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Class 12 - Chemistry - Electrochemistry
Class 12 - Chemistry - Electrochemistry
Chemistry
Chapter 3 – Electrochemistry
INTEXT Questions
1. How would you determine the standard electrode potential of the system
Mg 2 |Mg ?
Ans: A cell with Mg / MgSO4 (1M) as one electrode and standard hydrogen electrode
Pt, H, (1 atm)H (1M) as the second electrode will be set up, and the emf of the cell will
be measured along with the direction of deflection in the voltmeter. The direction of
deflection indicates that e move from the magnesium electrode to the hydrogen
electrode, implying that oxidation occurs on the magnesium electrode and reduction
occurs on the hydrogen electrode. As a result, the cell can be represented in the
following way:
put E o 1 0
H H2
2
EMg
o
2
/Mg
E o cell
Ans: Cu is less reactive than Zn , so Cu is easily shifted from CuSO 4 solution in the
following reaction:
Ecell Ecu 2 / Cu E zn 2 / Zn
As, The positive Ecell value indicates the occurrence of spontaneous reactions. if
CuSO 4 is stored in Zn pot, Zn will react will Cu and originality of CuSO 4 will not
be maintained.
Ans: In the process of oxidation of Fe 2 to Fe3 , i.e., Fe2 Fe3 e ; the reduction
potential value is negative in nature i.e. Eo ox 0.77 V . Only compounds with
powerful oxidizing agents and positive reduction potentials larger than 0.77 V may
oxidize Fe 2 to Fe3 , resulting in a positive emf of the cell reaction. This is true for
elements like halogens Br2 , Cl2 and F2 in the series below Fe3 / Fe2 .
Given: pH = 10
0.0591 1
0 log 10
1 10
pH = 10
= - 0.519 10
- 10
H = 10 M
0.591 V
o 0.0591 Ni 2 +
E cell = E cell - log 2
n Ag +
0.0519 0.160
1.05 V log
2 (0.002) 2
1.05
0.0591
2
log log 4 104
0.0591
1.05 (4.6021)
2
6. 0.236 V at 298 K . Calculate the standard Gibbs energy and the equilibrium
constant of the cell reaction.
Ans: 2Fe3 (zg) 2I (zq) 2Fe2 (zg) I2 ( g)
2 96500 0.236
45.55 kJ mol 1
Also, r G 2.303RTlog KC
, G o 45.55
log K c 7.983
2.303RT 2.303 8.314 103 298
9.616 107
The Kohlrausch Law says that when dissociation is complete at infinite dilution,
each ion adds a definite amount to the electrolyte's equivalent conductance,
regardless of the nature of the ion with which it is involved, and the value of
equivalent conductance at infinite dilution for any electrolyte is the sum of
contributions of its ionic species (cations and anions).
The values of HCl, NaOH and NaCl are known as they are strong electrolytes and
dissociates completely.. By putting their values in the above equation, we can have
value of m for H 2O .
9. The molar conductivity of 0.025 mol L1 methanoic acid is 46.1S cm 2 mol1.
Calculate its degree of dissociation and dissociation constant Given 0 H
349.6 cm 2 and HCOO 54.6 cm2 mol1
Ans:
om ( HCOOH ) H ( HCOO)
349.6 54.6
404.2 S cm 2 mol 1
cm 46.1
c 0.114
m 404.2
HCOOH HCOO H
Initial conc c 0 0
At equi, c(1 ) c c
c c c 2
Ka
c(1 ) 1
0.025 (0.114) 2
3.67 104
1 0.114
10. If a current of 0.5 ampere flows through a metallic wire for 2 hours, then
how many electrons would flow through the wire?
Ans: As from the formula,
Q It
6.02 1023
3600 2.246 1022 e1s
96500
12. Consider the reaction: CrO72 14H 6e 2Cr3 7H2O . What is the quantity
of electricity in coulombs needed to reduce 1 mol of Cr2O72
Ans: For the above reaction to take place, 1 mol of Cr2O72 will require 6 F
6 96500 579000C 0f electricity.
13. Write the chemistry of recharging the lead storage battery, highlighting all
the materials that are involved during recharging.
Ans: A lead storage battery has a lead anode, a lead cathode with lead dioxide
packed PbO2 in it, and a 38%H 2SO4 solution as the electrolyte. When the battery is
in operation, the following reactions occur:
The reverse process occurs when the battery is charged, in which PbSO4 deposited
on the electrodes is transformed back to Pb and PbO 2 , and H2SO4 is restored.
14. Suggest two materials other than hydrogen that can be used as fuels in fuel
cells.
Ans: Methane and Methanol.
NCERT Exercise
1. Arrange the following metals in the order in which they displace each other
from the solution of their salts: Al, Cu, Fe, Mg and Zn
Hg 2 / Hg 0.79 V
4. Calculate the standard cell potentials of galvanic cell in which the following
reactions take place
Given
o
ECr 2
,Cd
0.40 V
Ag 0.80 V
o
EAg
o
EFe 3
,
0.77 V
Fe2
Ans:
r Go nFE cell
6 96500Cmol1 0.34 V
196860CVmol1
196860 J mol1
196.86 kJ mol 1
or log K 34.5014
r Go nFE cell
1 96500CVmol1 (0.03 V)
2.895 kJ mol 1
or log K 0.5074
or K Antilog(0.5074) 3.22
5. Write the Nernst equation and emf of the following cells at 298 K .
Mg Cu 2 Mg 2 Cu(n 2)
Mg 2+
log 2 +
0.0591
Ecell = ECell -
2 Cu
0.0591 10 - 3
E cell = 0.34 - ( - 2.37) - log - 4
2 10
Fe 2H Fe2 H2 (n 2)
Fe 2+
log
o 0.0591
E cell = E cell - 2
2 H +
0.0591 10 - 3
Ecell = 0 - ( - 0.44) - log
2 (1)2
Sn 2H Sn 2 H2 (n 2)
0.0591 sn 2 +
E cell = Ecell- log 2
2 H +
0.0591 0.05
E cell = Ecell- log
2 (0.02) 2
0.0591 0.05
0 (0.14) log
2 (0.02) 2
0.0591
0.14 log125
2
0.0591
0.14 (2.0969) 0.078 V
2
0.0591 1
(0 1.08) log
2 (0.01) (0.03) 2
2
As a result, oxidation will take place at the hydrogen electrode, whereas reduction
will take place at the Br2 electrode.
6. In the button cells widely used in watches and other devices the following
reaction takes places:
Determine rG and E for the reaction.
Given
Zn Zn 2 2e , E 0.76 V
G 2.13 105 J
When the electrodes are one cm apart and the area of cross-section of the electrodes
is large enough that the entire solution is contained between them, the molar
conductivity of a solution at a dilution (V) is the conductance of all the ions produced
The conductivity of a solution (for both strong and weak electrolytes) diminishes as
the concentration of the electrolyte drops, i.e. as dilution occurs. This is owing to the
fact that when the solution is diluted, the number of ions per unit volume of the
solution decreases.
0.218 cm 1
1S cm 1
Ans: Using the following unit conversion factor, 1
100Sm 1
Concentration
K Sm1
K Scm1 m
1000 k
Scm2 mol1
C1/2 M1/2
(M) Molanity
11. Conductivity of 0.00241M acetic acid is 7.896 105 Scm 1. Calculate its.
Calculate its molar conductivity. If m for acetic acid is 390.5 S cm2 mol1 , what
is its dissociation constant?
1000
Ans: cm =
Molarity
7.896 10 5
S cm- 1 1000 cm3L 1
32.76 S cm2 mol- 1
1
0.241 molL
cm 32.76
8.4 102
m 390.5
2
2
C 2 0.24 8.4 10
ka 1.86 10 5
1 1 0.084
Ans: Aluminum ion have to lose three electrons to be in aluminum elemental state
and the reaction is Al3 3e Al . The amount of charge needed for reduction of 1 mol
will be: Al3 3 F 3 96500C 289500C .
(ii) 1 mol of Cu 2+ to Cu ?
Ans: cupric ion needs to lose two electrons to be in copper (0) state. The electrode
reaction occurring is as follows: Cu 2 2e Cu
The amount of charge required for conversion of
1 mol of Cu 2 2 F 2 96500 193000C .
MnO4 Mn 2 i.e. Mn 7 5e Mn 2
Ans: Ca 2 2e Ca
As There are two electrons transacted in the above reaction, therefore 1 mol of Ca
or 40 g of Ca will require 2 F electricity and 20 g of Ca will require 1 F of
electricity.
Ans: Al3 3e Al
3
= 40=4.44F of electricity.
27
(i) 1 mol of H 2O to O2
1
Or O2 -
O 2 + 2e -
2
The number of electrons transacting are two. Therefore the amount of electricity
needed 2 F 2 96500C 193000C
Ans: The oxidation reaction of FeO takes place in the following manner:
1 1
FeO O 2 Fe 2O3
2 2
Or Fe2 Fe3 e
The electron transfer is of one electron unit, therefore the Quantity of electricity
essential 1 F 96500C
Ni 2 2e -
Ni
Therefore, 2 For 2 96500C is the amount of charge deposit for 1 mol of Ni 58.7 g
Now,
58.7 6000
The 6000C of charge will deposit = 1.825 g of Ni
2 96500
W ZIt
Or
E
W= It
nF
E 2 31.75
1.45 108
=
W2 31.75
1.45 31.75
W2 =
108
W1 E
Using formula, = 1
W2 E2
1.45 108
=
W2 32.65
1.45 32.65
W2 = = 0.438 of Zn
108
o
ECu 2
,Cu
0.34V
o
E1/2 Br , Br
1.09V
2
o
EAg
, Ag
0.80V , EFe
o
3
, Fe2
0.77V
Ans: The reaction is feasible if the emf of the cell reaction is positive.
Ecell
o
EFe3 Fe2 E1/2
o
I f2
2,
Ecell
o
E o Ag Ag ECu
o
, Cu
1
(iii) Fe3 (aq) Br(aq ) Fe2 ( aq ) Br2( g)
2
1
Ans: Fe3 (aq) Br(aq ) Fe2 ( aq ) Br2( g)
2
o
Ecell 0.77 1.09 0.32v( Not feasible )
1
(v) Br2( g ) Fe 2 (aq ) Br(aq ) Fe3 (aq )
2
1
Ans: Br2( g ) Fe 2 (aq ) Br(aq ) Fe3 (aq )
2
o
Ecell 1.09 0.77 0.32V ( Feasible )
H2O H + + OH -
At anode: When the Ag anode is attacked by NO 3 ions, the Ag dissolves and forms
ions in the solution.
Ag(s)
Ag + (aq) + e -
Ans: At cathode: The discharge potential of Ag ions is lower than that of H ions.
As a result, Ag ions will be deposited as Ag rather than H ions.
At anode: Because the anode is not attackable, OH ions have a lower discharge
potential than NO 3 ions. As a result, OH will be evacuated first, followed by NO 3
ions, which will disintegrate and release O2 .
OH OH e
H2 O H + OH
At cathode: H e H
H H H2( g)
At anode: OH OH e
Therefore, Hydrogen gas is released at the cathode and O2 gas at the anode.
H2 O H + OH
Cu 2 2e Cu
At anode: Cl - ions will be released first, followed by OH - ions that will stay in
solution. Cl - Cl e
Cl Cl Cl2( g)
Hence, copper will get set down on the cathode and Cl 2 gas will be liberated at the
anode.