Electrochem 1

Vidyamandir Classes Electrochemistry - I
Electrochemistry - I
(Electrochemical Cells)
BASICS Section - 1
Electrochemisrty deals with the inter-conversion of electrical energy and chemical energy. This part of
Electrochemistry will deal with the conversion of chemical energy into electrical energy (Electrochemical
Cells).
Electrochemical Cells :
Consider the following redox reaction :
Zn(s) + Cu2+(aq) 
 Cu(s) + Zn2+(aq)
In the above reaction , Zn displaces copper ions (Cu2+) from aqueous solution. This reaction can be achieved
very easily in practice. Put a Zn rod into a solution of CuSO4 (containing Cu2+ ions). It is observed that blue
colour of CuSO4 solution disappears after sometime. What happens actually ? Zn loses 2e–s per atom and
Cu2+ ions in the solution accepts them. Cu2+ ions from solution in this manner are deposited out in form of
solid Cu and Zn goes into the solution as Zn2+ (colourless). The reaction can well be understood in terms of
two half reactions :
Oxidation :  Zn2+(aq) + 2e–
Zn(s) 
Reduction : Cu2+ (aq) + 2e– 

 Cu(s)
Note : (i) In this reaction, Zn atoms are directly giving electrons to the copper ions.
(ii) Another aspect of this reaction is that it is an exothermic reaction. This means decrease in energy of
the reacting system takes place which appears as heat.
Now, we can make the same reaction take place even if the copper ions and zinc rod are not in direct
contact. If we put the Cu2+ ions and Zn rod in two separate containers and connect the two by a conducting
metallic wire and introduce an inverted U shape instrument (called as salt-bridge), then electrons will still be
transferred through the connecting wires. The electrons from Zn rod travel to Cu2+ ions through the con-
necting wires and the same reaction takes place.
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In such an arrangement, the solution does not get heated up. The loss in energy now appears as the potential
difference which is used to do the work in transferring the electrons from Zn to Cu2+ ions. Such an arrangement
is called as electrochemical cell or Galvanic cell or Voltaic cell. The potential difference which drives the
electrons from Zn to Cu2+ ions, is called as electromotive force (E.M.F.) of a cell.
An electrochemical cell (shown in diagram) mainly consists of two compartments : left hand electrode
(LHE) and right hand electrode (RHE). In LHE, oxidation takes place and is called as anode. In RHE,
reduction takes place and is called as cathode.
Anode is generally of that metal (or substance) which readily loses electrons (i.e., oxidised easily). A rod of
that metal is prepared and put into one of its solution in LHE to get anode. In RHE, a rod of metal that loses
electrons less easily as compared to the metal of LHE (in the diagram, Zn is taken in LHE and Cu is taken
in RHE) is prepared and put into one of its solution to get cathode. LHE and RHE are also known as two
half-cells. Now the electrons move from anode (LHE) to cathode (RHE) and hence a current flow is
maintained in the external circuit.
The two half cells are connected by a inverted ‘U’ shaped tube called as salt-bridge. The salt-bridge
contains solution of strong ionic salts like NaCl, NaNO3, KNO3 and KCl, etc., (salts of most reactive alkali
metals) soaked in a colloidal solution of agar-gel which allows only the movement of ions of salts, not water.
The role of a salt-bridge is very important as it allows the continuous discharge of the cell (i.e., the supply of
voltage from cell). The salt-bridge keeps the two solutions (i.e., in LHE and RHE) electrically neutral to
each other. In the Zn-CuSO4 cell, in left hand cell as Zn loses electrons, excess of positive charge (in form
of Zn2+ ions) is collected near LHE and as Cu2+ ions gets discharged (accepting electrons from Zn) in right
hand cell, excess of negative charge (in form of SO 24  ions) is accumulated near RHE. Now the salt-bridge
provides positive charge to RHE (in form of K+, Na+ ions) and negative charge to LHE (in form of Cl–,
NO3– etc) and thus bringing about the neutrality of two solutions. If this does not take place, a reverse
potential difference is created in the two compartments and thus breaking the continuous supply of voltage
(current), which is the purpose of the cell.
The efficiency of a cell is determined by the tendency of LHE to loose electrons and the tendency of RHE
to accept electrons. A measure of cell efficiency is called as electromotive force (EMF) or the voltage or the
difference in potentials of two electrodes. EMF is defined as the difference in the potential across LHE and
RHE due to which electrons from anode travel to cathode.
EMF value of a cell made up of such two half-cells is a constant provided that the concentration of electro-
lyte, temperature and the pressure (if gases are involved) remains constant. It means that EMF values do
change with concentration, temperature and pressure. EMF values are hence standardised at a temperature
of 25°C (298 K), a pressure of 1 atm (if gases are involved) and at concentrations of 1.0 M for all solutes
prevent as electrolytes. EMF value under these conditions is called as standard EMF and is denoted as E0.
EMF of a cell is measured as the difference of potentials of anode and cathode. The potential of a half-cell
or EMF of a half-cell (i.e., a cathode or anode) is called as electrode potential. It is defined as the tendency
of an electrode either to get oxidised or to get reduced i.e., to loose or gain electrons. electrode potentials
are of two types :
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Oxidation Potential :
It is the tendency of an electrode to get oxidised, i.e., to loose electrons.
Reduction Potential :
It is the tendency of an electrode to get reduced, i.e., to accept electrons.
Electrode potentials at standard conditions (1 atm, 298 K and 1.0 M) are called as standard electrode
potentials.
Note :  Anode is the negatively charged electrode in electrochemical cell and positively charged in electrolytic
cell (to be discussed later) but it will always be the oxidation electrode (electrode on which oxidation
take place).
 Cathode is the positively charged electrode in electrochemical cell and negatively charged in electrolytic
cell (to be discussed later) but it will always be the reduction electrode (electrode on which reduction
takes place).
 We can also define cathode and anode electrodes as :
Anode : Electrode at which current enters.
Cathode : Electrode at which current leaves.
 An important property for an ionic salt to act as a salt bridge is that ionic mobility (ease with which
ions move in solution) of both cations anion should be similar. Also, it should not react with the
contents of either anode or cathode.
Types of Electrodes :
1. Metal in contact with its ions :
Metal (M) in contact with its ion (Mn+) is represented as M/Mn+ when it acts as oxidation electrode
(anode) and Mn+/M when it acts as reduction electrode (cathode). Whether a given electrode acts as
anode or cathode depends upon the other electrode with which it forms an electrochemical cell. So,
it is necessary to define both oxidation and reduction potentials for an electrode.
M / Mn+ is written as :
 Mn 
M(s)  (1.0 M)  ne  (oxidation electrode)
and its potential is called as oxidation potential and at standard state is represented as E0(M/Mn+).
Mn+ / M is written as :
M n  (1.0 M )  ne  
 M (s) (reduction electrode)
and its potential is called as reduction potential and at standard state is represented as E0(Mn+/M).
Note : Symbol “/” denotes the phase seperation between the two substances.

2. Gaseous electrode :
Gases like H2(g) can loose electrons to form H+ ions and hence can
act as anode and also H+ ion can add up electrons to form H2 (g)
and hence can act as cathode. Similarly gases like Cl2 (g) can add
electrons to form Cl ions and Cl ions can loose electrons to form
Cl2(g). The concentration of electrolytes is the value for [H+] ions
and we take pressure of gas in atm. A hydrogen electrode is made
by passing H2 (g) at 1 atm near an electric conductor made up of
platinum (for conduction of e–s) dipped in an aqueous solution
containing H+ ions (generally HCl) as shown in figure.
Electrode representation : Pt, H2/H+

or H+/H2, Pt
Its electrode potentials are represents as :
1
E (H 2 / H  ) :  H  (aq.)  e 
H 2 (g)  (oxidaion potential)
2
1
E(H  / H 2 ) : H  (aq.)  e 
 H 2 (g) (reduction potential)
2
1
E0 (H 2 / H  ) :  H  (1M)  e 
H 2 (1 atm)  (standard oxidation potential)
2
1
E0 (H  / H 2 ) : H  (1M)  e 
 H 2 (1atm) (standard reduction potential)
2
Similarly, Cl2/Cl– electrode is prepared by passing Cl2 gas and taking HCl (aq) or KCl (aq) as electrolyte.
3. Redox Electrodes :
In this type of electrode, an inert wire (e.g. Platinum) is placed in a solution (electrolyte) containing ions of an
element in more than one oxidation states. e.g. Pt wire dipped in an electrolyte of Fe2+ and Fe3+ ions. The
electrode (inert material wire) acts as a source / sink for electrons.
Electrode representation : Pt/Fe3+ , Fe2+
Electrode reaction : As cathode : Fe3+ (aq.) + e– 
 Fe2+ (aq.)
As anode : Fe2+ (aq.) 

 Fe3+ (aq.) + e–
Another example : Pt/ MnO 4 , Mn 2+ , H +
As cathode : MnO 4 (aq.)  8H  (aq.)  5e  

 Mn 2  (aq.)  4H 2 O   

Redox electrodes can also be made using substances that exist in two different oxidation states. Quinhydrone
is an equimolar mixture of benzoquinone (Q) and hydroquione (H2Q)
Electrode representation : Pt/H2Q, Q, H+
Electrode reaction : As anode :
Note : If two substances are in same solution then in the cell or electrode representation, they are separated by
comma (‘,’).
4. Calomel Electrode :
It consists of mercury covered with mercurous chloride (calomel) in contact with a solution of KCl :
Electrode representation : Hg / Hg2Cl2 / Cl–
Electrode reaction :  2 Hg ( ) + 2Cl– (aq.)

As cathode : Hg2Cl2 (s) + 2e– 
As anode :  Hg2Cl2 (s) + 2e–

2 Hg () + 2Cl– (aq.) 
Most common calomel electrode is the saturated catomel electrode (SCE) in which the concentration of
0
KCl is at its saturation (about 3.5 M). ESCE  0.24 V (w.r.t. SHE)
5. Silver - Silver Chloride Electrode :

It consists of a pure silver wire in a solution of KCl saturated with solid silver chloride.
Electrode representation : Ag/AgCl/Cl–
Electrode reaction : As cathode:  Ag(s) + Cl–(aq.)

AgCl(s) + e–  E0Reduction  0.222 V
As anode :  AgCl(s) + e–

Ag(s) + Cl–(aq) 
If saturated KCl solution, E0reduction become 0.197 V (w.r.t. SHE)
6. Mercury - Mercurous Sulphate Electrode :

In this electrode, the metal is mercury, the sparingly soluble compound is mercurons sulphate (Hg2SO4) and
the source of SO42– anions is H2SO4 or K2SO4. It represented as :

Electrode representation : Hg / Hg2SO4 / SO42–
Electrode reaction :  2 Hg( ) + SO42– (aq.)

As cathode : Hg2SO4(s) + 2e– 
E0Reduction  0.616 V (w.r.t. SHE)
As anode : 2 Hg( ) + SO42– (aq.) 

 Hg2SO4(s) + 2e–
Note : [1] Calomel electrodes, Silver - Silver Chloride electrodes and Mercury - Mercurons Sulphate electrodes
are secondary reference electrodes. Silver - Silver electrodes and calomel electrodes are the most
commonly used (practically) as a reference electrode rather than SHE / NHE due to practical difficulties
associated with its (SHE) used and maintenance.
[2] The potential of metal - metal ion electrode and metal-metal insoluble salt-slat anion electrode is same
while their standard potentials are not same. Statndard potential are related by the following equation.
2.303RT
E  E  log K sp (MX) [Refer example - 4]
X  / MX / M M  /M F
7. Amalgam electrodes :
This is the modified version of Metal / Metal - ion electrode in which metal strip is replaced by metal
amalgam.
e.g. Na (in Hg at c1 M) / Na+ (c2 M)
Electrode Potentials :
It is impossible to measure the absolute EMF’s (electrode potentials) for half electrodes. This is done by
arbitrarily selecting one half cell and setting its electrode potential as ‘0’ volts. The electrode potentials of
other half cells can then be measured by combining them with the standard reference electrodes in a cell
arrangement.
The reference electrode against which all other half cells are generally measured is the hydrogen electrode
half-cell at a concentration of H+ ions equal to 1.0 M and H2(g) at 1 atm pressure kept at 25°C (298 K). It
is also known as SHE (standard hydrogen electrode) or NHE (normal hydrogen electrode). Its potential is
taken as ‘0’ volts.
E0(H2 / H+) = 0 = E0(H+ / H2)
Now other half cells can be divided into two categories : One which will act as anode and other which will
act as cathode in a cell arrangement with SHE. Each type of cell arrangement will give an EMF value which
will be actually the EMF value of known electrode as EMF value of SHE is ‘zero’ volts (whether SHE acts
as anode or cathode).
For example : Cu electrode (half cell) acts as cathode with SHE, i.e., as :
Cu 2  / Cu : Cu 2  (aq) (1.0M )  2e  
 Cu (s) .

The experimental measurement of EMF value for this cell arrangement give 0.34 volts. Since Cu electrode
shows reduction with SHE, the given value of EMF represents the reduction potential of Cu half-cell.
E0 (Cu2+ / Cu) = 0.34 volts
The oxidation potential of Cu half-cell is just the negative of this value.

E0 (Cu/Cu2+) = – 0.34 volts [Note : Ereduction = – Eoxidation]
Note : Reduction potential is taken as a standard potential i.e. if electrode potential is given (and nothing is mentioned
whether it is oxidation or reduction), it is taken as the reduction potential, by default.
Rules for assigning sign (+ve or –ve) to electrode potentials :

1. The oxidation potential of half-cell (or an electrode) is given a positive sign if the given electrode acts
as anode in a cell arrangement with SHE and its reduction potential is given a negative sign with the
same magnitude. For example : oxidation potential of active metals like Na, Mg, Al, Zn, Fe etc. is
given a positive sign.
2. The reduction potential of half-cell (or an electrode) is given positive sign if the given electrode acts as
cathode in a cell arrangement with SHE and its oxidation potential is given a negative sign with the
same magnitude.
For example : reduction potential of less active metals like Cu, Ag etc is given a positive sign.
Note : Electrode potential measured in this manner are called as standard hydrogen scale potentials.
0 ):
Standard EMF of a Cell ( Ecell
E0cell can be defined in two ways as :
 
(i) E 0cell  standard reduction potential  standard reduction potential 
 of cathode of anode 

E0cell  E0reduction 
cathode
0

 Ereduction
anode

 
(ii) E0cell = standard oxidation potential  standard oxidation potential 
 of anode of cathode 

E0cell  E0oxidation 
anode
0

 Eoxidation 
cathode

Construction of a cell and writing cell representation :

It is clear that an electrochemical cell will be developed by two half-cells. If you arbitrarily select two half-
cells for the purpose of constructing a galvanic cell, then always act in following manner :
Compare the reduction potentials of two electrodes. The electrode whose reduction potential has greater
positive value is made the cathode and the other electrode is made the anode.
Note : (i) Constructing the cell in this manner will always give a positive EMF otherwise sometimes if an elec-
trode is chosen wrongly, the EMF comes out to be negative. In that case, you should reverse the
electrodes i.e., make anode the cathode and vice-versa.
(ii) It is now standardised to use the definition of EMF in terms of standard reduction potential.

E 0cell  E 0reductioncathode

 E 0reduction
anode

Cell Representation :
The cell representation of a cell is written as :
LHE | | RHE | | : represents salt-bridge
In general, if two electrodes at standard conditions are :
M/Mx+ and N/Ny+
and let E0(Mx+ / M) < E0 (Ny+ / N).
So M / Mx+ is the anode and N / Ny+ is the cathode. [ Electrode having higher reduction potential has to
be cathode.]
LHE  M(s) / M x  (1.0 M) and RHE  N y  (1.0 M) / N
M(s) / M x  (1.0M) || N y  (1.0M) / N(s) is the cell representation for a cell at standard state.
If the cell is not at standard state, then let c1 be the concentration of anode and c2 be the concentration of
cathode. In that case, cell representation will be :
M(s) / M x  (c1M) || N y+ (c 2 M) / N(s)
Analysis of a given cell representation :

Analyse : M(s) / Mx+ (c1 M) || Ny+(c2M)/N(s)
(i) Anode : M(s) /Mx+(c1M)
Half-cell reaction :  M x (c1 )  xe

M(s)  [oxidation]
(ii) Cathode : Ny+(c2M) / N(s)
Half-cell reaction : N y (c 2 )  ye 

 N(s) [reduction]

Overall Reaction : y M(s)  x N y  (c2 M) 

 yM x  (c1M)  xN(s)
[Balance the num ber of e–s transfered at Cathode and Anode]
Electrochemical Series :
In this series, the standard reduction potential measured on hydrogen scale are arranged in increasing order.
Half Cell Electrode reaction Reduction

Potentials (volts)
Li+ / Li Li+ (aq.) + e– 

 Li (s) – 3.04
K+ / K K+ (aq.) + e 
 K(s) – 2.93
Ca2+/Ca Ca2+(aq.) +2e– 

 Ca(s) – 2.87
Na+ / Na Na+ (aq.) + e– 

 Na(s) – 2.71
Mg2+ / Mg Mg2+ (aq.) + 2e 

 Mg(s) – 2.37
Pt, H2 / H H2 (g) + 2e  –

 2H (aq.) – 2.25
Al3+ / Al Al3+ (aq.) + 3e 

 Al(s) – 1.66
Oxidising Power decreases
Reducing Power increases

Mn2+/Mn Mn2+ (aq.) + 2e– 
 Mn(s) – 0.91
OH / H2 , Pt 2H2O () + 2e–  –

 H2(g) + 2 OH (aq.) – 0.83
Zn2+ / Zn Zn2+ (aq.) + 2e– 

 Zn(s) – 0.76
Cr3+ / Cr Cr3+ (aq.)+ 3e– 

 Cr(s) – 0.74
Fe2+ / Fe Fe2+ (aq.) +2e– 

 Fe(s) – 0.44
Cr3+ / Cr2+, Pt Cr3+ (aq.) + e– 

 Cr2+(aq.) – 0.41
Cd2+ / Cd Cd2+ (aq.) + 2e– 

 Cd(s) – 0.40
Co2+ / Co Co2+ (aq.) + 2e– 

 Co(s) – 0.28
Ni2+/Ni Ni2+ (aq.) + 2e– 

 Ni(s) – 0.25

I– / AgI / Ag AgI(s) + e– 
 Ag(s) + I (aq.) – 0.15

Sn2+ / Sn Sn2+ (aq.) + 2e– 

 Sn(s) – 0.14
Pb2+ / Pb Pb2+ (aq.) + 2e– 

 Pb(s) – 0.13
Fe3+ / Fe Fe3+ (aq.) + 3e 

 Fe(s) – 0.04
H+ / H2 , Pt 2 H+ (aq.) + 2e 
 H2(g) 0.00
Br / AgBr / Ag AgBr(s) + e–  –

 Ag(s) + Br (aq.) 0.10
Cu2+ / Cu+, Pt Cu2+ (aq.) + e  +

 Cu (aq.) 0.16
Sn4+ / Sn2+, Pt Sn4+ (aq.) + 2e– 

 Sn2+(aq.) 0.15
SO42–/H2SO3 SO42– (aq.) + 4H+ + 2e– 

 H2SO3 (aq.) + H2O() 0.17
Cl / AgCl/ Ag AgCl(s) + e 

 Ag(s) + Cl  (aq .) 0.22
Cl / Hg 2Cl2 / Hg  Pt  Hg2Cl2  s   2e  

 2 Hg     2 Cl  aq. 0.27
Oxidising Power decreases
Reducing Power increases

Cu2+ / Cu Cu2+ (aq.) + 2e– 
 Cu(s) 0.34

Pt, O 2 / OH  O2(g) + 2H2O() + 4e 
 4 OH (aq.) 0.40
Cu+ / Cu Cu+ (aq.) + e 

 Cu(s) 0.52
I2/I, Pt 1/2I2(s) + e  
 I (aq.) 0.54
Pt, O2 / H2O2 O2(g) + 2H+ (aq.) + 2e– 

 H2O2 (aq.) 0.68
Fe3+ / Fe2+, Pt Fe3+ (aq.) + e–  2+

 Fe (aq.) 0.77
Hg22+ / Hg (Pt) 1/2Hg22+ (aq.) + e– 

 Hg(s) 0.79
Ag+ / Ag Ag+ (aq.) + e 

 Ag(s) 0.80
Hg2+ / Hg22+ 2Hg2+ (aq.) + 2e–  2+

 Hg2 (aq.) 0.92
NO3– / NO, Pt NO3– + 4H(aq.) + 3e– 

 NO(g) + 2H2O() 0.97
Pt, Br2 / Br– Br2 () + 2e–  

 2 Br (aq.) 1.09
MnO2 / Mn2+ MnO2(s) + 4H+(aq.) + 2e–  2+
 Mn (aq.) + 2H2O() 1.23

H+ / O2 / Pt O2(g) + 4H+(aq.) + 4e– 

 2 H2O() 1.23
Cr2O72– /Cr3+ Cr2O72– (aq.) + 14H+ (aq.) + 6e–  3+

 2Cr (aq.) + 7H2O() 1.33
Cl2 / Cl 1/2 Cl2 (g) + e  

 Cl (aq.) 1.36
Au3+ / Au Au3+ (aq.) + 3e 

 Au(s) 1.40
MnO4/ Mn2+, H+/Pt MnO4 (aq.) + 8H+ (aq.) + 5e 

 Mn2+ (aq.) + 4H2O() 1.51
Ce4+ / Ce3+, Pt Ce4+ + e 

 Ce3+(aq.) 1.72
H2O2 / H2O H 2 O2 ()+ 2H+ (aq.) + 2e– 

 2H2O() 1.78
Co3+ / Co2+, Pt Co3+(aq.) + e 

 Co2+ (aq.) 1.81
O3 / O 2 O3 (g) + 2 H + (aq.)  2 e 
 O 2 (g) + H 2O() 2.07
Pt, F2 / F–  2F– (aq.)

F2(g) + 2e–  2.87
 Lower the reduction potential, higher will be the tendency of forming positive ions. This is related to
reactivity of metals. The order of reactivity of metals is : Li > K > Ca > Na > Mg > Al
 In this series oxidising character decreases and reducing character increases, e.g., the reducing char-
acter follow the order : Na > Mg > Zn > Fe > Ni > Cu > Ag
Illustration - 1
(a) If E0 (Ag+/Ag) = 0.8 V and E0 (H+/H2) = 0 V, in a cell arrangement using these two
electrodes, which will act as anode and cathode ? Also find the E0cell.
(b) Construct a cell using given electrodes at 25C. Find its standard EMF.
E0 (Zn2+/Zn) = –0.76 V and E0 (Cu2+/Cu) = 0.34 V
SOLUTION :
(a) Note that reduction potentials are given. Com-  
E0cell  E0reduction
cathode

 E0reduction 
anode
paring the two values, clearly
E0(H+/H2) < E0(Ag+ / Ag)
E0cell = 0.8  0 = 0.8 V
 Hydrogen electrode will acts as anode and
silver electrode will act as cathode. The cell (b) Note that E0(Zn2+/Zn) < E0(Cu2+ / Cu)
representation of the cell will be :
 Zinc electrode will act as anode and Cop-
Pt, H2 (1 atm.) / H+ (1.0M) || Ag+ (1.0 M)/Ag(s) per electrode will act as cathode.

The cell representation of the cell is :

Zn(s)/Zn2+ (1.0M) || Cu2+ (1.0M) / Cu(s) E0cell = 0.34  (0.76) = 1.1 V

E 0cell  E 0reduction 
cathode

 E 0reduction 
anode
Illustration - 2 The dry cell (flash light battery) used to power flashlights, clocks, radios etc . follows
following reaction : Zn(s) + 2 MnO2(s) + 8 NH4+ 

 Zn2+ + 2 Mn3+ + 8 NH + 4 H O
3 2
(a) Write anode and cathode reactions.
(b) 0 of the dry cell if the electrode potential of cathode ( 0

Calculate the Ecell Ereduction ) varies between
0
+ 0.49 V and + 0.74 V and of anode ( Ereduction ) is –0.76 V..
SOLUTION :
Anode :  Zn2+(1.0 M) + 2e– ; E 0reduction = – 0.76 V

Zn(s) 
Cathode : 2MnO2(s) + 8NH4+ (aq.) + 2e– 

 2Mn3+ (aq.) + 8 NH3 (g) + 4 H2O()
E 0reduction of cathode varies between + 0.49 to +0.74 V
For E0cathode = 0.49 V
 
E 0cell  E 0reduction
cathode
 
 E 0reduction
anode = 0.49  (0.76) = 1.25 V
For E0cathode = 0.74 V
0
Ecell = 0.74  (–0.76) = 1.50 V
0
 Ecell cell varies between 1.25 V to 1.50 V..
Note : A given electrode potential is to be taken as Reduction Potential. [as reduction potential is to be consid-
ered, “by default”.]

Illustration - 3 For each of the following cells :

(a) Write the equation for cell process. (b) Find E0 for each cell.
(c) Explain the significance of any negative answers in part (b).
1. Fe/Fe(NO3)2 (1.0M) || Zn2+(1.0 M)/Zn(s)
2. Pt,Cl2(g) / KCl(1.0M) || KCl(1.0M)/Hg2Cl2(s)/ Hg ( )

3. Cd/Cd2+(1.0M) || AgNO3(1.0M/Ag(s)
E0(Fe) = –0.41 V ; E0(Cd) = –0.40 V ; E0(Zn) = –0.76 V
E0(Cl– / Cl2) = – 1.36V ; E0(Ag) = + 0.80V ; E0 (Hg / Hg2 Cl2) = +0.27V
SOLUTION :
Cell Reaction : Hg2Cl2(s) 
 Cl2(1.0 atm)
Use:  
E0cell  E 0reduction
cathode + 2Hg(s)
E0cell = 0.27  (1.36) = 1.36 V

 E0reduction 
anode
Negative EMF value means that the cell will not
1. Anode :  Fe2+(1.0M) + 2e–
Fe(s)  work in the manner shown i.e., Cl/Cl2 as an-
ode and Hg2Cl2 as cathode. So reversing (in-
Cathode : Zn2+(1.0M) + 2e– 
 Zn(s) terchanging) the anode and cathode i.e., mak-
ing Hg2Cl2 (i.e., Hg/Hg2Cl2) as anode and Cl2/
Cell Reaction : Fe(s) + Zn2+ (1.0M) 
 Cl as cathode can make the cell work.
Fe2+(1.0M) + Zn(s) 3. Anode :  Cd2+ (1.0 M) + 2e–

Cd(s) 
E0cell = 0.76  (0.41) =  0.35 V
Cathode : Ag + (1.0M) + e– 
 Ag (s)
Negative EMF value means that the cell will not
work in the manner shown i.e., Fe as anode and Cell Reaction : Cd(s) + 2Ag+(1.0M) 

Zn as cathode. So reversing (interchanging) the
anode and cathode i.e., making Zn as anode and Cd2+(1.0M) + 2Ag(s)
Fe as cathode, can make the cell work.
E0cell = 0.8  (0.4) = 1.20 V
2. Anode :
EMF value is positive, hence cell will function
2 Cl (1.0M) 
 Cl2 (1.0 atm) + 2e– with Cd as anode and Ag as Cathode.
Cathode :
Hg2Cl2(s) + 2e 

2 Hg () + 2Cl(1.0 M)

Illustration - 4 For the reduction of NO3 ion in an aqueous solution, E° is +0.96 V. Values of E° for
some metal ions are given below :
V2+ (aq) + 2e– 

 V(s) E° = – 1.19 V . . .(i) Fe3+(aq) + 3e– 
 Fe(s) E° = –0.04 V . . .(ii)
Au3+(aq) + 3e– 
 Au(s) E° = 1.40 V  Hg ()
. . .(iii) Hg2+(aq) + 2e–  E° = + 0.86 V . . .(iv)
The pair(s) of metals that is oxidized by NO3 in aqueous solution is (aree) :
(A) V and Hg (B) Hg and Fe (C) Fe and Au (D) Fe and V
SOLUTION : (ABD)
E 0Re duction of (i), (ii) and (iv) is lesser than
NO3  e  
? E 0Reduction  0.96 V E 0Re duction for NO .
3
Check the reduction potential of the given metals So, NO3 will be able to oxidise V, Fe and Hg.
and compare it with that of NO3 reduction. So, pairs are V and Fe, V and Hg, Fe and Hg.
Illustration - 5 The following electrochemical cell has been set up :

Pt (1) | Fe3+ , Fe2+ (a = 1) || Ce4+, Ce3+ (a = 1) | Pt (2)
If an ammeter is connected between the two platinum electrodes, predict the direction of flow of current. Will
0
the current increase or decrease with time ? ( E  1.61V ; E 0  0.77 V )
Ce 4 / Ce3 Fe3 / Fe 2
SOLUTION :
For the electrochemical cell :
The net cell potential is :
Pt (1)  Fe3+, Fe2+ (a = 1) | | Ce4+, Ce3+
(a = 1) | Pt (2) E 0cell  (E 0reduction ) cathode  (E 0reduction )anode
The electrode reactions are as follows. = 1.61 V – 0.77 V = 0.84 V
Right half cell : Ce4+ + e– 

 Ce3+ Since E0cell is positive, the cell reaction will be
(Reduction) spontaneous.
Left half cell :  Fe3+ + e

Fe 2+  The current in the circuit will flow from Pt (2)
(which serves as cathode) to Pt (1), which serves
(Oxidation) as anode. With the passage of time, EMF of the
cell will decrease and so is the current in the
Cell reaction : Ce4+ + Fe2+ 
circuit.
Ce3+ + Fe3+

Note : Current in an electrochemical cell flows from cathode to anode where as the electron flow from anode to
cathode.
NERNST EQUATION Section - 2
Effect of concentration on EMF of half-cells and on EMF of a cell

(a) For an electrode M(s)/Mn+ (c M) c : concentration of electrolyte
(i)  Mn+ (c M) + ne–, then its oxidation

If it acts as oxidation electrode (i.e., as anode) : M(s) 
potential E(M/Mn+) at 25C is given as :
2.303 RT
E (M / M n  )  E(M / M n  )  l og10 Qoxidation
nF
0.059
E (M / M n  )  E(M / Mn  )  l og10 Qoxidation at 25C . . . . (i)
n
(n : number of e(s) transferred & F = charge on 1 mole electrons = 96500 C)
where Qoxidation : reaction coefficient of oxidation half reaction and is given as :
aM n  
 M n
Qoxidation   where [ ] denotes concentration ; ‘a’ denotes activity
aM M 
(ii) If it acts as reduction electrode (i.e., as cathode) : Mn+ (c M)+ ne– 

 M(s), then its reduction
n+
potential E(M /M) at 25C is given as :
2.303 RT
E (M n  / M)  E(M n  / M)  l og10 Qoxidation
nF
0.059
E (M n  / M)  E (Mn  / M)  l og10 Q reduction  at 25C  . . . . (ii)
n
where Qreduction. : reaction coefficient of reduction half reaction and is given as :
aM M
Qreduction  
a M n  
M n  
We can see that E(Mn+/M) =E(M/Mn+)

(b) For EMF of the cell : M(s)/Mx+ (c1 M) | | Ny+ (c2 M) / N(s)
(i) Anode :  Mx+(c1 M) + xe–

M(s)  [oxidation]
(ii) Cathode : Ny+(c2 M) + ye– 

 N(s) [reduction]
Overall reaction : yM(s) + xNy+ (c2 M) 

 yMx+ (c1 M) + xN(s)
EMF (Ecell) of such a cell at 25C is given is :
0.059
Ecell  E0cell  log10 Qcell . . . . (iii)
n cell
where Qcell : reaction coefficient of overall reaction ; E0cell : standard E.M.F. of the cell ;
ncell : Number of e– transfer in the cell reaction.
y y
Qcell 
 a M x   a N 
x M x 
 
(aN = aM = 1 for solids)
x x
 a M   a N y 
y N y 
 
y
M x  
0.059  
E cell  E 0cell  log10
n cell x
N y 
 
Illustration - 6 Find the reduction potentials of the following electrodes :

(a) Pt, H2 (1 atm) / HCl (0.1 M), (b) Pt, H2 (2 atm) / H2SO4 (0.01 M)
SOLUTION :
1
(a) Writing half-cell reaction :
H 2 (1atm)   H  (0.1M)  e
2
 H 
0.059
 + 0 +
E (H2/H ) =E (H2 / H ) – log10  
1 1/ 2
p  H2 
0.059  0.1
 E(H2/H+) = E0(H2/H+) – log10
1 (1)1/ 2
 E (H2/H+) = 0.059 V [ E 0(H2 / H+ ) = 0 V]  E(H+/ H2) = – 0.059 V
Note : In the expression of Q, we put the value of partial pressure (for gases) in atmospheric units (atm.).

1
(b) Writing the half-cell reaction :  H  (0.02M)  e
H 2 (2atm) 
2
0.059 [H  ]
 E (H2/H+) = E 0(H2 / H+ )  log10
1 PH 2
0.059 0.02
 E (H2/H+) = 0  log10 [ E0(H2 / H+ ) = 0 V]
1 2
 E (H2/H+) = 0.109 Volts  E 0(H+/H2) = – 0.109 V
Illustration - 7 For the cell : Zn(s)/Zn2+(x M)  Ag+(y M)/Ag(s)

(a) Write Nernst Equation to see how Ecell vary with concentration of Zn2+ and Ag+ ions.
(b) Find Ecell for [Zn2+] = 0.01 M and [Ag+] = 0.05 M. [E0 (Zn2+/Zn) = – 0.76 V E0 (Ag+/Ag) = 0.80]
(c) For what value of Q will the cell EMF be :
(i) 0.97 V (ii) 0.0V
SOLUTION :
First writing the two half-reactions :
(a) Anode :  Zn2+(x M) + 2e–

Zn(s) 
Cathode : Ag+(y M) + e– 
 Ag (s)
The cell reaction is :
Zn(s) + 2Ag+(yM) 
 Zn2+(xM) + 2Ag(s)

E 0cell  E 0reduction 
cathode

 E 0reduction 
anode = 0.80  (0.76) = 1.56 V
Now writing Nernst Equation :
0.059 [Zn 2  ]
E cell  E 0cell  log10 (Activity of Ag(s) and Zn(s) = 1)
n cell [Ag  ]2
0.059 0.118
 E 0cell  E cell  log10 [Zn 2  ]  log10 [Ag  ]
n cell n cell
 E0cell will decrease when [Zn2+] increases and [Ag+] decreases.

(b) If [Zn2+] = 0.01 M and [Ag+] = 0.05 M
0.059 0.01
 Ecell  1.56  log = 1.54 V
2  0.052
(c) (i) Ecell = 0.97 V ; E 0cell = 1.56 V
0 0.059 0.059
 Ecell  E cell  n log10 Qcell  0.97  1.56  log10 Qcell
cell 2
2  0.59
 log10 Q cell   20  Qcell = 1020
0.059
(ii) Ecell = 0.0 V ; E0cell = 1.56 V
0.059 0.059
0
 E cell  E cell  log10 Qcell  0.0  E 0cell  log10 Qcell
n cell 2
2  1.56 1  1 
 log10 Qcell =  52.88  53  0.15  log 10 10 53  log  log 10   10 53 
0.059 2  2 
 Qcell = 7.07  1052 [approximately]
Illustration - 8 The solution of CuSO4 in which copper rod is immersed is diluted to 10 times, the reduction
electrode potential will :
(A) Increase by 0.030 V (B) Decrease by 0.030 V
(C) Increase by 0.059 V (D) Decrease by 0.059 V
SOLUTION : (B)
Cu2+(aq.) + 2e 
 Cu(s)
0 0.059  1 
Initially : E  E
Cu 2  /Cu 1 Cu 2  /Cu

2
log10 
 [Cu 2  ] 
 1
(Using Nernst equation.)
0 0.059  1 
After Dilution : E 
Cu 2 / Cu 2
E
Cu 2  /Cu

2
log10 
 [Cu 2  ]
 2


(Using Nernst equation.)

0.059  [Cu 2 ] 
 E  
Cu 2 /Cu 2
 E 
Cu 2 /Cu 1

2
log10 
 [Cu 2  ]
2  = 0.059 log  1  = – 0.03 V
 2
10  
 10 
 1 
 Reduction potential of the electrode decreases by 0.03 V
Illustration - 9 For the cell : T | T + (0.001M) || Cu2+ (0.1M) | Cu, Ecell can be increased by :
(A) increasing [Cu2+] (B) increasing [T +] (C) decreasing [Cu2+] (D) decreasing [T+]
SOLUTION : (AD)
First write the cell reaction :
2T(s) + Cu2+(0.1 M) 
 2T+ (0.001 M) + Cu(s)
0.059
Using : E cell  E 0cell  log10 Qcell
n cell
0.059  [T ]2 
E cell  E 0cell  log10  
2  [Cu 2  ] 
 
 0.059
0
= E cell  0.059 log10[T ]  log10[Cu 2  ]
2
 Ecell can be increased by decreasing [T+] or increasing [Cu2+]
Condition of equilibrium (Ecell = 0.0 V)

When Ecell = 0.0 V, i.e., no potential difference is obtained between the terminals of cell (battery), the cell
reaction in such a state is said to be in equilibrium. So in such cases, when Ecell = 0, Q = Keq. = equilibrium
constant.
0.059
Ecell  E 0cell  log10 Qcell
n cell
0.059
 0.0  E 0cell  log10 K eq
n cell
0.059 2.303RT RT
 E0cell  log10 K eq  log10 K eq  nK eq
n cell n cell F n cell F
Note : Refer to the illustration-7, part (c), when Ecell = 0 volts.

 Qcell = Keq = 7.07 × 1052

Illustration - 10 If excess of Zn is added to 1.0 M solution of CuSO , find the concentration of Cu2+ ions at
4
equilibrium. The standard reduction potentials of Zn and Cu at 25C are –0.76 V and +0.34 V.
SOLUTION :
We know that at equilibrium, Ecell = 0.0 V and Let x be the concentration of Cu2+ at equilibrium.
the reaction coefficient Q = Keq. So first let us
Zn Cu2+ Zn2+ Cu
calculate the value of Keq. as follows :
Initial conc.  1.0 0 0

E = E 0reduction
0

Cathode
0

– E reduction
Anode
 Final conc.  1x x x
(Zn is in excess, so [Zn]= )
E0 = 0.34  ( 0.76) = 1.10 V
0.059 [Zn 2  ] x 1
Now using E0cell  log10 K eq K eq.    [ x  1]
n cell [Cu 2  ] 1 x 1  x
[At equilibrium] (Look at the value of equilibrium constant. Too high)
E 0cell  n cell 1 1

1.10  2  1 x    5 1038 M
log10 K eq   K eq 2.0 1037
0.059 0.059
= 37.288  37.30 = log10 1037 + log102  [Cu2+]eq = 1–x = 5 × 10–38 M
 Keq  2.0  1037
Note that aZn(s) = aCu(s) = 1
Now writing the reaction at equilibrium :
Zn(s) + Cu2+ (aq.) 


Zn2+ (aq.) + Cu(s)
Illustration - 11  2Fe2+ + I3–. The

Calculate the equilibrium constant for the reaction: 2Fe3+ + 3I 
standard reduction potentials in acidic conditions are 0.78 V and 0.54 V respectively for Fe3+/ Fe2+ and I3– /
I couples.
RT
[Use : 2.303 = 0.06 at 298 K ]
F
SOLUTION :

The given reaction is : 2Fe3+ + 3I–  The electrodes reactions are :

2Fe2+ + I3 Anode : 3I 
 I3 + 2e–
Cathode : Fe3+ + e–  Fe2+



 E 0cell  E 0 3 2  E 0 (2) (0.24 V)

Fe / Fe I / I3  log10 Keq. = (0.06 V) = 8.0
= 0.78 V – 0.54 V = 0.24 V
 Keq. = 108
Using the expression :
0
n E
log10 Keq. = cell cell (at 298 K) [ncell = 2]
0.06
CONCENTRATION CELLS Section - 3
By difference in concentration of a given electrode, we can construct a cell from only one type of electrode
as follows :
Let us take an electrode M/Mn+ and take two different concentrations of it.
M(s) / M n  (c1 ) and M(s) / M n  (c 2 )
A cell made by using these two electrodes is called as concentration cell. Its cell representation is given as :
M(s) / M n  (c1 ) || M n  (c 2 ) / M(s)
The two half-cell reactions are written as :
Anode :  M n  (c1 )  ne 
M(s) 
Cathode : M n+ ( c2 )  ne 
 M(s)
Overall reaction : Mn  (c 2 ) 
 M n  (c1 )
0.059
Using : Ecell  E 0cell  log10 Qcell
n cell
[M n  (c1 )]
Now, clearly E0cell = 0 volts and Qcell  [For a concentration cell : E0cell = 0 (always )]
[M n  (c 2 )]
0.059 [M n  (c1 )]
E cell   log10
n cell [M n  (c 2 )]
Note : For a concentration cell made by using hydrogen electrodes, derive the EMF of cell in terms of pH of two
electrodes. (Try yourself)
 1 (p H 2 )anode 
Ecell = 0.059  pH anode  pH cathode  log10 
 2 (p H 2 )cathode 


Illustration - 12 Find the EMF of the concentration cell formed by coupling the following electrodes :
(a) Pt, H2(1 atm) / HCl(0.1 M) (b) Pt, H2 (2 atm)/H2SO4 (0.01 M)
SOLUTION :
 1 (pH 2 )anode 
Using Ecell  0.059  pH anode  pH cathode  log10 
 2 (p H ) cathode

 2 
Assume electrode (a) to be anode :
 1 1
E cell  0.059 1  log10 0.02  log10  Volts = – 0.05 Volts
 2 2
Note : Ecell is negative which means that electrode (a) is cathode and electrode (b) is anode.
Illustration - 13 A cell contains two hydrogen electrodes. The negative electrode is in contact with a solu-
tion of 10–6 M H+ ions. The EMF of the cell is 0.118 V at 25C. Calculate the concentration of hydrogen ions
at the positive electrode.
SOLUTION :
The negative eletrode is taken as anode and the positive electrode is as taken as cathode. Let the concen-
tration of H+ ions at positive electrode (i.e., at cathode) is x M. Also, assume pH2  1atm at anode and
cathode.
1
Anode :  H+ (1 × 106 M) + 1e
H 2 (1atm) 
2
1
Cathode : H+ (x M) + 1e 
 H 2 (1atm)
2
 H+ (1 × 106 M)
Overall reaction : H+ (x M) 
 1 (pH 2 )anode 
Using : Ecell  0.059  pH anode  pH cathode  log10 
 2 (pH 2 )cathode 

 0.118 = 0.059 (6 – pHcathode + 0)
 pHcathode = 4  [H+]cathode = 10–4 M

E.M.F. vs WITH TEMPERATURE Section - 4
Free Energy
Let n faraday charge be taken out of a cell of emf E, then work done by the cell will be calculated as :
Work = Charge × Potential
Work done by the cell is equal to the decrease in the free energy.
G = nFE
Similarly, maximum obtainable work from the cell at standard condition will be :
Wmax = nF E0cell where E0cell = standard emf of standard cell potential
G = nF E0cell
Variation of E.M.F. (Ecell) with Temperature

The temperature coefficient of e.m.f. of the cell is written as :
 d ( G) 
 G   H+ T   . . . .(i)
 dT Const. Pressure
[This equation is known as Gibbs - Helmholtz equation. Learn this as a result]
 d( nFE cell ) 

  nFE cell   H  T 
dT    G   nFE cell 
 P
 dE cell   H E cell
  dT   nFT  T . . . .(ii)
 P
 d 
Enthalpy change : From eq. (i) : H  G  T   G  
 dT P
  dE  
  H   nF  E cell  T  cell   . . . .(iii)
  dT P 
Entropy change : Compare with equation : G = H – TS with (i)
 d   dE 
 S   ( G)   nF  cell 
 dT P  dT P

Illustration - 14 For the standard electromotive force of the cell : Fe | Fe2+(aq) || Cd2+ (aq) | Cd
If the temperature co-efficient of emf is –0.125 VK–1, the value of S at 25°C would be :
(A) –20.125 kJ K–1 (B) –24.125 kJ K–1 (C) –26.125 kJ K–1 (D) –22.125 kJ K–1
SOLUTION : (B)
dEcell S
Using : 
dT nF
 dE 
 S   cell   nF = – 0.125 × 2 × 96500 = – 24.125 KJ K
–1
 dT 
Illustration - 15 The Edison storage cell is represented as : Fe (s) / FeO (s) || KOH (aq) || Ni O (s) / NiO(s)
2 3
The half cell reactions are :

Ni2O3 (s) + H2O (l) + 2e 
 2NiO (s) + 2OH (aq.) ; E = + 0.40 V
 Fe (s) + 2OH (aq.)

FeO (s) + H2O (l) + 2e  ; E = – 0.87 V
(a) What is cell reaction ?
(b) What is the cell EMF ? How does it depend on the concentration of KOH ?
(c) What is the maximum amount of energy that can be obtained from one mole of Ni 2O3 ?
SOLUTION :
   
FeO(s) / Fe(s) will be anode
E 0cell  E 0reduction  E 0reduction
and Ni2O3(s)/NiO(s) will be cathode. cathode anode
= 0.4 – (–0.87) = 1.27 volts

(a) C : Ni2O3 (s) + H2O (l) + 2e 
 2NiO (s)
As KOH does not effect cell reaction, so EMF
+ 2OH
does not depend on concentration of KOH
A : Fe (s) + 2OH   FeO (s) + H2O (l) (c) Energy obtained from the cell = magnitude of
+ 2e free energy (G)
So cell reaction will be :
G = nF E0cell
Fe (s) + Ni2O3 (s) 
 FeO(s) + 2NiO (s)
 amount of energy = 2  96500  1.27
(b) In the cell reaction, all the species are solid, so
= 245.11 kJ.
their activities will be equal to unity.
Hence Ecell = E0cell

Illustration - 16 Find the standard electrode potential of MnO /MnO . The standard electrode potentials
4 2
of MnO4/ Mn2+ = 1.51 V and MnO2/Mn2+ = 1.23 V
SOLUTION :
Use : –G = nFE0
 MnO2 + 2 H2O , E0req. = ?

MnO4 + 4H+ + 3e– 
 G 0req.   3FE0req.
Given :
(i) MnO4 + 8H+ + 5e 

 Mn2+ + 4 H2O G1 = 5(F) (1.51)
(ii) MnO2 + 4H+ + 2e 

 Mn2+ + 2 H2O –G2= 2(F) (1.23)
(i) – (ii) gives the required equation
 G 0req.  G10  G 02 (G is a state function)
 3FE0req. =  5F (1.51)  [2F (1.23)]
 E0req.  1.7 V
Illustration - 17 E.M.F. of following cell is 0.265 V at 25C and 0.26 V at 35C. Calculate heat of the
reaction taking place at 25°C. Pt , H 2 ( g ) / HCl ( aq.)|| Cl  ( aq.) / AgCl ( s ) / Ag ( s )
SOLUTION :
L.H.S.  2H   aq.  2e

H 2  g  
R.H.S. 2AgCl  s   2e 

 2Ag  s   2Cl  aq.
H2  g   2AgCl  s   
 2H(aq.) 
 2Ag  s   2Cl(aq.)
  dE  
Use :  H   nF  E cell  T  cell  
  dT P 
Put n = 2, F = 96500 C
d E cell 0.260  0.265
  5.0  104 , E cell = 0.265 V (at 298 K)
dT 308  298
to get : H = –79.9 kJ.

BATTERIES Section - 5
There are two types of batteries.

1. Primary Batteries 2. Secondary Batteries
Primary Battery (Dry Cell) :

In this type of battery, the reaction occurs only once and battery then becomes dead after use over a period
of time and cannot be then re-used. It is also called as a primary voltaic cell. It has a cathode consisting of
carbon (graphite) rod surrounded by a paste consisting of MnO2 and powdered graphite and an anode of
zinc. The electrolyte is a moist paste of NH4Cl. The electrode reactions are :
Anode :  Zn2+ + 2e
Zn 
Cathode : 2 MnO2 + 2NH4+ + 4H2O + 2e– 

 2 Mn(OH)3 + 2 NH4OH
The cell potential is 1.6 V.
Another type of dry cell is Mercury cell which is suitable for the low current devices like hearing aids and
watches, etc., consists of Zn  Hg amalgam as anode and a paste of HgO and carbon as the cathode. The
electrolyte is a paste of KOH and ZnO. The electrode reactions for the cell are :
Anode : Zn (Hg) + 2OH 

 ZnO (s) + H2O + 2e
Cathode : HgO + H2O + 2e 
 Hg (l) + 2OH
The overall cell reaction is: Zn (Hg) + HgO (s) 

 ZnO (s) + Hg ()
The cell potential is approximately 1.35 V and remains constant during its life as the overall reaction does
not involve any ion in solution whose concentration can change during its life time.
Alkaline dry cell is also similar to ordinary dry cell. It contains potassium hydroxide. The reactions in alkaline
dry cell are:
Anode : Zn + 2OH  
 Zn(OH)2 + 2e
Cathode : 2MnO2 + 2H2O + 2e 
 2MnO(OH) + 2OH

The overall cell reaction is: Zn + 2MnO2 + 2H2O 

 Zn(OH)2 + 2MnO(OH).
The cell potential is 1.5 volts.
Secondary Battery or Reversible Galvanic or Voltaic Cell :

(Lead Storage Battery) :
A galvanic cell (or Voltaic cell) supplies a certain voltage. By imposing a higher voltage than the E.M.F. of
cell (external voltage), one can reverse the cell reactions i.e. anode becomes cathode and the cathode
becomes anode. The reversible lead storage battery is a typical example of it.

In a typical lead storage battery, the anode plates are made of lead, while the cathode plates are grids of
lead packed with lead dioxide. A solution of sulphuric acid (H2SO4) surrounds the plates and acts as
electrolyte. The half-cell reactions when the battery is being used up are :
Anode : Pb(s) + SO42   PbSO4(s) + 2e


Cathode : PbO2 + SO42 + 4H+ + 2e 

 PbSO4 + 2H2O
Overall cell reaction is : Pb  PbO2  4H   2SO42  

 2PbSO 4  2H 2 O ECell = 2.041 V
The battery is chargeable (reversible) since lead sulphate (product of both anode and cathode reactions)
sticks to the plates. From cathode reaction, we see that as the battery is used up, the sulphuric acid is used
up. Now we can determine the charge on the battery by measuring the concentration of H2SO4 in the cell.
When the density of solution is between 1.25 g/m and 1.30 g/m, the cell is considered as fully charged.
When its value goes down below 1.20 g/m, the battery is in need of charge. By applying external current we
can charge the battery again. The charging follows following reactions :
Anode :  PbO2 + SO42 + 4H+ + 2e

PbSO4 + 2H2O 
Cathode : PbSO4(s) + 2e 

 Pb(s) + SO42
Overall cell reaction is : 2PbSO4  2H 2O 

 Pb  PbO2  2H 2SO4
After many repeated charging and discharging cycles, some of the Lead sulphate falls to the bottom of the
container, the sulphuric acid concentration remains low and the battery cannot be recharged fully.
Another important secondary cell is the nickel-cadmimum cell which has longer life than the lead storage cell
but more expensive to manufacture. The discharging follows following reactions :
At Cd electrode : Cd + 2OH– 
 Cd(OH)2 + 2e–
–
At Ni electrode : Ni(OH)3 + e– 
 Ni(OH)2 + OH
The overall reaction during discharge is:
Cd (s) + 2Ni(OH)3 (s) 

 CdO (s) + 2Ni(OH)2 (s) + H2O (l)
Note :  Ni – cd cell has a cell potential of 1.2 V which changes a little as it discharges.
 Specific gravity of alkaline electrolyte remain same. So, it is not a guide to its change of state.

Otehr examples of rechargeable (secondary) cell are :

(i) Nickel - Metal hydride (NiMH) (ii) Lithium ion (Li - ion)
(iii) Lithium ion polymer (Li - ion polymer) (iv) Iron - nickel
Fuel Cell :
Fuel cells are another means by which chemical energy may be converted into electrical energy. The main
disadvantage of a primary cell is that it can deliver current for a short period only. This is due to the fact that
the quantity of oxidising agent and reducing agent is limited. But the energy can be obtained indefinitely from
a fuel cell as long as the outside supply of fuel is maintained. One of the examples is the hydrogen-oxygen
fuel cell. The cell consists of three compartments separated by a porous electrode. Hydrogen gas is intro-
duced into one compartment and oxygen gas is fed into another compartment. These gases then diffuse
slowly through the electrodes and react with an electrolyte that is in the central compartment. The electrodes
are made of porous carbon and the electrolyte is a resin containing concentrated aqueous sodium hydroxide
solution. Hydrogen is oxidized at anode and oxygen is reduced at cathode. The overall cell reaction pro-
duces water. The reactions which occur are :
Anode : 2H2 (g) + 4OH (aq) 

 4H2O () + 4e
Cathode : O2 (g) + 2H2O () + 4e 

 4OH (aq)
The overall cell reaction is: 2H2 (g) + O2 (g) 

 2H2O ()
The cell runs continuously as long as the reactants are supplied. Fuel cells produce electricity with an
efficiency of about 70% compared to thermal plants whose efficiency is about 40%. There has been tre-
mendous progress in the development of new electrode materials, better catalysts and electrolytes for
increasing the efficiency of fuel cell. These have been used in automobiles and space crafts. Fuel cells are
pollutions free and in view of their importance in future a variety of fuel cells have been fabricated and tried.
NOW ATTEMPT IN-CHAPTER EXERCISE-A BEFORE PROCEEDING AHEAD IN THIS EBOOK

SUBJECTIVE SOLVED EXAMPLES
Example - 1 Calculate the reduction potential of an electrode which was originally 0.1 M MnO4 and
0.5 M H+ and has been treated with 50% of the Fe2+ required to reduce all the MnO4 to Mn2+.
(E  2  1.51V )
MnO4 / Mn
SOLUTION :
MnO 4 + 8H+ + 5e– 
 Mn2+ + 4H2O
t0 0.1 M 0.5 M

(Concentration)
t  t final
 After 50% Fe2   0.1  0.5 × 0.1 0.5  0.05 × 8 0.05 M
  = 0.05 M = 0.1M
 treatment 
 E
0.059
Using : E  log10 QRe duction
MnO 4 / Mn 2 MnO 4 / Mn 2 n
[Mn 2  ]
 E
0.059
E  log10
MnO 4 /Mn 2  MnO 4 / Mn 2 5 [MnO 4 ][H  ]8
.059 0.05
 1.51  log10 = 1.42 volts
5 0.05  (0.1)8
Example - 2 Calculate the EMF of the following cell at 25C.
Pt, H2 (1 atm) / H+ (0.09 M) | | OH  (0.075 M) / H2 (1 atm), Pt (Kw of H2O = 1 × 1014)

SOLUTION :
Note that in this question, instead of H+ ions in pHAnode = – log10 0.09 = 1.05
RHE, OH– are given. Now, calculate [H+] from
concentration of OH in the solution. Use : Ecell = 0.059 (pHAnode – pHCathode)
pHcathode = 14 – pOHcathode = 0.059(1.05 – 12.87) = – 0.70 V
= 14 + log10(0.075) = 12.87
Note : The given cell is a Hydrogen concentration cell.
Self Study Course for IITJEE with Online Support Subjective Solved Examples 29
Example - 3 Calculate the reduction electrode potential at 25C of Cr2O72–/Cr3+ electrode at pOH =
11 in a solution of 0.01 M both in Cr3+ and Cr2O72 . E 0 1.33V . If this electrode is coupled with
Cr2O72 / Cr 3
a hydrogen gaseous electrode at pH = 3, find the emf of the spontaneous cell.
SOLUTION :
Writing balanced equation for Cr2O72  / Cr 3 electrode :
Cr2O72 + 14H+ + 6e– 

 2Cr3+ + 7H2O
pOH = 11  [H+] = 10–3 M
Using Nernst Equation :
0.059
ECr O 2 /Cr3  ECr O2 /Cr 3  log10 Q reduction
2 7 2 7 n
0.059 [Cr 3 ]2
 E  E  log10
Cr2 O72 /Cr 3 Cr2 O 27  / Cr 3 n [Cr2 O7 2  ] [H  ]14
0.059 [0.01]2
 E Cr O 2 /Cr3  1.33  log10  0.94V
2 7 6 [0.01] [103 ]14
Also, find the electrode potential of hydrogen electrode using Nernst Equation :
2H+(10–3M) + 2e– 
 H2 (1 atm)
0.059 1
E H / H  E 0   log10
2 H / H2 2 [H  ]2
0.059 1
E H / H  0  log10  0.177V
2 2 
[10 3 ]2
 The hydrogen electrode will serve as anode and Cr2O72/Cr3+ will serve as cathode
So, Ecell = (E reduction )Cathode  (E reduction )Anode = 0.94 – (–0.177) = 1.06 V
30 Subjective Solved Examples Self Study Course for IITJEE with Online Support
Example - 4 Find the Ksp of AgCl The standard electrode potential of Ag/AgCl/Cl is 0.22 V and Ag+/
Ag is 0.8 V.
SOLUTION :
The given electrode Ag/AgCl/Cl is visualized as : At equilibrium, Ecell = 0 V and Q = Ksp
 Ag(s) + Cl(aq.)
AgCl(s) + e–  0.059
 E0cell  log10 K sp
It is now coupled with silver electrode as anode n cell
Cathode : AgCl(s) + e–  
 Ag(s) + Cl (aq.) E 0  Ag / AgCl / Cl    E 0  Ag  / Ag 
Anode :  Ag+(aq.) + e–
Ag(s)  0.059
 log10 Ksp
 Overall cell reaction is : 1
0.22  0.8

 Ag+(aq.) + Cl (aq.)
AgCl(s)   log10 Ksp    9.85
0.059
At saturation (i. e. at equilibrium), the above reac-  Ksp = 1.4  10–10
tion gives the solubility of AgCl.
Example - 5 The standard reduction potential of Ag+/Ag electrode at 298 K is 0.80 volts. Ksp of AgI =
1.0  10–16. Find the electrode potential of Ag+/Ag in a saturated solution of AgI. Also, calculate standard
reduction potential of I –/AgI/Ag electrode.
SOLUTION :
First calculate the concentration of Ag+ in a satu- Ag+ + e 
 Ag
rated solution of AgI.
E(Ag  / Ag)  E (Ag  / Ag) 
 Ag (aq.)  I (aq.)
AgI(s)   
0.059 1
log 10
Let [Ag+] =x 1 [Ag  ]
 Ksp of AgI = [Ag+] [I] = x2
 E(Ag+/Ag) = 0.80 – 0.059 log10
 [Ag  ]  x  K sp  1.0  10 16 

1.0  10 8
–8
= 1.0  10 M
E(Ag+/Ag) = 0.33 volts
Now, calculate the reduction potential of silver
electrode at [Ag+] = 10–8 M For E of I/AgI/Ag, visualize the electrode as:

AgI + 1e 
 Ag + I
Now couple this electrode with Ag/Ag+ as an- Atequilibrium :

ode
 E0cathode  E0anode = 0.059 log10 Ksp [AgI]
+ 
Anode : Ag 
 Ag + 1e
 E0cathode  E0anode + 0.059 log10 Ksp [AgI]
  
Cathode : AgI  e 
 Ag  I
= 0.8 + 0.059 log10 10–16 = – 0.17 V
+ –
AgI 
 Ag + I
Example - 6 Find the solubility product of a saturated solution of Ag2CrO4 in water at 298 K if the emf
of the cell : Ag | Ag+ (saturated Ag2CrO4 solution) | | Ag+(0.1M) | Ag is 0.177 V at 298 K.
SOLUTION :
The given cell is :
Ag | Ag+ (sat. Ag2CrO4 solution) | | Ag+ (0.1M) | Ag If x is the solubility of Ag2CrO4 in solution, then :
[Ag+] = 2x and [CrO42–] = x
Anode : Left half-cell Ag(s)  (Ag+)
 L + e–
 Ksp = [Ag+]2[CrO42–] = (2x)2(x) = 4x3
Cathode : Right half-cell (Ag+)R +e– 
 Ag(s) or x = (Ksp/4)1/3
Cell reaction (Ag+)R  +  [Ag+]L = 2x = 2(Ksp/4)1/3 = (2Ksp)1/3

 (Ag )L
Using Nernst Equation, we get : Substituting the values in Nernst Equation, we have
:
RT [Ag  ]L 1/3
E cell  0  ln RT (2K sp )
F [Ag  ]R E cell   ln
F [Ag  ]R
( E0cell = 0 for concentration cells)
(2K sp )1/3
 0.177 V = – (0.059 V) log10
[Ag+]R = 0.1 M. Let [Ag+]L = 2x molar. (0.1)
In the left half-cell, the concentration of Ag+ will be  1/3 
related to the solubility product of Ag2CrO4 as 
log10 
2K sp     0.177   3
follows: 0.1  0.059
 
 2Ag+(aq) + CrO 2–(aq)
Ag2CrO4(s)  1/3
4

 2Ksp   103  K sp  5  1013
0.1
Example - 7 The standard potential of the following cell is 0.23 V at 15C and 0.21 V at 35C:
Pt, H2 (g) | HCl (aq) || KCl (aq) | AgCl (s) | Ag (s)
(i) Write the cell reaction.
(ii) Calculate H and S for the cell reaction by assuming that these quantities remain unchanged in the
range 15C to 35C.
(iii) Calculate the solubility of AgCl at 25C.
Given: The standard reduction potential of the Ag+(aq)|Ag(s) couple is 0.80 V at 25C ;
RT
2.303 at 25°C = 0.06 V
F
SOLUTION :
The given cell is : Pt , H2(g) | HCl(aq) || KCl(aq) | AgCl(s) | Ag(s)
(i) The cell reactions are as follows.
Right cell: 2AgCl  s  +2e 

 2Ag  s  +2Cl  aq   Reduction 
Left cell:  2H +  aq  +2e 
H 2  g    Oxidation 
Cell reaction:  2Ag(s) + 2H+(aq) + 2Cl–(aq)
2AgCl(s) + H2(g) 
0 –1
(ii) G15 º C = nF Ecell = (2) (96500 C mol ) (0.23 V)
= 44390 J mol–1
G035 º C = nF Ecell = (2) (96500 C mol–1) (0.21 V)
= 40530 J mol–1
0 –1
Now, G15 º C = H – (288 K) S = –44390 J mol
and G035 º C = H – (308 K) S = – 40530 J mol–1
[Using G = H– TS and assuming H and S at 298 K and temperature inde-
pendent i.e. H15°C = H° and H35°C = H°]
Solving for H and S, we get,
H = –99974 J mol1 and S = – 193 J K–1 mol1

(iii) The value of G at 25C is calculated as follows :
G = H  (298 K) S = – 99974 J mol–1 – (298 K) (293 J K–1 mol–1)
= – 42460 J mol–1
The value of E 0 
at 25C will be :
Cl | AgCl | Ag
0
Ecell 
G 0cell


 42460 Jmol1  = 0.22 V
nF  2   96500Cmol
1

 E0   E0   0.22 V
Cl / AgCl/ Ag H /H 2
 
 E0   0.22 V  E 0  0V
Cl / AgCl/ Ag  H / H2 
For determination of Ksp, constructing the cell :
Ag/Ag+ || Cl– /AgCl/ Ag
Anode : Ag  Ag+ + 1e–
Cathode : AgCl + le  
 Ag  Cl
 Ag+ + Cl

Cell Reaction : AgCl 
RT
Now using the expression : E 0cell  E    E   ln K sp (at equlibrium)
Cl / AgCl/ Ag Ag / Ag F
 0.22 V  0.80 V = (0.06 V) log10 Ksp
 0.22  0.80  V
 log10 Ksp =  10.0
 0.06 V 
 Ksp = 1.0  10–10
Example - 8 Two Daniel cells contain the same solution of ZnSO4 but differ in the CuSO4 solution. The
emf of the cell containing 0.5 M CuSO4 is higher than the other cell by 0.06 V. Calculate the concentration of
CuSO4 in the other cell.
 2.303 RT 
Use :  0.06 
 F 
SOLUTION :
The reaction occurring in a Daniell cell is : Zn(s) + Cu2(aq) 

 Zn2+(aq) + Cu(s)
RT [Zn 2  ]
The EMF of the cell is given as : Ecell  E0cell  ln
2F [Cu 2  ]
For the two cells, we have :
RT  [Zn 2  ]1  
 Ecell 1  E 0cell  ln   
2F  [Cu 2  ]1   RT  [Cu 2 ]2 
  Ecell 2   Ecell 1  ln  2  
RT  [Zn 2 ]2   2F  [Cu ]1 
0
 Ecell 2  E cell  ln  
2F  [Cu 2  ]2  
= 0.06 [Taking [Cu2+]2 = 0.5 M]
 0.5 
 log10  2  [Cu2+]1 = 0.5 × 10–2 = 5 × 10–3 M
 [Cu 2  ] 
 1
Example - 9 During the discharge of a lead storage battery, the density of sulphuric acid fell from 1.294
g/ml to 1.139 g/ml. Sulphuric acid of density 1.294 g/ml was 39% H2SO4 by wt. while acid of density 1.139 g/
ml contains 20% acid by wt. The battery holds 3.5 L of acid and the value remained practically same through
the discharging. Calculate the number of amp/hr for which the battery must have been used. The charging
and discharging reactions are :
PbO2 + SO42 + 4H+ + 2e 

 PbSO4 + 2H2O (discharging)
PbSO4 (s) + 2e– 

 Pb (s) + SO42 (charging)
SOLUTION :
Note that density of sulphuric acid has decreased, i.e discharging of battery takes place.
First write both the reaction for discharging.
Anode :  PbSO4(s) + 2e

Pb(s) + SO42 
Cathode : PbO2 + SO42 + 4H+ + 2e 

 PbSO4 + 2H2O
Overall reaction : Pb(s) + 2H2SO4 + PbO2  2 PbSO4(s) + 2H2O


 For the consumption of 2 molecules of H2SO4, 2e– are transferred
 For the consumption of 2 moles of H2SO4, 2 moles of e– s are transferred
 2 mole of H2SO4  2F of electricity
(Note : 1F  Charge on 1 mole of electrons)
Now let us calculate the decrease in moles of H2SO4 from the data given.
Volume of solution = 3.5 L = 3500 ml
Let the mass of H2SO4 before discharging = mi
And the mass of H2SO4 after discharging = mf
39
 mi =  
 3500   1.294  1766.3 gm
 100 
 20 
 mf =   3500   1.139  797.3 gm
 100 
 m (the decrease in mass) = 1766.3  797.3 = 969 gm
 m 970
 moles of H2SO4 consumed    9.89
98 98
Now 1 mole of H2SO4  1 F of charge
 9.89 moles  1  9.89 F of charge  9.89  96500 = 954385 C of charge
Q 954385
Now Q = I t  I  I  265 amp
t I  60  60
Example - 10 Determine the degree of hydrolysis and hydrolysis constant of aniline hydrochloride in M/
32 solution of salt at 298 K from the following cell data at 298 K. :
+
Pt | H2(1 atm) | H+ (1M) || C6H5 N H 3 Cl–(M/32) | H2 (1 atm), Pt. Ecell = – 0.177V
SOLUTION :
Note : Given cell is a Hydrogen Concentration cell.  h = 32 × 10–3 = 0.032
Ecell = 0.059 (pHAnode – pHCathode)
 K
= 0.059 (0 – pHCathode) = 0.059 log10 
h
C6 H5 N H3  H2O 
 C6 H5 NH2  H3O

[H+]Cathode
t=0 c
= – 0.177 t = teq c – ch ch ch
 [H+] Cathode =
10–3M
ch.ch 103.103
Kh    3.31105
 c  ch 1
Note : Aniline Hydrochloride : C6 H5 N H 3 Cl  103
32
[salt of SA – WB]
 [H+]Cathode = 10–3 = ch
1
(c = M ; h = degree of hydrolysis)
32
Example - 11 Calculate the quantity of electricity delivered by a Daniel cell initially containing 1L, 1M
Cu 2+ ion and Zn 2+ ion which is operated until its potential drops to 1.041 V.
(E 0   0.76 V ; E 0   0.34 V )
Zn 2  / Zn Cu 2  / Cu
SOLUTION :
Cell Reaction : Zn (s) + Cu2+(aq.) 

 Zn2+(aq.) + Cu(s)
t 0
1 1
(concentration )
t = teq 1 –x 1+x
0.059 [Zn 2  ]
Using Nernst equation : E cell  E
cell  log10
n cell [Cu 2  ]
 E  0.34  ( 0.70)  1.1V 

0.059 [Zn 2  ]  cell 
1.041 = 1.1  log10  n 2  write half  
2 [Cu 2  ]  cell  cell reactions  
 
0.059 [Zn 2  ]
 0.059 = log10
2 [Cu 2  ]
1x 1 x 99
 log10 2  100  x
1 x 1 x 101
Moles of Cu2+ (initially) = 1 × 1L = 1
99 2
Moles of Cu2+ (left) = 1 – x = 1  
101 101
For each ion of Cu2+ to Cu, 2e–s are transferred.
99
Thus, no. of electrons transferred = x × 96500 = × 2 × 96500 C = 189178.2 C
101
Example 12 - 14 Read the following passage :

Tollen’s test is used for detection of aldehydic group in organic compounds like glucose. The test is as follows
: An aqueous solution of AgNO3 is added to an aqueous slolution of glucose in a test tube. When concentrated
ammonia is added, silver is deposited. This is a redox reaction as Ag+ is reduced to Ag and glucose is oxidized
to gluconic acid. The following half-cell reactions and the standard half-cell potentials are given :
Ag+ + e– 
 Ag 0
Ered  0.8V
 C6H12O7 +2H+ + 2e–

C6H12O6 + H2O  0
Eox   0.05V
[Ag(NH3)2]+ + e– 
 Ag + 2NH3 0
Ered  0.37 V
Given : 2.303 RT/F = 0.0592 V, F/RT = 38.90 V–1 at 298 K
Example - 12 The logarithm of the equilibrium constant (lnK) of the reaction is :
 C H O + 2H+ + 2Ag

C6H12O6 + 2Ag+ + H2O  6 12 7
(A) 66.1 (B) 29.2 (C) 58.4 (D) 116.8

SOLUTION : (C)
Create cell as :
Cathode : Ag+ + e– 
 Ag E 0reduction  0.8V
E 0reduction  0.05V
Anode :  C6H12O7 + 2H+ + 2e–
C6H12O6 + H2O 
2Ag + + C6 H12O6 + H 2O 
 2Ag + C6 H12O7 + 2H +
When the reaction reaches equilibrium, Qcell = Keq and Ecell = 0
0 F
Using : n K eq  E cell .n cell . = 0.75 × 2 × 38.90 = 58.35 (E 0cell  0.8  0.05  0.75 V)
RT
Example - 13 On the addition of conc. NH , the pH of the solution rises to 11. Ignoring any changes in
3
the concentration of glucose and gluconic acid, identify which of the half-cell electrodes will be sensitive to
pH and the corresponding change in half-cell potential (E) relative to the standard half-cell potential (E0)
(A) 0 by an amount 0.65 V (B)

an increase of Eox over Eox 0 by an
an increase of Ered over Ered
amount 0.65 V
(C) 0 by an amount 0.65 V

decrease of Eox over Eox (D) 0 by an amount
decrease of Ered over Ered
0.65 V
SOLUTION : (AD)
0.0592
Consider : 
0
E ox  E ox  log10 [H  ]2
2
 C6H12O7 + 2H+ + 2e–
C6H12O6 + H2O  [Take other compounds activity to be unity]
E 0ox   0.05V 0
 E ox  E ox  0.0592 pH
Using Nernst Equation : 0
 E ox  E ox = 0.0592 × 11 = 0.65 V
0 2.303RT
E ox  E ox  log10 Qoxidation  There is an increase in E ox over E 0ox by
nF
0.65 V or decrease in E red over E 0red by
0.65 V
Note : Only glucose electrode will be sensitive to pH changes as other electrodes do not depend on [H+].
Example - 14 The reaction does not proceed efficiently without addition of NH . Moreover, addition of
3
any other base is not recommended. Which of the following statements about the role of NH3 must be incor-
rect ?
(A) Ag(NH3)2+ is weaker oxidizing agent than Ag+
(B) NH3 complex Ag+ efficiently
(C) In absence of NH3, silver salts of gluconic acid would precipitate.
(D) NH3 alters the standard electrode potential of the glucose / gluconic acid electrode.
SOLUTION : (D)
0
(A) E0  0.37 V and E  0.8 V

[Ag(NH3 )2 ] / Ag Ag  / Ag
 Ag+ has a stronger tendancy to get reduced than [Ag(NH3)2]+. So, Ag+ is a stronger oxidising agent
than [Ag(NH3)2]+.
(B) NH3 forms highly stable complex with Ag+.

(C) NH3 keeps most of Ag+ in solution in the form of [Ag(NH3)2]+. So, gluconate ion gets a very less chance
to form silver salt of gluconic acid.
(D) Standard electrode potential of the glucose / gluconic acid electrode is fixed and does not change with the
addition of NH3 in the solution.
Example - 15 (a) Calculate rG0of the reaction : Ag  (aq )  Cl  (aq) 

 AgCl ( s )
Given : fG0(AgCl) = –109 kJ/mol ; fG0 (Cl–) = –129 kJ/mol ; fG0(Ag+) = 77 kJ/mol
0 and find K
Represent the above reaction in the form of a cell. Also, calculate Ecell .
SP[AgCl]
(b) 6.539 × 10–2 g of metallic Zn was added to 100 mL of saturated solution AgCl. Calculate
[ Zn 2  ]
log10
[ Ag  ]2
Given that Ag   e 
 Ag E0 = 0.80 V
Zn 2   2e  
 Zn E0 = – 0.763 V
Also find how many moles of Ag will be formed. [Given : KSP[AgCl] 10–10]
SOLUTION :
(a) Ag  (aq.)  Cl  (aq.) 

 AgCl(s)
 r G 0   f G (AgCl)
0
 f G 0    f G 0  = – 109 – (–129) – 77 = – 57 kJ/mol
(Cl ) (Ag )
Cathode : Ag  (aq)  e  
 Ag(s)
Anode : Ag(s)  Cl  
 AgCl(s)  e 
Ag (aq)  Cl(aq)


 AgCl(s)
0 0 0 3
Using :  r G   n F E cell   1  96500 E cell   57  10  E 0cell = + 0.59 volts
1 E 0cell . n cell 0.59  1 1

Using : log10    10 [ Note : K eq.  ]
K sp[AgCl] 0.059 0.059 KSP[AgCl]
 Ksp [AgCl]  10–10
(b) Cathode : Ag   e  
 Ag E 0red  0.8 V
Anode :  Zn 2   2e
Zn  E0red   0.763V
2Ag   Zn 
 2Ag  Zn 2  
E 0cell  E0 
reduction cathode

 E0 
reduction anode
= 0.8 – (– 0.763) = 1.563 V

Initially 10–5M 0.01 M
  [Zn 2  ]   E 0cell . n cell 1.563  2

At equilibrium : log10  K eq      53
  [Ag  ]2   0.059 0.059
 
[Zn 2  ]
 K eq   1053 (i.e. whole of Ag+ is almost consumed.)
 2
[Ag ]
Mmoles of Ag formed = Mmole of Ag+ used = 10–5 × 100 = 10–3

 Moles of Ag formed =10–6
Electrochemistry - II Vidyamandir Classes
Electrochemistry - ll
The process in which an electric current causes a chemical change (conversion of electric energy to chemical
energy) is called as electrolysis. There are mainly two ways in which analysis is done in electrolysis :
(i) Qualitative Analysis : Study of possible products formed at cathode and anode during electrolys is.
(ii) Quantitative Analysis : Study of amount /moles /volume of the products formed at cathode and
anode during electrolysis.
QUANTITATIVE ANALYSIS Section - 6
To understand the process of electrolysis more clearly, first let us consider

electrolysis of molten salts (e.g., NaCl) and then aqueous solution of salts
in an electrolytic cell shown.
Molten NaCl (an electrolyte) means free sodium ions (Na+) and chloride
ions (Cl), so it conducts current with the help of ions. As electric current is
passed in the cell, Cl ions are attracted to anode (+ve electrode) and Na+
ions to cathode (ve electrode). Both ions are discharged at respective
electrode as follows :
Anode : 2 Cl 
 Cl2  g   2e  [Oxidation]
Cathode : Na   e  
 Na  s  [Reduction]
Overall Reaction : 2 Na   2Cl 

 2 Na  s   Cl2  g 
This type of cell is also called as electrolytic cell. The basic difference between an electrolytic cell and a
galvanic (or voltaic) cell is that a voltaic cell produces electricity; an electrolytic cell consumes electricity.
The importance of electrolytic cell is that they are widely used in isolation and purification of various elements
and gases.
Products of electrolysis depends mainly on the following factors :
(i) Electrode potential of various possible reactions (deposition or liberation) at cathode or anode.
(ii) Over potential of gases w.r.t. the electrode (material) at which they are liberating.
(iii) Concentration of the ions (to be oxidised or reduced) in the solution.
(iv) Type of electrodes [reacting or non-reacting (e.g. Pt, C (graphite))]
Now, we will discuss the products formed at cathode and anode for the most of the solutions as follows :

Vidyamandir Classes Electrochemistry - II
1. Aqueous NaCl solution :

Note : When electrode is not mentioned, assume it to be Pt.
In aqueous solution of NaCl, Na+, Cl, H+ (from water) and OH– (from water) ions are free to move for the
conduction of electric current. When electric current is passed, Na+ and H+ ions are attracted to cathode
and Cl and OH– ions to anode.
The solution now contains four ions Na+, Cl (from NaCl), H+, OH– (from water) and there is a race
amongst them for their discharge at their respective electrodes.
The following electrode reactions are possible :
Cathode : Na+ (aq.) + e– 

 Na (s) E   2.71V
Na  / Na

2H 2O()  2e 
 H 2 (g)  2OH  (aq.) E H 2O/ H 2   0.83 V
Anode : 2 Cl (aq.) 

 Cl2  g   2e E   1.36 V
Cl /Cl2
 O 2 (g)  4H  (aq.)  4e 
2H 2O()  EH 2 O/O2   1.23V
Overall Reaction : 2NaCl(aq .) + H 2O( ) 

 2 NaOH (aq .) + H 2(g) + Cl2(g)
In this electrolysis, H2 at cathode and Cl2 at anode are given off. Now, question is, why Na+ ions and
OH ions are not discharged ? The reason lies in the reduction potential values. Clearly,
E  EH 2O/ H 2
Na  / Na
 Although Cl– has a lesser tendency to discharge (oxidize) [Cl– will be at Anode where oxidation takes
place] as compared to OH– (Cl– lies below OH– in the Electrochemical series) at anode still OH– will
not be discharged (oxidize) due to the concept of Overpotential (Extra potential required to initiate
a reaction at a required rate). Formation of O2 from H2O is kinetically very slow (i.e. low rate). Thus,
OH– ions will remain in the solution.
 The aqueous solution of NaCl will become alkaline (due to the presence of OH– ions) after the
electrolysis.
 In case of electrolysis of NaX (aq.) (where X– is Br–, I–), X2 will be liberated at anode. Using NaF,
 
O2 gas will be liberated at anode instead. Also, E Br  / Br   1.09 V and E I / I   0.54 V
2 2

but E F /F   2.87 V
2

2. Aqueous CuSO4 solution :

Possible reactions at :
Cathode : Cu 2  (aq.)  2e  
 Cu  s  E   0.34 V
Cu 2 / Cu
2H 2O()  2e 
 H 2 (g)  2OH  (aq.) EH 2O/ H 2   0.83 V
Anode :  O 2 (g)  4H  (aq.)  4e 
2H 2O()  EH 2 O/O2   1.23V
2SO24  (aq.) 
 S2O82  (aq.)  2e  E   2.01V
SO24  /S2 O82 
Overall Reaction : 2H 2O()  2Cu 2  (aq.) 

 2Cu(s)  O2 (g)  4H  (aq.)
In this electrolysis, Cu at cathode and O2 at anode are produced. Also, the aqueous solution of CuSO4 will
become acidic (due to the presence of H+ ions) after the electrolysis.
3. Aqueous Na2SO4 solution :
Cathode : Na  (aq.)  e  
 Na(s) E   2.71V
Na  / Na
2H 2O()  2e 
 H 2 (g)  2OH  (aq.) EH 2O/ H 2   0.83 V
Anode : 2SO24  (aq.) 

 S2O82  (aq.)  2e  E   2.01V
SO24  /S2 O82 
 O 2 (g)  4H  (aq.)  4e 
2H 2O()  EH 2 O/O2   1.23V
Clearly, at cathode, Na+(aq.) ions will not be deposited due to their lower reduction potential than H2O.
Similarly, SO2–
4 will not be oxidised due to their lower oxidation potential than H2O.
Thus, electrolysis of Na2SO4/K2SO4/CaSO4/MgSO4/Li2SO4 etc. is actually equivalent of electrolysis of

H2O.
4. Aqueous NaCl solution(very dilute) :

 Na(s) E   2.71V
Na  / Na
2H 2O()  2e 
 H 2 (g)  2OH  (aq.) EH 2 O/ H 2   0.83 V

Anode : 2Cl (aq.) 

 Cl2 (g)  2e E   1.36 V
Cl /Cl2
 O2 (g)  4H  (aq.)  4e 
2H 2O()  EH 2 O/O2   1.23 V
When NaCl is highly dilute, there is a very less chance of Cl– (due to their less availability) getting oxidised.
So, instead H2O will get oxidised.
Note : 2Cl (aq.) 

 Cl2 (g)  2e
0.059 pCl2 0.059

E   E   log10  E   log10 pCl2  0.059 log10 [Cl  ]
Cl /Cl2 Cl /Cl2 2  2 Cl /Cl 2
[Cl ] 2
Thus, E decreases as [Cl–] decreases making the oxidation of H2O more favorable.
Cl  /Cl 2
5. Aqueous NaCl solution (using Hg electrodes) :

 Na(s) E   2.71V
Na  / Na
2H 2O()  2e 
 H 2 (g)  2OH  (aq.) EH 2O/ H 2   0.83 V
Anode : 2Cl (aq.) 

 Cl2 (g)  2e E   1.36 V
Cl  /Cl2
 O2 (g)  4H  (aq.)  4e 
2H 2O()  EH 2 O/O2   1.23V
When Hg electrodes are used instead of Pt, Na+(aq.) gets deposited which furthur reacts with Hg to form
Sodium-Amalgam.
Na(s)  Hg(s) 
 NaHg(s)
Thus, when NaCl(aq.) is electrolyzed using Hg as electrode sodium amalgam is formed at cathode and
Cl2 (g) is evolved at anode.

6. Aqueous CuSO4 solution (using Cu electrodes) :
Cathode : Cu 2  (aq.)  e 
 Cu(s) E  0.34 V
Cu 2  /cu
2H 2O()  2e 
 H 2 (g)  2OH  (aq.) EH 2 O/ H 2   0.83 V
Anode : 2SO24  (aq.) 

 S2O82  (aq.)  2e E   2.01V
SO 24 /S2O82 
 O 2 (g)  4H  (aq.)  4e 
2H 2O()  EH 2 O/O2   1.23V

 Cu 2  (aq.)  2e
Cu(s)  E  0.34 V
Cu /Cu 2 
Thus, when Cu is electrolysed using Cu electrodes, Cu is dissolved (at Cu anode) and Cu is deposited (at
Cu cathode).
Note : [Cu2+] in solution remain constant during electrolysis.

 This technique is used in refining of Cu.
7. Aqueous AgNO3 solution (using Ag electrodes) :

Cathode : Ag  (aq.)  e   E  0.8 V

 Ag(s) Ag  / Ag
2H 2O()  2e 
 H 2 (g)  2OH  (aq.) EH 2O/ H 2   0.83 V
Anode :  O 2 (g)  4H  (aq.)  4e 

2H 2O()  EH 2 O/O2   1.23V
NO3 (aq.) 
 (No reaction)
 Ag  (aq.)  e  E   0.8 V
Ag(s)  Ag  / Ag
Thus, when aq. AgNO3 is electrolysed using Ag electrodes, Ag is dissolved (at anode) and Ag is deposited
(at cathode).
 [Ag+] in the solution remains constant during electrolysis.
8. Aqueous H2SO4 solution:

1
Cathode : H   aq.  e  
 H 2 (g) E 0V
2 H / H2
Anode : 2SO24  (aq.) 

 S2O82  (aq.)  2e  E   2.01V
SO4 2 /S2O82 
 O2 (g)  4H  (aq.)  4e

2H 2O()  EH 2 O/O2   1.23V
In actual practice, SO42– ions can be oxidised to S2O82– if either of the following conditions are satisfied :
(A) High current density (B) High [SO42–] (i.e. highly conc. H2SO4 solution]

9. A q u e o u s N iSO 4 solution:
Cathode : Ni 2  (aq.)  2e  
 Ni(s) E   0.25 V
Ni 2 / Ni
2H 2O()  2e 
 H 2 (g)  2OH  (aq.) EH 2O/ H 2   0.83 V
Anode : 2SO24  (aq.) 

 S2O82  (aq.)  2e  E   2.01V
SO 24 /S2O82 
 O 2 (g)  4H  (aq.)  4e 
2H 2O()  EH 2 O/O2   1.23V
In practice, it has been observed that H2 gas also gets liberated at cathode along with Ni.
10. Aqueous RCOONa solution (Kolbe’s Electrolysis):

Cathode : Na   aq.  e  
 Na(s) E   2.71V
Na  / Na
2H 2O()  2e 
 2OH  (aq.)  H 2 (g) EH 2O/ H 2   0.83 V
Anode : 2RCOO  (aq.) 

 R  R(g or )  2CO2 (g)  2e 
 O 2 (g)  4H  (aq.)  4e 
2H 2O()  EH 2 O/O2   1.23V
QUANTITATIVE ANALYSIS Section - 7
Faraday’s Law of Electrolysis (a quantitative analysis of electrolysis)

Faraday proposed following two laws for the quantitative analysis for the product of electrolysis :
Ist Law :
It states that “the amount of any substance that is deposited or liberated at an electrode is directly proportional
to the quantity of electricity passing through the electrolytic cell”.
The amount of electricity means quantity of charge (Q) in coulombs. If I is the current in amperes (A) and t
is the time in seconds, then Q = I t.

If w is the amount of substance liberated or deposited, then

wQ
w=ZQ Z : electrochemical equivalent of a substance
 w=ZIt
IInd Law :
It states that “when a given quantity of electricity is passed through different electrolytes, the amounts of
different substances produced at the electrodes are directly proportional to the respective equivalent weights”.
For two substances A and B in two different electrolytic cells ;
w A EA

w B EB
Experimentally it is seen that 1 gm eq. of a substance is deposited by passing 1 Faradays of electricity.

Magnitude of charge carried by 1 mole of electrons is 96487 C (6 × 1023 × 1.6 × 10–19 = 96487 C). It is
also known as one faraday i.e., 1F = 96500 C. [96500 C is the widely accepted value of 1 F].
It can also be seen by combining Ist and IInd Laws as follows :
wQ (Ist Law)
wE (IInd Law)
QE 1 1  w Q
 w     
F  F 96500  E F
No. of gram equivalents = No. of Faradays of electricity
 1 gm eq = any substance = 1 F of electricity
Now there are three approaches to solve a problem.
Q It
First calculate the number of faradays of electricity by using : No. of faradays  
F 96500
(i) Now by using the definition : 1 gm. eq. of any substance  1 F of electricity passed
 g
Calculate the number of gm. eq. and by using the definition of gm.eq.  gm.eq   , determine the
 E
amount of substance deposited.
(ii) Using anodic and cathodic reactions as follows :
Let us consider a typical cathode reaction : Mn+ + ne– 

 M

 n (e–s)  1 molecule of M  1 ion of Mn+

 N0 (n e–s)  N0 molecule of M (N0 : Avogadro number)
 N0 (n e–s)  1 mole of M  1 mole of Mn+
 n F  1 mole of M  1 mole of Mn+ (charge of N0 electrons  1 F = 96500 C)
So in this approach, first write anodic and cathodic reactions and derive the mole Vs faraday relation.
For example : Al3+ + 3e 

 Al  3F  1 mole of Al  1 mole of Al3+ ions
2Cl 
 Cl2 + 2e  2F  1 mole of Cl2  2 mole of 2Cl ions
(iii) Using the combined relation obtained from Ist and IInd Laws :
w=ZIt
EIt
 w
96500
Illustration - 18 In the electrolysis of aq. CuSO , a current of 2.50 Amp is allowed to flow for exactly 3.0
4
hr. How many grams of Cu and lts of O2 are produced at 25oC and 1 atm. pressure?
SOLUTION :
In the electrolysis of aqueous solution, following  2F  1 mole of Cu
reactions will take place :
 0.28 F  1/2  0.28 moles of Cu
Cathode : Cu2+ + 2e– 
 Cu (s)  1/2  0.28  63.5 gm
 8.9 gm of Cu have been deposited
Anode :  O2 + 4H+ + 4e
2H2O 
Now from anode :
(Sulphate ions and H+ ions remain in the solution
to given an acidic solution)  O2 + 4H+ + 4e–
2H2O 
Now from cathode : Cu2+ + 2e– 
 Cu (s)  4F  1 mole of O2
 2F  1 mole of Cu  0.28 F  1/4 × 0.28 = 0.07 moles of O2
It 2.5  3  3600 Now using gas equation : PV = nRT
No. of faradays = 
96500 96500
nRT 0.07  0.0821  298
= 0.28 F V   1.71 L Of O 2
P 1

Illustration - 19 Calculate the quantity of electricity required to reduce 12.3 gm of nitrobenzene to aniline
if the current efficiency for the process is 50%. If the potential drop across the cell is 3.0 V, how much energy
is consumed ?
SOLUTION :
Writing the half cell reaction for the reduction of nitro-benzene as follows :
C6H5NO2 + 6H+ + 6e– 

 C6H5NH2 + 2H2O
 1 mole of C6H5NH2 6 F of charge
0.6  100
Now, moles of nitro-benzene = 12.3/123 No. of Faradays required =
50
= 0.1 moles
= 1.2 F = 1.2 × 96500 C
 0.1 mole  0.6 F
Now potential difference = 3V
Hence, 0.6 F of electricity are used to reduce
The energy (E) consumed is given by :
12.3 gm of nitro-benzene if the current efficiency
is 100 %. But it is given that current efficiency is E = charge × potential difference
50 %, so
 E = (1.2  96500 × 3) = 347400 J
= 347.4 kJ
Illustration - 20 A potassium salt of ternary acid of Molybdenum (at. mass = 96) has the formula K MoO .
2 n
When an acidified solution of K2MoOn is electrolysed, O2 gas is liberated corresponding to a volume of 0.112
L at STP & 0.32 gm of Mo is deposited. Find the formula of salt.
SOLUTION :
The given situation in the question is possible 0.32
 0.02   x=6
only if MoO 2n  ion gets dissociated to M 0x 96 / x
which moves towards cathode. Mox+ + 6e–   Mo0
No. of faradays passed  gmeq of O2  gmeq  oxidation state of Mo = 6
of Mo
In K2MoOn, we have 2 (+1) +6 + n (2) = 0
4F  1 mole of O2  n=4
0.112  molecular formula is K2MoO4
 gmeq of O2 = 4   0.02
22.4
 gmeq of Mo = 0.02
g
= gmeq of Mo
E

NOW ATTEMPT IN-CHAPTER EXERCISE-B BEFORE PROCEEDING AHEAD IN THIS EBOOK
SUBJECTIVE SOLVED EXAMPLES
Example - 16 During an electrolysis of conc. H2SO4, perdisulphuric acid (H2S2O8) and O2 form in
equimolar amount. The moles of H2 that will form simultaneously wil be :
(A) thrice that O2 (B) twice that O2 (C) equal to that O2 (D) half of that O2
SOLUTION : (A)
This is a special case of electrolysis where two So, if x moles of O2 are being produced,
products are being obtained at anode : electricity being passed at anode is :
At anode : 4x (For O2) + 2x (3For S2O82–) = 6x F
At cathode :
4OH– 
 O2 + 2H2O + 4e– . . . . (i)
2H+ + 2e– 
 H2 . . . . (iii)
2– 2– –
2SO4  S2O8 + 2e
 . . . . (ii)
2 F electricity  1 mole H2 is produced
1 mole O2 requires 4 F electricity and 1 mole S2O82–
 6x F electricity  3x mole H2 is produced
(  H2S2O8) requires 2 F electricity.
 Moles of H2 produced at cathode = 3
moles of O2 produced at anode.
Example - 17 Assume that impure copper contains iron, gold and silver as impurities. In the purification
of copper, after passing a current of 142 amperes for 482.5 seconds, the mass of anode decreased by 22.6 gm
and that of cathode increased by 22.0 gm. Estimate % of iron and copper originally present.
SOLUTION :
Note : Silver and gold form the anode mud. Also, Now, No. of faradays passed at cathode
Impure Cu forms anode while pure Cu is made as = Gm eq of Cu deposited
cathode in the refining of impure Cu.
22
At Impure Cu electrode ( anode in the Cu  0.69 = No. of fardays passed at anode.
63.5 / 2
purification), both iron and Cu will go into the solution.
So, mass of iron and Cu dissolved in solution is 22.6 It 142  482.5
Total faradays passed = 
gm. 96500 96500
At cathode (pure Cu electrode), mass of Cu = 0.71 (at anode and cathode )
deposited is 22.0 gm. So, amount of Cu in 22.6 gm
Thus, faradays taken upby Fe at at anode
dissolved at anode is 22.0 gm.
= 0.71 – 0.69 = 0.02
Thus, 22.6 – 22.0 = 0.6 gm contains Fe, Au and
Ag.
 Fe2+ + 2e–
Fe 
 2F electricity  1 mole Fe
0.02 22
 0.02 electricity  Mole Fe % Cu in the original sample  ×100%
2 22.6
 0.01 × 56 gm Fe = 97.3%
0.56 gm Fe 0.56
and % Fe in the original sample  × 100%
22.6
= 2.4%
Example - 18 If 6.43 × 105 Coulombs of electricity are passed through an electrolytic cell containing
NaClO3 . 245 gm of NaClO4 are produced at the anode at the end of electrolysis. Determine the anode
efficiency.
SOLUTION :
Anode efficiency
actual wt.of any substance deposited

 100 4  96500
theoretical wt.deposited  Anode efficiency =  100
6.43  105
or Anode efficiency
 Anode efficiency = 60.03 %
actual No. of faradays used up Alternative Method :
  100
total No. of faradays used
First calculate the theoretical amount of NaClO4
produced by passing 6.43 × 105 C.
Let us write anode reaction first :
 2 F  1 mole of NaClO4
 
ClO3 
 ClO4
6.43  105 1 6.43  105
Balancing by ion electron method :  F 
96500 2 96500
ClO3 + H2O 
 ClO4 + 2H+ + 2e moles of NaClO4
 2F  1 moles of NaClO4 1 6.43  105

   122.5
 1 mole of NaClO4  2 F of charge 2 96500
= 408.12 gm of NaClO4
245 245
 moles of NaClO4  2  =4F But in actual only 245 gm of NaClO4 are produced
122.5 122.5
(some of the current is lost as heat and against the
So for the production of 245 gm of NaClO4, 4F of resistance to flow of ions).
electricity i.e., 4×96500 C of charge is actually
consumed. But we are given that a total of 6.43 × 245
 Anode efficiency =  100 = 60.03 %
105 C of electricity is passed through the cell, so 408.12
some of the charge is wasted.
Note :Electro-synthesis
It is a method of producing chemical compounds through non-spontaneous reactions carried out by electrolysis.
The above example is an illustration of electro-synthesis. Similarly, by electrolysing a solution of MnSO4 in
H2SO4, MnO2 may be produced at anode.
Mn2+ + 2H2O   MnO2(s) + 4H+ + 2e–

 2F  1 mol of MnSO4  1 mol of MnO2
Example - 19 During the electrolysis of water, a total volume of 33.6 mL of hydrogen and oxygen gas
was collected at STP. Find the amount of electricity that passed during electrolysis.
SOLUTION :
From two electrode reactions, it clear that hydrogen
Cathode : 2H+ + 2e– 
 H2
and oxygen are evolved in the mole ratio of 2 : 1,
 2F  1 mole of H2  22400 mL hence their volumes will also be in the same ratio.
or 1F  0.5 mole of H2  11200 mL  volume of H2 = 2/3 (33.6) = 22.4 mL
As 2F  22400 mL H2
Anode : 4OH 
 O2 + 4e– + 2H2O
 0.002 F of charge is passed through the
 4F  1 mole of O2  22400 mL electrolytic cell.
or 1F  0.25 mole of O2  5600 mL  amount of electricity = 0.002  96500 C
= 193.0 Coulombs.
Example - 20 A current of 1.0 A is passed for 96.5 sec through a 200 mL solution of 0.05 M LiCl solution.
Find :
(a) the volume of gases produced at STP. (b) the pH of solution at the end of electrolysis :
SOLUTION :
No. of faradays passed  0.5 × 10–3 × 22400 ml H2 at STP
It 1.0  96.5  11.2 ml H2 STP
   103 F
96500 96500
Anode : 2Cl   Cl2 + 2e–
Cathode : 2H+ + 2e– 
 H2 [O2 will be not be liberated due to over potential]
(Li+ will remain in solution)  2F  1 mole of Cl2
 2F  1 mole of H2 or 1  10–3 F  0.5  10–3 moles of Cl2
or 1  103 F  0.5  10–3 mole of H2  0.5  10–3 × 22400 ml Cl2 at STP

 11.2 ml Cl2 at STP
In solution, Li+ and OH are left. Since H2O produces equal no. of H+ and OH– ions,
mmoles of OH– ions left in excess = 10–3
To calculate the pH of solution, first calculate the
mmoles of H+ ions electrolysed. 103

 [OH ]   5  103 M
 mmoles of H+ ions electrolysed = Meq. 200 /1000
of H+ ions electrolysed = No. of faradays [Neglect OH– from dissociation of H2O]
passed
 pOH = – log10 (5 × 10–3)
–3
= 10 F
= 3 – log10 5 = 2.3
 pH = 14 – pOH = 14 – 2.3 = 11.7
Example - 21 An acidic solution of Cu2+ salt containing 0.4 gm of Cu2+ is electrolysed until all the copper
is deposited. The electrolysis is contained for seven more minutes with the volume of solution kept at 100 ml
and the current at 0.965 amp. Calculate the volume of gases evolved at STP during the entire electrolysis.
SOLUTION :
Writing electrode reactions : Cathode : 2H2O + 2 e 
 H2 + 2OH
Cathode : Cu2+ + 2e 

 Cu(s)  O2 + 4H+ + 4 e
Anode : 2H2O 
Numbers of faradays passed in 7 minutes are
Anode : 2H2O   O2 + 4H+ + 4e calculated as follows :
At Cathode : 2F  1 mole of Cu(s)
It 0.965  7  60
No. of faradays = 
0.4 0.4 96500 96500
 moles of Cu  2  = 0.0125 F
63.5 63.5
= 4.2 mF
At Anode : 4F  1 mole of O2(g)
At Cathode : 2F  1 moles of H2(g)
1 4.2 m F  1/2 × 0.0042 = 2.1 × 10–3 moles of H2
 0.0125 F   0.0125
4
At Anode : 4F  1 mole of O2(g)
= 3.13  103 moles of O2 4.2 mF  1/4 × 0.0042 = 1.05×103 moles of O2(g)
After all the copper ions are deposited as copper, During entire electrolysis, moles of all gases produced
electrolysis is continued for 7 minutes (for what ?).
Now electrolysis of water is carried out to produce = moles of O2 (with Cu) + (moles of H2 + moles of
H2(g) and O2(g) at cathode and anode respectively O2)
as follows : = 3.13 × 103 + (2.1 × 103 + 1.05 × 10–3)
= 6.28 × 10–3
Volume of all gases at STP
= (6.28 × 103) × 22400 ml = 140.67 ml
Example 22 - 23 Read the following passage :

A student prepare 2L buffer solution of 0.3 M NaH2PO4 and 0.3 M Na2HPO4. The solution is divided in half
between the two compartment (each containing 1 L buffer) of an electrolysis cell, using Pt. electrodes. As-
sume that the only reaction is the electrolysis of water and electrolysis is carried out for 200 min with a
constant current of 0.965 A.
 
 Assume that pK a( H PO  )  7.2
 2 4 
Example - 22 pH at anode is :
(A) 7.2 (B) 6.83 (C) 7.57 (D) 7.0
SOLUTION : (C)
 0.12 Felectricity  0.12 mole H+ consumed

 0.12 mole OH– left in excess
0.12
 After 200 min, [OH–] =  0.12M
1
Now, these OH– ions will react H 2 PO 4 with ions

( Acid).
H 2 PO4  OH 
 HPO42   H 2O
No. of faradays passed during electrolysis
0.3 M 0.12 M 0.3 M
It 0.965  200  60
=   0.12 0.18 M - 0.42 M
96500 96500
[Salt]
At cathode : 2H+ + 2e– 
 H2  pHsolution  pK a  log10
[Acid]
 1 F electricity  1 mole H+ consumed
0.42
 7.2  log10  7.57
0.18
Example - 23 pH at cathode is :
(A) 7.2 (B) 6.83 (C) 7.57 (D) 7.0
SOLUTION : (B)
At anode : 4OH– 
 O2 + 2H2O + 4e–
 1 F electricity  1 mole OH– consumed
 0.12 F electricity  0.12 mole OH– consumed  0.12 mole H+ left in excess
0.12
 After 200 min, [H+–] =  0.12M
1
Now, these H+ ions will react HPO 24  with ions ( Salt).
HPO24   H  
 H 2 PO4
0.3 M 0.12 M 0.3 M

0.18 M - 0.42 M
[Salt] 0.18
 pHsolution  pK a  log10  7.2  log10  6.83
[Acid] 0.42
Note : In a buffer solution of H 2 PO4 / HPO 42  , H 2 PO4 will act as an acid and H P O 24  will act as a salt and this
will behave as an acidic buffer.
Read the following passage :

Chemical reactions involve interaction of atoms and molecules. A large number of atoms/molecules (approxi-
mately 6.023 × 1023 ) are present in a few grams of any chemical compound varying with their atomic/
molecular masses. To handle such large numbers conveniently, the mole concept was introduced. This con-
cept has implications in diverse areas such as analytical chemistry, biochemistry, electrochemistry and radio-
chemistry. The following example illustrates a typical case, involving chemical/ electrochemical reaction,
which requires a clear understanding of the mole concept.
A 4.0 molar aqueous solution of NaCl is prepared and 500 mL of this solution is electrolysed. This leads to the
evolution of chlorine gas at one of the electrodes (atomic mass : Na = 23, Hg = 200; 1 Faraday = 96500
coulombs).
Example - 24 (i) The total number of moles of chlorine gas evolved is :

(A) 0.5 (B) 1.0 (C) 2.0 (D) 3.0
(ii) If the cathode is a Hg electrode, the maximum weight (g) of amalgam formed from this solution is :
(A) 200 (B) 225 (C) 400 (D) 446
(iii) The total charge (coulombs) required for complete electrolysis is :
(A) 24125 (B) 48250 (C) 96500 (D) 193000
SOLUTION : (i)-(B), (ii)-(D), (iii)-(D)
Mole of NaCl in the solution = 4 × 0.5 = 2
At anode : 2Cl– 
 Cl2 + 2e–
Moles of Cl– in the solution to be electrolysed = moles NaCl = 2
1
 Moles of Cl2 produced = 2  = 1 2 F electricity  2 × 96500 C 193000 C
2
At cathode : Na+ + e– 
 Na (when Hg electrode)
Na + Hg 
 NaHg (Sodium Amalgam)
 1 F electricity  1 mole Na
 2 F electricity  2 mole Na  2 moles NaHg 2 × (23 + 200) = 446 gm
Electrochemistry - III Vidyamandir Classes
Electrochemistry - III
(Electrolytic Conductance)
In this chapter, we will deal with the Conductance of electricity (charge) through Electrolytic solutions
(Electrolytic Conductance).
BASICS Section - 8
Electrical conductors (materials/substances which conduct electricity) are of two types :
(i) Metallic or Electronic Conductors : Conductors which transfer electric current by transfer of electrons,
without transfer of any matter, are known as metallic or electronic conductors. These materials contain
electrons which are relatively free to move. The passage of current through these materials has no observable
effect other than a rise in their temperature.
(ii) Electrolytic Conductors : Conductors like aqueous solutions of acids, bases and salts in which the flow
of electric current is accompanied by chemical decomposition are known as electrolytic conductors. With
the increase in temperature, the resistance decreases unlike in metallic conduction.
(a) The substances whose aqueous solutions allow the passage of electric current and are chemically
decomposed are termed electrolytes. Solutions of NaCl, KCl, CH3COOH etc. are examples of
electrolytes.
(b) The substances whose aqueous solutions do not conduct electric current are called non-electrolytes.
Solutions of cane sugar, glycerine, alcohol, etc., are examples of non-electrolytes.
Conductance
The conductance (G) is the property of the conductor (metallic as well as electrolytic) which facilitates the
flow of electricity through it. It is equal to the reciprocal of resistance (R), i.e.
1 1
Conductance (G) =  . . . . (i)
Resistance R
 It is expressed in the unit called reciprocal ohm (ohm1 or mho) or siemens (S) (S.I. unit).
The term Conductance can be further classified in the following ways :
(i) Conductivity () :

The resistance of any conductor varies directly as its length () and inversely as its cross-sectional
area (A), i.e.,
 
R  or R =ρ . . . . (ii)
A A

Vidyamandir Classes Electrochemistry - III
where  is called the resistivity or specific resistance (This name is now outdated as per IUPAC
convention)
If  = 1 cm and A = 1 cm2, then R = 
The resistivity () is, thus, defined as the resistance of one centimeter cube of a conductor.
The reciprocal of resistivity () is termed the conductivity or it is the conductance of one centimeter
cube of a conductor. It is denoted by the symbol  (abbreviation for “Kappa”). Thus,
1
κ=
ρ
Conductivity () is also called as specific conductance (Outdated as per IUPAC convention).
From equation (ii), we have :
A 1  1
ρ= . R or = .
 ρ A R
  
κ= ×G  = cell constant and is denoted by G* 
A  A 
or Conductivity () = Conductance (G)  cell constant (G*)
Note :  The unit of conductivity () is ohm1 cm1 or S cm–1.

 Conductivity can also be defined as the conductance of one centimeter cube of a conductor.
 For the conductance measurement of a solution,  is the distance between the electrodes and A is the
area of the electrodes.
 G* is difficult to calculate using /A. It is calculated more precisely by using a solution having known
values of  at some concentration [Calibration Technique].
(ii) Molar conductance (Ùm)

The molar conductance is defined as the conductance of all the ions produced by the ionisation of 1 g
mole of an electrolyte when present in V ml of solution. It is denoted by m.
Molar conductance (m) =   V
where V is the volume in ml containing 1 gm mole of the electrolyte.
If c is the concentration of the solution in g mole per litre, then :
1000
m = κ × where c is the concentration of the solution in M
c

Its units are ohm1 cm2 mol1 or S cm2 mol1
Also, if AxBy is an electrolyte dissociating as :  xA y   yBx 

A x By 
  m A x By  x   m (A y )  y   m (B x  )
For example :  m Al (SO )  2  m 3  3  m

2 4 3 (Al ) (SO 42  )
(iii) Equivalent Conductance (eq)

One of the factors on which the conductance of an electrolytic solution depends is the concentration
of the solution. In order to obtain comparable results for different electrolytes, it is necessary to take
equivalent conductance.
 It is defined as the conductance of all the ions produced by one gram equivalent of an electrolyte
in a given solution. It is denoted by eq.
At concentration c (in gm-equivalent/L i.e., normality), equivalent conductance is denoted by
eq.
 eq 

1000  conductivity ohm 1cm 1   1000  
c  or Normality N
If ‘V’ is the volume in ml containing 1 gm equivalent of the electrolyte, the above equation can be
written as :
eq =   V
Its units are ohm1 cm2 equiv1 or S cm2 equiv1.
Also, Equivalent conductance
Molar conductance Molecular mass

= where x   n  factor
x Equivalent mass
Also, if AxBy is an electrolyte dissociating as :  xA y   yB x 

A x B y 
eq   eq  eq
(A x B y ) (A y  ) (B x  )
For example : eq Al2 (SO 4 )3   eq (Al3 )   eq (SO 2 )

4

Illustration - 21 Resistance of a decimolar solution between two platinum electrodes 0.02 m apart and
4cm2 in area was found to be 40 ohms. Calculate : (a) cell constant (b) conductance (c) conductivity
SOLUTION :
(a) Cell constant (G*)
(c) Conductivity () = G.G* = 50 × 0.025 S/m
 0.02
=  m 1  50m 1
A 4  104 =1.25 S/m
1 1
(b) Conductance (G) =  S  0.025S
R 40
Illustration - 22 The resistance of 0.1 M solution of a salt (type : AB) is found to be 2.5 × 103 ohm. The
equivalent conductance of the solution is (Cell constant = 1.15 cm–1) :
(A) 4.6 (B) 5.6 (C) 6.6 (D) 7.6
SOLUTION : (A)
Use :
1000 4.6 104 1000
= G.G* eq  
N 0.1
1  1 = 4.6 S cm–1 eq–1.
 G  R 
= 1.15 = 4.6 × 10–4
2.5 103
Illustration - 23 The conductivity of 0.02 M KCl solution at 25C is 2.78  103 ohm1 cm1. The resistance
of this solution at 25C when measured with a particular cell was 250 ohms. The resistance of 0.01 M CuSO4
solution at 25C measured with the same cell was 8330 ohms. Calculate the molar conductivity of the copper
sulphate solution
SOLUTION :
Conductivity( ) of KCl 1
Cell constant (G*) = and Conductance of KCl (G) =
Conduc tan ce(G) of KCl R
2.78  103
 Cell constant(G*) = = 2.78 × 10–3 × 250 cm–1
1/ 250
For 0.01 M CuSO4 solution :
Conductivity () = Cell constant (G*)  conductance (G)
1

 2.78  103  250   8330
ohm 1cm 1
1000  2.78 103  250  1000

Molar conductance (^m) = Conductivity ()    = 8.3 ohm1 mol–1 cm2
c  8330 
  0.01

EFFECT OF DILUTION Section - 9
Effect on conductance
(i) Conductance of a solution increases with increase in the number of solute molecules/ions and decreases
with decreases in the number of solute molecules/ions.
(ii) Conductance of a solution increases with dilution as the interactions between the molecules/ions
decreases due to increase in the average distance between the molecules/ions.
Effect on degree of dissociation

(i) Strong electrolytes : There is almost no change in the degree of dissociation (as it is already close
to unity).
(ii) Weak elect rolyt es : With dilution, degree of dissociation increases rapidly and thus, the number of
molecules increases.
Effect on Molar and Equivalent conductance

Both m and eq increases with dilution as conductance increases with dilution.
For strong electrolytes, the increase in m and eq is relatively small as increase in the number of molecules/
ions is very small.
For weak electrolytes, the increase in m and eq is large and rapid as ‘’ increases with dilution.
Effect on Conductivity
On dilution, number of molecules/ions per ml of the solution decreases. Since, coductivity is defined as the
conductance of one ml of the solution, conductivity decreases with dilution (due to decrease in the
conductance).
Infinite Dilution
When addition of water doesn’t bring about any further change in the conductance of a solution, this situation
is referred to as Infinte Dilution.
(a) Strong Electrolytes : When infinite dilution is approached,
the conductance of a solution of strong electrolyte approaches
a limiting value and can be obtained by extrapolating the curve
between m and c as shown: (Note: the behavior/variation
is linear)
The molar conductivity of strong electrolytes is found to vary with concentration as :

 m   0m  b c where b is a constant depending upon the type of electrolyte (e.g.
AB, A2B etc. ), the nature of the solvent and the temperature.

This equation is known as Debye HuckelOnsages equation and is found to hold good at low
concentrations.
(b) Weak Electrolytes : When infinite dilution is approached,

the conductance of a solution of weak electrolyte increases
very rapidly and thus, cannot be obtained through
extrapolation. Also, the variation between m and c is not
linear at low concentrations.

Note : (i) lim  m  m and lim eq  eq
c 0 c 0
(ii) Conductance of a weak electrolyte at infinite dilution can be calculated by using Kohlrausch’s’s law of
Independent Migration of Ions.
Ionic Conductance
Conductance of an ion in the solution in inversely proportional to its size in the solution.
e.g. Li+ ion has a very high charge to size ratio due to which it gets hydrated to a large extent, when dissolved
in water. Thus, Size of Li+ (aq.) >> Size of Li+(g).
Note :  r r r but r r r
K + (g) Na  (g) Li  (g) K + (aq) Na  (aq) Li  (aq)
^ ^ ^
 m K + (aq) m Na  (aq) m Li  (aq)
 A heavily hydrated ion has to drag water molecules along with it when it moves in a solution which
makes it less mobile (or less conducting).
 Size of H+ (g) and OH– (g) ions are extremely small yet they have a very high conductance value in the
solution (as opposed to what you might have expected). Infact, H+ ion has the highest ^m at any
temperature followed by OH– ions. This is due to the mechanism by which they travel in the aqueous
solution.
H H H H
| | | |
H+ moves in the solutions as shown : H  O  H  O  H 
 H  O H  O  H
 
Illustration - 24 Arrange the following compounds in the orders of increasing conductionce. HCl, LiCl,
NaCl, KCl.
SOLUTION :
Note that anion (Cl–) is same in all the given Since,  m H +   m K +   m Na    m Li 
compounds. So, look for the conductance values
of cations only. So,  m HCl   m KCl   m NaCl   m LiCl

KOHLRAUSCH’S LAW OF INDEPENDENT MIGRATION OF IONS Section - 10
As per Kohlrausch’s Law of Independent Migration of Ions “At infinite dilution, when dissociation is complete,
each ion makes a definite contribution towards molar conductance of the electrolyte irrespective of the
nature of the ion with which it is associated and the value of molar conductance at infinite dilution for any
electrolyte is the sum of contribution of its constituent ions, i.e., anions and cations”.
As per Kohlrausch’s law, at infinite dilution, the conductance of any ion is independent of its association with
the other ion in the electrolyte i.e. 0m (K+) will be same in infinitely diluted solution of KCl or KBr or
KNO 3 .
Illustration - 25 The equivalent conductance of sodium chloride, hydrochloric acid and sodium acetate at
infinite dilution are 126.45, 426.16 and 91.0 S cm2 equiv1, respectively, 25C. Calculate the equivalent
conductance of acetic acid at infinite dilution. If the equivalent conductance of N/100 solution of acetic acid
is 3.9 S cm2 eq–1, calculate the degree of dissociation of acetic acid at this dilution.
SOLUTION :
According to Kohlrausch’s law, 0eq CH COONa  0  0  91.0 . . . (i)

3 eq CH3COO eq Na 
Similarly, we have :
eq HCl      426.16 . . . (ii)

eq H  eq Cl
0eq NaCl  0   0  126.45 . . . (iii)

eq Na eq Cl
Adding Equations (i) and (ii) and subtracting (iii),
we get :   0 0   0 0   0 0 
             eq Na    eq Cl 
 eq CH3COO eq Na   eq H eq Cl   
= 91.0 + 426.16 – 126.45
 0 0 
   eq CH COO   eq H    390.7
 3 
 0eq CH COOH  390.7 Scm 2 equiv1

3
eq 3.9
Also,   0   0.01  1%
eq 390.7
0
Note : eq Cl has been taken as same in equation (ii) and (iii). This is from the direct result of Kohlrausch’s law..

Applications of Kohlrausch’s law :

(i) Solubility Product of a Sparingly Soluble Salt :
If solute is sparingly soluble in a given solvent, its concentration is taken as its solubility in the saturated
solution.
1000  conductivity 1000  
Thus, 0m  
c c
0m can be computed using Kohlrausch’s law:
Thus, c can be computed and can be used to calculate the solubility product.
For example : For Al(OH)3 : KSP = [Al3+](3(OH]–)3
= (c) (3c)3  KSP = 27c4
(ii) Degree of dissociation :
At any dilution, the equivalent conductance is proportional to the degree of dissociation. Thus,
 eq Equivalent conductance at a given concentration

Degree of dissociation ()  
 0eq Equivalent conductance at infinite dilution
m Molar conductance at a given concentration

 
 0m Molar conductance at infinite dilution
Illustration - 26
The conductivity of a saturated solution of water chloride is 2.30  10–6 mho cm1 at

25C. Calculate the solubility of silver chloride at 25C if    61.9 mho cm mol
2 1
and
 2 1 m Ag
  76.3 mho cm mol
mCl  .
SOLUTION :
Let the solubility of AgCl be x gram mole per 0m AgCl  61.9 + 76.3 = 138.2 mho cm2 mol1
litre (i.e., mole/L). [Note : NAgCl = MAgCl]
Using : 1000  2.30  106
 138.2 
x
1000  specific conductance 1000  
0m   2.30  103
c x  x  1.66  105 mol / L
138.2
Now find the equivalent conductance of AgCl
at infinite dilution.  Solubility in gm/L = 1.66  10–5  143.5
= 2.38  10–3
0m AgCl  0   0 
m Ag m Cl

(iii) Ionisation constant of weak electrolytes :

Let AB be a weak electrolyte of concentration c.

AB  A+ + B–
At t = 0 c 0 0
At equilibrium c – c c c
[A  ][B ]
Thus, Equilibrium Dissociation Constant = K d 
 AB
cα  cα cα 2
Kd =  . . . (i)
c – cα 1  
Kd
For weak electrolytes,  << 1  Kd  c2  =
c
As concentration decreases, degree of dissociation increases.
  rq
Now,   0m  0
m eq
2 2
    eq 
m
c 0  c 0 
    eq 
Putting this value of  in (i) we get : Kd   m    
. . . (ii)
m  eq
1 0 1 0
m  eq
Equation (ii) is known as Ostwald equation.
Illustration - 27 Resistance of a solution (A) is 50 ohm and that of solution (B) is 100 ohm, both solutions
being taken in the same conductivity cell. If equal volumes of solutions (A) and (B) are mixed, what will be the
resistance of the mixture, using the same cell ? Assume that there is no increase in the degree of dissociation
of (A) and (B) on mixing.
SOLUTION :
1
Let us suppose 1 and 2 are the specific Also, conductance =
conductance of solutions ‘A’ and ‘B’ respectively R
and cell constant is ‘y’. 1
 For (A) : 1  y
We know that : 50
Specific conductance = Conductance  cell 1
constant and For (B) :  2  y
100

When equal volumes of (A) and (B) are mixed, 1 y y  1

the volumes becomes double. Then,    y
2  50 100  R

  2
Specific conductance of mixture = 1 1 1 1
2    R = 200/3
100 200 R
1   2 1 = 66.66 ohm
  y
2 R
Illustration - 28 The solubility product of sparingly soluble AgBr(s) is 12 × 10–14 mol2 dm–6. Calculat the
conductivity in units of 10–7 Sm–1 of saturated solution of AgBr upon addition of 1 × 10–7 mol dm–3 aqueous
AgNO3. The limiting ionic molar conductivity of Ag+, Br–, and NO3– at infinite dilution are 6 × 10–3,
8 × 10–3 and 7 × 10–3 S m2 mol–1, respectively. [Conductivity of pure water = 350 × 10–7 S m–1] (Neglect any
effect due to concentration dependence of conductiance)
(A) 39 (B) 55 (C) 15 (D) 405
SOLUTION : (D)
2
 mol 
KSP AgBr = 12  1014  2
 12  1014 M 2
 dm 
When 10–7 AgNO3 is added into the saturated solution of AgBr :
 Ag   NO3
AgNO3 
107 M 107 M
 Ag   Br 
AgBr 
[where x : Solubility of AgBr in the presence of 10–7 M AgNO3]
xM xM
At equilibrium :
KSP AgBr = [Ag+][Br–] = (x + 10–7) . x = 12 × 10 –14
 x2 + 10–7 x – 12 × 10 –4 = 0
Solve to get : x = 3 ×10–7 M
 At equilibrium, [Ag+] = x + 10–7 = 4 × 10–7 M = 4 × 10–4 mol m–3 ; [Br–] = x = 3 × 10–7 M
= 3 × 10–4 mol m–3
[NO3–] = 10–7 M = 10–4 mol m–3 [Using : 1 M 1000 mol m–3]

Total conductivity of solution =  Ag    Br    NO   H 2O

3
= ^0
 . [Ag  ]  ^ 0  . [Br  ]  ^ 0 
. [NO3 ]   H 2O
m (Ag ) m (Br ) m (NO3 )
= 6 × 10–3 × 4 × 10–4 + 8 × 10–3 × 3 × 10–4 + 7 × 10–3 × 10–4 + 350 × 10–7

= 405 × 10–7 S m–1
CONDUCTOMETRIC TITRATIONS Section - 11
Measurement of conductance of resulting solution form an acid and base titration may used to calculate the
equivalence point if there is a regular change in the conductance and sharp change at the equivalence point.
CASE : I Strong Acid (HCl) vs. Strong Base (NaOH) :
Region I : Initially the solution has the conductance due to the presence of H+ and Cl– ions. As NaOH
is added, following reaction takes place :
(H   Cl )  (Na  OH  ) 
 (Na   Cl  )  H 2O
 
Initially Finally
Thus, highly conducting H+ ions are replaced by lower conducting Na+ ions, resulting in a
decrease in the conductance of solution. As more and more NaOH is added (till the equivalence
point), conductance goes on decreasing.
Region II : Just after the equivalence point, as more NaOH is added, now there are more ions
(Noneutralisation)
(Na+ + Cl–) + (Na+ + OH–)

So, conductance will increase due to the presence of more number of ions in the solution.

As we can see that equivalence point, there is a sharp change in the curve definition and we can easily
calculate the equivalence point.
CASE : II Weak Acid (CH3COOH) vs Strong Base (NaOH) :
Region I : As more NaOH is added, it will directly react with CH3 COOH to form highly ionizable salt,
CH3COO– Na+. So, conductance will start increase (slowly as CH3COO– and Na+ have
low conductance)
Region II : Just after equivalence point, there will be an increase in the number of ions.
(Na++CH3OO–) + (Na+ + OH–)
So, conductance will increase sharply (OH– ions have highly conductance) and we can easily
find the equivalence point required through the titration.
Case : III Strong acid (HCl) vs Weak Base (NH4OH) :
Follows similar discussion as in case II.

Illustration - 29 An aqueous solution of X is added slowly to an aqueous solution of Y as shown in List I.

The variation in conducitivity of these reaction is given in List II. Match List I with List II.
List l List ll
[P] (C2 H5 )3 N  CH3 COOH 1. Conductivity decreases and then increases.

X Y
[Q] KI  0.1M   AgNO 3  0.01M  2. Conductivity decreases and then does not change much
X Y
[R]  CH3COOH   KOH 3. Conductivity increases and then does not changes much
X Y
[S] NaOH  HI 4. Conductivity does not change much and then increases
X Y
SOLUTION :
1. EtN in CH3COOH solution
When Et 3 N solution is added to CH 3COOH. '  ' of CH3COOH will increase, so through H  ions
ions will be consumed by Et 3 N, the overall number of ions in the solution will increase and hence conductivity

increase initially. Once almost all of CH 3COOH is consumed, a lot of and Et 3 N H will be
present in the solution and now further addition Et 3 N doesn’t cause much change in the total number of
ions as Et 3 N will not be able to extract H  ion from H 2O (because their will be suppression due to

already present Et 3 N H ions) and hence conductivity will almost remain the same.
2. Kl solution in AgNO3 solution
Initially : Ag    
KI aq
(a)  NO3  aq    AgI  s    K aq  NO3 aq
 aq     
 Number of ions remain the same  Conductivity does not change much.
(b) After all Ag  ions have been precipitated out, then the conductivity will increase because we are adding a
more concentrated solution and consequently number of ions per unit volume will increase.
3. CH3COOH in KOH
 CH COOH  aq 
(a) Initially : K (aq)  OHaq  
3
 H 2O     K aq  CH3COOaq 
 
 Number of ions remains the same, but number of OH  ions decrease  Conductivity
decrease.

(b) After all of OH  ions have been consumed, then further addition of CH 3COOH will not have much effect
as CH 3COOH will not break up much, as its dissociation will be suppressed by the already present
ions.
4. NaOH in Hl
NaOH
(a) Initially : H   I   H 2O     Na aq  Iaq 
 
 Numner of ions remains the same, but number of H  decrease  Conductivity decreases.
(b) After all the H  ions have been consumed, then further addition of a strong electrolyte NaOH (which will

give O H ions in the solution will increase conductivity..
ANSWER : [P-3] [Q-4] [S-1]
IN-CHAPTER EXERCISE - C
1. Given the following molar conductivities at 25C ; HCl , 426  cm mol  ;
NaCl , 126  cm mol  ; NaC (sodium crotonate) 83  1 cm 2 mol 1. What is the ionization
constant of crotonic acid ?
The conductivity of a 0.001 M crotonic acid solution is 3.83  105 1cm 1.
NOW ATTEMPT IN-CHAPTER EXERCISE-C FOR REMAINING QUESTIONS
NOW ATTEMPT OBJECTIVE WORKSHEET BEFORE PROCEEDING AHEAD IN THIS EBOOK

Electrochemistry Vidyamandir Classes
THINGS TO REMEMBER
1. In an electrochemical cell, cathode is the electrode with higher reduction potential or lower oxidation
potential.
°

°
Also, Ecell = E reduction cathode   E°reduction anode
2. Electrode potential of an electrode or cell varies with concentration, partial pressure of the species involved
and temperature.
 2.303RT 0.059 
E reduction  E °reduction    at 25° C  log10Qreduction
 nF n 
°  2.303RT 0.059 
and Ecell = Ecell   n F  n at 25°C  log10Qcell
 cell cell 
3. For a concentration cell, E°cell = 0
 1 (p H 2 )anode 
For a hydrogen concentration cell, Ecell = 0.059  pH Anode  pHcathode + log10 
 2 (p ) 
H 2 cathode 

4. Gibbs Helmholtz equation :
 d ( G )    dE  
G  H  T   H  ncell F T  cell   Ecell 
 dT T   dT  P 
 dE 
and S  ncell F  cell 
 dT P
5. In electrolysis, cations move towards cathode and anions move towards anode and the “chance” of their
deposition/liberation depends on their electrode potential, concentration, overpotential etc.
6. Faraday’s law : W = ZIt . . . . (i)
WA WB
 . . . . (ii)
E A EB
It
No. of Faradays supplied  = No. of gm eq. of the substance deposited/liberated at the electrode.
96500
7. Molar/ equivalent conductance and degree of dissociation of a electrolyte increases with dilution whereas
conductivity decreases with dilution.
 
G .G*   ; m  1000  ; eq.  1000 
C C
72 Things to Remember Self Study Course for IITJEE with Online Support
8. Molar/equivalent conductance of a strong electrolyte increases linearly with dilution whereas the change is
very rapid for weak electrolytes at high dilutions.
To calctrolytes the molar/equivalent conductance of a weak electrolyte at infinite dilution, use Kohlrausch’s
law of independent migration of ions.
 eq
Also,   m  
 m eq
9. For a smaller ion in gaseous state i.e. larger ion in aqueous, molar conductance is a small value. However,
H + and OH  ions are exceptions with high molar conductance values.
IN-CHAPTER EXERCISE-C
C 1. 1.11 10 5
SOLUTIONS TO IN-CHAPTER EXERCISE-C
1. Let crotonic acid be HC

0HC   0NaC   0HCl   0NaCl = 83 + 426 – 126 = 383
3.83  105  103 38.3

cHL   38.3    0.1
0.001 383
C 2 0.001  .12
Ka    1.11  105
1 1  0.1
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Vidyamandir Classes Electrochemistry - I

Reduction : Cu2+ (aq) + 2e– 

Self Study Course for IITJEE with Online Support Section 1 1

2 Section 1 Self Study Course for IITJEE with Online Support

Self Study Course for IITJEE with Online Support Section 1 3

Electrode representation : Pt, H2/H+

As anode : Fe2+ (aq.) 

Another example : Pt/ MnO 4 , Mn 2+ , H +

As cathode : MnO 4 (aq.)  8H  (aq.)  5e  

4 Section 1 Self Study Course for IITJEE with Online Support

Electrode reaction :  2 Hg ( ) + 2Cl– (aq.)

As anode :  Hg2Cl2 (s) + 2e–

5. Silver - Silver Chloride Electrode :

Electrode reaction : As cathode:  Ag(s) + Cl–(aq.)

As anode :  AgCl(s) + e–

If saturated KCl solution, E0reduction become 0.197 V (w.r.t. SHE)

6. Mercury - Mercurous Sulphate Electrode :

Self Study Course for IITJEE with Online Support Section 1 5

Electrode representation : Hg / Hg2SO4 / SO42–

Electrode reaction :  2 Hg( ) + SO42– (aq.)

As anode : 2 Hg( ) + SO42– (aq.) 

6 Section 1 Self Study Course for IITJEE with Online Support

E0 (Cu2+ / Cu) = 0.34 volts

The oxidation potential of Cu half-cell is just the negative of this value.

Rules for assigning sign (+ve or –ve) to electrode potentials :

E0cell can be defined in two ways as :

Self Study Course for IITJEE with Online Support Section 1 7

Construction of a cell and writing cell representation :

M(s) / M x  (c1M) || N y+ (c 2 M) / N(s)

Analysis of a given cell representation :

Half-cell reaction :  M x (c1 )  xe

Half-cell reaction : N y (c 2 )  ye 

8 Section 1 Self Study Course for IITJEE with Online Support

Overall Reaction : y M(s)  x N y  (c2 M) 

Half Cell Electrode reaction Reduction

Li+ / Li Li+ (aq.) + e– 

Ca2+/Ca Ca2+(aq.) +2e– 

Na+ / Na Na+ (aq.) + e– 

Mg2+ / Mg Mg2+ (aq.) + 2e 

Pt, H2 / H H2 (g) + 2e  –

Al3+ / Al Al3+ (aq.) + 3e 

Reducing Power increases

OH / H2 , Pt 2H2O () + 2e–  –

Zn2+ / Zn Zn2+ (aq.) + 2e– 

Cr3+ / Cr Cr3+ (aq.)+ 3e– 

Fe2+ / Fe Fe2+ (aq.) +2e– 

Cr3+ / Cr2+, Pt Cr3+ (aq.) + e– 

Cd2+ / Cd Cd2+ (aq.) + 2e– 

Co2+ / Co Co2+ (aq.) + 2e– 

Ni2+/Ni Ni2+ (aq.) + 2e– 

Self Study Course for IITJEE with Online Support Section 1 9

Sn2+ / Sn Sn2+ (aq.) + 2e– 

Pb2+ / Pb Pb2+ (aq.) + 2e– 

Fe3+ / Fe Fe3+ (aq.) + 3e 

Br / AgBr / Ag AgBr(s) + e–  –

Cu2+ / Cu+, Pt Cu2+ (aq.) + e  +

Sn4+ / Sn2+, Pt Sn4+ (aq.) + 2e– 

SO42–/H2SO3 SO42– (aq.) + 4H+ + 2e– 