reduction, E0 = - 0.337 volt

EOcell = EOoxiaatim- Eooxidatim
= - 0.799 - (- 0.337)
= - 0.462 volts
Since the value of e.m.f. is negative, the forward reaction is not spontaneous. The
reverse reaction would be spontaneous, that is

will have +ve value of emf and hence it is possible to displace Ag from the solution
of Ag+ions with Cu cell in Cu I cu2+I Ag+ I Ag

SAQ 7
' 1) a) No. The reduction Potential of cu2+I Cu is more positive.
b) Any metal above Ag in the electrochemical series, eg., Cu, Zn, Fe
c) M is a reductant.
2) E0 cell = 0.645 V
Equillhrla LQ Electrochemistry SAQ 8
1 ) a) Ionic conduction is facile.
b) Reduction potential of zn2+ I Zn is more negative.
c) Predictions are them~odynamicallybased.
2) Zn, Mg, Al.

sac) 9
1) Ref :Text
2) Ref :Text