Electrochem TheoryExercise 1653476390832

Electrochemistry
Introduction :
Batteries are everywhere in modern societies. They provide the electric current to start our
automobiles and to power a host of products such as pocket calculator, digital watches,
heart pacemaker, radio, and tape recorders.
Electrochemistry is the area of chemistry concerned with the interconversion of chemical
energy and electrical energy. A battery is an electrochemical cell, a device for interconverting
chemical and electrical energy. A battery takes the energy released by a spontaneous chemical
reaction and uses it to produce electricity.
Electrochemical cell :
It is device for converting chemical energy in to electrical energy.
Electrochemical cell are of two types
Galvanic cells or Voltaic cell

 A spontaneous chemical reaction
Electrolytic cell
An electric current drives a
i r
generates an electric current.
Thus the two types of cells are reverse of each other.
nonspontaneous reaction.
S
Construction/ Working principle
t a
Whenever a metal strip is put in an electrolyte the process of oxidation and reduction takes place
and the liquid phase.
u p
simultaneously within the system. Due to this there is a potential difference between the metal phase
On joining the metal strips through a wire (of negligible resistance) the current flows as long as the
I Anode : G
potential difference exists between the metal phase and the liquid phase.
m
Some metals (which are reactive) are found to have tendency to go into the solution phase when these
are placed in contact with their ions or their salt solution.
a
For example : Zn rod is placed in ZnSO4 solution.
u p
A n
Figure : 1 Figure : 2 Figure : 3

+2
The Zn atom or metal atoms will move in the solution to form Zn . After some time following equilibrium
will be established. Zn(s) Zn2+ +2e–
There will be accumulation of sufficient negative charge on the rod which will not allow extra zinc ions
to move in the solution. i.e. solution will be saturated with Zn+2 ions.
The extra positive charge of the solution will be more concentrated around the negatively charged rod.
An electrical double layer is developed in the system and hence a potential difference is created
between the rod and the solution which is known as electrode potential.
Corporate Office: CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.)-324005
Website : www.resonance.ac.in | E-mail : [email protected]
Toll Free : 1800 200 2244 | 1800 258 5555 | CIN: U80302RJ2007PLC024029
ADVECH - 1
Electrochemistry
This particular electrode is known as anode :
 On anode oxidation will take place. (release of electron).
 To act as source of electrons.
 It is of negative polarity.
 The electrode potential is represented by EZn(s) / Zn2+ (aq)
II Cathode :
Figure : 1 Figure : 2
r
Figure : 3
i
Some metals (Cu, Ag, Au etc.,) are found to have the opposite tendency i.e., when placed in contact
with their aqueous ions, the ions from the solution will get deposited on the metal rod.
The following equilibrium will be established : Cu2+ +2e– Cu(s). S
a
So rod will have deficiency of electron (positive charge). Extra negative charge will surround this
positively charged rod and form double layer. An electrical double layer is developed in the system and
t
hence a potential difference is created between the rod and the solution which is known as electrode
potential. This will be known as cathode.
u p
 At cathode reduction will take place. (gain of e– will take place)
 To act as sink of electron.
 Positive polarity will be developed.
G
 Their electrode potential can be represented by : E Cu2+(aq)/Cu(s)
a m
Is where oxidation occurs
Anode : Is where electrons are produced
Has a negative sign
Is where reduction occurs
Cathode : Is where electrons are consumed
Has a positive sign
Construction of Cell :

u p
It has two half–cells, each having a beaker containing a metal strip that dips in its aqueous
solution.
A n
 The metal strips are called electrodes and are connected by an conducting wire.
 Two solutions are connected by a salt bridge.
 The oxidation and reduction half reactions occur at a separate electrodes and electric current flows
through the wire.
ADVECH - 2
Electrochemistry
Selection of electrolyte for Salt Bridge :
 The electrolyte in salt bridge should be such that speed of it's cation equals speed of it's anion
in electrical field.
 For that charge and sign of the ions should be almost equal.
Transport number of cation = Transport number of anion
or
Mobility of cation = Mobility of anion
KCl is generally preferred but KNO3 or NH4NO3 can also be used.
 If Ag+, Hg22+, Pb2+, Tl+ ions are present in a cell then in salt bridge KCl is not used because
there can be formation of precipitate of AgCl, Hg2Cl2, PbCl2 or TlCl at mouth of tube which will
prevent the migration of ions and its functioning will stop.
Functions of Salt Bridge :

 A salt bridge is a U–shaped inverted tube that contains a gel permeated with an inert electrolyte.
 It connects the solution of two half cell to complete the circuit.
 It minimize the liquid junction potential. The potential difference between the junction of two
liquids.

of current.
i r
It maintains the electrical neutrality of the solution in order to give continuous flow or generation
"The simultaneous electrical neutrality of the anodic oxidation chamber and cathodic reduction
 If the salt bridge is removed then voltage drops to zero. S

chamber is due to same mobility or velocity of K+ and NO3– ions taken into salt bridge.

oxidised or reduced at the electrodes.
t a
The ions of the inert electrolyte do not react with other ion in the solution and the ions are not

p
Generally tube is filled with a paste of agar-agar powder with a natural electrolyte/generally not
common to anodic/cathodic compartment with porous plugs at each mouth of tube.
u
It prevents mechanical mixing of two electrolytic solution.
Liquid-Liquid Junction Potential :
G
The potential difference which arises between two solutions (during the progress of reaction) when in
contact with each other.
Electrode Potential :
a m

u p
The driving force that pushes the negative charge electrons away from the anode and pulls
them towards the cathode is an electrical potential called electromotive force also known as
A n
cell potential or the cell voltage. Its unit is volt
The potential difference developed between metal electrode and its ions in solution in known as
electrode potential.
 Electrode potential depends upon :
 Concentration of the solution.  Nature of the metal.
 Nature of the electrolyte.  Pressure temperature conditions.
 The potential difference developed between metal electrodes and the solution of its ions at 1 M
concentration at 1 bar pressure and at a particular temperature is known as standard electrode
potential.
Oxidation Potential (O.P.) : Reduction Potential (R.P.)

The electrode potential for The electrode potential for
oxidation half reaction reduction half reaction
Tendency to get oxidised. Tendency to get reduced.
 Greater the O.P. then greater  Greater the R.P. greater will
will be tendency to get oxidised. be tendency to get reduced.
ADVECH - 3
Electrochemistry
Type of Electrode Electrode reaction in standard condition Representation

1. Metal electrode Reduction : Zn2+ + 2e–  Zn(s) E 0Zn2  / Zn( s) ( SRP)
(Zn electrode, Oxidation : Zn(s)  Zn2+ + 2e– E 0Zn( s) / Zn2 (SOP)

Cu electrode etc.)
2. Hydrogen peroxide Reduction : 2e– + 2H+ + H2O2  2H2O EH0 2O 2 / H2O
electrode Oxidation : H2O2  O2 + 2H+ + 2e– E H0 2O 2 / O 2
0
3. Redox electrode Reduction : MnO4– + 8H+ + 5e–  Mn2+ + 4H2O EMnO 
/ Mn2 
4
4. Metal-Metal Reduction : AgCl(s) + e–  Ag(s) + Cl– E0AgCl( s ) / Ag( s ) / Cl
insoluable salt Oxidation : Ag(s) +Cl–  AgCl(s) + e– E 0Ag( s) / AgCl( s) / Cl

electrode
Reference electrode :


between two electrodes can be accurately measured using a reference electrode.
i r
The potential of a single electrode cannot be determined what were the potential difference
An electrode is chosen as a reference with respect to which all other electrodes are valued.

is arbitrarily assumed to be 0.00 volt. S
Standard Hydrogen Electrode (SHE) is taken as standard reference electrode. Its electrode potential
a
Standard Hydrogen Electrode (SHE) consists of a platinum electrode in contact with H2 gas and
aqueous H+ ions at standard state conditions (1 atm H2 gas, 1 M H+ (aq),).
2H+ (aq, 1M) + 2e–  H2 (g, 1 atm) E° = 0 V
t
Cell potential :
H2(g, 1atm)  2H+ (aq, 1M) + 2e–
u p E° = 0 V

G
The difference in electrode potentials of the two half cell reactions (oxidation half cell and
reduction half cell) is known as emf of the cell or cell potential.
The emf of the cell or cell potential can be calculated from the values of electrode potential of
a m
the two half cell constituting the cell. The following three method are in use :
 When oxidation potential of anode and reduction potential of cathode are taken into account :
u p
E°cell = oxidation potential of anode + reduction potential of cathode
= E°ox (anode) + E°red(cathode)
 When reduction potential of both electrodes are taken into account :
A n
E°cell = Reduction potential of cathode – Reduction potential of anode
= E°cathode – E°anode both are reduction potential.
 When oxidation potential of both electrodes are taken into account :
E°cell = oxidation potential of anode – Oxidation potential of cathode
= E°ox (anode) – E°ox (cathode)
 The standard cell potential E° is the cell potential when both reactants and products are in
their standard states–solutes at 1 M concentration, gases at a partial pressure of 1 atm, solids
and liquids in pure from, with all at a specified temperature, usually 25° C.
 E°cell is intensive property so on multiplying/Dividing cell reaction by any number, the E°cell value
would not change.
Free energy changes for cell reaction :

 The free energy change G (a thermochemical quantity) and the cell potential E(an
electrochemical quantity) both measure the driving force of a chemical reaction.
 The values of G and E are directly proportional and are related by the equation,
G = –nFE
where n = Number of moles of electron transferred in the reaction.
F = Faraday constant = 96485 C/mole e–  96500 C/mole e–
ADVECH - 4
Electrochemistry
Shorthand Notation for Galvanic Cells
 We require two half cells to produce an electrochemical cell, which can be represented by following few rules;
 The anode half-cell is always written on the left followed on the right by cathode half cell.
 The separation of two phases (state of matter) is shown by a vertical line.
 The various materials present in the same phase are shown together using commas.
 The salt bridge is represented by a double slash (||).
 The significant features of the substance viz. pressure of a gas, concentration of ions etc. are
indicated in brackets immediately after writing the substance.
 For a gas electrode, the gas is indicated after the electrode for anode and before the electrode
in case of cathode. (i.e Pt H2 / H+ or H+ /H2 Pt)
Example-1
Solution
r
Write short hand notation for the following reaction, Sn2+ (aq) + 2Ag+ (aq)  Sn4+ (aq) + 2Ag(s).
The cell consists of a platinum wire anode dipping into an Sn+2 solution and a silver cathode
dipping into an Ag+ solution therefore Pt(s) | Sn2+(aq), Sn4+ (aq) || Ag+ (aq) | Ag(s).
i
Example-2
be the positive terminal in each cell ?
(a) Zn | Zn2+ || Br–, Br2 | Pt (b) Cr| Cr3+ || I– , I2 | Pt
S
Write the electrode reaction and the net cell reaction for the following cells. Which electrode would
Solution
(c) Pt | H2, H+ || Cu2+ | Cu
(a) Oxidation half cell reaction, Zn  Zn2+ + 2e– a
(d) Cd | Cd2+ || Cl– , AgCl | Ag
t
reduction half cell reaction,
Net cell reaction
(b) Oxidation half reaction, [Cr 
u p
Br2 + 2e–  2Br–
Zn + Br2  Zn2+ + 2Br–
3+ –
Cr + 3e ] x 2
(Positive terminal : cathode Pt)
reduction half reaction,

Net cell reaction
G
[I2 + 2e–  2I–] x 3
2Cr + 3I2  2Cr3+ + 6I– (Positive terminal : cathode Pt)
(c) Oxidation half reaction,
a m H2  +
2H + 2e
Cu2+ + 2e–  Cu
–
u p
Net cell reaction
(d) Oxidation half reaction,
H2 + Cu2+  Cu + 2H+
Cd  Cd2+ + 2e–
(Positive terminal : cathode Cu)
A n
Net cell reaction
[AgCl + e–  Ag + Cl–] x 2
Cd + 2AgCl  Cd2+ + 2Ag + 2Cl– (Positive terminal : cathode Ag)
Calculation of electrode potential :
At Anode At Cathode
H2(g) 2H+ + 2e– 2H+ + 2e– H2(g)
Oxidation potential O.P. = EH ( g) / H ( aq.) Reduction Potential (R.P.) E  = RP
2 H / H2 ( g )
Under standard state  Under standard state.
 E0H2 ( g) / H ( aq.) = SOP  EH0  / H = SRP
2 ( g)
ADVECH - 5
Electrochemistry
 For SHE reference potential is taken to be zero at all temperature.
SOP = – SRP = 0 for SHE.
  To calculate standard potential of any other electrode a cell is coupled with standard hydrogen
electrode (SHE) and it's potential is measured that gives the value of electrode potential of that electrode.
Anode : Zinc electrode
Cathode : SHE
Cell : Zinc electrode || SHE
Cell potential :
Ecell = EH / H2 ( g ) – E°Zn2+/Zn
= 0.76 V (at 298 K experimentaly)
So, E0Zn2+/Zn = – 0.76 V (SRP)
E0 Zn/Zn2+(aq) = 0.76 V(SOP)
 So, w.r.t. H2 , Zn has greater tendency
to get oxidised.
In similar manner reduction potentials
(SRP) at 298 K f or m any other
electrodes are calculated and are
arranged in a series increasing order
known as electrochemical series.
i r
Electrochemical Series :
Electrode Reaction S
SRP (at 298 K)
* Li
K
Ba
Li+ + e–  Li(s)
K+ + e–  K (s)
t a – 3.05 V
– 2.93 V
Ca
Na
Ca+2 + 2e–  Ca(s)
Na+ + e–  Na(s)
Mg+2 + 2e–  Mg(s)
u p – 2.87 V
– 2.71 V
*
Mg
Al
Electrolytes (H2O)
G
H2O(l) + e–  21 H2 + OH–
– 2.37 V
– 0.828 V
* Zn
Cr
a m Zn+2 + 2e–  Zn(s)
Cr+3 + 3e–  Cr(s)
– 0.76 V
– 0.74 V
* Fe
Cd
u p Fe2+ + 2e-  Fe
Cd+2 +2e–  Cd(s)
– 0.44 V
– 0.40 V
A nCo
Ni
Sn
Pb
Ni+2 + 2e–  Ni(s)
Sn+2 + 2e–  Sn(s)
Pb+2 + 2e–  Pb(s)
– 0.24 V
– 0.14 V
– 0.13 V
* H2 2H+ + 2e–  H2(g) 0.00 V
Cu Cu2+ + 2e–  Cu(s) 0.34 V
2
Fe Fe3+ + e–  Fe2+ 0.77 V
Hg Hg22+ + 2e-  Hg(l) 0.79 V
Ag Ag+ + e–  Ag 0.80 V
Hg Hg2+  Hg(l) 0.85 V
Br2 Br2 + 2e–  2Br– 1.06 V
1
* Electrolytes 2
O2 + 2H+ + 2e–  H2O() 1.23 V
* Cr2O72– + 14H+ + 6e–  2Cr+3 + 7H2O 1.33 V
* Cl2  Cl2 +2e–  2 Cl– 1.36 V
* MnO4– + 8H+ + 5e–  Mn2+ + 4H2O 1.51 V
* F2 + 2e–  2F– 2.87 V
ADVECH - 6
Electrochemistry
Example-3 Calculate E0cell of (at 298 K), Zn(s) / ZnSO4(aq) || CuSO4(aq) / Cu(s)
given that E0Zn/Zn2+(aq) = 0.76 V, E0Cu(s) / Cu2+(aq) = – 0.34 V
Solution E0cell = (S.R.P)cathode – (S.R.P)anode
= 0.34 – (– 0.76) = 1.1 V
Example-4 Given the cell Ag AgCl(s) | NaCl (0.05 M) || Ag NO3 (0.30 M) | Ag
(a) Write half reaction occurring at the anode.
(b) Write half reaction occurring at the cathode.
(c) Write the net ionic equation of the reaction.
(d) calculate E°cell at 25°C.
(e) Does the cell reaction go spontaneous as written ?
0
(Given E°AgCl,Cl = + 0.22 volt) ; E Ag / Ag = + 0.80 volt)
Solution (a) LHS electrode is anode and half reaction is oxidation.
Ag+ + Cl–  AgCl(s) + e– ... (i)
(b) RHS electrode is cathode and half reaction is reduction.
Ag + e  Ag(s) ... (ii)
i r
(c) From equation (i) and (ii) cell reaction is : Cl– (0.05 M) + Ag+ (0.30 M)  AgCl(s)
(d) E°cell = E°right – E°left
= (0.80 – 0.22 volt = 0.58 volt S
a
(e) Yes, the e.m.f. value is positive, the reaction will be spontaneous as written in the cell reaction.
t

p
Calculation of Electrode Potential of unknown electrode with the help of given (two) electrode.
u
Obtain the reaction of the 3rd electrode with the help of some algebraic operations on reactions of
the given electrodes.
G
Then calculate Gº of the 3rd reaction with the help of some algebaric operations of G 0 of 1st and
2nd reactions.
a m
 Use G0 = –nF E0elec. to calculate unknown E.P.
E 0cell is intensive property so if we multiply/Divide electrode reaction by any number the E 0cell value
would not changed
i.e.
u p
Zn2+ + 2e–  Zn(s) E° = – 0.76 V
A n
Multiply by 2
2Zn2+ + 4e–  2Zn(s) E° = – 0.76 V (remain same)
Example-5 Given that E0Cu2+/Cu = 0.337 V and E0Cu+ /Cu2+ = – 0.153 V. Then calculate E0 Cu /Cu.
+
Solution (i) Cu2+ + 2e–  Cu G1

(ii) +
Cu  Cu + e2+ – G2
after adding Cu++ e–  Cu

G1 + G2 = G3
–2F E10 – F E 02 = – F E 03
E3 = 2 E10 + E 02
= 2 x 0.337 – 0.153
= 0.674 – 0.153 = 0.521 V
ADVECH - 7
Electrochemistry
Example-6 E0Mn2  / MnO4 = –1.51 V
E0MnO2 / Mn2 = + 1.23 V
E0MnO4 / MnO2 = ? (All in acidic medium)
Solution 4H2O + Mn2+  Mn O4 + 8H+ + 5e– G1
(i) Mn O4 + 8H + + 5e–  4H2O + Mn2+ –G1

2e– + MnO2 + 4H+  Mn2+ + 2H2O G2
(ii) 2H2O + Mn2+  MnO2 + 4H+ + 2e– –G2
(iii) 4H+ + Mn O4 + 3e–  MnO2 + 2H2O G3
(i) + (ii) = (iii)
G3 = – G1 – G2
–3E3F = 5 E10 F + 2 E 02 F
[5E1  2E2 ] [5( 1.51)  2(1.23 )] [ 7.55  2.46 ] 5.09
E= = = = = 1.69 V
3 3 3 3
anodecathode
i r
Example-7 Will Fe2+ disproportionate or not
3+
Fe    0.77 V 0.44 V
  Fe   2+
  Fe
S
Solution This is known as latimer diagram.
t a -0.036
S.R.P to right of the species greater than SRP of it's left species will undergo disproportionation.
Nernst Equation :
u p
G
Cell potentials depend on temperature and on the composition of the reaction mixtures.
It depends upon the concentration of the solute and the partial pressure of the gas, if any.
The dependence upon the concentration can be derived from thermodynamics.
From thermodynamics
G = G° + RT ln Q
a m
– nFE = – nFE° + 2.303 R T log Q
E = E° –
u p
2.303RT
nF
log Q
Take
n
T = 298 K , R = 8.314 J/mol K, F = 96500 C
A
Now we get, E = E° –
0.059
n
log Q
Where n = number of transfered electron, Q = reaction quotient
Nernst equation can be used to calculate cell potentials for non standard conditions also.
Nernst equations can be applied to half cell reactions also.
Applications of Nernst equation
Nernst Equation for Electrode Potential
Mn+(aq) + ne– M(s)
0
RT  M(s) 
ERedn = Ered – n  n 
nF M 
0
2.303 RT  M(s) 
ERedn = Ered – log  n 
nF M 
0 0.059  1 
at 298K, ERedn = ERedn – log  n 
n M 
ADVECH - 8
Electrochemistry
 Hydrogen Electrode
H2(g) 2H+(aq) + 2e–
0.0591  (H )2 
E = E0 – log  
2  PH2 
 Metal–metal soluble salt electrode.

Zn2+ + 2e–  Zn(s)
0 2.303 RT  1 
ERedn = ERedn
 log  2  at 298K
nF  Zn 
0 0.059  1 
ERedn= Ered  log  2 
2  Zn 
 Gas – electrode Hydrogen electrode.

2H+ + 2e–  H2(g)
0
ERedn= ERedn

0.059
2
 PH 
 2 
log   2 
 [H ] 
i r
 Redox electrode
4H2O + Mn2+  Mn O4 + 8H+ + 5e– S

EOX = E0ox 
0.059
5
log
[MnO4 ][H ]8
[Mn2 ]
t a
u p
Example-8
G
Calculate R.P. of hydrogen electrode at 298K which is prepared with the help of aq. solution of
acetic acid with 0.1 M concentration at 1 atm pressure Ka = 1.8 x 10–5.
Solution [H+] = Ka  c =
2H+ + 2e–  H2
a m
1.8  10 5  10 1 = 1.8  10  6
0
ERedn= Ered
up 0.059
2
PH2
log  2
[H ]
(E0Redn = 0)
A n
ERedn= 
0.059
2

log 
1
6
 1.8  10 


 = 
0.059
2
[6 – log (1.8)]
0.059
ERedn =  x 5.74 = –0.169 V
2
Example-9 Which is stronger oxidizing agent
(i) K2Cr2O7 in solution in which
[Cr2O72–] = 0.1 M, [Cr3+] = 10–2 M and [H+] = 10–1 M
(ii) KMnO4 in a solution in which
[MnO4–] = 10–1M, [Mn2+] = 10–2M, [H+] = 10–2 M
E0 Cr2O72 – / Cr 3 = 1.33 V E0MnO4 / Mn 2 = 1.51 V
Solution (i) 14H+ + Cr2O72–  2Cr+3 + 7H2O + 6e–
 104  10 
0.059 0.059
ERedn = 1.33 – log  
14  = 1.33 – x 11
1
6  10  6
0.649
ERedn = 1.33 – = 1.330 – 0.108 = 1.222 V
6
ADVECH - 9
Electrochemistry
(ii) 5e– + 8H+ + Mn O4  Mn2+ + 4H2O
0.059
 10 2 
ERedn = 1.51 – log  16  = 1.51 – 0.059 x 3 = 1.51 – 0.18 = 1.33 V
5  10  10 1 
ERedn is more so, good oxidising agent
 Nernst Equation for cell Potential :

aA + bB cC + dD
RT
Ecell = E0cell – lnQ
nF
n – no. of electrons which gets cancelled out while making cell reaction.
Equilibrium in electrochemical cell
G0 = – nF Eºcell
G = – nF Ecell
From thermodynamics
G = G0 + RTnQ
at chemical equilibrium G = 0
Ecell = 0  cell will be of no use
so, G0 = – RTn Keq
i r
at equilibrium – nF Eºcell = –2.303 RT log (Keq)
nF
log Keq = 2.303 RT Eºcell
S
at 298 K and R = 8.314 J/mol K
n
t a
log Keq =
0.059
Eºcell
u p
Example-10
Cl2 (g) Cl (aq)
Calculate Ecell of Pt(s) 0.1 atm 2
10 M
G Cr2O72 ,Cr 3  in H2SO4   0.05M Pt
0.01 M 0.1 M
given that E 0Cr O 2 

2 7
a m
/ Cr  3
= 1.33 V
Solution
u p
E0 Cl– | Cl2 = –1.36 V
6e– + 14H+ + Cr2O72–  2Cr+3 + 7H2O
[2Cl–  Cl2 + 2e–] x 3
A n
14H+ + 6Cl– + Cr2O72–  3Cl2 + 2Cr+3 + 7H2O
E0cell = 1.33 – (+1.36) = – 0.03
0.059 [Cr 3  ]2 [PCl2 ]3 0.059  23

Ecell = – 0.03 – log  14  6 = – 0.03 –
6 [H ] [Cl ] [Cr2O72 ] 6
Ecell = – 0.26 V
Example-11 The E°cell for the reaction Fe + Zn2+ Zn + Fe2+, is – 0.32 volt at 25°C. What will be the
equilibrium concentration of Fe2+, when a piece of iron is placed in a 1 M Zn2+ solution ?
Solution We have the Nernst equation at equilibrium at 25°C
0.0591
E° = log K ... (i)
n
Since E°Cell for the given reaction is negative, therefore, the reverse reaction is feasible for which
E°cell will be + 0.32 V, Thus for
Zn + Fe2+ Fe + Zn2+ ; E°Cell + 0.32 V
– x – (1–x)
ADVECH - 10
Electrochemistry
0.0591 [ Zn2 ] 0.0591 [Zn2 ]

Now , E° = log or 0.32 = log
n [Fe 2 ] 2 [Fe2 ]
[Zn2 ]
log = – 10.829 Taking antilog,
[Fe2 ]
[Fe2+] = 1.483 × 10–11 M
Work done by a cell :

(i) 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 = nFE
(ii) Work done by cell = Decrease in free energy
so – G = nFE or W max = + nFEº where Eº is standard EMF of the cell
Example-12 Calculate the maximum work that can be obtained from the Daniel cell given below -
Zn(s) | Zn2+ (aq) || Cu2+ (aq) | Cu (s). Given that Eº Zn2  / Zn = – 0.76 V and Eº Cu2  / Cu = + 0.34 V..
Solution Cell reaction is : Zn(s) + Cu2+ (aq)  Cu(s) + Zn2+ (aq)
Eºcell = Eºcathode – Eºanode (On the basis of reduction potential)
i r
Here n = 2
= + 0.34 – (0.76) = 1.10 V

We know that : W max = Gº = – nFEº S
or W max = – 212300 J
t a
= – (2 mol) × (96500 C mol) × (1.10 V) = – 212300 C.V. = – 212300 J
Concentration cells :

u p
A concentration cell consists of two electrodes of the same material, each electrode dipping in a
 The two solutions are separated by a salt bridge.

G
solution of its own ions and the solution being at different concentrations.
e.g. Ag(s) | Ag+ (a1) || Ag+ (a2) | Ag(s) (a1 < a2) a1 , a2 are concentrations of each half cell
At LHS electrode Anode :
At RHS electrode Cathode :
a m
Ag (s)  Ag+(a1) + e–
Ag+(a2) + e–  Ag(s)
The nernst eq. is
u p
The net cell reaction is : Ag (a2)  Ag+ (a1)
+
A n
Ecell = –
0.059
n
a1
log a
2
(Here n = 1, Temp, 298 K)
Likewise, the e.m.f. of the cell consisting of two hydrogen electrodes operating at different pressure
P1 and P2 (P1 > P2 ) and dipping into a solution HCl is :
0.059 P1
Ecell = log P (at 298 K)
2 2
Electrolysis & Electrolytic cell :

Electrolysis :
 Electrolyte is a combination of cations and anions which in fused state or in aqueous solution can
conduct electricity.
 This is possible due to the movement of ions from which it is made of.
 The process of using an electric current to bring about chemical change is called electrolysis.
 Electrolysis is a process of oxidation and reduction due to current in the electrolytic solution.
 The product obtained during electrolysis depends on following factors.
 The nature of the electrolyte
 The concentration of electrolyte
 The charge density flowing during electrolysis.
 The nature of the electrode
ADVECH - 11
Electrochemistry
Active vs Inactive electrodes :
 The metal electrodes in the cell that are active, because the metals themselves are components
of the half reactions.
 As the Daniel cell operates, the mass of the zinc electrode gradually decreases, and the [Zn2+]
in the anode half – cell increases. At the same time, the mass of the copper electrode increases
and the [Cu2+] in the cathode half – cell decreases; we say that the Cu2+ "plates out" on the
electrode.
 For many redox reactions, however, there are no reactants or products capable of serving as
electrodes. Inactive electrodes are used, most commonly rods of graphite or platinum, materials
that conduct electrons into or out of the cell but cannot take part in the half -reactions.
 In a voltaic cell based on the following half reactions, for instance, the species cannot act as
electrodes :
2I–(aq)  I2(s) +2e– [anode ; oxidation]
MnO4– (aq) + 8H+ (aq) + 5e–  Mn2+ (aq) + 4H2O() [cathode ; reduction]
Therefore, each half – cell consists of inactive electrodes immersed in an electrolyte solution that
contains all the species involved in that half -reaction. In the anode half-cell, I– ions are oxidized to solid
I2. The electrons released flow into the graphite anode, through the wire, and into the graphite cathode.
From there, the electrons are consumed by MnO4– ions as they are reduced to Mn2+ ions.
Examples of Electrolysis
i r
 Using inert (Pt/graphite) electrodes.
Cathode (red) : Pb2+ + 2e–  Pb(s) E0 = 0.126V
Anode : 2Br-  Br2 + 2e- E0 = – 1.08 V
S

Ecell = – 0.126 – (0.108) x 10 = – 1.206 V
Eext > 1.206 V
t a
Electrolysis of CuSO4 molten
Cathode :
Anode :
Cu2+ + 2e–  Cu
2 SO24  S2 O 82 + 2e–
u p
E0 = +0.34 V
E0 = – 2.05 V
H2S2O8 – Marchall's acid peroxy disulphuric acid.
G
Ecell = 0.34 – (2.05) = – 1.71 V (negative  not feasible)
O
H O S O O S O H
O
a m

O O
u p
Electrolysis of aq CuSO4
Cathode :
A n Cu2+ + 2e–  Cu(s)

2e + 2H2O()  H2(g) + 2OH–(aq)
E0 = 0.34 V
E0 = –0.83V
Anode : 2 SO24  S2 O 82 + 2e– E0 = –2.05 V
2H2O()  O2 + 4H+ + 4e– E0 = –1.23 V
 Electrolysis of aq NaBr solution (initially PH = 7)
Cathode : Na+(aq) + e–  Na(s) E0 = – 2 V
2e– + 2H2O()  H2 + 2OH– E0 = – 0.83 V
Anode : 2Br-  Br2 + 2e– E0OX = – 1.08 V
2H2O ()  O2 + 4H+ + 4e– E0OX = – 1.23 V
 Electrolysis of aq NaCl
Cathode : Na+ + e–  Na E0 = – 2V
2e– + 2H2O()  H2(g) + 2OH- E0 = –0.83 V
Anode : 2Cl–  Cl2 + 2e– E0OX = –1.30 V
2H2O()  O2 + 4H+ + 4e– E0OX = –1.23 V
Rate of production of Cl2 is more than rate of production of O2 gas.
ADVECH - 12
Electrochemistry
 Electrolysis of CH3COONa
Cathode : 2H2O + 2e–  H2(g) + 2OH–
Anode : 2CH3COO–  2CO2 + C2H6 + 2e–
Note : According to thermodynamics, oxidation of H2O to produce O2 should take place on anode but
experimentally (experiment from chemical kinetics) the rate of oxidation of water is found to be very
slow. To increase it's rate, the greater potential difference is applied called over voltage or over potential
but because of this oxidation of Cl– ions also become feasible and this takes place on anode.
Electrolysis using attackable (reactive) electrodes.
 Electrolysis of aq. CuSO4 using Cu electrode.
Cathode (reduction) : Cu2+ + 2e–  Cu Eº = + 0.34 V
2H2O() + 2e–  H2(g) + 2OH– Eº = –0.83 V
Anode (oxidation) : SO24  S2 O 82 + 2e– E0OX = – 2.05 V
2H2O()  O2 + 2H+ + 4e– Eº = 1.23 V
Cu(s)  Cu2+ + 2e– Eº = –0.34 V
electrolytic refining
 AgNO3(aq) using Cu cathode & Ag anode.
Cathode : Ag+ + e–  Ag(s)
2H2O () + 2e–  H2(g) + 2OH–
Eº = 0.8 V
Eº = – 0.83 V
i r
Anode : NO3–  X (No reaction)
2H2O()  O2 + 4H+ + 4e–
Ag(s)  Ag+(aq) + e–
S
Eº = – 1.23 V
Eº = – 0.80 V
 Faraday's Law of Electrolysis :

t a
 1st Law : The mass deposited/released/produced of any substance during electrolysis is proportional
to the amount of charge passed into the electrolyte.
WQ
u p
W = ZQ
Z – electrochemical equivalent of the substance. G
Unit of Z =
mass
coulomb
a m
= Kg/C or g/C
Z = Mass deposited when 1 C of charge is passed into the solution.
u p
Equivalent mass (E) : mass of any substance produced when 1 mole of e– are passed through the
solution during electrolysis.
E=
A n 
Molar mass
no. of e involved in oxidation / reduction
M M
e.g. Ag+ + e–  Ag E= Cu2+ + 2e-  Cu(s) E=
1 2
M
Al3+ + 3e–  Al(s) E=
3
1 mole of e– = 1 Faraday of charge.
 96500 C – Charge deposit E gram metal charge
 E  E
 1C   g Z=
 96500  96500
EQ Molar mass Q
W= = x
96500 (no. of e involved ) 96500
ixt Molar mass

 
dQ = i dt Q = it W=
96500
x
(no. of e  involved )
ADVECH - 13
Electrochemistry
 2nd Law : When equal charge is passed through 2 electrolytic cells and this cells are connected in
series then mass deposited at electrode will be in the ratio of their electrochemical equivalents or in the
ratio of their equivalent masses.
EQ
W = ZQ =
96500
W1 z1 E1
W2 = z2 = E 2 ( Q = same)
Current Efficiency :
charge actually used in electricity
Current efficiency = ch arg e passed × 100
mass actually produced
Current efficiency = mass that should have been produced × 100
Example-13 Calculate volume of the gases liberated at STP if 1 L of 0.2 molar solution of CuSO4 is electrolysed
by 5.79 A current for 10000 seconds.
Solution No. of moles of e– =

5.79  10000
96500
Cu2+ + 2e-  Cu(s)
=
579
965
= 0.6
i r
Cathode :
0.2 mole 0.4 mole
2H2O() + 2e–  H2 + 2OH– S
0.2 mole of e–  0.1 mole of H2 at S.T.P..
Anode : 2H2O()  O2 + 4H+ + 4e–
4 mole of e–  1 mole of O2
t a
so, total moles = 0.25 mole
u p
0.6 mole of e–  0.15 mole of O2
Example-14
Total volume = 5.6 Ltr.
G
The electrochemical equivalent of copper is 0.0003296 g coulomb–1. Calculate the amount of copper
deposited by a current of 0.5 ampere flowing through copper sulphate solution for 50 minutes.
Solution
m
According to Faraday's first law, W = Zit
a
W = 0.5 × 50 × 60 × 0.003296 = 0.4944 g
Example-15
u p
An electric current is passed through three cells connected in series containing ZnSO4, acidulated
water and CuSO4 respectively. What amount of Zn and H2 are liberated when 6.25 g of Cu is deposited?
Eq. wt. of Cu and Zn are 31.70 and 32.6 respectively.
Solution
A

n Eq. of Cu = Eq. of Zn = Eq. of H2
6.25
31.70
=
WZn
32.6
=
WH2
1
Example-16 The cell consists of three compartments
separated by porous barriers. The first
contains a cobalt electrode in 5.00 L of
0.100 M cobalt (II) nitrate; the second 0.20 M NO 3
–
0.10 M NO3
–
0.10 M NO 3
–
contains 5.00 L of 0.100 M KNO3 and Co Ag

2+ + +
third contains 0.1 M AgNO3. Assuming 0.10 M Co 0.10 M K 0.10 M Ag
that the current within the cell is carried
equally by the positive and negative ions,
5.0 L 5.0 L 5.0 L
tabulate the concentrations of ions of
each type in each compartment of the cell after the passage of 0.100 mole electrons.
Given Co2+ + 2e–  Co Eº = – .28 V
Ag+ + e–  Ag Eº = 0.80 V
ADVECH - 14
Electrochemistry
Solution Spontaneous reaction is : 2Ag+ + Co Co2+ + 2Ag Eº = 1.08
In the left compartment. cobalt will be oxidized to cobalt (II) ion. In the right compartment, silver ion will
be reduced to silver. The passage of 0.100 mol electrons will cause the following quantities of change.
Compartment 1 Compartment 2 Compartment 3
Effect of electrode + 0.0500 mol Co3+ – 0.100 mol Ag+
2+ 2+
Positive ion movement –0.0250 mol Co + 0.0250 mol Co + 0.0500 mol K+
+
– 0.0500 mol K
Negative ion movement + 0.0500 mol NO3– – 0.0500 mol NO3–
Changing the numbers of mol to concentrators in 5.0 L compartments and adding or subtracting
yields the following results :
Final concentrations (M) Co2+ 0.015 Co2+ 0.00500 Ag+ 0.0800
– +
NO3 0.210 K 0.090 NO3– 0.0900
– +
NO3 0.100 K 0.0100
Electrolytic Conductance :
i r
S
t a
Factors Affecting Conductance & Resistance :
u p
1.
G
Solute – Solute interactions (Inter – Ionic force of attraction) Greater the force of attraction,
greater will be the resistance.
Force  Charge
2.
Greater the solvation
a m
Solute – Solvent Interaction (Hydration/Solvation of Ions)
u p
Solvation  Charge 
size
greater will be resistance
Li+ (Hydrated largest) Cs+ (Hydrated smallest)
resistance of LiCl > resistance of CsCl
3.
4.
A n
Solvent-solvent interaction (Viscosity) : greater the viscosity greater will be resistance
Temperature
T R
5. Nature of electrolyte
Weak electrolyte – High resistance Strong electrolyte – Low resistance
Resistance :
V
R= (Ohm's law (  ))


R=
A
 – resistivity/specific resistance
– resistance of unit length wire of unit area of cross section = constant = (  m)
RA
 =

ADVECH - 15
Electrochemistry
Resistivity of a solution is defined as the resistance of the solution between two electrodes of 1 cm 2
area of cross section and 1 cm apart.
or
Resistance of 1 cm3 of solution will be it's resistivity.
Conductance :
1
C= = mho =  –1
R
= S (Siemens)
Conductivity/specific conductance
1  
= = =
 RA A
unit  –1 cm –1
= conductivity of 1 cm 3 of solution
 concentration of ions
1 1
= C=
 R
  ( no. of ions) no. of charge carriers

i r
Since conductivity or resistivity of the solution is dependent on it's concentration, so two more

type of conductivities are defined for the solution.
Molar conductivity/molar conductance ( m) :
S
length apart.
Let the molarity of the solution 'C'
t a
Conductance of a solution containing 1 mole of an electrolyte between 2 electrodes which are unit
 C moles of electrolyte are present in 1 Lt. of solution.

so molar conductance =  m
u p
 m = V m =
  1000
C G 
  1000
 m = molarity


a m
Its units are Ohm –1 cm 2 mol–1
Equivalent conductance : Conductivity of a solution containing 1 g equivalent of the electrolyte.
  1000
u p
 eq – equivalent conductivity/conductance.
 eq

A n
= Normality
Its units are Ohm –1 cm 2 eq–1

 Ionic Mobility
 Ionic Mobility = speed of the ion per unit electrical field
speed speed
 = electrical field = potential gradient
 Its units are V–1 cm 2 sec–1

0
M 0
Ionic mobility = u = = M
96500 F
 Transport Number
Transport Number of any ion is fraction of total current carried by that ion.
0
M
Transport Number of cation = 0
M electrolyte
ADVECH - 16
Electrochemistry
Example-17 If resistivity of 0.8 M KCl solution is 2.5 x 103  cm calculate  m of the solution.
Solution  = 2.5 x 10–3  cm
103
K= = 4 x 102
2.5
4  102  1000  10
m = = 5 x 105 –1 cm 2 mole–1
0.8
 Variation of conductivity and molar conductivity with concentration

 Conductivity always decreases with the decrease in concentration both for weak and strong
electrolytes.
 The number of ions per unit volume that carry the current in a solution decreases on dilution.
 Molar conductivity increases with decreases in concentration. This is because the total volume,
V of solution containing one mole of electrolyte also increases.
 Molar conductivity is the conductance of solution.
 When concentration approaches zero, the molar conductivity is known as limiting molar
conductivity and is represented by the symbol  .
i r
Strong Electrolytes :
 S
For strong electrolytes.  increases slowly with dilution and can be represented by the equation

 =  – A C
1/2
t a
The value of the constant 'A' for a given solvent and temperature depends on the type of electrolyte
solution.
u p
i.e. the charges on the cations and anion produced on the dissociation of the electrolyte in the
Example : Thus NaCl, CaCl2, MgSO4 are known as 1-1 , 2-1 and 2-2 electrolyte respectively.

G
All electrolytes of a particular type have the same value for 'A'.
a m
u p
A n
Weak electrolytes
 Weak electrolytes like acetic acid have lower degree of dissociation at higher concentration and hence
for such electrolytes, the change in  with dilution is due to increases in the number of ions in total
volume of solution that contains 1 mol of electrolyte.
 At infinite dilution (i.e. concentration c  zero) electrolyte dissociates
completely ( = 1), but at such low concentration the conductivity of
the solution is so low that it cannot be measured accurately.
 Molar conductivity versus c1/2 for acetic acid
(weak electrolyte) and potassium chloride
(strong electrolyte in aqueous solutions.
ADVECH - 17
Electrochemistry
Kohlarausch's Law :
 "At infinite dilution, when dissociation is complete, each ion makes a definite contribution towards
equivalent conductance of the electrolyte irrespective of the nature of the ion with which it is associated
and the value of equivalent conductance at infinite dilution for any electrolyte is the sum of contribution
of its constituent ions."
i.e.,  = + + –
 At infinite dilution or near zero concentration when dissociation is 100%, each ion makes a definite
contribution towards molar conductivity of electrolyte irrespective of the nature of the other ion. (because
interionic forces of attraction are zero)
0 0
 0m electrolyte =   m +   m
 + = no. of cation in one formula unit of electrolyte
 – = no. of anions in one formula unit of electrolyte
For NaCl,  + = 1  – = 1
For Al2(SO4)3,  + = 2  – = 3
0eq electrolyte = eq
 
 + eq
0
0
m m Al3
0eq =
charge on the cation
 0m
0eq .Al3+ =
3
0
i r
0eq =
charge on the anion
0eq , electrolyte =
S m electrolyte
total  ve charge on cation
or
0eq Al2(SO 4)3 = 0eq Al3+ + 0eq SO24

0 3
m Al
t a
0 SO2
+ m 4
total  ve charge on anion
0
2 mAl3   3
0
u p
=
3 2
0eq Al2(SO4)3 =
6
mSO2 
4
G
Example-18 0
m
a m
Na+ = 150  –1 cm 2 mole–1 ; 0eq Ba2+ = 100  –1 cm 2 eq–1
u p
0eq SO24 = 125  -1 cm 2 eq–1 ; 0
m Al3+ = 300  –1 cm 2 mole–1
A n
0
m NH4 = 200  –1 cm 2 mole–1
Then calculate
(a) 0eq , Al3+
;
(b) 0eq Al2(SO4)3

0
m , Cl– = 150  –1 cm 2 mole–1
0
(c) m (NH4)2SO4
0
(d) m NaCl, BaCl2. 6H2O 0
(e) m , (NH4)2 SO 4 Al2(SO4)3 . 24H2O (f) 0eq NaCl
300
Solution (a) 0eq Al3+ = = 100 (b) 0eq Al2(SO4)3 = 100 + 125 = 225
3
0
(c) m (NH4)2SO4 = 2 x 200 + 2 x 125 = 650
0
(d) m NaCl.BaCl2.6H2O = 150 + 200 + 3 x 150 = 800 r–1
0
(e) m (NH4)2 SO4 Al2(SO4)3.24H2O = 400 + 600 + 4 x 250 = 2000
(f) 0eq NaCl = 300  –1 cm 2 eq–1
ADVECH - 18
Electrochemistry
Example-19 0
To calculate m or 0eq of weak electrolyte
0 0 0
Sol. mCH3 COOH
=  mCH COO +  m H+
3
0 0 0 0 0 0
= (  mCH3COO + mNa  ) – 
mNa
+ mH + mCl – mCl
 0CH3COOH =  mCH
0
3 COONa
0
+  mHCl –  0mNaCl
0
Example-20 Calculate m of oxalic acid, given that
0eq Na2C2O4 = 400  –1 cm 2 eq–1

0
m H2SO4 = 700  –1 cm 2 mole–1
0eq Na2SO4 = 450  –1 cm 2 eq–1

0
Solution m H2C2O4 = 700 + 800 – 900 = 600  –1 cm 2 mole
700
0eq = 400 +
m
2
– 450
i r
2
= 350 – 50 = 300
 m = 600 S
Applications of Kohlaraushch's law
Calculate  for any electrolyte from the  of individual ions.
t a
u p
Determine the value of its dissociation constant once we known the  and  at a given concentration c.
Degree of dissociation : At greater dilution the ionization become 100%, therefore called infinite dilution.
become lower,
i.e.,  eq < °eq
G
At lower dilution the ionization (dissociation into ions) is less than 100% and equivalent conductance
 degree of dissociation
 eq
a m
equivalent conduc tan ce at a given concentrat ion
=
 0eq =
p
equivalent conduc tan ce at at inf inite dilution
u
Dissociation constant of weak electrolyte :
KC =
A
C 2
1 
n;  = degree of dissociation
C = concentration
 The degree of dissociation then it can be approximated to the ratio of molar conductivity  c at the
concentration c to limiting molar conductivity, º, Thus we have :
 = /º
But we known that for a weak electrolyte like acetic acid.
C 2 c2 c2
Ka = = =
(1   ) 1   /    
Solubility(s) and KSP of any sparingly soluble salt.
Sparingly soluble salt = Very small solubility
Solubility = molarity = 0
so, solution can be considered to be of zero conc or infinite dilution.
K  1000 K  1000
 m, saturated = M = So lub ility S = M0 KSP = S2 (for AB type salt)
ADVECH - 19
Electrochemistry
Example-21 If conductivity of water used to make saturated solution of AgCl is found to be 3.1 x 10–5  –1
cm –1 and conductance of the solution of AgCl = 4.5 x 10–5  –1 cm –1
If M0 AgNO3 = 200  –1 cm 2 mole–1, M0 NaNO3 = 310  –1 cm 2 mole–1
calculate KSP of AgCl
Solution M0 AgCl = 140
Total conductance = 10–5
140  4  10 5  1000 1.4  10  4

S= =
140 14
S = 5.4 x 10–4
S2 = 1 x 10–8
Example-22 To calculate KW of water

H2O() + H2O()  H2O+(aq) + OH–(aq)
r
0
m = M,H2O = M0 H+ + M0 OH–
K  1000
= molarity - Concentration of water molecules 100% dissociated Ask
S i
K  1000
molarity = [H+] = [OH–] =
M
2
t a
KW
 K  1000 
= [H+][OH–] =  0
  M 

p
Ka or Kb =
u
[H ][OH ]
H2 O
Variation of ,  m & eq of solutions with Dilution

G
  conc. of ions in the solution. In case of both strong and weak electrolytes on dilution the concentration
 m or  eq
a m
of ions will decrease hence  will decrease.
(  C) strong electrolyte
p
1000  
u
 m = molarity (  K aC ) weak electrolyte.
A n 1000  
 eq = normality
 C
For strong electrolyte m   = constant
C C
 KaC 1
For weak electrolyte m   
C C C
Some Primary Cells
 Primary cells : These cells can not be recharge i.e., dry cell (lechlanche cells)
mercury cells (miniature cell used in the electronic devices)
Ecell = constant
as all substances used are either pure solids or pure liquids.
DRY CELLS and alkaline batteries :

• Cell potential = 1.5 V
• Anode : Zn (s)  Zn+2(aq) + 2e–
ADVECH - 20
Electrochemistry
• Cathode : MnO2 + NH4+ + e–  MnO(OH) + NH3
Zn2+ + 4NH3  [Zn(NH3)4]2+
• Alkaline batteries contain basic material inside it.
• NaOH / KOH is used instead of the acidic salt NH4Cl
• Cathode : 2MnO2(s) + H2O() + 2e–  Mn2O3(s) + 2OH–(aq)
Anode : Zn(s) + 2OH–(aq)  ZnO(s) + H2O() + 2e–
• Voltage produced by these cells = 1.54 V
• The cell potential does not decline under high current loads because no gases are formed.
Hg cell :
• Suitable for law current devices - Hearingaeds, watches
• Anode : Zn(Hg) + 2OH–  ZnO(s) + H2O + 2e–
Cathode : HgO + H2O + 2e–  Hg() + 2OH–
•
Cell reaction : Zn(Hg) + HgO(s)  ZnO(s) + Hg()
Cell potential = 1.35 V and remains constant.
i r
 Secondary cells : Lead storage batteries used is automobiles (Cars/bikes)
Anode : Pb(s) S
Cathode : PbO2(s)
H2SO4(conc.) about 38% solution of H2SO4 is taken.
Anode : Pb(s)  Pb2+ (aq) + 2e–
t a
Pb2+(aq) + SO24 (aq)  PbSO 4(s)
Pb(s) + SO24 (aq)  PbSO4 + 2e–
u p
G
Most of the PbSO4(s) ppt sticks to the lead rod.
Cathode : 2e– + 4H+ + PbO2(s)  Pb2+(aq) + 2H2O()
Pb2+(aq) + SO24 (aq) + 4H+ + 2e–  PbSO4(s) + 2H2O()
a m
PbSO4(s) sticks to cathode rod.
Pb(s) + PbO2 + 4H+ + 2 SO24 (aq)  2PbSO4(s) + 2H2O()
p
Ecell = 2.05 V
u
A n
Note : During the working of the cell or discharge H2SO4 will be consumed so it's concentration in the solution
hence density of the solution will decrease, during charging of the cell PbSO4 will get converted into
Pb(s) and, PbO2(s) and H2SO4 will be produced.
Nickel – cadmium battery.

Ecell = constant as cell reaction has pure solid/liquids only.
Anode : Cd(s)
Cathode : NiO2(s)
Electrolyte : KOH
Cd + 2OH–  Cd(OH)2 + 2e–
2e– + NiO2 + 2H2O  Ni(OH)2(s) + 2OH–
Cd(s) + NiO2(s) + 2H2O()  Cd(OH)2(s) + Ni(OH)2(s)
Fuel cells (H2 – O2 cell) :
Anode : H2  2H+ + 2e– x 2
Cathode : 4e– + 4H+ + O2  2H2O
–––––––––––––––––––––––
2H2 + O2  2H2O()
–––––––––––––––––––––––
ADVECH - 21
Electrochemistry
CH4 – O2 fuel cells :
Anode : 2H2O + CH4  CO2 + 8H+ +8 e–
Cathod : 4e– + 4H+ + O2  2H2O
–––––––––––––––––––––––
CH4 + 2O2  CO2 + 2H2O()
Mechanism of corrosion
Oxidation : Fe(s)  Fe2+ (aq) + 2e–

Reduction : 2O2–(g) + 4H+ (aq)  2H2O(I)
Atmospheric
Oxidation : 2Fe2+(aq) + 2H2O(l) + 1/2O2  Fe2O3(s) + 4H+(aq)
i r
Example-23
S
During the discharge of a lead storage battery the density of H2SO4 falls from 1 g/cc to 2 g/
t a
C, H2SO4 of density of 1 g/C. C is X% by weight and that of density of 2 g/c.c is Y% by
weight. The battery holds V litre of acid before discharging. Calculate the total charge released
At anode :
At cathode :
u p
at anode of the battery. The reactions occurring during discharging are.
Pb + SO24  PbSO4 + 2e–
PbO2 + 4H+ + SO42– +2e–  PbSO4 + 2H2O
Solution G
Mass of acid solution before discharge of lead storage battery (LSB) = (V x 103 x 1) g
= (1000 x V1)g
m  X 
Mass of H2SO4 before discharge of LSB = 1000  V1  100  g = (10 x V1 X)g
a  
u p
Net reaction during discharging : Pb + PbO2 + 2H2SO4  PbSO4 + 2H2O
From the reaction, it is evident that the moles of electron exchanged (lost at anode and gain at
cathode) is equal to the moles of H2SO 4 consumed or moles of H2O produced. Let the moles of
A n
H2SO4 produced be x, then
Mass of H2O produced during discharge of LSB = (18x) g
Mass of H2SO4 consumed during discharge of LSB = (98x) g
 Mass of H2SO4 after discharge of LSB = [(10V1 X)] – 98x] g
Mass of acid solution after discharge of LSB = [(1000 V1)– 98x + 18x] = [(1000 V1) – 80x]g
Mass of H2SO4 after disch arg e
 % of H2SO4 after discharge of LSB = Mass of acid solution after disch arg e × 100
[(1000  V1)  98 x ]
Y = [(1000  V )  80 x] x 100 x can be calculated as all other quantities are known.
1
 Total charge released at cathode, Q = nF = xF..
Example-24 A lead storage cell is discharged which causes the H2SO 4 electrolyte to change from a
concentration of 34.6% by weight (density 1.261 g ml–1 at 25°C) to one of 27% by weight. The
original volume of electrolyte is one litre. Calculate the total charge released at anode of the
battery. Note that the water is produced by the cell reaction as H2SO4 is used up. Over all
reaction is.
Pb(s) + PbO2(s) + 2H2SO4()  2PbSO4(s) +2H2O()
ADVECH - 22
Electrochemistry
Solution Before the discharge of lead storage battery,
Mass of solution = 1000 x 1.261 = 1261 g
1261 34.6
Mass of H2SO4 = = 436.3 g.
100
Mass of water = 1261 – 436.3 = 824.7 g
After the discharge of lead storage battery,
Let the mass of H2O produce as a result of net reaction during discharge
(Pb + PbO2 + 2H2SO4  2PbSO4 + 2H2O) is x g
x
 Moles of H2O produced = 18 = moles of H2SO4 consumed
x
Mass of H2SO4 consumed = x 98
18
98 x
Now, mass of solution after discharge = 1261 – +x
18
Mass of H2SO4 left
% by the mass of H2SO4 after discharge = x 100 = 27
Mass of solution after disch arg e
98x
=
436.3 
1261 
18
98x
18
x
x 100 = 27  x = 22.59 g
i r
Summary S
t a
Electrochemistry is the area of chemistry concerned with the interconversion of chemical and electrical
energy. Chemical energy is converted to electrical energy in a galvanic cell, a device in which a spontaneous
p
redox reaction is used to produce an electric current. Electrical energy is converted to chemical energy in an
electrolytic cell, a cell in which an electric current drives a nonspontaneous reaction. It’s convenient and
reduction occur at separate electrodes.
u
G
The electrode at which oxidation occurs is called the anode, and the electrode at which reduction occurs is
called the cathode. The cell potential E (also called the cell voltage or electromotive force is an electrical
measure of the driving force of the cell reaction. Cell potentials depend on temperature, ion concentrations,
a m
and gas pressure. The standard cell are in their standard states. Cell potentials are related to free-energy
changes by the equations G = –nFE and  G0 = –nFE0, where F = 96,500 C/mol e– is the faraday, the
p
charge on 1 mol of electrons.
The standard reduction potential for the a half-reaction is defined relative to an arbitrary value of 0 V for the
u
standard hydrogen electrode (S.H.E.):
A n
2H+ (aq, 1 M ) + 2 e–  H2 (g, 1 atm) E0 = 0V
Tables of standard reduction potentials--- are used to arrange oxidizing and reducing agents in order of
increasing strength, to calculate E0 values for cell reactions, and to decide whether a particular redox reaction
is spontaneous.
Cell potential under nonstandard-state conditions can be calculated using the Nernst equation,
0.0592
E = E0 – log Q in volts, at 250C
n
where Q is the reaction quotient. The equilibrium constant K and the standard cell potential E0 are related by
the equation
0.0592
E0 = log K in volts, at 250 C
n
A battery consists of one or more galvanic cells. A fuel cell differs from a battery in that the reactants are
continuously supplied to the cell. Corrosion of iron (rusting) is an electrochemical process surface and
oxygen is reduced in a cathode region. Corrosion can be prevented by covering iron with another metal, such
as zinc, in the process called galvanizing, or simply by putting the iron in electrical contact with a second
metal that is more easily oxidized, a process called cathodic protection.
ADVECH - 23
Electrochemistry
Electrolysis, the process of using an electric current to bring about chemical change, is employed to
produce sodium, chlorine, sodium hydroxide, and aluminum ( Hall-Heroult process) and is used in
electrorefining and electroplating. The product obtained at an electrode depends on the reduction potentials
and overvoltage. The amount of product obtained is related to the number of moles of electrons passed
through the cell, which depends on the current and the time that the current flows.
Electrochemistry
relates
Electrore fining
Chemical energy Electrical energy and
Batteries electroplating
used in
i r
used in
interconverted in
S
Shorthand
notation
represented
using Galvanic cells
(Voltaic cells)
t a
Electroytic cells
process
called
Electrolysis
having
reaction are
u p reaction are
Spontaneous
G Nonspontaneous
Standard
cell potential, E
o
a m
oxidation-reduction
producing
oxidation-reduction
requiring
related to
u p G = – Electric current G = (+)
1) Free energy
change, G
A
2) Equilibrium
n
constant, K
o
E=+ E = (–)
oxidation half-reaction reducing half-reaction

occurring at the occurring at the
Anode Cathode
calculate from used in
Standard Nernst
reduction equation
potentials
.0592 (Pr oducts) .0592 ( Anodic ion concentrat ion)

E = E° – log  E = E° – log (Cathodic ion concentrat ion)
n (Re ac tan ts) n
ADVECH - 24
Electrochemistry
MISCELLANEOUS SOLVED PROBLEMS (MSPs)
1. Na-amalgam is prepared by electrolysis of NaCl solution using liquid Hg as cathode. How long should the
current of 10 amp. is passed to produce 10% Na – Hg on a cathode of 10 g Hg. (atomic mass of Na = 23).
(A) 7.77 min (B) 9.44 min. (C) 5.24 min. (D) 11.39 min.
Sol. (A)
90 g Hg has 10 g Na
10 10
 10 g Hg = x 10 = g Na
90 9
M ixt
 weight of Na = x
n 96500
10 23 10 x t
= x [ Na+ + e  Na]
9 1 96500
10 x 96500
 t = 9 x 10 x 23 = 7.77 min
2. We have taken a saturated solution of AgBr. Ksp of AgBr is 12 × 10–14 . If 10–7 mole of AgNO3 are added to 1 litre
of this solution then the conductivity of this solution in terms of 10–7 Sm–1 units will be
[Given º(Ag+) = 4 × 10–3 Sm2 mol–1 , º(Br–) = 6 × 10–3 S m2 mol–1 , º(NO –) = 5 × 10–3 Sm2 mol–1]
(A) 39 (B) 55 (C) 15
3
(D) 41
i r
Sol. (A)
The solubility of AgBr in presence of 10–7 molar AgNO3 is 3 × 10–7 M.
Therefore [Br–] = 3 × 10–4 m3, [Ag+] = 4 × 10–4 m3 and [NO3–] = 10–4 m3
S
3.
Therefore total = Br– + Ag+ + NO – = 39 Sm–1
3
t a
A hydrogen electrode X was placed in a buffer solution of sodium acetate and acetic acid in the ratio a : b and
u p
another hydrogen electrode Y was placed in a buffer solution of sodium acetate and acetic acid in the ratio
b : a. If reduction potential values for two cells are found to be E1 and E2 respectively w.r.t. standard hydrogen
electrode, the pKa value of the acid can be given as
(A)
E1  E 2
0.118
(B) –
E1  E 2
0.118
G E1
(C) E  0.118 (D)
E 2  E1
0.118
Sol. (B)
1
a m 2
H+ + e–  H (g)
2 2
E1 = 0 – .0591 log
u p1
A n (H  )1
E1 = 0 + .0591 log [H+]1 = – .0591 pH1
E2 = – .0591 pH2
Salt
pH1 = pka + log
Acid
a
pH1 = pka + log .............. (1)
b
b
pH2 = pka + log
a
a
pH2 = pka – log .............. (2)
b
Add (1) & (2)
pH1 + pH2 = 2 pka
E1 E2  E1  E 2 
2pka = –   pka = –  
0.0591 0.0591  0.118 
ADVECH - 25
Electrochemistry
[Br  ]
4. At what does the following cell have its reaction at equilibrium?
[CO32 ]
Ag(s)  Ag2 CO3(s)  Na2CO3 (aq) KBr(aq) AgBr(s)  Ag(s)
KSP = 8 × 10–12 for Ag2 CO3 and KSP = 4 × 10–13 for AgBr
(A) 1 × 10–7 (B) 2 × 10–7 (C) 3 × 10–7 (D) 4 × 10–7

Sol. (B)
Anode : Ag(s)  Ag+ (aq) + 1e–
Cathode : Ag+ (aq) + 1e–  Ag
––––––––––––––––––––––––––––––––––––
 
1e
net : Ag( AgBr )  Ag( Ag2CO 3 )
 K SP AgBr 
 
 [Br  ]  K SP AgBr K SP Ag2CO 3
0.059  
0=0+
1
log
K SP Ag 2CO3
[CO 23  ]
 
[Br ]
=
[CO32 ]
i r

4  10 13
=
[Br  ]

[Br  ]
= 2 × 10
–7
S
5.
8  10 12 [CO32 ] [CO32 ]
A resistance of 50 is registered when two electrodes are suspended into a

t a
u p
beaker containing a dilute solution of a strong electrolyte such that exactly half of
the them are submerged into solution. If the solution is diluted by adding pure
G
water (negligible conductivity) so as to just completely submerge the electrodes,
the new resistance offered by the solution would be
Sol.
(A) 50 
(A)
1 
(B) 100 
a m (C) 25  (D) 200 
R=
k A
u p
The k is halved while the A is doubled. Hence R remains 50 .
6.
A n
Calculate the cell EMF in mV for
Pt  H2 (1atm)  HCl (0.01 M)  AgCl(s)  Ag(s) at 298 K
if Gf° values are at 25°C
kJ kJ
– 109.56 for AgCl(s) and – 130.79 for (H+ + Cl– ) (aq)
mol mol
(A) 456 mV (B) 654 mV (C) 546 mV (D) None of these
Sol. (A)
G 0cell reaction = 2 (– 130.79) – 2 (– 109.56) = – 42.46 kJ/mole
(for H2 + 2AgCl  2Ag + 2H+ + 2Cl– )

42460
 E0cell = = + 0.220 V
 2  96500
0.059 1
Now Ecell = + 0.220 + log = 0.456 V = 456 mV..
2 (0.01) 4
ADVECH - 26
Electrochemistry
7. Consider the cell Ag(s)|AgBr(s)|Br(aq)||AgCl(s) | Cl(aq)| Ag(s) at 25º C. The solubility product constants of
AgBr & AgCl are respectively 5 x 1013 & 1 x 1010. For what ratio of the concentrations of Br & Cl ions
would the emf of the cell be zero ?
(A) 1 : 200 (B) 1 : 100 (C) 1 : 500 (D) 200 : 1
Sol. (A)
0 0 0.059
EBr 
AgBr Ag = E Ag Ag + log KSP AgBr = E 0Ag Ag
– 0.7257
1
0 0 0.059 0
and E Cl AgCl Ag = E Ag Ag + log KSP AgCl = E Ag Ag – 0.59
1
Now cell reaction is
Ag + Br–  AgBr + 1e–
AgCl + 1e–  Ag + Cl–
–––––––––––––––––––––––––––––––––––
1e
Br– + AgCl  Cl– + AgBr
0.059 [Br  ] [Br  ]

0 = (0.7257-0.59) +
1
log
[Cl ]

[Cl ]
= 0.005
i r
8.
S
The conductivity of a solution may be taken to be directly proportional to the total concentration of the charge
carries (ions) present in it in many cases. Using the above find the percent decrease in conductivity (k) of a
solution of a weak monoacidic base BOH when its 0.1 M solution is diluted to double its original volume. (Kb
Sol.
= 10–5 for BOH)( take 50 = 7.07) (Mark the answer to nearest integer),
Initially [OH–] = 10 5  0.1 = 10

–3
t a
[ions]total = 2 × 10–3 M
1
u p
later [OH ] =– 10 5

20
= 50 × 10 M–4
G


[ions]total = 2 50 × 10–4 M
% change on [ions]total =
a m 2 50  20
× 100 = – 29.29%
Ans. 29
u p 20
9.
A n
At 0.04 M concentration the molar conductivity of a solution of a electrolyte is 5000 –1 cm2 mol–1 while at
0.01 M concentration the value is 5100 –1 cm2 mol–1. Making necessary assumption (Taking it as strong
electrolyte) find the molar conductivity at infinite dilution and also determine the degree of dissociation of
strong electrolyte at 0.04 M.
Sol.
From the graph we can see the M value of 5200 –1 cm2 mol–1.
Hence
5000
= = 0.9615 ~ 0.96
5200
Ans. 96
ADVECH - 27
Electrochemistry
 Marked Questions may have for Revision Questions.
PART - I : SUBJECTIVE QUESTIONS
Section (A) : Galvanic cell, its Representation & salt bridge
Commit to memory :
Notation for Galvanic cell :
 LOAN  left oxidation- Anode-negative
i r
2+ +
S
A-1. In the galvanic cell Cu | Cu || Ag | Ag, the electrons flow from Cu-electrode to Ag-electrode. Answer the
following questions regarding this cell :
(a) Which is the anode ?
(b) Which is the cathode ?
(c) What happens at anode-reduction or oxidation ?
t a
(d) What happens at cathode-oxidation or reduction ?
(e) Which electrode loses mass ?
(f) Which electrode gains mass ?
u p
(g) Write the electrode reactions.
(h) Write the cell reaction G
m
(i) Which metal has greater tendency to loss electron-Cu or Ag ?
(j) Which is the more reactive metal-Cu or Ag ?
a
(k) What is the function of salt bridge represented by the symbol || ?
A-2.
u p
Write cell reaction of the following cells :
(a) Cu Cu2 (aq) Ag (aq) Ag (b) Pt Fe2 ,Fe3 MnO4– , Mn2 ,H Pt
A n
(c) Pt,Cl2 Cl (aq) Ag (aq) Ag (d) Cd Cd2 (aq) H (aq) H2 Pt
A-3. Write cell notation of each cell with following cell reactions :
(a) Zn (s) + 2H+ (aq)  Zn2+ (aq) + H2 (g)
(b) 2 Fe3+ (aq) + Sn2+ (aq)  2Fe2+ (aq) + Sn4+ (aq)
(c) Pb (s) + Br2 (I)  Pb2+ (aq) + 2Br– (aq)
Section (B) : Electrochemical series & its Applications
Commit to memory :
1 1
SRP  Oxidising power  reducing power  Non-metallic character  Metallic character
B-1. The reduction potential values are given below

Al3+/Al = –1.67 volt, Mg2+/Mg = –2.34 volt, Cu2+/Cu = +0.34 volt
2 /¯ = +0.53 volt. Which one is the best reducing agent ?
ADVECH - 28
Electrochemistry
B-2. The standard reduction potential value of the three metallic cations X, Y and Z are 0.52, – 3.03 and – 1.18 V
respectively. Write the decreasing order of reducing power of the corresponding metals :
B-3. (i) Which of the following oxides is reduced by hydrogen ?

MgO, CuO and Na2O
(ii) Which of the following oxides will decompose most easily on heating ?
ZnO, CuO, MgO, and Ag2O
(iii) The value of EºOX for electrode reactions,
Fe  Fe2+ + 2e– Cu  Cu2+ + 2e– and Zn  Zn2+ + 2e–
are 0.444, –0.337 and 0.763 volt respectively. State which of these metals can replace the other two
from the solution of their salts ?
B-4. For the cell reaction 2Ce4+ + Co  2Ce3+ + Co2+

ECell is 1.89 V. If E 2  is – 0.28 V, what is the value of E 4  3  ?
Co |Co Ce |Ce
B-5. Determine the standard reduction potential for the half reaction :
Given
Cl2 + 2e–  2Cl–
Pt2+ + 2Cl–  Pt + Cl2, ECell = – 0.15 V
i r
Pt2+ + 2e–  Pt
B-6. What is ECell if :

E° = 1.20 V
S
2Cr + 3H2O + 3OCl–  2Cr3+ + 3Cl– + 6 OH–
Cr3+ + 3e–  Cr,
t a
E° = – 0.74 V
OCl– + H2O + 2e–  Cl– + 2OH–
Section (C) : Concept of G u p E° = 0.94 V
Commit to memory :
G
a m
Eºcell is an intensive property, so on multiplying or dividing electrode reaction, Eºcell remains same.
Calcualte Eºcell for 3rd reaction with the help of 1st and 2nd reaction using Gº = –nF Eºcell.
Eºtarget =
u
n target
p
n1E1  n 2E 2
where n1 = electrons participating in 1st reaction.
A n n2 = electrons participating in 2nd reaction.

ntarget = electrons participating in target reaction.
  
C-1. If EFe2 |Fe =–0.44 V, EFe3  |Fe2  = 0.77 V. Calculate EFe3  |Fe
C-2. Consider the standard reduction potentials (in volts) as shown in Fig. Find Eº.
 0 .936 1 0 .576
SO 24    SO 32   S 2 O 32 

2
E  ? __________ 
|__________ __________
 1.5 V  1.0 V
C-3. The standard oxidation potentials for Mn3+ ion acid solution are Mn2+  Mn3+   MnO2 . Is the
reaction 2 Mn3+ + 2 H2O  Mn2+ + MnO2 + 4H+ spontaneous under conditions of unit activity ? What is the
change in free energy ?
ADVECH - 29
Electrochemistry
C-4. Using the G0 for the reactions
C + O2  CO2 G0 = 395 kJ / mole,
2Al(l) + 3/2O2  Al2O3(s) G0 = 1269 kJ/mole
Al2O3(s)  Al2O3 (melt) G0 = 16 kJ/mole
Calculate the EMF for the cell reaction
2Al2O3 (melt) + 3C  4Al() + 3CO2(g)
The number of electrons involved in the reaction is 12.
Section (D) : Nernst equation & its Applications (including concentration cells)
Commit to memory :
RT
Nernst equation : Ecell = Eºcell – ln Q
nf
0.0591
At 25ºC, Ecell = Eºcell – log Q
n
where, n = number of transferred electron, Q = reaction quotient.
D-1.
For concentration cell Eºcell = 0
Calculate the oxidation potential of a hydrogen electrode at pH = 1 (T = 298 K).

i r
D-2. Calculate the equilibrium constant for the reaction : S
2+ 4+ 3+
Fe + Ce  Fe + Ce , [Given : 3+ E0Ce4  / Ce3  = 1.61 V;
0
EFe
t a3
/ Fe 2  = 0.77V]
D-3. The standard reduction potential of Cu2+ / Cu couple is 0.34 V at 25°C. Calculate the reduction potential at
pH = 14 for this couple.
(Given : Ksp, Cu (OH)2 = 1.0 × 10–19).
u p
G
D-4. The EMF of the cell M |Mn+ (0.02 M) || H+ (1M) | H2 (g) (1 atm) , Pt at 25°C is 0.81V. Calculate the valency
of the metal if the standard oxidation potential of the metal is 0.76V.
D-5.
m
Consider the following electrochemical cell :
(a) Write a balanced net ionic equation
a
place in the cell.
u p
for the spontaneous reaction that take
A n
(b) Calculte the standard cell potential
Eº for the cell reaction.
(c) If the cell emf is 1.6 V, what is the
concentration of Zn2+ ?
(d) How will the cell potential be affected
if KI is added to Ag+ half-cell ?
D-6. NO3  NO2 (acid medium), E0 = 0.790 V

NO3  NH3OH+ ( acid medium), E0 = 0.731 V..
At what pH, the above two will have same E value? Assume the concentration of all other species NH3OH+
except [H+] to be unity.
D-7. The standard oxidation potential of Zn referred to SHE is 0.76V and that of Cu is –0.34V at 25ºC. When
excess of Zn is added to CuSO4, Zn displaces Cu2+ till equilibrium is reached. What is the approx value of
[ Zn2  ]
log at equilibrium?
[Cu2 ]
ADVECH - 30
Electrochemistry
Section (E) : Electrolysis
Commit to memory :
Higher SOP means higher tendency of oxidation.
Higher SRP means higher tendency of reduction.
SOP order : SO42– < NO3– < Cl– < H2O < Br– < Ag < I– < OH– < Cu....< Li
SRP order : Follow ECS
E-1. ELECTROLYTE ANODE Product CATHODE Product

1 NaCl (Molten) with Pt electrode
2 NaCl (aq) with Pt electrode
3 Na2SO4 (aq) with Pt electrode
4 NaNO3 (aq) with Pt electrode
5 AgNO3 (aq) with Pt electrode
6 CuSO4 (aq) with Inert electrode
7 CuSO4 (aq) with Copper electrode
Section (F) : Faraday laws & its Applictions

i r
Commit to memory : S
Faraday's law of electrolysis :
Ist law W = ZQ =
EQ
t a
Q = it
96500
u p
2nd law
W1 Z1 E1
W2 = Z 2 = E 2 (Q = same) G
a m
actual amount of product
Current efficiency () = theortical amount of product × 100
 EQ  
u p
W actual =  96500  100
F-1.
A n
Find the number of electrons involved in the electrodeposition of 63.5 g of copper from a solution of copper
sulphate is :
F-2. A current 0.5 ampere when passed through AgNO3 solution for 193 sec. deposited 0.108 g of Ag . Find the
equivalent weight of Ag :
F-3. A certain metal salt solution is electrolysed in series with a silver coulometer. The weights of silver and the
metal deposited are 0.5094 g and 0.2653g. Calculate the valency of the metal if its atomic weight is nearly
that of silver.
F-4. 3A current was passed through an aqueous solution of an unknown salt of Pd for 1Hr. 2.977g of Pd+n was
deposited at cathode. Find n. (Given Atomic mass of Pd = 106.4)
F-5. How long a current of 2A has to be passed through a solution of AgNO3 to coat a metal surface of 80cm2 with
5m thick layer? Density of silver = 10.8g/cm3.
ADVECH - 31
Electrochemistry
F-6.^ A certain electricity deposited 0.54g of Ag from AgNO3 Solution. What volume of hydrogen will the same
quantity of electricity liberate at STP (Vm = 22.4 L/mol).
F-7. A current of 3.7A is passed for 6hrs. between Ni electrodes in 0.5L of 2M solution of Ni(NO3)2. What will be
the molarity of solution at the end of electrolysis?
F-8. Cd amalgam is prepared by electrolysis of a solution of CdCl2 using a mercury cathode. How long should a
current of 5A be passed in order to prepare 12% Cd-Hg amalgam when 2 g Hg is used as cathode (atomic
weight of Cd = 112.4)
F-9. Electrolysis of a solution of HSO4– ions produces S2O82–. Assuming 75% current efficiency, what current
should be employed to achieve a production rate of 1 mole of S2O82– per hour ?
Section (G) : Commercial Cells & Corrosion
Commit to memory :
At STP, Vm (molar volume of the gas) = 22.4 L/mol
Volume of gas required at STP = moles of gas × 22.4
many litres of CH4(g) (STP) would be required ? (Vm = 22.4 L/mol) (F = 96500). Assume 100% efficiency.
i r
G-1. A fuel cell uses CH4(g) and forms CO32– at the anode. It is used to power a car with 80 Amp. for 0.96 hr. How
G-2. Find Eº of cell formed for rusting of iron ?

0
E Fe / Fe 2  = +0.44 V
S
EH0 O|O
2 2 |H
 = –1.23 V
t a
Section (H) : Electrical Conductance
u p
Commit to memory :
 1 
G
Conductivity () = C ×

A
=
R
×
A
a m
where,
A
u p
= cell constant, C = conductance, R = resistance.
A = surface area of electrodes,  = distance between electrodes.
A n
Molar conductance (m) =
Equivalent conductance (eq) =

  1000
  1000
M
S cm2 mol–1
S cm2 eq–1
N
where, M = molarity, N = normality and N = M × valence factor
H-1.^ The resistance of a M/10 KCl solution in 245 ohms. Calculate the specific conductance and the molar
conductance of the solution if the electrodes in the cell are 4 cm apart and each having an area of 7.0 sq. cm.
H-2.^ The resistance of a solution 'A' is 50 ohms and that of solution 'B' is 100 ohms, both solutions being taken in
the same conductivity cell. If equal volumes of solution 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.
H-3.^ In a conductivity cell the two platinum electrodes, each of area 10 sq, cm, are fixed 1.5 cm apart. The cell
contained 0.05 M solution of a salt. If the two electrodes are just half dipped into the solution which has a
resistance of 50 ohms, find molar conductance of the salt solution.
ADVECH - 32
Electrochemistry
H-4.^ The equivalent conductance of 0.10 N solution of MgCl2 is 97.1 mho cm2 eq.–1 at 25°C. A cell with electrodes
that are 1.50 cm2 in surface area and 0.50 cm apart is filled with 0.1N MgCl2 solution. How much current will
flow when the potential difference between the electrodes is 5 volts ?
H-5. The specific conductance of a N/10 KCl solution at 18°C is 1.12 × 10–2 mho cm–1. The resistance of the
solution contained in the cell is found to be 65 ohms. Calculate the cell constant.
Section (I) : Kohlrausch law and its applications
Commit to memory :
Kohlrausch law : At infinite dilution, ºm, electrolyte =    ºm +    ºm

where, + = number of cations in one formula unit of electrolyte.
– = number of anions in one formula unit of electrolyte.
At infinite dilution equivalent conductance : ºeq, electrolyte = ºeq+ + ºeq–
m  eq
Degree of dissociation (D.O.D.) =  =  º = 0
m  eq
C 2
i r
For weak electrolyte, dissociation constant (Ka) =
1 
S
, where, C = concentration of electrolyte.
  1000
Solubility (s) =  º
m
and Ksp = S2 for AB type salt.
t a
u p
I-1.^ The molar conductance of an infinitely dilute solution of NH4Cl is 150 and the ionic conductances of OH¯ and
Cl¯ ions are 198 and 76 respectively. What will be the molar conductance of the solution of NH4OH at infinite
G
dilution. If the molar conductance of a 0.01 M solution NH4OH is 9.6, what will be its degree of dissociation?
I-2.^
m
Given the molar conductance of sodium butyrate, sodium chloride and hydrogen chloride as 83, 127 and 426
a
mho cm2 mol–1 at 25°C respectively. Calculate the molar conductance of butyric acid at infinite dilution.
I-3.
u p
Calculate Ka of acetic acid if its 0.05 N solution has equivalent conductance of 7.36 mho cm2 at 25°C.
( CH 3 COOH  390 . 7 ) .
A n
I-4.^ The specific conductance of a saturated solution of AgCl at 25°C after subtracting the specific conductance
of conductivity of water is 2.28 × 10 –6 mho cm –1. Find the solubility product of AgCl at 25°C.
( AgCl  138 .3 mho cm 2 )
Section (J) : Conductometric Titration
Commit to memory :
H+ and OH– ions are highly conducting.
J-1. Draw approximate titration curve for following –

(1) HCl(aq) is titrated with NaOH (2) CH3COOH(aq) is titrated with NaOH
(3) Equimolar mixture of HCl and HCN titrated withNaOH (4) NH4Cl(aq) is titrated withNaOH
ADVECH - 33
Electrochemistry
PART - II : ONLY ONE OPTION CORRECT TYPE

* Marked Questions are having more than one correct option.
Section (A) : Galvanic cell, its Representation & salt bridge
A-1. In a galvanic cell
(A) Chemical reaction produces electrical energy (B) electrical energy produces chemical reaction
(C) reduction occurs at anode (D) oxidation occurs at cathode
A-2. Which of the following is/are function(s) of salt - bridge ?

(A) It completes the electrical circuit with electrons flowing from one electrode to the other through external
wires and a flow of ions between the two compartments through salt - bridge
(B) it minimises the liquid - liquid junction potential
(C) both correct
(D) none of these
A-3. Salt bridge contains :

(A) calomel (B) sugar (C) H2O
r
(D) agar-agar paste
i
A-4. The emf of the cell, Ni | Ni2+ (1.0 M) || Ag+ (1.0M) | Ag [E° for Ni2+ / Ni = – 0.25 volt, E° for Ag+/Ag = 0.80
volt] is given by :
(A) –0.25 + 0.80 = 0.55 volt
(C) 0 + 0.80 – (–0.25) = + 1.05 volt
(B) –0.25 – (+0.80) = –1.05 volt
(D) –0.80 – (–0.25) = – 0.55 volt
S
Section (B) : Electrochemical series & its Applications
t a
(A) 2.8 V (B) 1.4 V
1
B-1. E0 for F2 + 2e  2F– is 2.8 V, E0 for F2 + e  F– is
2
u
(C) – 2.8 V
p (D) – 1.4 V
B-2. Consider the cell potentials E º 2

Mg | Mg G
= – 2.37 V and E º 3 
Fe | Fe
= – 0.04 V. The best reducing agent would be
(A) Mg2+
a m
(B) Fe3+ (C) Mg
B-3. If a spoon of copper metal is placed in a solution of ferrous sulphate -

(D) Fe
u p
(A) Cu will precipitate out
(C) Cu and Fe will precipitate
(B) iron will precipitate
(D) no reaction will take place
n
B-4. The position of some metals in the electrochemical series in decreasing electropositive character is given as
A
Mg > Al > Zn > Cu > Ag. What will happen if a copper spoon is used to stir a solution of aluminium nitrate ?
(A) The spoon will get coated with aluminium (B) An alloy of aluminium and copper is formed
(C) The solution becomes blue (D) There is no reaction
B-5. For Zn2+ / Zn, E° = –0.76 V, for Ag+/Ag E° = 0.799 V. The correct statement is -
(A) the reaction Zn getting reduced Ag getting oxidized is spontaneous
(B) Zn undergoes reduction and Ag is oxidized
(C) Zn undergoes oxidation Ag+ gets reduced
(D) No suitable answer
B-6. Electrode potential data are given below.

Fe3+ (aq) + e–  Fe2+ (aq); E0 = + 0.77
3+ – 
Al (aq) + 3e  Al (s); E0 = – 1.66 V
Br2 (aq) + 2e–  2Br– (aq) ; E0 = + 1.08 V
Based one the data given above, reducing power of Fe2+, Al and Br – will increase in the order :
(A) Br – < Fe2+ < Al (B) Fe2+ < Al < Br – (C) Al < Br – < Fe2+ (D) Al < Fe2+ < Br –
ADVECH - 34
Electrochemistry
B-7. KCl can be used in salt bridge as electrolyte in which of the following cells?
(A) Zn | ZnCl2 || AgNO3 | Ag (B) Pb | Pb(NO3)2 || Cu(NO3)2 | Cu
(C) Cu | CuSO4 || AuCl3 | Au (D) Fe | FeSO4 || Pb(NO3)2 | Pb
B-8. Consider the following Eº values :

0
EFe 3
/ Fe 2  = + 0.77 V ; E 0Sn2  / Sn = – 0.14 V
Under standard conditions the potential for the reaction is

Sn (s) + 2 Fe3+ (aq)  2Fe2+ (aq) + Sn2+ (aq)
(A) 1.68 V (B) 1.40 V (C) 0.91 V (D) 0.63 V
Section (C) : Concept of G

C-1. Given standard electrode potentials :
Fe3+ + 3e¯  Fe ; E° = –0.036 volt
Fe2+ + 2e¯  Fe; E° = –0.440 volt
The standard electrode potential E° for Fe3+ + e¯  Fe2+

(A) –0.476 volt (B) –0.404 volt (C) 0.440 volt
i r
(D) 0.772 volt
C-2. S
Cu+ + e–  Cu, E° = x1 volt; Cu2+ + 2e–  Cu, E° = x2 volt, then for Cu2+ + e–  Cu+, E° (volt)
will be :
(A) x1 – 2x2 (B) x1 + 2x2 (C) x1 – x2

t a (D) 2x2 – x1
true?
u p
C-3. Which of the following statements about the spontaneous reaction occurring in a galvanic cell is always
(A) Eºcell > 0, Gº < 0, and Q < K

(C) Eºcell > 0, Gº > 0, and Q > K G
(B) Eºcell > 0, Gº < 0, and Q > K
(D) Ecell > 0, G < 0, and Q < K
m
Section (D) : Nernst equation & its Applications (including concentration cells)
a
(A) 1.10 volt
u p
D-1. The standard emf for the cell reaction Zn + Cu2+  Zn2+ + Cu is 1.10 volt at 25°C. The emf for the cell
reaction when 0.1 M Cu2+ and 0.1 M Zn2+ solutions are used at 25°C is
(B) 0.110 volt (C) –1.10 volt (D) –0.110 volt
D-2.
A n H2 (Pt ) H3 O  (aq) Ag
Consider the cell 1 atm
pH  5.03 x M

Ag. The measured EMF of the cell is 1.0 V. What is the value of
0
x ? E Ag ,Ag = + 0.8 V. [T = 25°C]
(A) 2 × 10–2 M (B) 2 × 10–3 M (C) 1.5 × 10–3 M (D) 1.5 × 10–2 M
D-3. Zn | Zn2+ (C1)|| Zn2+ (C2)|Zn. for this cell G is negative if -

(A) C1 = C2 (B) C1 > C2 (C) C2 > C1 (D) None
H H H H
D-4. Pt (p21) (1M) (1M) (p22 ) Pt (where p1 and p2 are pressures) cell reaction will be spontaneous if :
(A) p1 = p2 (B) p1 > p2 (C) p2 > p1 (D) p1 = 1 atm
ADVECH - 35
Electrochemistry
D-5. Pt | (H2) | pH = 1 || pH = 2 | (H2)Pt
1 atm 1 atm
The cell reaction for the given cell is :
(A) spontaneous (B) non - spontaneous (C) equilibrium (D) none of these
M
D-6. The EMF of a concentration cell consisting of two zinc electrodes, one dipping into sol. of zinc sulphate
4
M
& the other into sol. of the same salt at 25C is
16
(A) 0.0125 V (B) 0.0250 V (C) 0.0178 V (D) 0.0356 V
Section (E) : Electrolysis

E-1. In an electrolytic cell of Ag/AgNO3/Ag, when current is passed, the concentration of AgNO3
(A) Increases (B) Decreases (C) Remains same (D) None of these
E-2. If 0.224 L of H2 gas is formed at the cathode, the volume of O2 gas formed at the anode under identical
conditions, is
(A) 0.224 L (B) 0.448 L (C) 0.112 L (D) 1.12 L
i r
E-3. The two aqueous solutions, A (AgNO3) and B (LiCl) were electrolysed using Pt. electrodes. The pH of the
resulting solutions will
(A) increase in A and decrease in B
(C) increase in both
(B) decrease in both
(D) decrease in A and increase in B.
S
E-4. In the electrolysis of aqueous CuBr2 using Pt electrodes :
t a
(A) Br2 gas is not evolved at the anode
(B) Cu (s) is deposited at the cathode
(C) Br2 gas is evolved at anode and H2 gas at cathode
u p
(D) H2 gas is evolved at anode.
G
E-5. During electrolysis of CuSO using Pt-electrodes, the pH of solution
(A) increases
(C) remains unchanged
4
a m (B) decreases
(D) cannot be predicted
p
Section (F) : Faraday laws & its Applictions
u
F-2.
(A) 1
A n
F-1. How many faradays are required to reduce one mol of MnO4¯ to Mn2+ -
(B) 2 (C) 3 (D) 5
Three faradays of electricity was passed through an aqueous solution of iron (II) bromide. The mass of iron
metal (at. mass 56) deposited at the cathode is -
(A) 56 g (B) 84 g (C) 112 g (D) 168 g
F-3. A current of 2 A was passed for 1 h through a solution of CuSO4 0.237g of Cu2+ ions were discharged at
cathode. The current efficiency is
(A) 42.2% (B) 26.1% (C) 10% (D) 40.01%
F-4. A current of 9.65 ampere is passed through the aqueous solution NaCl using suitable electrodes for 1000 s.
The amount of NaOH formed during electrolysis is
(A) 2.0 g (B) 4.0 g (C) 6.0 g (D) 8.0 g
F-5. Salts of A (atomic mass 15), B (atomic mass 27) and C (atomic mass 48) were electrolysed using same
amount of charge. It was found that when 4.5 g of A was deposited, the mass of B and C deposited were 2.7g
and 9.6 g. The valencies of A, B and C respectively.
(A) 1, 3 and 2 (B) 3, 1 and 3 (C) 2, 6 and 3 (D) 3, 1 and 2
ADVECH - 36
Electrochemistry
Section (G) : Commercial Cells & Corrosion
G-1. During discharge of a lead storage cell the density of sulphuric acid in the cell :
(A) Increasing (B) decreasing
(C) remians unchanged (D) initially increases but decrease subsequently
G-2. In H2  O2 fuel cell the reaction occuring at cathode is :

(A) 2 H2O + O2 + 4 e  4 OH (B) 2 H2 + O2  2 H2 O (l)
1
(C) H+ + OH  H2O (D) H+ + e  H .
2 2
G-3. Which is not correct method for prevention of iron from Rusting -
(A) Galvanisation (B) Connecting to sacrificial electrode of Mg
(C) Making medium alkaline (D) Making medium acidic
Section (H) : Electrical Conductance

H-1. Which of the following curve represents the variation of M with C for AgNO3 ?
i r
(A) (B) (C)
S(D)
C C
t aC C
H-2. Which has maxmium conductivity :

(A) [Cr(NH3)3 Cl3] (B) [Cr(NH3)4 Cl2]Cl
u p
(C) [Cr(NH3)5Cl]Cl2 (D) [Cr(NH3)6]Cl3
H-3.
G
Resistance of decimolar solution is 50 ohm. If electrodes of surface area 0.0004 m2 each are placed at a
distance of 0.02 m then conductivity of solution is :
(A) 1 s cm–
a m
(B) 0.01 s cm– (C) 0.001 s cm– (D) 10 s cm–
H-4. V1 Litre of solution A (Resistance = 50 ohm) is mixed with V2 Litre of solution B (Resistance = 100 ohm).
u p V2
Resistance of final solution is 80 ohm then V will be (using same cell)
(A) 1
A n (B) 2
Section (I) : Kohlrausch law and its applications

1
(C) 3 (D) 4
I-1. The ionization constant of a weak electrolyte (HA) is 25 × 10–6 while the equivalent conductance of its 0.01
M solution is 19.6 S cm 2 eq –1. The equivalent conductance of the electrolyte at infinite dilution
(in S cm2 eq–1 ) will be
(A) 250 (B) 196 (C) 392 (D) 384
I-2. The conductivity of a saturated solution of BaSO4 is 3.06 × 10–6 ohm–1 cm–1 and its equivalent conductance
is 1.53 ohm–1 cm2 equiv–1. The Ksp for BaSO4 will be
(A) 4 × 10–12 (B) 2.5 × 10–13 (C) 25 × 10–9 (D) 10–6
I-3. Molar conductance of 0.1 M acetic acid is 7 ohm 1 cm2 mol 1. If the molar cond. of acetic acid at infinite
dilution is 380.8 ohm 1 cm2 mol 1, the value of dissociation constant will be :
(A) 226  10 5 mol dm 3 (B) 1.66  10 3 mol dm 1
(C) 1.66  10 2 mol dm 3 (D) 3.442  10 5 mol dm 3
ADVECH - 37
Electrochemistry
I-4. The conductivity of a solution of AgCl at 298 K is found to be 1.382 × 10–6 –1 cm–1. The ionic conductance
of Ag+ and Cl– at infinite dilution are 61.9 –1 cm2 mol–1 and 76.3 –1 cm2 mol–1, respecitvley. The solubility
of AgCl is
(A) 1.4 × 10–5 mol L–1 (B) 1 × 10–2 mol L–1 (C) 1 × 10–5 mol L–1 (D) 1.9 × 10–5 mol L–1
I-5. Molar conductances of BaCl2, H2SO4 and HCl at infinite dilutions are x1, x2 and x3, respectively. Equivalent
conductance of BaSO4 at infinite dilution will be :
[ x1  x 2  x 3 ] [ x1  x 2  x 3 ] [ x1  x 2  2x 3 ]
(A) (B) (C) 2 (x1 + x2 – 2x3) (D)
2 2 2
Section (J) : Conductometric Titration

J-1. 20 ml KOH solution was titrated with 0.2 mol/l H2SO4 solution in conductivity
Conductivity
cell
Concentration of KOH solution was :
(A) 0.3 M
(B) 0.15
(C) 0.12 15 30
(D) None of these 0 Volume of H2 SO 4 (ml)
J-2. Following curve for conductometric titration is obtained when –
i r

S
Conduction
x = Equivalence point
x
t a
(A) NaOH solution is added in to HCl solution
Volume of Solutions 
u p(B) NaOH solution is added in to CH3COOH solution

(C) NH4OH solution is added in to HCl solution
G (D) NH4OH solution is added in to CH3COOH solution
1. Match the column

a m
PART - III : MATCH THE COLUMN
Column I
(A) Zn | Zn+2 | | Mg2+ | Mg
u p Column II
(p) Ecell = 0
c1
A n +2
c2
(B) Zn | Zn | | Ag | Ag+
at. equilibrium
(c1 = c2)
(q) E0cell 0
(C) Ag | Ag+ | | Ag+ | Ag (r) E0cell = +ve

c1 c2 (c1 = c2)
(D) Fe | Fe | | Ag | Ag+
+2
(s) E0cell = –ve
c1 c2 (c1 = c2)
0
2.^ Match Matrix ( E Ag / Ag = 0.8).
Column – I Column – II
+ +
(A) Pt | H2 (0.1 bar) | H (0.1 M) || H (1 M) | H2 (0.01 bar) | Pt (p) Concentration cell
(B) Ag | Ag+ (10–9 M) || Ag+ (10–2 M) | Ag (q) Ecell > 0
2+ 2+
(C) Cu | Cu (0.1 M) || Cu (0.01 M) | Cu (r) Eºcell = 0 but cell is working.
(D) Pt | Cl2 (1bar) | HCl (0.1 M) || NaCl (0.1M) | Cl2 | Pt (1 bar) (s) non working condition
ADVECH - 38
Electrochemistry
 Marked Questions may have for Revision Questions.
PART - I : ONLY ONE OPTION CORRECT TYPE

1. Given : Eº(Cu2+ | Cu) = 0.337 V and Eº (Sn2+ | Sn) = – 0.136 V. Which of the following statements is correct?
(A) Cu2+ ions can be reduced by H2(g) (B) Cu can be oxidized by H+
2+
(C) Sn ions can be reduced by H2(g) (D) Cu can reduce Sn2+
2. Red hot carbon will remove oxygen from the oxide AO and BO but not from MO, while B will remove oxygen
from AO. The activity of metals A, B and M in decreasing order is
(A) A > B > M (B) B > A > M (C) M > B > A (D) M > A > B
AgBr (s), Br ¯ Fe3 , Fe 2

3. What is the emf at 25° C for the cell, Ag , Pt
a  0.34 a  0.1 a  0.02
are + 0.0713 V and + 0.770 V respectively.

i r
The standard reduction potentials for the half-reactions AgBr + e¯  Ag + Br¯ and Fe3+ + e¯  Fe2+
(A) 0.474 volt (B) 0.529 volt (C) 0.356 volt (D) 0.713 volt
S
4.
t a
A hydrogen electrode placed in a buffer solution of CH3COONa and CH3COOH in the ratios of x : y and y : x
has electrode potential values E1 volts and E2 volts, respectively at 25ºC. The pKa values of acetic acid is (E1
and E2 are oxidation potentials)
(A)
E1  E 2
0.118
(B)
E 2  E1
0.118
u p
(C) –
E1  E 2
0.118
(D)
E1  E 2
0.118
5. G
The electrode oxidation potential of electrode M(s)  Mn+(aq) (2M) + ne– at 298 K is E1. When temperature
a m
(in ºC) is doubled and concentration is made half, then the electrode potential becomes E2. Which of the
following represents the correct relationship between E1 and E2 ?
6.
(A) E1 > E2
u p (B) E1 < E2 (C) E1 = E2 (D) Cann’t be predicted
Two weak acid solutions HA1 and HA2 each with the same concentration and having
(A) 0.21 V
n
pKa values 3 and 5 are placed in contact with hydrogen electrode (1 atm, 25ºC) and
are interconnected through a salt bridge. The emf of the cell is :
A (B) 0.059 V (C) 0.018 V (D) 0.021 V
7. Electrolysis of a solution of MnSO4 in aqueous sulphuric acid is a method for the preparation of MnO2.
Passing a current of 27A for 24 hours gives 1kg of MnO2. The current efficiency in this process is :
(A) 100% (B) 95.185% (C) 80% (D) 82.951%
8. During the preparation of H2S2O8 (per disulphuric acid) O2 gas also releases at anode as byproduct, When
9.72 L of H2 releases at cathode and 2.35 L O2 at anode at STP, the weight of H2S2O8 produced in gram is
(A) 87.12 (B) 43.56 (C) 83.42 (D) 51.74
9. When the sample of copper with zinc impurity is to be purified by electolysis, the appropriate electrode are
(A) pure zinc as cathode and pure copper as anode
(B) impure sample as cathode and pure copper as anode
(C) impure zinc as cathode and impure sample as anode
(D) pure copper as cathode and impure sample as anode
ADVECH - 39
Electrochemistry
10. A galvanic cell is composed of two hydrogen electrodes, one of which is a standard one. In which of the
following solutions should the other electrode be immersed to get maximum emf ? Ka(CH3COOH) = 2 × 10–5,
Ka (H3PO4) = 10–3.
(A) 0.1 M HCl (B) 0.1 M CH3COOH (C) 0.1 M H3PO4 (D) 0.1 M H2SO4
11. When iron is rusted, it is :
(A) reduced (B) oxidised (C) evaporated (D) decomposed
12. Which statement is correct.
(A) In SHE, the pressure of dihydrogen gas should be low and pH of solution should be zero.
(B) In the reaction H2O2 + O3  2H2O + 2O2, H2O2 is oxidised to H2O.
(C) The absolute value of electrode potential cannot be determined.
(D) According to IUPAC conventions, the standard electrode potential pertains to oxidation reactions only.
13. Using the standard potential values given below, decide which of the statements I, II, III, IV are correct.
Choose the right answer from (a), (b), (c) and (d)
Fe2+ + 2e– = Fe, Eº = – 0.44 V
2+ –
Cu + 2e = Cu, Eº = + 0.34 V
Ag+ + e– = Ag, Eº = + 0.80 V
I. Copper can displace iron from FeSO4 solution
II. Iron can displace copper from CuSO4 solution
i r
III. Silver can displace Cu from CuSO4 solution
IV. Iron can displace silver from AgNO3 solution S
14.
(A) I and II (B) II and III (C) II and IV
t a (D) I and IV
When the electric current is passed through a cell having an electrolyte, the positive ions move towards
p
cathode and negative ions towards the anode. If the cathode is pulled out of the solution
(A) the positive and negative ions will move towards anode
u
(B) the positive ions will start moving towards the anode while negative ions will stop moving
G
(C) the negative ions will continue to move towards anode while positive ions will stop moving
(D) the positive and negative ions will start moving randomly
15.
m
Four moles of electrons were transferred from anode to cathode in an experiment on electrolysis of water.
a
The total volume of the two gases (dry and at STP) produced will be approximately (in litres)
(A) 22.4
u p (B) 44.8 (C) 67.2
PART - II : SINGLE AND DOUBLE VALUE INTEGER TYPE

(D) 89.4
1.
A n
How many of the following comparisons are correct with respect to their m ?
(A) K  Na  (B) K   H3O  (C) Ca 2  Na 
(D) Mg2  NH4  (E) H3 O   Mg2 (F) K   Mg2

2. m (weak mono basic HA acid) = 390.7 S cm2 mol–1
 m of HA at 0.01 M is 3.907 S cm2 mol–1

Find pH of 0.01 M HA ?
o
3. The conductivity of a solution which is 0.1 M in Ba(NO3)2 and 0.2 M in AgNO3 is 5.3 Sm–1. If (Ag ) = 6 × 10–3 Sm2
o o
mol–1 & (Ba2  ) = 13 × 10–3 Sm2 mol–1, determine (NO3– ) in same unit. Report your answer after multiplying
by 1000.
ADVECH - 40
Electrochemistry
4. H4XeO6 + 2H+ + 2e–  XeO3 + 3H2O Eº = 3 V
F2 + 2e–  2F¯ Eº = 2.87 V
O3 + 2H+ + 2e–  O2 + H2O Eº = 2.07 V
Ce4+ + e–  Ce3+ Eº = 1.67 V
2HClO + 2H+ + 2e–  Cl2 + 2H2O Eº = 1.63 V
ClO4– + 2H+ + 2e–  ClO3– + H2O Eº = 1.23 V
–
ClO¯ + H2O + 2e  Cl¯ + 2OH¯ Eº = 0.89 V
BrO¯ + H2O + 2e–  Br¯ + 2OH¯ Eº = 0.76 V
ClO4– + H2O + 2e–  ClO3– + 2OH¯ Eº = 0.36 V
3– – 4–
[Fe(CN)6] + e  [Fe(CN)6] Eº = 0.36 V
Based on the above data, how many of the following statements are correct ?
(A) F2 is better oxidizing agent than H4X6O6.
(B) Ozone can oxidize Cl2
(C) ClO–4 is better oxidizing agent in basic medium than in acidic medium
(D) Ferrocyanide ion can be easily oxidized by ClO¯, Ce4+, Li+, Br2O¯
(E) ClO¯ can oxidize Br¯ and ClO3– in basic medium
(F) Ce4+ can oxidize Cl2 in acidic medium under standard conditions.
i r
 = 3.4 × 10–6 ohm –1 cm –1 and that of H2O () used is
5. For a saturated solution of AgCl at 25°C,
S
2.02 × 10–6 ohm–1 cm–1. m for AgCl is 138 ohm–1 cm2 mol–1 then the solubility of AgCl in mili moles per m3
will be :
6.
t a
Estimate the cell potential of a Daniel cell having 1.0M Zn++ and originally having 1.0M Cu++ after sufficient
NH3 has been added to the cathode compartment to make NH3 concentration 2.0M at equilibrium. Given Kf
u p
for [Cu(NH3)4]2+ = 1 × 1012, E° for the reaction, Zn + Cu2+  Zn2+ + Cu 1.1V. (Take
2.303 RT
F
= 0.06, log
7.
6.25 = 0.8) Respond as 10  your answer.
G
Molar conductivity of 0.04 MgCl2 solution at 298 k is 200 Scm2mole–1. A conductivity cell which is filled with
a m
MgCl2 have area of cross-section of electrode 4cm2 & distance between electrode is 8 cm. If potential
difference between electrode is 10V then find current flow in miliampere.
8.
u p
At 298 K, the conductivity of pure water is 5.5 × 10–6 S m–1. Calculate the ionic product of water using the
following data : ºm values (in S m2 mol–1) : Ba(OH)2 = 5.3 × 10–2, HCl = 4.25 × 10–2, BaCl2 = 2.8 × 10–2 .
9. n
Does your answer match with experimental value. Write 20 for yes & 40 for No.
A
A hydrogen gas electrode is made by dipping platinum wire in a solution of NaOH of pH = 10 and by passing
hydrogen gas around the platinum wire at one atm pressure. The oxidation potential of electrode is 10x
2.303 RT
milivolt. Find x ? (Take = 0.059)
F
PART - III : ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

   
1. Given E Ag  / Ag = 0.80V, E Mg2 / Mg = –2.37V,, E Cu2 / Cu = 0.34V, E Hg2 / Hg = 0.79 V..
Which of the following statements is/are correct
(A) AgNO3 can be stored in copper vessel (B) Mg(NO3)2 can be stored in copper vessel
(C) CuCl2 can be stored in silver vessel (D) HgCl2 can be stored in copper vessel
2. Any redox reaction would occur spontaneously, if :

(A) the free energy change ( G) is negative (B) the Gº is positive
(C) the cell e.m.f. (Eº) is negative (D) the cell e.m.f. is positive
ADVECH - 41
Electrochemistry
3. On electrolysis, in which of the following, O2 would be liberated at the anode ?
(A) dilute H2SO4 with Pt electrodes (B) aqueous AgNO3 solution with Pt electrodes
(C) dilute H2SO4 with Cu electrodes (D) aqueous NaOH with a Fe cathode & a Pt anode
4. A current of 2.68 A is passed for one hour through an aqueous solution of CuSO4 using copper electrodes.
Select the correct statement(s) from the following :
(A) increase in mass of cathode = 3.174 g
(B) decrease in mass of anode = 3.174 g
(C) no change in masses of electrodes
(D) the ratio between the change of masses of cathode and anode is 1 : 2 .
5. Three moles of electrons are passed through three solutions in succession containing AgNO3, CuSO4, and
AuCl3, respectively. The molar ratio of amounts of cations reduced at cathode will be
1 1 1
(A) 1 : 2 : 3 (B) : : (C) 3 : 2 : 1 (D) 6 : 3 : 2
1 2 3
6. Mark out the correct statement(s) regarding electrolytic molar conductivity.
(A) It increase as temperature increases.
(B) It experiences resistance due to vibration of ion at the mean position.
weak electrolyte.
i r
(C) Increase in concentration decreases the electrolytic molar conductivity of both the strong as well as the
7.
(D) Greater the polarity of solvent, greater is the electrolytic molar conduction.
S
If same quantity of electricity is passed through three electrolytic cells containing FeSO4, Fe2(SO4)3 and
Fe(NO3)3, then
(A) the amount of iron deposited in FeSO4 and Fe2(SO4)3 are equal
t a
(B) the amount of iron deposited in FeSO4 is 1.5 times of the amount of iron deposited in Fe(NO3)3.
u p
(C) the amount of iron deposited in Fe2(SO4)3 and Fe(NO3)3 are equal
(D) the same amount of gas is evolved in all three cases at the anode.
8. When a lead storage battery is discharged then :
(A) SO2 is evolved
(C) sulphuric acid is consumed G
(B) lead sulphate is produced at both electrodes
(D) water is formed
9.
m
Consider an electrolytic cell E being powered by a galvenic cell G, as shown in the
figure. Then :
a
u p
(A) Anode of E is connected to cathode of G
(B) Anode of E is connected to anode of G
A n
(C) Cathode of E is connected to anode of G
(D) Cathode of E is connected to cathode of G
10. On increasing dilution following will increase :

(A) Equivalent conductivity (B) Conductivity
(C) Molar conductivity (D) All of these
11. The resistances of following solutions of KCl were measured using conductivity cells of different cell constants,
at same temperature. (Consider that at concentration less than 0.1 M, the specific conductivity of solution is
directly proportional to the concentration of solution.)
Concentration of Solution Cell Constant
1. 0.1 M 1 cm-1
2. 0.01 M 10 cm-1
3. 0.005 M 5 cm-1
4. 0.0025 M 25 cm-1
Which of the following comparisons between their conductances (G) is/are correct ?
(A) G1 is maximum (B) G4 is minimum (C) G3 >> G2 (D) G4 is maximum
ADVECH - 42
Electrochemistry
12. Identify correct statements :
(A) Kohlraush law is applicable only on weak electrolyte.
(B) On increasing dilution conductance, molar conductivity, equivalent conductivity increases but conductivity
decreases.
K
(C)  m = following formula has units  m   – dm2/mol K   – dm—1 C  mol/
C
(D) equation  m = m  b C is applicable on weak as well as strong electrolyte.
13. Select the correct option(s):
ºeq Al  ºeq SO 

(A)
3
3
= ºm Al  &
3
2
2–
4 º
= m SO 
2–
4
º ºm Al 
3 º ºm SO 2
(B)  eq Al 
3 = &  eq 
SO 24   = 4
3 2
ºm Al 
3 ºm SO  2
(C) ºeq (Al2(SO4) 3) = + 4
(D) ºm (Al2(SO4) 3) = 6 × ºeq (Al2(SO4) 3)

2
i r
14. Which of the following order is correct related to their mobility in solution:

(A) Csaq 
> Rbaq 
> K aq 
> Naaq 
> Liaq 2
(B) Be aq 
> Liaq 
> Csaq
S

(C) Haq 
> Liaq 2
> Be aq 
> Naaq 2
> Mgaq
a 2
(D) Haq > Na aq  > Liaq  > Be aq
t 
15.
o
M = M – AC½
u p
For strong electrolyte M increases slow with dilution and can be represented by the equation
Select correct statement

o
(A) Plot of M against C½ is obtain a straight line with intercept M G
& and slope ‘–A’’
a m
(B) Value of A depends upon temperature solvent and nature of electrolyte.
(C) NaCl and KCl have different value of constant ‘A’
u p
(D) NaCl and MgSO4 have different value of constant ‘A’.
PART - IV : COMPREHENSION
Comprehension # 1
A n
Read the following passage carefully and answer the questions.
If an element can exist in several oxidation states, it is convenient to display the reduction potentials
corresponding to the various half reactions in diagrammatic form, known as Latimer diagram. The Latimer
Diagram for chlorine in acid solution is
ClO4–  1
.20V  ClO – 
 1
.18
V  HClO 
1
.60
V  HClO 1
.67
 V  Cl 1
.36
 V  Cl–
3 2 2
in basic solution.
0.37 V 0.30 V 0.68 V 0.42 V 1.36 V
ClO4–    ClO3–    ClO2–    ClO–    Cl2   Cl–
The standard potentials for two nonadjacent species can also be calculated by using the concept that G°
as an additive property but potential is not an additive property and G° = – nFx0. If a given oxidation state is
a stronger oxidising agent than in the next higher oxidation state, disproportionation can occur. The reverse
of disproportionation is called comproportionation. The relative stabilities of the oxidation state can also be
understood by drawing a graph of G°/F against oxidation state, known as Frost diagram, choosing the
stability of zero oxidation state arbitrarily as zero. The most stable oxidation state of a species lies lowest in
the diagram. Disproportionation is spontaneous if the species lies above a straight line joining its two product
species.
ADVECH - 43
Electrochemistry
1. Which of the following couple have same value of potential at pH = 0 and pH = 14?
ClO 4 ClO2 ClO Cl2

(A) (B) (C) (D)
ClO3 Cl2 Cl2 Cl 
ClO
2. What is the potential of couple at pH = 14 ?
Cl
(A) 1.78 V (B) – 0.94 V (C) 0.89 V (D) – 0.89 V
3. Which of the following statement is correct ?

(A) Cl2 undergoes disproportionation into Cl– and ClO– both at pH = 0 and pH = 14.
(B) Cl2 undergoes disproportionation into Cl– and ClO– at pH = 14 but not at pH = 0.
(C) Cl2 undergoes disproportionation into Cl– and ClO– at pH = 0 but not at pH = 14.
(D) None of these
4. For a hypothetical element, the Frost diagram is shown in figure?

Which of the following oxidation state is least stable?
(A) – 1
(B) 0
(C) + 2
(D) + 3
i r
5. Which of the following statement is correct ? According to Q.4
(A) A+1 undergoes disproportionation into A and A2+.
S
(B) A2+ undergoes disporportionation in A and A3+.
(C) A undergoes comporportionation in A+1 and A–1.
(D) All of the above.
t a
Comprehension # 2
u p
The molar conductance of NaCl varies with the concentration as shown in the following table.
and all values follows the equation
Cm = m – b C
G
Where Cm = molar specific conductance
a m m = molar specific conductance at infinite dilution

C = molar concentration
u
Molar Concentrationp Molar Conductance
A n
of NaCl
4 x 10-4
9 x 10-4
in ohm-1 cm2 mole-1
107
97
16 x 10-4 87
When a certain conductivity cell (C) was filled with 25 x 10–4 (M) NaCl solution. The resistance of the cell was
found to be 1000 ohm. At Infinite dilution, conductance of Cl– and SO4–2 are 80 ohm–1 cm2 mole–1 and 160
ohm–1 cm2 mole–1 respectively.
6. What is the molar conductance of NaCl at infinite dilution ?
(A) 147 ohm–1 cm2 mole–1 (B) 107 ohm–1 cm2s mole–1
–1 2 –1
(C) 127 ohm cm mole (D) 157 ohm–1 cm2 mole–1
7. What is the cell constant of the conductivity cell (C)
(A) 0.385 cm–1 (B) 3.85 cm–1 (C) 38.5 cm–1 (D) 0.1925 cm–1
8. If the cell (C) is filled with 5 x 10–3 (N) Na2SO4 the observed resistance was 400 ohm. What is the molar
conductance of Na2SO4.
(A) 19.25 ohm–1 cm2 mole–1 (B) 96.25 ohm–1 cm2 mole–1
(C) 385 ohm–1 cm2 mole–1 (D) 192.5 ohm–1 cm2s mole–1
ADVECH - 44
Electrochemistry
9. If a 100 mL solution of 0.1M HBr is titrated using a very concentrated solution of NaOH, then the conductivity
(specific conductance) of this solution at the equivalence point will be (assume volume change is negligible
due to addition of NaOH) . Report your answer after multipling it with 10 in Sm–1.
º
[Given (Na ) = 8 × 10–3 Sm2 mol–1 , º(Br  ) = 4 × 10–3 S m2 mol–1]
(A) 6 (B) 12 (C) 15 (D) 24
PART - I : JEE (ADVANCED) / IIT-JEE PROBLEMS (PREVIOUS YEARS)

* Marked Questions are having one or more than one correct options.
1. Standard electrode potential data are useful for understanding the suitability of an oxidant in a redox titration.
Some half cell reactions and their standard potentials are given below : [JEE 2002, 3/84]
MnO4–(aq.) + 8H+(aq.) + 5e–  Mn2+(aq.) + 4H2O() E0 = 1.51 V
Cr2O72–(aq.) + 14H+(aq.) + 6e–  2Cr3+(aq.) + 7H2O() E0 = 1.38 V
3+ – 2+
Fe (aq.) + e  Fe (aq.) E0 = 0.77 V
– –
Cl2(g) + 2e  2Cl (aq.) E0 = 1.40 V
i
Identify the only INCORRECT statement regarding the quantitative estimation of aqueous Fe(NO3)2 :r
2.
(A) MnO4– can be used in aqueous HCl.
–
(C) MnO4 can be used in aqueous H2SO4.
S
(B) Cr2O72– can be used in aqueous HCl.
(D) Cr2O72– can be used in aqueous H2SO4.
Two students use the same stock solution of ZnSO4 and different solutions of CuSO4 to make Daniel cell.
t a
The emf of one cell is 0.03 V higher than the other. The concentration of CuSO4 solution in the cell with
higher emf value is 0.5 M. Find out the concentration of CuSO4 solution in the other cell.

 Given :

2.303 RT
F

 0.06  .

u p [JEE 2003, 2/60]
3. The emf of the cell,

G
Zn | Zn2+(0.01 M) || Fe2+(0.001 M) | Fe
0.32
(A) e 0.0295 a m
at 298 K is 0.2905 V. Then the value of equilibrium constant for the cell reaction is :[JEE 2004, 3/84]
0.32 0.26
(C) 10 0.0295
0.32
10 .059
0
p 10 0295
(B) 0 . (D)
4.
n u
Find the equilibrium constant at 298 K for the reaction :
Cu2+(aq) + In2+(aq) Cu+(aq) + In3+(aq)
[JEE 2004, 4/60]
5. A
Given that EºCu2+ / Cu+ = 0.15 V, EºIn3+ / In+ = – 0.42 V, EºIn2+ / In+ = – 0.40 V.
The half cell reactions for rusting of iron are :

1
2H+ + O + 2e–  H2O; Eº = +1.23 V & Fe2+ + 2e–  Fe ; Eº = – 0.44 V
2 2
Gº (in kJ/mol) for the overall reaction is : [JEE 2005, 3/84]
(A) – 76 (B) – 322 (C) – 122 (D) – 176
Comprehension # 1
Tollen’s reagent is used for the detection of aldehyde. When a solution of AgNO3 is added to glucose with
NH4OH, then gluconic acid is formed.
Ag+ + e–  Ag ; Eºred = 0.8 V
+ –
C6H12O6 + H2O  C6H12O7 (Gluconic acid) + 2H + 2e ; Eºoxd = – 0.05 V
+ –
Ag(NH3)2 + e  Ag(s) + 2NH3 ; Eº = – 0.337 V
RT F
[Use 2.303 × = 0.0592 and = 38.92 at 298 K]
F RT
ADVECH - 45
Electrochemistry
Now answer the following three questions :
6. 2Ag+ + C6H12O6 + H2O  2Ag(s) + C6H12O7 + 2H+
Find ln K of this reaction : [JEE 2006, 5/184]
(A) 66.13 (B) 58.38 (C) 28.30 (D) 46.29
7. When ammonia is added to the solution, pH is raised to 11. Which half-cell reaction is affected by pH and by
how much : [JEE 2006, 5/184]
(A) Eoxd will increase by a factor of 0.65 for Eºoxd (B) Eoxd will decrease by a factor of 0.65 for Eºoxd
(C) Ered will increase by a factor of 0.65 for Eºred (D) Ered will decrease by a factor of 0.65 for Eºred
8. Ammonia is always is added in this reaction. Which of the following must be INCORRECT :
(A) NH3 combines with Ag+ to form a complex. [JEE 2006, 5/184]
(B) Ag(NH3)2+ is a weaker oxidising reagent than Ag+.
(C) In absence of NH3, silver salt of gluconic acid is formed.
(D) NH3 has affected the standard reduction potential of glucose/gluconic acid electrode.
9. We have taken a saturated solution of AgBr. Ksp of AgBr is 12 × 10–14. If 10–7 mole of AgNO3 are added to 1
litre of this solution, find conductivity (specific conductance) of this solution in terms of 10–7 Sm–1.
Given : º(Ag+) = 6 × 10–3 Sm2mol–1, º(Br–) = 8 × 10–3 Sm2mol–1, º(NO –) = 7 × 10–3 Sm2mol–1.
Comprehension # 2
3
r
[JEE 2006, 6/184]
i
S
Chemical reactions involve interaction of atoms and molecules. A large number of atoms/molecules
(approximately 6.023 × 1023) are present in a few grams of any chemical compound varying with its
atomic/molecular masses. To handle such large number conveniently, the mole concept was introduced.
t a
This concept has implications in diverse areas such as analytical chemistry, biochemistry, electrochemistry
and radiochemistry. The following example illustrates a typical case, involving chemical/electrochemical
reaction, which requires a clear understanding of the mole concept.
the evolution of chlorine gas at one of the electrodes.

u p
A 4.0 molar aqueous solution of NaCl is prepared and 500 mL of this solution is electrolysed. This leads to
10.
G
(Given : Atomic masses : Na = 23, Hg = 200 ; 1 Faraday = 96500 coulombs)
Now answer the following three questions :
The total number of moles of chlorine gas evolved is : [JEE 2007, 4/162]
11.
(A) 0.5 (B) 1.0
a m (C) 2.0 (D) 3.0

If the cathode is Hg electrode, the maximum weight (in g) of amalgam formed from this solution is :
(A) 200
u p (B) 225 (C) 400 (D) 446
[JEE 2007, 4/162]
12.
(A) 24125
Comprehension # 3
n
The total charge (in coulombs) required for complete electrolysis is :
A (B) 48250 (C) 96500

[JEE 2007, 4/162]
(D) 193000
Redox reactions play a pivoted role in chemistry and biology. The values of standard redox potential (Eº) of
two half-cell reactions decide which way the reaction is expected to proceed. A simple example is a Daniel
cell in which zinc goes into solution and copper gets deposited. Given below is a set of half-cell reactions
(acidic medium) along with their Eº values with respect to normal hydrogen electrode. Using this data, obtain
the correct explanations to questions 13 - 14.
I2 + 2e–  2I– Eº = 0.54 V
– –
Cl2 + 2e  2Cl Eº = 1.36 V
3+ – 2+
Mn + e  Mn Eº = 1.50 V
Fe3+ + e–  Fe2+ Eº = 0.77 V
+ –
O2 + 4H + 4e  2H2O Eº = 1.23 V
13. Among the following, identify the correct statement : [JEE 2007, 4/162]
2+
(A) Chloride ion is oxidised by O2 (B) Fe is oxidised by iodine
(C) Iodine ion is oxidised by chlorine (D) Mn2+ is oxidised by chlorine
ADVECH - 46
Electrochemistry
14. While Fe3+ is stable, Mn3+ is not stable in acid solution, because : [JEE 2007, 4/162]
(A) O2 oxidises Mn2+ to Mn3+ (B) O2 oxidises both Mn2+ to Mn3+ and Fe2+ to Fe3+
(C) Fe3+ oxidises H2O to O2 (D) Mn3+ oxidises H2O to O2
15. Electrolysis of dilute aqueous NaCl solution was carried out by passing 10 milliampere current. The time
required to liberate 0.01 mole of H2 gas at the cathode is : (1 Faraday = 96500 C) [JEE 2008, 3/163]
(A) 9.65 × 104 sec (B) 19.3 × 104 sec (C) 28.95 × 104 sec (D) 38.6 × 104 sec
16.* For the reduction of NO3– ion in an aqueous solution, Eº is +0.96 V. Values of Eº for some metal ions are
given below :
V2+(aq) + 2e–  V Eº = –1.19 V
3+ – 
Fe (aq) + 3e Fe Eº = –0.04 V
Au3+(aq) + 3e–  Au Eº = +1.40 V
2+ – 
Hg (aq) + 2e Hg Eº = +0.86 V
The pair(s) of metals that is(are) oxidized by NO3– in aqueous solution is(are) : [JEE 2009, 4/160]
(A) V and Hg (B) Hg and Fe (C) Fe and Au (D) Fe and V
Comprehension # 4
r
The concentration of potassium ions inside a biological cell is at least twenty times higher than the outside.
The resulting potential difference across the cell is important in several processes such as transmission of
i
nerve impulses and maintaining the ion balance. A simple model for such a concentration cell involving a
metal M is :
M(s) | M+(aq ; 0.05 molar) || M+(aq ; 1 molar) | M(s) S
For the above electrolytic cell, the magnitude of the cell potential is | Ecell | = 70 mV.
17.
Now answer the following two questions :
For the above cell :
t a [JEE 2010, 3/163]
18.
(A) Ecell < 0 ; G > 0 (B) Ecell > 0 ; G < 0
u p
(C) Ecell < 0 ; Gº > 0 (D) Ecell > 0 ; Gº < 0
If the 0.05 molar solution of M+ is replaced by a 0.0025 molar M+ solution, then the magnitude of the cell
potential would be :
(A) 35 mV (B) 70 mV G (C) 140 mV
[JEE 2010, 3/163]
(D) 700 mV
19.
a m
AgNO3(aq.) was added to an aqueous KCl solution gradually and the conductivity of the solution was
measured. The plot of conductance () versus the volume of AgNO3 is : [JEE 2011, 3/180]
u p
A n
(A) (P) (B) Q (C) (R) (D) (S)
20. Consider the following cell reaction : [JEE 2011, 3/180]
+ 2+
2Fe (s) + O2 (g) + 4H (aq)  2Fe (aq) + 2H2O (l) Eº = 1.67 V
2.303 R (298)
At [Fe2+] = 10–3 M, P(O2) = 0.1 atm and pH = 3, the cell potential at 25ºC is : (Take = 0.06)
F
(A) 1.47 V (B) 1.77 V (C) 1.87 V (D) 1.57 V
ADVECH - 47
Electrochemistry
Comprehension # 5
The electrochemical cell shown below is a concentration cell.
M|M2+ (saturated solution of a sparingly soluble salt,MX2)|| M2+ (0.001 mol dm–3) |M
The emf of the cell depends on the difference in concetration of M2+ ions at the two electrodes. The emf of the
cell at 298 is 0.059 V
21. The solubility product (Ksp ; in mol3 dm–9) of MX2 at 298 K based on the information available in the given
concentration cell is : (Take 2.303× R × 298/F = 0.059 V) [IIT-JEE 2012, 3/66]
(A) 1 × 10–15 (B) 4 × 10–15 (C) 1 × 10– 12 (D) 4 × 10–12
22. The value of G (in kJ mol–1) for the given cell is : (Take 1F = 96500 C mol–1 ) [IIT-JEE 2012, 3/136]
(A) – 5.7 (B) 5.7 (C) 11.4 (D) –11.4
23. An aqueous solution of X is added slowly to an aqueous solution of Y as shown in list I. The variation in
conductivity of these reactions is given in List II. Match List I with List II and select the correct answer using
the code given below the lists : [JEE(Advanced) 2013, 3/120]
List I List II
P. (C2H5)3N + CH3COOH 1. Conductivity decreases and then
X Y increases
Q. KI (0.1M) + AgNO3(0.01M) 2. Conductivity decreases and then
R.
X
CH3COOH + KOH
X
Y
Y
3.
does not change much
i
Conductivity increases and then
does not change much
r
S. NaOH + HI
X Y
4.
S
Conductivity does not change much
and then increases
Codes :
(A)
P
3
Q
4
R
2
S
1 (B)
P
4
t a Q
3
R
2
S
1
24.
(C) 2 3 4 1 (D)
u p
The standard reduction potential data at 25ºC is given below.
1 4 3 2
[JEE(Advanced) 2013, 3/120]
Eº (Fe3+.Fe2+) = + 0.77 V ;
Eº (Fe2+.Fe) = – 0.44 V ;
Eº (Cu2+.Cu) = + 0.34 V ;
G
Eº (Cu+.Cu) = + 0.52 V ;
a m
Eº (O2(g) + 4H+ + 4e–  2H2O) = + 1.23 V ;
Eº (O2(g) + 2H2O + 4e–  4OH) = + 0.40 V
u p
Eº (Cr3+.Cr) = – 0.74 V ;
Eº (Cr2+.Cr) = – 0.91 V
P.
n
Match Eº of the rebox pair in List I with the values given in List II and select the correct answer using the code
given below the lists :
AList I
Eº (Fe3+, Fe)
List II
1. – 0.36 V
Q. Eº (4H2O 4H+ + 4OH–) 2. –0.4 V
R. Eº (Cu2+ + Cu  2Cu+) 3. –0.04 V
S. Eº(Cr3+, Cr+2) 4. –0.83 V
Codes :
P Q R S P Q R S
(A) 4 1 2 3 (B) 2 3 4 1
(C) 1 2 3 4 (D) 3 4 1 2
25. In a galvanic cell, the salt bridge [JEE(Advanced) 2014, 3/120]
(A) does not participate chemically in the cell reaction.
(B) stops the diffusion of ions from one electrode to another.
(C) is necessary for the occurrence of the cell reaction.
(D ensures mixing of the two electrolytic solutions.
ADVECH - 48
Electrochemistry
26. All the energy released from the reaction X  Y, rGº = – 193 kJ mol–1 is used for oxidizing M+ as M+  M3+
+ 2e– , Eº = – 0.25 V.
Under standard conditions, the number of moles of M+ oxidized when one mole of X is converted to Y is
[F = 96500 C mol–1] [JEE(Advanced) 2015, 4/168]
27. The molar conductivity of a solution of a weak acid HX (0.01 M) is 10 times smaller than the molar
0 0
conductivity of a solution of a weak acid HY (0.10 M). If  X–   Y – , the difference in their pKa values,
pKa (HX) – pKa (HY), is (consider degree of ionization of both acids to be <<1)
[JEE(Advanced) 2015, 4/168]
PART - II : JEE (MAIN) / AIEEE PROBLEMS (PREVIOUS YEARS)

1. For the following cell with hydrogen electrodes at two different pressure p1and p2,
Pt | H2(g) | H+(aq) | H2 (g) | Pt
p1 1M p2
emf is given by : [AIEEE 2002, 3/225]
(1)
RT
F
p
log e 1
p2
(2)
RT
2F
p
log e 1
p2
(3)
RT
F
p
log e 2
p1
(4)
RT
2F
i r p
log e 2
p1
2. Which of the following reactions is possible at anode :

(1) 2 Cr3+ + 7H2O Cr2O72– + 14H+ (2) F2 2F– S [AIEEE 2002, 3/225]
(3)
1
O + 2H+  H2O
2 2
a
(4) displacement reaction
t
3. For a cell given below :
Ag | Ag+ || Cu2+ | Cu
– +
u p [AIEEE 2002, 3/225]
Ag+ + e–  Ag
Cu2+ + 2e–  Cu,
The value of Eºcell is :
G
Eº = x
Eº = y
4.
(1) x + 2y (2) 2x + y
a m (3) y –x (4) y – 2x
Conductance (with unit Siemens S) is directly proportional to area of the electrode plates and the concentration
(1) Sm mol–1.
u p
of the solution in the cell and is inversely proportional to the separation between the electrode plates. Then
the unit of the constant of proportionality is :
(2) Sm2 mol–1. (3) S–2m2 mol.
[AIEEE 2002, 3/225]
(4) S2m2 mol–1.
5.
n
For a cell reaction involving a two electron change, the standard emf of the cell is found to be 0.295 V at 25°C.
A
The equilibrium constant of the reaction at 25°C will be :
(1) 1 × 10–10 (2) 29.5 × 10–2 (3) 10
[AIEEE 2003, 3/225]
(4) 1 × 1010
6. Standard electrode potentials of three metals A, B and C are + 0.5 V, – 3.0 V and – 1.2 V respectively. The
reducing power of these metals is in the order : [AIEEE 2003, 3/225]
(1) B > C > A (2) A > B > C (3) C > B > A (4) A > C > B
7. Consider the following E0 values :
E0 3  2 = + 0.77 V ; E0 2 = – 0.14 V
Fe / Fe Sn / Sn
Under standard conditions, the cell potential for the reaction given below is : [AIEEE 2004, 3/225]
Sn(s) + 2Fe3+(aq)  2Fe2+(aq) + Sn2+(aq)
(1) 1.68 V (2) 1.40 V (3) 0.91 V (4) 0.63 V
8. The limiting molar conductivities º for NaCl, KBr and KCl are 126, 152 and 150 S cm2 mol–1 respectively. The
value of º for NaBr is : [AIEEE 2004, 3/225]
2 –1 2 –1 2 –1
(1) 128 S cm mol (2) 176 S cm mol (3) 278 S cm mol (4) 302 S cm2 mol–1
ADVECH - 49
Electrochemistry
9. In a cell that utilizes the reaction Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g),
addition of H2SO4 to cathode compartment will : [AIEEE 2004, 3/225]
(1) lower the E and shift equilibrium to the left.
(2) lower the E and shift the equilibrium to the right.
(3) increase the E and shift the equilibrium to the right.
(4) increase the E and shift the equilibrium to the left.
0
10. The EM3  / M2  values for Cr, Mn, Fe and Co are – 0.41, + 1.57, + 0.77 and + 1.97 V respectively. For which
one of these metals, the change in oxidation state from +2 to +3 is easiest : [AIEEE 2004, 3/225]
(1) Cr (2) Mn (3) Fe (4) Co
11. The highest electrical conductivity among the following aqueous solutions is of : [AIEEE–2005, 3/225]
(1) 0.1 M acetic acid (2) 0.1 M chloroacetic acid
(3) 0.1 M fluoroacetic acid (4) 0.1 M difluoroacetic acid
12. Aluminium oxide may be electrolysed at 1000ºC to furnish aluminium metal (At.Mass of Al = 27 amu ;
1 Faraday = 96,500 Coulombs). The cathode reaction is Al3+ + 3e–  Al0. To prepare 5.12 kg of aluminium
metal by this method, one would require : [AIEEE–2005, 3/225]
(1) 5.49 × 107 C of electricity (2) 1.83 × 107 C of electricity
13.
(3) 5.49 × 104 C of electricity (4) 5.49 × 1010 C of electricity
i r
The molar conductivities 0NaOAc and 0HCl at infinite dilution in water at 25°C are 91.0 and 426.2 Scm2/mol
respectively. To calculate 0HOAc , the additional value required is :

S [AIEEE–2006, 3/165]
14.
0
(1) H2O
Given data is at 25°C :

(2) 0KCl (3) 0NaOH
t a (4) 0NaCl
Ag + – Ag + e– ; E° = 0.152 V
Ag Ag+ + e– ; E° = – 0.800 V
u p
What is the value of log Ksp for AgI :
(1) – 8.12 (2) + 8.612
G
(Take
0.474
0.059
= 8.065)
(3) – 37.83
[AIEEE–2006, 3/165]
(4) – 16.13
15.
a m
Resistance of a conductivity cell filled with a solution of an electrolyte of concentration 0.1 M is 100 . The
conductivity of this solution is 1.29 Sm–1. Resistance of the same cell when filled with 0.02 M of the same
u p
solution is 520 . The molar conductivity of 0.02 M solution of the electrolyte will be : (Take
129
520
= 0.248)
A n
(1) 124 × 10–4 Sm2mol–1
(3) 1.24 Sm2mol–1
(2) 1240 × 10–4 Sm2mol–1
(4) 12.4 × 10–4 Sm2mol–1
[AIEEE–2006, 3/165]
16. The equivalent conductances of two strong electrolytes at infinite dilution in H2O (where ions move freely
through a solution) at 25°C are given below : [AIEEE–2007, 3/120]
0CH = 91.0 Scm2/equiv and 0HCl = 426.2 Scm2/equiv
3COONa
What additional information/quantity one needs to calculate º of an aqueous solution of acetic acid :
(1) The limiting equivalent conductance of H+ (H  ) (2) º of chloroacetic acid (ClCH2COOH)
(3) º of NaCl (4) º of CH3COOK
17. The cell Zn | Zn2+(1M) || Cu2+(1M) | Cu : (E°cell = 1.10V) was allowed to completely discharge at 298 K. The
 Zn2  
    1 .1
2+
relative concentration of Zn to Cu 2+   is : (Take = 18.65) [AIEEE–2007, 3/120]
 Cu2   0.059
 
 
 
(1) 1037.3 (2) 9.65 × 104 (3) antilog (24.08) (4) 37.3
ADVECH - 50
Electrochemistry
0 0
18. Given : ECr 3  / Cr = – 0.72, EFe2 / Fe = – 0.42 V
2.303 R ( 298 )
The potential for the cell Cr | Cr3+(0.1 M) || Fe2+(0.01 M) | Fe at 298 K is : (Take = 0.06)
F
[AIEEE–2008, 3/105]
(1) 0.339 V (2) – 0.339 V (3) – 0.26 V (4) 0.26 V
0 0
19. Given : EFe3  / Fe = – 0.036 V, EFe2  / Fe = – 0.439 V [AIEEE 2009, 8/144]
3 2
The value of standard electrode potential for the change, Fe(aq) + e–  Fe(aq) will be :
(1) 0.385V (2) 0.770V (3) –0.270V (4) –0.072V
20. The Gibbs energy for the decomposition of Al2O3 at 500ºC is as follows :
2 4
Al O  Al + O2 ; rG = + 966 kJmol–1. The potential difference needed for electrolytic reduction of Al2O3
3 2 3 3
at 500ºC is at least : [AIEEE 2010, 4/144]
(1) 4.5 V (2) 3.0 V (3) 2.5 V (4) 5.0 V
21. The reduction potential of hydrogen half-cell will be negative, if : [AIEEE 2011(1), 4/120]
+
(1) p(H2) = 1 atm and [H ] = 2.0 M
(3) p(H2) = 2 atm and [H+] = 1.0 M
+
(2) p(H2) = 1 atm and [H ] = 1.0 M
(4) p(H2) = 2 atm and [H+] = 2.0 M
i r
22.
The reaction X + Y2+  X2+ + Y will be spontaneous, when : S
The standard reduction potentials for Zn2+/Zn, Ni2+/Ni and Fe2+/Fe are –0.76, – 0.23 and –0.44 V respectively.
[AIEEE 2012, 4/120]
23.
(1) X = Ni, Y = Fe
0
(2) X = Ni, Y = Zn
0
(3) X= Fe, Y = Zn
Given : E Cr 3 / Cr = –0.74 V ; EMnO  / Mn2  = 1.51 V

t a(4) X= Zn, Y = Ni
E0
Cr2O72  / Cr 3 
4
0
= 1.33 V ; E Cl / Cl = 1.36 V
u p
(1) Cl (2) Cr3+ G
Based on the data given above, strongest oxidising agent will be :
(3) Mn2+
[JEE(Main) 2013, 4/120]
(4) MnO4–
24.
m
Resistance of 0.2 M solution of an electrolyte is 50 . The specific conductance of the solution is 1.4 S m–1. The
resistance of 0.5 M solution of the same electrolyte is 280 . The molar conductivity of 0.5 M solution of the
electrolyte in S m2 mol–1 is :
a [JEE(Main) 2014, 4/120]
25.
(1) 5  10–4
u p (2) 5  10 –3 (3) 5  103 (4) 5  102

The equivalent conductance of NaCl at concentration C and at infinite dilution are C and , respectively.
A n
The correct relationship between C and  is given as : (where the constant B is positive)
(1) C =  + (B)C (2) C =  – (B)C (3) C =  – (B) C

[JEE(Main) 2014, 4/120]
(4) C =  + (B) C
26. The metal that cannot be obtained by electrolysis of an aqueous solution of its salts is :
[JEE(Main) 2014, 4/120]
(1) Ag (2) Ca (3) Cu (4) Cr
27. Given below are the half-cell reactions : [JEE(Main) 2014, 4/120]
Mn2+ + 2e¯ Mn ; Eº = –1.18 V
2(Mn3+ + e¯  Mn2+) ; Eº = +1.51 V
The Eº for 3Mn2+  Mn + 2Mn3+ will be :
(1) –2.69 V ; the reaction will not occur (2) –2.69 V ; the reaction will occur
(3) –0.33 V ; the reaction will not occur (4) –0.33 V ; the reaction will occur
28. Two Faraday of electricity is passed through a solution of CuSO4. The mass of copper deposited at the
cathode is : (at. mass of Cu = 63.5 amu) [JEE(Main) 2015, 4/120]
(1) 0 g (2) 63.5 g (3) 2 g (4) 127 g
29. Galvanization is applying a coating of : [JEE(Main) 2016, 4/120]
(1) Cr (2) Cu (3) Zn (4) Pb
ADVECH - 51
Electrochemistry
EXERCISE - 1
PART - I
A-1. (a) Cu (b) Ag
(c) oxidation (d) reduction
(e) Cu (f) Ag
(g) anode-Cu  Cu + 2e ; cathode-Ag+ + e–  Ag
2+ –
(h) Cu + 2Ag+  Cu2+ + 2Ag (i) Cu

(j) Cu (k) to complete circuit and maintain electrical neutrality in solution
A-2. (a) 2Ag+ + Cu  2Ag + Cu2+ (b) 8H  MnO 4–  5Fe 2  5Fe 3  Mn 2   4H2O
(c) 2Ag   2Cl –  2 Ag  Cl2 (d) Cd  2H  Cd2  H2
A-3.
2 
(a) Zn Zn H H2 Pt
2 4 3 2
(b) Pt Sn , Sn Fe ,Fe Pt
2 –
(c) Pb Pb Br Br2 Pt
i r
B-1.
B-3.
Mg B-2. Y>Z>X
(i) CuO : Cu is below hydrogen in series, so it can reduce from CuO to Cu. S
(ii) Ag2O : Lower in series stability of oxide become lesser.
t a
(iii) Lower S.R.P. metal can displace higher S.R.P. metals ions from solution.
B-4.
C-2.
1.61 V
0.756 V
B-5.
C-3.
1.35 V B-6.
Spontaneous,  48250 J
u p
1.68 V C-1.
C-4.
– 0.036 V
1.14 volt
D-1. 0.059 volt D-2. 1014
G
D-3. – 0.2214 V D-4. n=2
D-5.
(b) 1.56 V
a m
(a) The spontaneous cell reaction : Zn + 2Ag+ (aq)
(c) [Zn2+] = 4 × 10–4 M
Zn2+ (aq) + 2Ag (s)
(d) As we add KI to cathode chamber, some Ag+ will precipitate out as :
u p
Ag+ + I–  AgI
The above reaction reducing [Ag+] from cathode chamber. This will reduce Ecell according to Nernst’s equation.
D-6. pH = 1.5.
A n
ELECTROLYTE
D-7. log [Zn2+] / [Cu2+] = 37.22
ANODE Product CATHODE Product

E-1.
1 NaCl (Molten) with Pt electrode Cl2(g) Na
2 NaCl (aq) with Pt electrode Cl2(g) H2(g)
3 Na2SO4 (aq) with Pt electrode O2(g) H2(g)
4 NaNO3 (aq) with Pt electrode O2(g) H2(g)
5 AgNO3 (aq) with Pt electrode O2(g) Ag
6 CuSO4 (aq) with Inert electrode O2(g) Cu
7 CuSO4 (aq) with Copper electrode Cu dissolve Cu
F-1. 12.04 x 1023 F-2. 108. F-3. 2 F-4. n=4

F-5. t = 193 sec. F-6.^ v(H ) = 56.0 mL. F-7. Ni2+ = 2M F-8. t = 93.65 sec.
2
F-9.  71.5 amp G-1. 8 G-2. 1.67 V
ADVECH - 52
Electrochemistry
H-1.^ 2.332 × 10–3 mho cm–1, 23.32 mho cm2 mol–1. H-2.^ R = 66.67 ohms
H-3.^ 120 mho cm2 mol–1 H-4.^ 0.1456 amp H-5. 0.728 cm–1. I-1.^ 272, 0.0353
I-2.^ 382 mho cm2 mol–1. I-3. 1.76 × 10–5 mole/litre.
I-4.^ 2.70 × 10–10 (mole/litre)2.

Conductance
Conductance
J-1. (1) (2)
Volume of NaOH Volume of NaOH

Conductance
(3) (4)
i r
Volume of NaOH
PART - II
S
A-1. (A) A-2. (C) A-3. (D)
t a A-4. (C) B-1. (A)
B-2.
B-7.
(C)
(C)
B-3.
B-8.
(D)
(C)
B-4.
C-1.
u p
(D)
(D)
B-5.
C-2.
(C)
(D)
B-6.
C-3.
(A)
(D)
D-1.
D-6.
(A)
(C)
D-2.
E-1.
(A)
(C) G
D-3.
E-2.
(C)
(C)
D-4.
E-3.
(B)
(C)
D-5.
E-4.
(B)
(B)
E-5.
F-5.
(B)
(C)
F-1.
G-1.
(D)
(B)
a m F-2.
G-2.
(B)
(A)
F-3.
G-3.
(C)
(D)
F-4.
H-1.
(B)
(A)
H-2.
I-3.
(D)
(D)
u p
H-3.
I-4.
(B)
(C)
H-4.
I-5.
(C)
(D)
I-1.
J-1.
(C)
(A)
I-2.
J-2.
(D)
(C)
1. A n
(A - s) ; (B - p,r) ; (C - p,q) ; (D - r)
PART - III
2.^ (A - p, q, r) ; (B - q) ; (C - p, s) ; (D - p, s)
EXERCISE - 2
PART - I
1. (A) 2. (C) 3. (D) 4. (A) 5. (B)
6. (B) 7. (B) 8. (B) 9. (D) 10. (B)

11. (B) 12. (C) 13. (C) 14. (D) 15. (C)
PART - II
1. 4 2. 4 3. 7 4. 2 5. 10
6. 7 7. 40 8. 20 9. 59
ADVECH - 53
Electrochemistry
PART - III
1. (B,C) 2. (A,D) 3. (A,B,D) 4. (A,B) 5. (B,D)
6. (A,C,D) 7. (B,C,D) 8. (B,C,D) 9. (A,C) 10. (A,C)
11. (A,B) 12. (B,C) 13. (B,C,D) 14. (A,D)
15. (A,B,D)
PART - IV
1. (D) 2. (C) 3. (B) 4. (D) 5. (A)
6. (C) 7. (D) 8. (D) 9. (B)
EXERCISE - 3
PART - I
1. (A) 2. 0.05 M 3. (B) 4. KC = 1010 5. (B)
6.
11.
(B)
(D)
7.
12.
(A)
(D)
8.
13.
(D)
(C)
9.
14.
55 S m–1
(D)
i r 10.
14.
(B)
(B)
16.* (A,B,D) 17. (B) 18. (C) 19. S(D) 20. (D)
21.
26.
(B)
(4)
22.
27.
(D)
(3)
23. (A)
t a 24. (D) 25. (A)
1. (2) 2. (1)
PART - II
3.
u p
(3) 4. (2) 5. (4)
6. (1) 7. (3) 8.G (1) 9. (3) 10. (1)
11.
16.
(4)
(3)
12.
17.
(1)
(1)
a m 13.
18.
(4)
(4)
14.
19.
(4)
(2)
15.
20.
(1)
(3)
21.
26.
(3)
(2)
22.
u
27.p (4)
(1)
23.
28.
(4)
(2)
24.
29.
(1)
(3)
25. (3)
A n
ADVECH - 54

Electrochem TheoryExercise 1653476390832

Uploaded by

Copyright:

Available Formats

Electrochem TheoryExercise 1653476390832

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Electrochem TheoryExercise 1653476390832

Uploaded by

Copyright:

Available Formats

Electrochemistry

Galvanic cells or Voltaic cell

and the liquid phase.

Figure : 1 Figure : 2 Figure : 3

Functions of Salt Bridge :

 If the salt bridge is removed then voltage drops to zero. S

Oxidation Potential (O.P.) : Reduction Potential (R.P.)

Type of Electrode Electrode reaction in standard condition Representation

(Zn electrode, Oxidation : Zn(s)  Zn2+ + 2e– E 0Zn( s) / Zn2 (SOP)

electrode Oxidation : H2O2  O2 + 2H+ + 2e– E H0 2O 2 / O 2

4. Metal-Metal Reduction : AgCl(s) + e–  Ag(s) + Cl– E0AgCl( s ) / Ag( s ) / Cl

insoluable salt Oxidation : Ag(s) +Cl–  AgCl(s) + e– E 0Ag( s) / AgCl( s) / Cl

Free energy changes for cell reaction :

reduction half reaction,

Solution (i) Cu2+ + 2e–  Cu G1

after adding Cu++ e–  Cu

Example-6 E0Mn2  / MnO4 = –1.51 V

E0MnO2 / Mn2 = + 1.23 V

E0MnO4 / MnO2 = ? (All in acidic medium)

Solution 4H2O + Mn2+  Mn O4 + 8H+ + 5e– G1

(i) Mn O4 + 8H + + 5e–  4H2O + Mn2+ –G1

 Metal–metal soluble salt electrode.

 Gas – electrode Hydrogen electrode.

4H2O + Mn2+  Mn O4 + 8H+ + 5e– S

ERedn is more so, good oxidising agent

 Nernst Equation for cell Potential :

given that E 0Cr O 2 

0.059 [Cr 3  ]2 [PCl2 ]3 0.059  23

0.0591 [ Zn2 ] 0.0591 [Zn2 ]

Work done by a cell :

= + 0.34 – (0.76) = 1.10 V

 The two solutions are separated by a salt bridge.

The nernst eq. is

Electrolysis & Electrolytic cell :

A n Cu2+ + 2e–  Cu(s)

 Faraday's Law of Electrolysis :

Z = Mass deposited when 1 C of charge is passed into the solution.

ixt Molar mass

Solution No. of moles of e– =

contains 5.00 L of 0.100 M KNO3 and Co Ag

 C moles of electrolyte are present in 1 Lt. of solution.

Equivalent conductance : Conductivity of a solution containing 1 g equivalent of the electrolyte.

Its units are Ohm –1 cm 2 eq–1

 Its units are V–1 cm 2 sec–1

 Variation of conductivity and molar conductivity with concentration

0eq Al2(SO 4)3 = 0eq Al3+ + 0eq SO24

(b) 0eq Al2(SO4)3

(f) 0eq NaCl = 300  –1 cm 2 eq–1

0eq Na2C2O4 = 400  –1 cm 2 eq–1

0eq Na2SO4 = 450  –1 cm 2 eq–1

140  4  10 5  1000 1.4  10  4

Example-22 To calculate KW of water

Variation of ,  m & eq of solutions with Dilution

DRY CELLS and alkaline batteries :

Nickel – cadmium battery.

Oxidation : Fe(s)  Fe2+ (aq) + 2e–

oxidation half-reaction reducing half-reaction

.0592 (Pr oducts) .0592 ( Anodic ion concentrat ion)

(A) 1 × 10–7 (B) 2 × 10–7 (C) 3 × 10–7 (D) 4 × 10–7