e Electrochemistry 1

ELECTROCHEMISTRY

Very Short Answer Type Questions [1Marks]

Q.1. Why does the conductivity of a solution decrease with dilution?

Q.2. Suggest a three metals that are extracted electrolytically.
Q.3. Consider the reaction : Cr2O72  + 14H+ + 6e–  2Cr+ + 7H2O

What is the quantity of electricity in columns needed to reduce 1 mol of Cr2O72  .

Q.4. Suggest two materials other than hydrogen can be used as fuels in fuel cells.
Q.5. Arrange the following metals in the order in which the) displace each other from the solution of their
salts.
Al, Cu, Fe, Mg and Zn.
Q.6. The conductivity of 0.20 M solution of KCl at 298 K is 0.0248 S/cm. Calculate its molar conductivity.
Q.7. In the internal circuit of a galvanic cell, which is responsible to carry electric current.
Q.8. Express mathematically relationship among the resistance (R) specific conductivity ?
Q.9. What is meant by cell constant?
Q.10. State the factors that influence the value of cell potential of the following cell :
Mg(s) / Mg2+ (aq) || Ag+ (aq) | Ag(S)
Q.11. What is the relationship between the standard EMF of the cell and the equilibrium constant of the cell
reaction at 298 K?
Q.12. Why is it not possible to measure the single electrode potential?
Q.13. Why does an aqueous solution of NaI on electrolysis give H 2 gas at the Cathode and not sodium metal?
Q.14. What is the overall electrochemical reaction taking place in rusting?
Q.15. Which type of metal can be used in cathodic protection of iron against rusting?
Q.16. Write Nernst equation for half cell reaction Mn   ne  M .
Q.17. How much charge is required for the reductions of 1 mol of CH3NO2 to CH3 NH2 ?

Short Answer Type Questions [2 Marks]

Q.1. Suggest a way to determine the m value of water.

Q.2. Can you store copper sulphate solutions in a zinc pot?
Q.3. If a current of 0.5 ampere flows through a metallic wire for two hours, then how many electrons flow
through the wire?
Q.4. Calculate the potential of a zinc-zinc ion electrode in which the zinc ion activity is 0.001 M.
(EZn 2 / Zn  0.76V, R  8.314 JK 1mol 1 , F  96,500 C mol 1 )

Q.5. Calculate the equilibrium constant for the following reaction at 298 K :
Cu (s) + Cl2(g)  CuCl2 (aq) R = 8.314 JK–1 mol–1, ECu2 /Cu = 034 V ECl2 /Cl = 1.36 V,

Q.6. Calculate the equilibrium constant of the reaction:

Cu (s) + 2 Ag+ (aq)  Cu2+ (aq) + 2 Ag (s) E°Cell = 0.46 V
Q.7. What is the effect of temperature on the electrical conductance of
(i) metallic conductor (ii) electrolytic conductor.
Q.8. (a) State the factors that influence the value of cell potential of the following cell:
Mg (s) |Mg2+ (aq) ||Ag+ (aq)|Ag (s)
(b) Write Nernst equation to calculate the cell potential of the above cell.
Q.9. Can you store copper sulphate solution in a zinc pot?

www.thechemistryguru.com
2 e Electrochemistry

Q.10. Why does the molar conductance increase on diluting the solution of a weak electrolyte? Electrolytic
conductivity of 030 M solution of KCI at 295 K is 3.72 x 10"1 S cm*1. Calculate Its molar conductivity.

Q.11. The resistance of a conductivity cell containing 0.001M KCI solution at 298 K is 1500 . What is the cell
constant if conductivity of 0.001 M KCI solution at 298K is 0.146 × 10 –3 S/cm?

Q.12. With the help of ionic equations describe what happens when
(i) pH of a solution of dichromate ions is raised,
(ii) potassium manganate is electrochemically oxidised.

Q.13. How much electricity in terms of Faraday is required to produce?

(i) 20.0 g of Ca from molten CaO2 (ii) 40.0 g of Al from molten Al2O3

Q.14. Why is a salt bridge or a porous plate not needed in a lead storage battery?

Q.15. Explain. Why?

(i) E° fur Mn3+ /Mn2+ couple is more positive than that for Fe3+ /Fe2+. (At. Nos. Mn = 25, Fe = 26)
(ii) Ce3+ can be easily oxidised to Ce4+. (At. No. Ce = 58)

Very Long Answer Type Questions [3 Marks]

Q.1. Calculate the E.M.F. of the following cell at 298 K : Mg | Mg2+ (0.1M) || Ag+ (0.1 M)| Ag
Given: Eo Mg2 / mg  2.37 V, Eo Ag / Ag  0.8V,

Q.2. Show that for two half reactions having potential E 1 and E2 which are combined to give a third half
n E  n2 E2
reaction having potential E3 is E3  1 1 ; where ni is the number of electrons exchanged in half
n3
cell reactions.

Q.3. What is corrosion? Describe electrochemical phenomenon of rusting of Iron.

Q.4. Three electrolytic cells A, B and C containing solutions of zinc sulphate, silver nitrate and copper
sulphate, respectively are connected in series. A steady current of 1.5 ampere was passed through them
until 1.45 g of silver were deposited at the cathode of cell B. How long did the current flow? What mass
of copper and what mass of zinc were deposited in the concerned cells? (Atomic masses of Ag = 108, Zn =
65.4, Cu = 63.5)

Q.5 (A) The resistance of a conductivity cell containing 0.001 M KCI solution at 298 K is 15000. What is the
cell constant, if the conductivity of 0.001 M KCI solution at 298 K is 0.146 ×10 -3 S cm-1?
(B) Predict the products of electrolysis in the following: A solution of H2SO4 with platinum
electrodes.

Q.6. Calculate the pH of the following half cell: Pt(s) H2(g) H2SO4 (aq)

For the cell the oxidation potential is +0.3V, pH2 (g) =1 atm

Q.7. Calculate the standard cell potential of the galvanic cell in which the following reaction takes place: 2 Cr
(s) + 3 Cd2+ (aq)  2 Cr3+ (aq) + 3 Cd (s)
Also calculate the  r G  value of the reaction.
(Given: E Cr3 /Cr  0.74V; E Cd2 /Cd = – 0.40 V and F = 96500 C mol-1

Q.8. State what you will observe when

(i) an electrolyte is added to a colloidal solution.
(ii) an electric current is passed through a colloidal solution,
(iii) a beam of light is passed across pure water and then across a colloidal solution of sulphur when you
are not in the path of light.

www.thechemistryguru.com
 e Electrochemistry 3

Long Answer Type Questions [5 Marks]

Q.1. (a) Calculate the emf of the cell Mg(s) | Mg2+ (0.1 M) || Cu2+ (1 × 10-3 M) | Cu (s)
Given : E  Cu2 /Cu = + 0.34 V, E  Mg2+/Mg = – 2.37V
(b) Explain with examples the terms weak and strong electrolytes.

Q.2. A solution of CuSO4 is electrolyzed for 16 minutes with a current of 1.5 amperes. What is the mass of
copper deposited at the cathode?

3   2Fe2  I3

Q.3. Calculate the equilibrium constant for the reaction : 2Fe  3I 

The standard reduction potentials in acidic conditions are 0.77 and 0.54 V respectively for Fe 3+ | Fe2+
and I3 | I  couples.

Q.4. (a) State the products or electrolysis obtained on the cathode and the anode in the following cases :
(i) A dilute solution of H2SO4 with platinum electrodes
(ii) An aqueous solution of AgNO3 with silver electrodes
(b) Write the cell formulation and calculate the standard cell potential of the galvanic cell in which the
following reaction takes place: Fe2+ (aq) + Ag+ (aq)  Fe3+ (aq) + Ag (s)
Calculate Af G° for the above reaction.
[Given: E°Ag+/Ag = + 0.80 V and E°Fe3+/Fe2+ = + 0.77 V; F = 96500 C mo–1]

www.thechemistryguru.com
4 e Electrochemistry

ELECTROCHEMISTRY solution
Very Short Answer Type Questions [1Marks]

1. Conductivity of a solution is the conductance of ions present in a unit volume of the solution. On dilution
the number of ions per unit volume decreases. So, the conductivity decreases.
2. Na, Ca, Mg and Al.
3. From The given reaction, 1 mol of Cr2 072– ions require 6 mole electrons
Charge= 6F = 6 × 96500 C = 579000 C of electricity for reduction to Cr 3+.
4. Methane and Methanol.
5. Mg, Al, Zn, Fe and Cu.
K  1000 0.0248S / cm 1000cm3 / L
6. m  =
Molarity 0.20mol / L
m  124 S cm2 mol–1
7. Ions.
1 1
8. k 
R a
Where k  specific conductivity
R  resistance
1
 cell constant
a
1
9. Cell constant is the ratio of distance between electrodes and area of cross section. Ii is denoted by .
a
Its unit is cm–1.
10. Concentration of Mg2+ and Ag+ ions in the solution and temperature
0.0591
11. Ecell  log K c
n
12. Oxidation and reduction always take place together. Moreover, electrode potential is a relative tendency
and can be measured with respect to a reference electrode only.
13. This is because of the fact that standard reduction potential of water is greater than that of sodium.
14. 2Fe(s) + O2(g) + 4H+ (aq)  2Fe2+ (aq) + 2IH2O (e)
15. A metal which is more electropositive than iron such as Al. Zn, Mg can be used in cathodic protection of
iron against rusting.
16. Consider the electrode reaction
Mn+ + ne-  M
The Nernst equation for this reaction is
 M 
n
 M 
n

log  log 
2.303RT 0.059
E Mn  / M  E Mn  / M   E M n  / M  , where n is no. of electrons.
nF M n M
17. The electrode reactions is
CH3NO2  6e  6H  CH3NH2  2H2O
Quantity of charge required for reduction of 1 mol of CH3NO2 = 6F = 6 × 96500 = 579000 C

Short Answer Type Questions [2 Marks]

1. The molar conductance of water at infinite dilution can be obtained from the knowledge of molar
conductance at infinite dilution of sodium hydroxide, hydrochloric acid and sodium chloride.
m0  m0 H  m0OH
m (H2O)  m (NaOH)  m(HCl)  m (NaCl)

www.thechemistryguru.com
 e Electrochemistry 5

2. Ezn2 / Zn  0.76V, ECu2 /Cu  0.34V.

We have to check whether the following reaction takes place or not.

Zn (s) + Cu SO4 (aq)  Zn SO4 (aq) + Cu(s)
ECl  ECu2 / Cu  E2n2 / Zn =0.34V    0.76 V   1.1V

Since E°Cell is positive, the reaction takes place and we cannot store.
3. Q (Columb) = 1 (ampere) = 1 (s)
3600 C = (0.5 ampere) (2 × 60 × 60s)
A flow of 96500 C »s equivalent to the flow of 1 mole of electrons,
.02 1023
 3600 C is equivalent to flow of electrons   3600 = 6.02 × 1023 electrons
96500
2.303RT
4. E  E  log[M n  ]
nF
2.303  8.314  298
E  0.76  Or E = – 0.76V + 0.0295V
2  96,500
E = – 0.7305 V.
5. Anode reaction : Cu (S)  Cu2+ (aq) + 2e– (oxidation)
Cathode reaction Cl2 (g) + 2e–  2 Cl– (aq) (reduction)
Net cell reaction ; Cu (s) + Cl2(g)  CuCl2(aq), Here n = 2
Ecell  Ecathode  Eanode  0.34  1.36  1.04V
n 2
log K C   ECell =  (0.04) = – 35.2542 = 36.7458
0.059 0.059
K C  5.569 1036
0.059
6. ECell  log K C Here n  2, ECell  0.46
n
0.046  2
 0.46   15.6 ; K C  anti log15.6 ; K C  3.92  1015
0.059
7. With increase in temperature, the electrical conductance of metallic conductor decreases whereas that
of electrolytic conductor increases.
8. (a) Cell potential depends the concentration of the electrolytes containing Mg 2* and Ag' ions and the
temperature at which the cell is operated.
0.303RT  Mg 2  (aq) 
(b) E cell  ECell  log 2
[Here n = 2]
2F  Ag  (aq) 

9. No, because zinc is more reactive than copper and it will displace copper from copper sulphate solution
as : Zn(s) + Cu SO4 (aq)  Zn SO4 (aq) + Cu(s)
As a result, zinc will gradually pass into the solution and copper will be precipitated.
10. When the solution of a weak electrolyte is diluted, its degree of ionisation increased sharply. There is a
sharp increase in the number of ions in the solution. Hence the molar conductivity of a weak electrolytes
increased sharply on dilution.
Numerical : Electrolytic conductivity,  = 3.72 × 10–2 S cm–1
M = 0.30M
1000 1000  3.72 102
Molar conductivity,  m   = 124 S cm2 mol–1
M 0.30
Conductivity
11. Cell constant, G* =
Conduc tan ce
1
Conductance = S
1500

www.thechemistryguru.com
6 e Electrochemistry

0.146 103 Z / cm
Cell constant =  0.219cm1
1
1500
12. (i) Dichromate (orange) changes to chromate (yellow) when the pH of solution is raised.
K2Cr2O7 (aq) + 2KOH  2K2CrO4 (aq) + H2O
Cr2O72+ + 2OH–  2 CrO42– + H2O
(ii) K 2 MnO 4  2K   MnO 42  ; H 2 O  H   OH 
At cathode : 2H   2e   H 2 
At anode: MnO 4  KMnO 4

13. (i) Ca2+ + 2e–  Ca

1 mol of Ca
i.e. 40g require electricity = 2F
2  20
20 g of Ca will require electricity = F  1F
40
(ii) Al3+ + 3e–  Al
1 mol of Al = 27g
 27 g of Al require electricity = 3F
3
40 g of Al will require electricity  40F  4.4F
27
14. The half cells in a cell must be separated only if the oxidizing and reducing agent can migrate to the
other half cell. In lead storage cell, the oxidizing agent, PbO2 and the reducing agent, Pb as well as their
oxidation and reduction products PbSO4 are solids. Therefore, their is no need to separate half cells.
15. (i) 25 Mn 2  : [Ar] 3d5 (Stable configuration)

25 Mn 3 : [Ar] 3d4
26 Fe 2  : [Ar] 3d6
3
26 Fe : [Ar] 3d5 (Stable configuration) Thus Mn2+ is more stable than Mn3+ While
Fe3+ is more stable than Fe2+. Hence E° for Mn3+ / Mn2+ couple is more positive than for Fe3+ / Fe2+ couple,
(ii) Ce3+ ion having the configuration 4f1 5d° 6s° can easily lose electron to acquire the configuration 4f°
5d° 6s° and form Ce4+ ion.

Very Long Answer Type Questions [3 Marks]

1. The cell is
Mg | Mg2+ (0.1M) || Ag+ (0.1 M)| A
Eo  Eo Ag / Ag  Eo Mg2 / Mg = 0.8 V – (  2.37 V) = 3.17V

2.303 RT [Mg 2  ]
E cell  E o cell  log
nF [Ag  ]2
Substituting the given values, we get
2.303  8.31JK 1mol1  298 K [Mg 2  ]
E cell  3.17 V  1
log
2  96,500 C mol [Ag  ]2
[0.1mol L1 ]
 E cell  3.17 V  0.0295l og
[0.1mol L1 ]2
 Ecell  3.17 V  0.0295V  3.14 V
2. Let G1 G2 and G3 arc the free energy changes for the half cell reactions having potentials E 1 E2 and
E3 respectively, then

www.thechemistryguru.com
 e Electrochemistry 7

G3 = G1 + G2.

Since G =  nFE or –n3 FE3 =  n1FE1 – n2FE
Dividing both sides by –n3F
n E  n 2E2
E3 = 1 1
n3
3. Corrosion is the process of slowly eating away of the metal due to attack of the atmospheric gases on the
surface of the metal resulting into the formation of compounds such as oxides, sulphides, carbonates, etc.
The corrosion of iron is called rusting.
According theory of rusting, impure iron surface behaves as a small electrochemical cell in the
presence of water containing dissolved oxygen or CO2.
The pure iron acts as anode and impure surface as cathode.
At anode: Iron atoms undergo oxidation spontaneously forming Fe 2+ ions.
Fe  Fe2 (aq)  2e Eo red  0.44V
Fe2+ ions move into solution and electrons into cathodic area where they are picked up by H + ions of the
solution.
1
At cathode: 2H   O2  2e  H 2 O E o red  1.23V
2
H+ ions are produced by secondary reactions either form H 2O or from H2 CO3 (CO2 + H2O).
H 2 O  H   OH 
H 2 CO3  H   HCO3
The overall reaction of the corrosion cell may be represented as
1
Fe (s)  2H  (aq)  O2  Fe 2  (aq)  H 2 O
2
E o cell  1.67 V
The Fe2+ ions more than through water and come at the surface where these are further oxidized into
Fe3+ ions by atmospheric oxygen to form hydrate Ferric oxide known as rest, Fe 2 O3. xH2O
1
2Fe2  O2  2H2 O  Fe2 O3  4H
2
Fe 2 O3  xH 2 O  Fe 2 O3 .xH 2 O
rust
4. 
Ag  e 
 Ag
 108 g of Ag is deposited by 1 F = 96500C

 1.45g of Ag is deposited by 1 F = 96500  1.45  1295.6 C

108
 Q = It
 t = Q  1295.6  863.75sec.
I 1.5
Now, Cu 2  2e 
Cu
63.5
 Copper, Cu deposited   1295.6  0.426g
2  96500
Also, Zn 2  2e 
 Zn
65.4 84732.24
Zinc, Zn deposited  1295.6   0.439 g
2  96500 193000
5. (A) Given
Resistance = 1500 ohm
Conductivity = 0.146 × 10-3 S cm-1
Molarity of KCI = 0.001 M

www.thechemistryguru.com
8 e Electrochemistry

Cell Cons tan t

 Conductivity =
Re sis tan ce
Cell Cons tan t
0.146 × 10-3 =
1500
 Cell Constant = 0.146 × 10-3 × 1500 = 0.219 cm-1
(B) H 2SO 4  2H   SO 42 
1
At anode: 2OH   H 2 O  O2  2e Cathode: 2H   2e   H 2
2
6. Oxidation potential of the given electrode = + 0.3 V
Reduction potential of the given electrode = – 0.3 V
The electrode reaction may be given as: 2H  (aq)  2e   H 2 (g)
0.059 1
Applying Nernst equation, E  Eo  log  2
2 [H ]
0.59
 0.3  0  (2log[H  ])
2
 0.3  0.059pH
0.3
pH   5.085
0.059
7. E  cell  E  Cd2 / Cd  E  Cr3 / Cr = 0.40 –(– 0.74) = – 0.40 + 0.74 = + 0.34 V

The half-cell reactions are

2Cr  s   2Cr 3  6e –
3Cd 2   6e   3Cd(s)
2 Cr  s   3Cd 2   2Cr 3  3Cd  s 

No. of electrons, n = 6
  r G   nF E  = – 6 × 96500 × 0.34 = – 196.86 kJ mole–1
8. (i) The addition of electrolyte causes coagulation of the colloidal solution. For example, when a solution
of K2 SO4 is added to the ferric hydroxide (positively charged) solution. the sol gets coagulated by the
negatively charged SO 24  ions furnished by the added electrolyte.
(ii) The charged colloidal particles move towards the oppositely charged electrodes on passing electric
current through the colloidal solution.
(iii) The path of the beam of light is not visible through pure water but it becomes visible through the
colloidal solution of sulphur due to the scattering of light by colloidal particles (Tyndal effect).

Long Answer Type Questions [5 Marks]

1. (a) The cell reaction is Mg + Cu2+ (aq)  Mg2+ (aq) + Cu

Nernst equation for the cell e.m.f. is

 0.059  Mg 2  (aq) 
E cell  E Cell  log
n Cu 2  (aq) 
E  Cell  E  Cu 2 / Cu  E  Mg2 / Mg

= 0.34 – (–2.37) = 0.34 + 2.37 = 2.71 V

0.059 0.1
 E cell  2.71  log
2 1 103
= 2.71– 0.0295 log 0.1 × 103 = 2.71 – 0.0295 log 102 = 2.71 – 0.0295 × 2 log 10
= 2.71– 0.059 = 2.659 V.

www.thechemistryguru.com
 e Electrochemistry 9

(b) Weak Electrolytes : The electrolytes which are not completely dissociated into ions in solution arc
called weak electrolytes. Examples: CH3 COOH, NH4OH, HCN etc.
Strong Electrolytes: The electrolytes which are completely dissociated into ions in solution
are called strong electrolytes. Examples: HCl, KCl, NaOH, NaCl etc.

2. According to the reaction : Cu2+ (aq) + 2e–  Cu (s)

Charge required to deposit 1 mole or 63 g of Cu = 2F
1 F (Faraday) = 96500 C mole–1
Charge required to deposit 63 g of Cu = 2 × 96500 C mole–1.
Also, total charge q = It = 10 × 60 × 1.5 (
t = 10 min = 10 × 60s) = 900C
63  900
For 900 C charge Mass of Cu deposited   0.2938g
2  96500
3. Oxidation half reaction : 3I   I3  2e 
Reduction half reaction : Fe3  e   Fe 2  ]  2
__________________________________________
Cell reaction : 2Fe3  3I   2Fe 2   I3
ECell  0.77  0.54  0.23V
Applying Nernst equation : = 272.18 g
0.059 [Fe2 ]2 [I3 ]
E  ECell  log 2 3
n Fe3   I 
0.059
Or 0  0.23  log K c (At Equilibrium E = 0)
2
0.059
Or log K c  0.23
2
0.23  2
log K C  ; K C  6.26  107
0.059

4. (a) (i) Electrolysis of dilute H, SO4 with platinum electrodes

H2 SO4 (aq)  2H+ (aq) + SO42– (aq)

H2 O   H+ + OH–


At cathode : H+ + e–  H, i.e. H + H  H2 (g)

At anode : OH–  OH + e–, i.e, 4OH  2H, O + O, (g)
Thus H2 is liberated at the cathode and O2 at the anode.
(ii) Electrolysis of aqueous solution of Ag NO 3 with silver electrodes
Ag NO3 (s) + aq  Ag+ (aq) + NO3 (aq), H2 O 

 H+ + OH


At cathode : Ag+ ions have lower discharge potential than H+ ions. Hence Ag+ ions will be
deposited as Ag in preference to ions
At anode : As Ag anode is attacked by NO3– ions, Ag of anode will dissolve to form Ag + ions in
the solution.
Ag  Ag+ + e–
(b) Here iron electrode is anode and silver electrode is cathode. The cell formulation is
Fe2+ (aq)|Fe3+ (aq) ||Ag+ (aq)|Ag(s)
E cell  0.80  0.77  0.03V , r G  n F ECell
ΔG0 = – 1 mole × 96500 C mole–1 × 0.03 V
ΔG0= – 2895 J mole–1 = – 2.895 kJ mole–1

www.thechemistryguru.com