Electrochemistry

3
Chapter

1 TYPE OF CELLS 4 NERNST EQUATION 6 ELECTROCHEMICAL SERIES

m Electrochemical cell : Device used to convert chemical m
n+
For the reaction : M + ne ¾® M– m A negative E° means that the redox couple is stronger
energy of a redox reaction into electrical energy. It is also reducing agent than the H+/H2 couple.
RT [M]
known as galvanic cell. E = E° - ln m A positive E° means that the redox couple is a weaker
nF [Mn + ]
reducing agent than the H+/H2 couple.
m Electrolytic cell : Device which uses electricity to bring 0.0591 1 Oxidised form Reduced form E°/V
about a non-spontaneous redox reaction. E = E° - log n +
n [M ] F2(g) + 2e– ® 2F– 2.87
ne - Co3+ + e– ® Co2+ 1.81
2 DANIELL CELL
m For the reaction : aA + bB ¾¾¾ ® cC + dD Cl2(g) + 2e– ® 2Cl– 1.36
2+ 2+
RT [C]c [D]d O2(g)+ 4H+ + 4e– ® 2H2O 1.23

Increasing Strength of Oxidising Agent

m Cell reaction : Zn(s) + Cu (aq.) ¾® Zn (aq.) + Cu(s) Ecell = E°cell - ln
nF [A]a [B]b Br2 + 2e– ® 2Br– 1.09
m When external opposite potential is applied to the cell in Ag+ + e– ® Ag(s) 0.80
standard state m For a reaction at equilibrium, Ecell = 0. Fe3+ + e– ® Fe2+ 0.77
(a) Eext = 1.1 V, no flow of electrons. 2.303 RT 0.0591 O2(g) + 2H+ + 2e– ® H2O2 0.68
m E°cell = log K C = log K C I2 + 2e– ® 2I
–
0.54
(b) Eext > 1.1 V, electrons flow from Cu rod to Zn rod. nF n
Cu2+ + 2e– ® Cu(s) 0.34
(c) Eext < 1.1 V, electrons flow from Zn rod to Cu rod. 5 GIBBS ENERGY 2H+ + 2e– ® H2(g) 0.00
m It is the reversible work done by the galvanic cell. Pb2+ + 2e– ® Pb(s) –0.13
3 CELL POTENTIAL m DrG = –nF Ecell Sn2+ + 2e– ® Sn(s) –0.14
m Electrode potential : It is the potential difference developed m DrG° = –nF E°cell Cr3+ + 3e– ® Cr(s) –0.74
between the electrode and the electrolyte. When the m DrG° = –RT ln K = –2.303 RT log K Zn2+ + 2e– ® Zn(s) –0.76
concentration of all the species involved is unity it is known 2H2O + 2e– ® H2(g) + 2OH–(aq) –0.83
as standard electrode potential. 7 CONDUCTANCE OF ELECTROLYTIC SOLUTIONS Na+ + e– ® Na(s) –2.71
m Cell potential : The difference between the electrode Ca2+ + 2e– ® Ca(s) –2.87
potentials (reduction potentials) of the cathode and anode. m Resistance : R = rl , unit = ohm K+ + e – ® K(s) –2.93
A
m EMF of cell : The cell potential when no current is drawn RA Li+ + e– ® Li(s) –3.05
through the cell. m Resistivity : r = , unit = ohm - cm
l
m Ecell = Eright – Eleft 8 DILUTION EFFECT ON CONDUCTANCE
m Conductance : G = 1 = k A , unit = ohm -1 or S m Conductivity always decreases with decrease in
m E°cell = E°R – E°L R l
concentration (means on dilution) both for weak and strong
m In a galvanic cell : l
m Cell constant : G* = , unit = cm –1 electrolytes.
(a) Anode has negative potential w.r.t solution. A m For weak electrolytes, molar conductivity increases steeply
(b) Cathode has positive potential w.r.t solution. Gl on dilution.
-1 -1
m Standard hydrogen electrode :
m Conductivity : k = , unit = ohm cm
A m For strong electrolytes, molar conductivity increases slowly
1 with dilution.
H+ (aq.) + e - ¾® H2 (g), E° = 0 Volt (Assumed)
2 m Molar conductivity : L = k ´ 1000 , unit = S cm2 mol-1
(1M)
(1bar ) m
M
m For strong electrolyte : L m = L °m - A C .

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NCERT Maps Electrochemistry 73

9 KOHLRAUSCH LAW OF INDEPENDENT 12 BATTERIES m Secondary batteries : Which can be recharged

MIGRATION OF IONS (1) Lead storage battery :
m Primary Batteries : Which cannot be reused.
m Limiting molar conductivity of an electrolyte can be
(1) Dry cell : (Leclanche cell) discharging
represented as the sum of the individual contributions of the ˆˆˆˆˆˆˆ
Pb(s) + PbO 2 (s) + 2H2SO 4 (aq.) ‡ˆˆˆˆˆˆ †
ˆ
2+ – charging
anion and cation of the electrolyte at infinite dilution. Anode : Zn(s) ¾® Zn + 2e
+
2PbSO 4 (s) + 2H2O( l )
m If an electrolyte on dissociation given v+ cations and v– anions Cathode : MnO2 + NH + e– ¾® MnO(OH) + NH3
4
(2) Nickel cadmium cell : It has longer life than lead
then L °m = v + l °+ + v - l °-
storage cell :
l l°m : H+ > Ca2+ > Mg2+ > K+ > Na+ Carbon rod
(cathode) Cd(s) + 2Ni(OH)3(s) ® CdO(s) + 2Ni(OH)2(s) + H2O(l)
l l°m : OH– > SO42 – > Br– > Cl– > CH3 COO– m Fuel cells : Galvanic cell that converts the energy produced
during combustion of fuel directly into electrical energy
l For a weak electrolyte : a = Lm/L°m
2 e.g: H2 — O2 fuel cell
Ca 2 CL m
l For acetic acid : K a = = –
1 - a L° ( L° - L ) Anode : H2(g) + 2OH (aq.) ¾® 2H2O(l) + 2e–
m m m
–
Cathode : O2(g) + 2H2O(l) + 4e– ¾® 4OH (aq.)
10 FARADAY’S LAW OF ELECTROLYSIS
The cell was used in Apollo space programme
E H 2O
m First law : w = ZQ = ZIt = ´ It + Cathode
96500 Anode –
w1 E1 Zinc cup MnO2 +
m Second law : = (anode) carbon black Aqueous electrolyte
w2 E2
+ NH4Cl paste NaOH
m 1F = Charge on 1 mol electron = 96487 C ; 96500 C
Fig. A commercial dry cell consists of
a graphite (carbon) cathode in a zinc
H2 O2
11 PRODUCTS OF ELECTROLYSIS container; the latter acts as the anode.
m Molten NaCl : Anode : Cl2, Cathode : Na (2) Mercury cell : Cell potential (; 1.35 V) remains constant
m Aqueous NaCl : Anode : Cl2, Cathode : H2 during its life
–
m Dilute H2SO4 : Anode : O2, Cathode : H2 Anode : Zn(Hg) + 2OH ¾® ZnO(s) + H2O + 2e–
–
m
2–
Concentrated H2SO4 : Anode : S2O8 , Cathode : H2 Cathode : HgO + H2O + 2e– ¾® Hg(l) + 2OH Fig. Fuel cell using H2 and O2 produces electricity

13 CORROSION
O2 + Fe2+ 4H+(aq) + O2
m It slowly coats the surfaces of metallic objects with oxides or other salts of metal.
Fe2+ Fe2+ 2H2O
m Corrosion of iron is called rusting. It is an electrochemical phenomenon. Fe2O3
Fe Fe
m Rust is Fe2O3 · xH2O.
4e–
m Prevention of rusting can be done by 2e– 2e–
(i) Covering the surface with paint or by chemicals (e.g. bisphenol) Oxidation : Fe(s) ® Fe2+(aq) + 2e–
(ii) Cover the surface by other metals (Sn, Zn etc.) Reduction : O2(g) + 4H+(aq) + 4e– ® 2H2O(l)
Atmospheric oxidation : 2Fe2+(aq) + 2H2O(l) + 1/2O2(g) ® Fe2O3 + 4H+
(iii) Provide a sacrificial electrode of other metal (Mg, Zn etc.) Fig. Corrosion of iron in atmosphere

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 74 Electrochemistry NCERT Maps

1. If an external opposite potential is applied to 4. The conductivity (κ) of an electrolyte (1) a and c only
Daniell cell (in standard state) the reaction solution depends on [NCERT Pg. 77] (2) b and d only
continues to take place till the opposite (1) The concentration of electrolyte (3) b and c only
voltage reaches the value of (2) Nature of solvent (4) a, b, c and d
[NCERT Pg. 66] (3) Temperature 7. For the electrode reaction
Mn+(aq.) + ne– → M(s),
(1) 1.1 V (2) 1.8 V (4) All of these
the Nernst equation is given by
5. Select the incorrect statement among the [NCERT Pg. 70]
(3) 2.1 V (4) 2.3 V
following [NCERT Pg. 70, 88, 93]
RT [M]
2. The cell potential is called emf of the cell (1) Electrochemical principles are relevant (1) E(Mn+ /M) =
E°(Mn+ /M) − log n+
nF [M ]
when [NCERT Pg. 68] to the hydrogen economy
RT [M]
(2) Corrosion of metals is an (2) E(Mn+ /M) =
E°(Mn+ /M) − ln
(1) Electrodes are in standard state nF [Mn+ ]
electrochemical phenomenon
(2) One ampere current is drawn through RT [M]
(3) Batteries are very useful forms of (3) E(Mn+ /M) =
E°(Mn+ /M) + ln n+
the cell nF [M ]
electrolytic cells
RT [M]
(3) No current is drawn through the cell (4) Electrochemical cells are used for (4) E(Mn+ /M) =
E°(Mn+ /M) + log n+
nF [M ]
determining solubility product
(4) Platinum electrodes are used in the cell
8. Incorrect relation among the following is
6. Select the correct statements among the
3. For the cell reaction : [NCERT Pg. 74]
following
(1) ∆rG = –2.303 RT log K
Cu(s) + 2Ag+(aq.) → Cu2+(aq.) + 2Ag(s) (a) A negative E° means that the redox
[NCERT Pg. 68] couple is a stronger reducing agent than 2.303 RT
(2) E°cell = log K c
the H+/H2 couple nF
=
(1) Ecell E −E (b) F2 is strongest oxidising agent among
Cu2 + /Cu Ag+ / Ag (3) ∆rG° = –RT ln K
halogens
(4) ∆rG = –nFEcell
Ecell E
(2)= + −E 2+ (c) Among alkali metals lithium is the most
Ag / Ag Cu /Cu
powerful reducing agent in aqueous 9. The oxidation potential of hydrogen
solution electrode which is in contact with a solution
Ecell E
(3)= +E
Ag+ / Ag Cu2 + /Cu having pH = 10 is [NCERT Pg. 75]
(d) The potential of individual half-cell can
not be measured (1) 0.591 V (2) 0.295 V
=
(4) Ecell 2E + +E 2+
Ag / Ag Cu /Cu [NCERT Pg. 68, 70, 71] (3) 1.182 V (4) 0.886 V

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NCERT Maps Electrochemistry 75

10. The emf of cell 18. The mass of Ni deposited at cathode by

14. In the equation : Λm =Λ°m − A C , the value
Ni(s)|Ni2+(0.16 M)||Ag+(0.002 M)|Ag(s), passing 5 A current for 20 min through
of A will be same for [NCERT Pg. 81]
Ni(NO3)2 solution using Pt-electrodes will be
is ( E°cell = 1.05 V ) [NCERT Pg. 75] (1) NaCl and KCl (Atomic mass of Ni = 58.7) [NCERT Pg. 94]
(2) NaCl and CaCl2 (1) 1.56 g
(1) –0.91 V (2) +0.46 V
(3) CaCl2 and MgSO4 (2) 2.46 g
(3) +0.91 V (4) –0.75 V
(4) KCl and MgSO4
(3) 1.23 g
11. The equilibrium constant of the given
reaction at 298 K will be 15. If the Λ°m of 0.025 M formic acid is (4) 1.82 g
46.1 S cm2 mol–1 then the Ka for formic acid 19. Select the correct statement for lead storage
2Fe3+(aq.) + 2I–(aq.) → 2Fe2+(aq.) + I2(s),
will be nearly (given : λ°(H+) = 349.6 S cm2 battery [NCERT Pg. 89]
E°cell = 0.237 V [NCERT Pg.75] mol–1 and λ°(HCOO–) = 54.6 S cm2 mol–1)
(1) It consists a grid of lead packed with
[NCERT Pg. 85]
(1) 1012.25 (2) 108.02 PbO2 as anode
(1) 2.5 × 10–5
(3) 106.8 (4) 109.76 (2) A 50% solution of sulphuric acid is used
(2) 2.8 × 10–4 as an electrolyte
12. Which among the following options have
(3) 3.6 × 10–4 (3) On charging the battery PbSO4(s) on
highest conductivity? [NCERT Pg. 78]
(4) 5.9 × 10–5 anode is converted into Pb
(1) Pure water (2) 0.1M HCl
(4) On charging the battery concentration of
(3) 0.01M HAc (4) 0.01M NaCl 16. If the Λ°m for KCl, HCl and CH3COOK are x,
H2SO4 decreases
13. Among the following incorrect statement is y and z S cm2 mol–1 respectively then Λ°m for
20. A steady current of 1.5 amperes was passed
[NCERT Pg. 81, 83] CH3COOH will be [NCERT Pg. 84] through two electrolytic cells A and B
(1) For strong electrolytes, Λm increases (1) y + z – x containing CuSO4 and AgNO3 respectively
slowly with dilution (2) y + x – z and connected in series. If 1.45 g of Ag is
(2) For strong electrolytes, conductivity deposited at the cathode of cell B than the
(3) x + y + z
decreases with decrease in mass of copper deposited in cell A will be
(4) z + x – y
concentration [NCERT Pg. 94]
17. One faraday is equal to [NCERT Pg. 86]
(3) For weak electrolytes, Λm increases (1) 0.43 g
(1) 96778 C
steeply with dilution especially near
(2) 96487 C (2) 0.36 g
lower concentration
(3) 96685 C (3) 0.51 g
(4) For weak electrolytes, conductivity
increases with decrease in concentration (4) 96587 C (4) 0.59 g

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 76 Electrochemistry NCERT Maps

1. The reversible work done by a galvanic cell 8. The slope of plot Λm vs C1/2 for strong 16. The amounts of different substances
is equal to decrease in its ________. electrolytes is equal to _______. liberated by the same quantity of electricity
[NCERT Pg. 74] [NCERT Pg. 81] passing through the electrolytic solution are
2. Ecell is an ________ parameter. 9. Prevention of corrosion can be done by proportional to their chemical _______.
covering the metal surface by chemicals [NCERT Pg. 85]
[NCERT Pg. 74]
_______. [NCERT Pg. 91]
17. At any concentration C, the degree of
3. The SI unit of resistivity is ________
– –
[NCERT Pg. 75] 10. Among OH , Cl , Na+
and K+
ions, the dissociation of a weak electrolyte is
limiting molar. Conductivity in water at 298 approximated to the ratio of its molar
4. Nowadays a number of ceramic materials K is maximum for _______.[NCERT Pg. 83] conductivity (Λm) to the its _______.
and mixed oxides show super conductivity
11. Standard hydrogen electrode is assigned a [NCERT Pg. 84]
at temperatures as high as ________.
________ potential at all temperatures.
[NCERT Pg. 76] 18. Fuel cells using the reaction of hydrogen
[NCERT Pg. 68]
5. The conductivity of electrolytic solution with oxygen to form water used for providing
12. The cell potential of mercury cell is
________ with the increase of temperature. electrical power in the ________ space
approximately _______. [NCERT Pg. 89]
programme. [NCERT Pg. 90]
[NCERT Pg. 77] 13. The number of Faraday needed to reduce 1
2− 19. The molar conductivity (in S cm2 mol–1) of
6. The cell constant is usually determined by mol of Cr2O7 into Cr3+ is _______.
measuring the resistance of the cell 0.2 M solution of KCl at 298 K having
[NCERT Pg. 88] conductivity 0.0248 S cm–1 will be _______.
generally containing a solution of ________
whose conductivity is already known. 14. During the electrolysis of aqueous NaCl, on [NCERT Pg. 93]
account of _______ of oxygen, oxidation of
[NCERT Pg. 78] 20. On electrolysis of aqueous solution of
Cl– is preferred. [NCERT Pg. 87]
AgNO3 with silver electrodes, concentration
7. In a galvanic cell, anode has a ________ 15. During the electrolysis of high concentrated
potential with respect to the solution. of Ag+ _______ in the solution.
H2SO4, formation of _______ is preferred at
[NCERT Pg. 67] anode. [NCERT Pg. 88] [NCERT Pg. 94]

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