Chapter 3 - Electrochemistry
Chapter 3 - Electrochemistry
Chapter 3 - Electrochemistry
Electrochemistry
Intext Questions
Question 1:
How would you determine the standard electrode potential of the system Mg2+1 Mg?
Solution 1:
A cell will be set up consisting of Mg/MgSO4 (1 M) as one electrode and standard hydrogen
electrode Pt, H, (1 atm)H+/(l M) as second electrode, measure the emf of the cell and also note
the direction of deflection in the voltmeter. The direction of deflection shows that e-1s flow from
Mg electrode to hydrogen electrode, i.e., oxidation takes place on magnesium electrode and
reduction on hydrogen electrode. Hence, the cell may be represented as follows:
Mg|Mg2+(1 M) || H+(1 M) | H2, (1 atm) Pt
Ecell E 1
EMg 2 /Mg
2
Put E 1 0
H H2
2
E 0 Mg 2 / Mg E 0cell
Question 2:
Can you store copper sulphate solutions in a zinc pot?
Solution 2:
Zn being more reactive than Cu, displaces Cu from CuSO4 solution as follows:
Zn(s) + CuSO4 (aq) ZnSO4 (aq)+Cu(s)
In terms of emf, we have
Zn|Zn2+|| Cu2+| Cu
Ecell ECu2 /Cu En n
= 0.34 V - (-0.76 V) = 1.10V
As Ecell is positive, reaction takes place, i.e., Zn reacts with copper and hence, we cannot store
CuSO4 Solution in zinc pot.
Question 3:
Consult the table of standard electrode potentials and suggest three substances that can oxidize
ferrous ions under suitable conditions.
Solution 3:
3.Electrochemistry
Class XII – NCERT – Chemistry Chapter 3
Electrochemistry
Oxidation of Fe2+converts it to Fe3+, i.e., Fe2+ Fe3++e-; EOX= - 0.77 V Only those substances
can oxidise Fe2+to Fe3+which are stronger oxidizing agents and have positive reduction potentials
greater than 0.77 V, so that emf of the cell reaction is positive. This is so for elements lying
below Fe3+/Fe2+in the series ex: Br2, Cl2 and F2
Question 4:
Calculate the potential of hydrogen electrode in contact with a solution whose pH is 10.
Solution 4:
For hydrogen electrode, H++ e- 1/2 H2
Applying Nernst equation,
0.0591 1
E 1 E 1 log
H H2
2
H
2
H2 n [H ]
0.0591 1
0 log 10
1 10
pH 10
10 0.0519 10
[ H ] 10 M
= 0.591 V
Question 5:
Calculate the emf of the cell in which the following reaction takes place: Ni(s)+2Ag+(0.002 M)
Ni2+(0.160 M)+2Ag(s) Given that = Eo (cell)1.05 V.
Solution 5:
Applying Nernst equation
0.0591 [ Ni 2 ]
Ecell Ecell log
n [ Ag ]2
3.Electrochemistry
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Electrochemistry
0.0519 0.160
1.05V log
2 (0.002) 2
0.0591
1.05 log log 4
2
0.0591
1.05 (4.6021)
2
Question 6:
The cell in which the following reaction occurs: 2Fe3+(aq) + 21-(aq) 2Fe2+(aq) + l2(s) has Ecell=
0.236 V at 298 K. calculate the standard Gibbs energy and the equilibrium constant of the cell
reaction.
Solution 6:
2 Fe3+(aq) + 2I- (aq) 2Fe2+(aq) + I2 (s)
For the given cell, n = 2
r G nF E cell
= -2 96500 0.236
= -45.55 kJ mol-1
Also, r G = -2.303 RT log KC
r G 45.55
log K C 7.983
2.303RT 2.303 8.314 10 3 298
KC = antilog (7.983)
= 9.616 107
Question 7:
Why does the conductivity of solution decrease with dilution?
Solution 7:
Conductivity of a solution is the conductance of ions present in a unit volume of the solutions.
On dilution, number of ions per unit volume decreases. Hence, the conductivity decreases.
Question 8:
Suggest a way to determine the value m of water.
Solution 8:
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By using Kohlrausch’s law, m for H2O can be calculated, we can write,
m = m (Hcl) + m (NaOH) - m (NaCl)
Being strong electrolytes, m values of HCl, NaOH and NaCl are known.
By substituting their values, we can obtain m for H2O.
Question 9:
The molar conductivity of 0.025 mol L-1methanoic acid is 46.1 S cm2mol-1. Calculate its degree
of dissociation and dissociation constant Given 0 ( H ) = 349.6 cm2and (HCOO- ) = 54.6
cm2mol-1
Solution 9:
m ( HCOOH ) ( H ) ( HCOO)
= 349.6 + 54.6
= 404.2 S cm2 mol-1
C m = 46.1 S cm2 mol-1
C m 46.1
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
Question 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?
Solution 10:
We know Q = It
= 0.5 (2 60 60) = 3600 C
1F 96500C 1 mole of e-1 s
6.02 1023 e-1 s
3600 C is equivalent to the flow of e-1s
3.Electrochemistry
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6.02 1023
3600 2.246 1022 e1s
96500
Question 11:
Suggest a list of metals that are extracted electrolytically.
Solution 11:
Na, Ca, Mg, and Al
Question 12:
Consider the reaction: Cr2O72- + 14H++ 6e - 2Cr3++ 7H2O. What is the quantity of electricity
in coulombs needed to reduce 1 mol of Cr2O72-
Solution 12:
From the reaction 1 mol of Cr2O72- require 6F
= 6 96500 = 579000 C
579000 C of electricity are required for reduction of Cr2O72-to Cr3+
Question 13:
Write the chemistry of recharging the lead storage battery, highlighting all the materials that are
involved during recharging.
Solution 13:
A lead storage battery consists of anode of lead, cathode of a gird of lead packed with lead
dioxide (PbO2) and 38% H2SO4 solution as electrolyte. When the battery is in use, the reaction
taking place are:
Anode : Pb( s ) SO4 2 ( aq ) PbSO4 ( s ) 2e
Cathode : PbO2 ( s ) SO4 2 ( aq ) 4 H ( aq ) 2e PbSO4( s ) 2 H 2O( l )
Over all reaction : Pb( s ) PbO2 ( s ) 2 H 2 SO4 ( aq ) 2 PbSO4 ( s ) 2 H 2O(l )
On charging the battery, the reverse reaction takes place, i.e., PbSO4 deposited on electrodes is
converted back to Pb and PbO2 and H2SO4 is regenerated.
Question 14:
Suggest two materials other than hydrogen that can be used as fuels in fuel cells.
Solution 14:
Methane and Methanol.
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Class XII – NCERT – Chemistry Chapter 3
Electrochemistry
Question 15:
Explain how rusting of iron is envisaged as setting up of an electro chemical cell
Solution 15:
The Water present on the surface of iron dissolves acidic oxides of air like CO2, SO2 etc, to form
acids which dissociate to give H+ ions:
H2O + CO2 H2CO3 2H+ + CO32-
In the presence of H+, iron loses e-1to form Fe3+. Hence, this spot acts as anode:
Fe(s) Fe2+(aq) + 2e-
The e-1released move through the metal to reach another spot, where H+ions and dissolved
oxygen take up these e-1s and reduction occurs. This spot, thus acts as cathode:
O2 (g) + 4H+ (aq) +4e- 2H2O (l)
The overall reaction is:
2Fe(s) + O2 (g) + 4H+(aq) 2Fe2+(aq) + 2H2O(l)
Thus, an electro chemical cell is set up on the surface.
Ferrous ions are further oxidized by atmospheric oxygen to ferric ions which combine with water
to form hydrated ferric oxide, Fe2O3. XH2Owhich is rust.
NCERT EXERCISES
Question 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.
Solution 1:
Mg, Al, Zn, Fe, Cu, Ag
Question 2:
Given the standard electrode potentials,
K+/K = 2.93 V, Ag+/Ag= 0.80 V,
Hg2+/Hg = 0.79 V
Mg2+/Mg =- 2.73V, Cl3+/Cr = 0.74V
Arrange these metals in their increasing order of reducing power.
Solution 2:
Higher the oxidation potential more easily it is oxidized and hence greater is the reducing power.
Thus, increasing order of reducing power will be Ag < Hg <Cl< Mg < K.
Question 3:
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Solution 3:
The set-up will be similar to as shown below,
Question 4:
Calculate the standard cell potentials of galvanic cell in which the following reactions take place
(i) 2Cr(s) + Cd2+ (aq) 2Cr3+ (aq) + 3Cd(s)
(ii) Fe2+ (aq) + Ag+(aq) Fe3+ (aq) + Ag(s)
Calculate the r G o and equilibrium constant of the reactions
Given
o
ECr 3
, Cr
0.74 V ,
o
ECd 2
, Cd
0.40V ,
E Ag Ag 0.80V ,
E Fe3 Fe 2 0.77V .
Solution 4:
(i) Ecell = Ecathode -EAnode
= -0.40 V - (-0.74 V) = + 0.34V
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r G nFE cell
= -6 96500 C mol-1 0.34 V
= 196860 C V mol-1
= 196860 J mol-1
= - 196.86 kJ mol-1
- r G = 2.303 x8.314 x 298 log K
196860 =2.303 8.314 298 log K
or log K = 34.5014
K = Antilog 34.5014 = 3.172 1034
(ii) Ecell = +0.80 V - 0.77 V = + 0.03V
r G = nFECell
= -1 (96500 C V mol-1) (0.03 V)
= -2.895 C V mol-1= -2895 J mol-1
= 2.895 kJ mol-1
r G = 2.303 RT log K
-2895 = -2.303 8.314 298 log K
or log K = 0.5074
or K = Antilog (0.5074) = 3.22
Question 5:
Write the Nernst equation and emf of the following cells at 298 K.
(i) Mg(s) | Mg2+(0.001 M) || Cu2+(0.0001 M) Cu(s)
(ii) Fe(s) | Fe2+(0. 001 M) || H+(1M) H2 (g) (1 bar) Pt(s)
(ii) Sn(s) | Sn2+(0. 050 M) || H+(0.020 M) | H2 (g) (1 bar) | Pt(S)
(iv) Pt(s) | Br2(l) | Br-(0.010 M) || H+(0.030 M) H2(g) (1 bar) | Pt(s)
Given ECell Mg2+, Mg = -2.37V,
Ecu2+, Cu = +0.34 V, EFe2+Fe = -0.44V.
E Sn2+ /Sn = -0.14 V
E1/2 Br 2/Br - = + 1.08V
Solution 5:
(i) Cell reaction:
Mg + Cu2+ Mg2++ Cu (n = 2)
Nernst equation:
0.0591 [ Mg 2 ]
Ecell E Cell log
2 [Cu 2 ]
0.0591 103
Ecell 0.34 (2.37) log 4
2 10
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0.0591 1
(0 1.08) log
2 (0.01) (0.03) 2
2
0.0591
1.08 log(1.111 10 7 )
2
0.0591
1.08 (7.0457)
2
= -1.08 - 0.208 = -1.288 V.
Thus, oxidation will occur at the hydrogen electrode, and reduction will occur on Br2 electrode.
3.Electrochemistry
Class XII – NCERT – Chemistry Chapter 3
Electrochemistry
Question 6:
In the button cells widely used in watches and other devices the following reaction takes places:
Zn(s) + Ag2O(s) + H2O(l) Zn2+(aq) + 2 Ag(s) + 2OH- (aq)
Determine r Go and Efor the reaction.
Given Zn Zn2++ 2e-, E= 0.76 V;
Ag2O + H2O + 2e- 2Ag + 2OH-, E= 0.344 v.
Solution 6:
Zn is oxidized and Ag2O is reduced.
Ecell E Ag2O, Ag ( reduction) EZn/Zn2 (oxidation)
= 0.344 + 0.76 = 1.104 V
G = nFEcell = -2 96500 1.104 J
o
= -2.13 105 J.
Question 7:
Define conductivity and molar conductivity for the solution of an electrolyte. Discuss their
variation with concentration.
Solution 7:
Conductivity of a solution is defined as the conductance of a solution of 1 cm length and having
1 sq. cm as the area of cross-section.
Molar conductivity of a solution at a dilution (V) is the conductance of all the ions produced
from one mole of the electrolyte dissolved in V cm3of the solution when the electrodes are one
cm apart and the area of cross-section of the electrodes is so large that the whole of the solution
is contained between them. It is usually represented by m.
The conductivity of a solution (both for strong and weak electrolytes) decreases with decrease in
concentration of the electrolyte, i.e., on dilution. This is due to the decrease in the number of ions
per unit volume of the solution on dilution. The molar conductivity of a solution increases with
decrease in concentration of the electrolyte, i.e., on dilution. This is due to the decrease in the
number of ions per unit volume of the solution on dilution. The molar conductivity of a solution
increases with decrease in concentration of the electrolyte. This is because both number of ions
as well as mobility of ions increases with dilution. When concentration approaches zero, the
molar conductivity is known as limiting molar conductivity.
Question 8:
The conductivity of 0.20 M solution of KCl at 298 K is 0.0248 S cm-1. Calculate its molar
conductivity.
Solution 8:
3.Electrochemistry
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Question 9:
The resistance of a conductivity cell containing 0.001 M KCl solution at 298 K is 1500 .What
is the cell constant if conductivity of 0.001 M KCl solution at 298 K is 0.146 10-3S cm-1?
Solution 9:
Conductivity
Cell constant =
Conductance
=Conductivity Resistance
= 0.146 10-3S cm-1 1500
= 0.218 cm-1
Question 10:
The conductivity of NaCl at 298 K has been determined at different concentrations and the
results are given below:
Concentration/M 0.001 0.010 0.020 0.050 0.100
10 K/S m
2 -1
1.237 11.85 23.15 55.53 106.74
Calculate m for all concentrations and draw a plot between m and
C1/2.
Find the value of mo
Solution 10:
1S cm 1
1 (unit conversion factor)
100S m 1
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Class XII – NCERT – Chemistry Chapter 3
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Question 11:
Conductivity of 0.00241 M acetic acid is 7.896 10-5 Scm-1. Calculate its. Calculate its molar
conductivity. If om for acetic acid is 390.5 S cm2mol-1, what is its dissociation constant?
Solution 11:
1000
cm
Molarity
7.896 10 5
S cm1 1000cm3L1
0.00241 mol L-1
= 32.76 S cm2 mol-1
cm 32.76
8.4 102
m 390.5
o
Question 12:
How much charge is required for the following reductions:
(i) 1 mol of Al3+to Al?
(ii) 1 mol of Cu2+to Cu?
(iii) 1 mol of MnO4-to Mn2+?
Solution 12:
3.Electrochemistry
Class XII – NCERT – Chemistry Chapter 3
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Question 13:
How much electricity in terms of Faraday is required to produce.
(i) 20.0 g of Ca from molten CaCl2?
(ii) 40.0 g of Al from molten Al2O3?
Solution 13:
(i) Ca2++ 2e- Ca
Thus, 1 mol of Ca, i.e., 40g of Ca require = 2F electricity
20 g of Ca require = 1 F of electricity
(ii) Al3++ 3e- A1
Thus, 1 mole of Al, i.e., 27g of Al require = 3 F electricity
40g of Al will require electricity
3
40 4.44 F of electricity.
27
Question 14:
How much electricity is required in coulomb for the oxidation of
(i) 1 mol of H2O to O2
(ii) 1 mol of FeO to Fe2O3
Solution 14:
(i) The electrode reaction for 1 mol of H2O is
1
H 2O H 2 O2
2
1
i.e., O 2 O2 2e
2
Quantity of electricity required
= 2F = 2 96500 C = 193000 C
(ii) The electrode reaction for 1 mol of FeO is
1 1
FeO O2 Fe2O3
2 2
i.e., Fe Fe + e-
2+ 3+
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Class XII – NCERT – Chemistry Chapter 3
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Question 15:
A solution of Ni(NO3)2 is electrolysed between platinum electrodes using a current of 5 amperes
for 20 minutes. What mass of Ni is deposited at the cathode?
Solution 15:
Quantity of electricity passed = (5A) (20 60 sec) = 6000 C
Ni2+ + 2e- Ni
Thus, 2F, i.e., 2 96500 C of charge deposit = 1 mole of Ni = 58.7 g
6000 C of charge will deposit
58.7 6000
1.825g of Ni.
2 96500
Question 16:
Three electrolytic cells, A, B, C containing solutions of ZnSO4, AgNO3 and CuSO4 , respectively
are connected in series. A steady current of 1.5 amperes was passed through them until 45 g of
silver deposited at the cathode of cell B. How long did the current flow? What mass of copper
and zinc were deposited?
Solution 16:
Given: I = 1.5 A, W = 1.5 g of Ag t = ?, E = 108, n = 1
E
Using Faraday’s 1 st law of electrolysis W = ZIt or W It
nF
1.45 96500
or, t = = 863.73 seconds.
1.5 108
Now for Cu, W1 = 1.45 g of Ag E1 = 108, W2 = ?
E2 = 31.75
W E
Form Faraday’s 2ndlaw of electrolysis 1 1
W2 E2
1.45 108 1.45 31.75
W2
W2 31.75 108
=0.426 g of Cu
Similarly, for Zn, W1 = 1.45 g of Ag, E1 = 108,
W2 = ? E2 = 32.65
W E
Using formula, 1 1
W2 E2
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1.45 108
W2 32.65
1.45 32.65
W2 0.438 of Zn
108
Question 17:
Predict if the reaction between the following is feasible:
(i) Fe3+(aq) and I-(aq)
(ii) Ag+(aq) and Cu(S)
(iii) Fe3+(aq) and Br- (aq)
(iv) Ag(S) and Fe3+(aq)
(v) Br2 (aq) and Fe2+(aq).
Given standard electrode potentials:
E1/o 2, I I
0.541 V ,
2,
o
ECu 2
, Cu
0.34 V ,
E1/o 2 Br , Br 1.09 V ,
2
E o
Ag , Ag
0.80 V , EFe
o
3
, Fe 2
0.77 V .
Solution 17:
The reaction is feasible if the emf of the cell reaction is positive.
1
(i) Fe3 ( aq ) I ( aq ) Fe 2 ( aq ) I 2 ( g )
2
i.e., Pt/I 2 /I (aq ) || Fe3 ( aq ) | Fe 2 (aq ) | Pt
E cell E Fe3+ ,Fe2+ E 1/2 I
2 ,I
1
(iii) Fe3 ( aq ) Br ( aq ) Fe 2 ( aq ) Br2 ( g )
2
Ecell 0.77 1.09 0.32V Not feasible.
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1
(v) Br2 ( g ) Fe 2 ( aq ) Br ( aq ) Fe3 ( aq )
2
Ecell 1.09 0.77 0.32V Feasible .
Question 18:
Predict the products of electrolysis in each of the following .
(i) An aqueous solution of AgNO3 with silver electrodes.
(ii) An aqueous solution of AgNO3 With platinum electrodes.
(iii) A dilute solution of H2SO4 with platinum electrodes.
(iv) An aqueous solution of CuCl2 with platinum electrodes.
Solution 18:
(i) AgNO3 (s) + aq Ag+(aq) + NO-3(aq)
H 2O H OH
At cathode: Ag+ions have lower discharge potential than H+ ions. Hence, Ag+ ions will be
deposited as Ag in preference to H+ ions:
Ag+ (aq) + e- Ag(S)
At anode: As Ag anode is attacked by NO3-ions, Ag of the anode will dissolve to form Ag+ ions
in the solution.
Ag(S) Ag+(aq) + e-
(ii) At cathode: Ag+ ions have lower discharge potential than H+ ions. Hence, Ag+ ions will be
deposited as Ag in preference to H+ ions.
At anode: As anode is not attackable, out of OH-and NO-3ions, OH-ions have lower discharge
potential. Hence OH- will be discharged in preference to NO-3ions, which then decompose to
give out O2.
OH-(aq) OH + e-
4OH 2H2O (l) + O2(g)
(iii) H2SO4 (aq) 2H+(aq) + SO42- (aq)
H 2O H OH
At cathode: H++ e- H,
H + H H2(g)
At anode: OH- OH + e-
4OH 2H2O + O2(g)
3.Electrochemistry
Class XII – NCERT – Chemistry Chapter 3
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3.Electrochemistry