ELECTROCHEMISTRY
ELECTROCHEMISTRY
ELECTROCHEMISTRY
ANS: It is a cell in which products cannot be changed back into reactants, i.e. it is not
rechargeable, e.g. dry cell and mercury cell. In this cell, electrical energy is produced by the redox
reaction occurring in the cell.
ANS: Those cells which are rechargeabe, i.e. products can be converted back into reactants.
4 Arrange the following metals in the order in which they displace each other from the solution of
their salts. 1
Al, Cu, Fe, Mg and Zn.
ANS: Mg, Al, Zn, Fe, Cu is the decreasing order of their reactivity.
ANS: Specific conductance is defined as the conductance of electrolyte when distance between
electrodes is 1 cm and area of cross section is 1 cm2.
7 Complete: Λ° Na2SO4 = 1
ANS:
10 (a) Following reactions occur at cathode during the electrolysis of aqueous silver chloride solution: 2
1
On the basis of their standard reduction electrode
potential (E°) values, which reaction is feasible at the cathode and why?
(b) Define limiting molar conductivity. Why conductivity of an electrolyte solution
decreases with the decrease in concentration?
11 (a) Following reactions occur at cathode during the electrolysis of aqueous copper (II) chloride
solution:
12 Following reactions occur at cathode during electrolysis of aqueous sodium chloride solution:
13 The standard electrode potential (E°) for Daniel cell is +1.1 V. Calculate the ∆G° for the reaction:
2
ANS:
14 Zinc rod is dipped in 0.1 M solution of ZnSO4. The salt is 95% dissociated at this dilution at 298 K.
2
Calculate the electrode potential. Given = – 0.76 V.
2
ANS:
15 Give an example of a fuel cell and write the cathode and anode reactions for it. 2
ANS: Fuel cells are those cells in which chemical energy of a fuel is converted into electrical
energy.
16 Write the overall reaction that occurs during use (discharging) of nickelcadmium cell. Is it a
2
primary or a secondary cell. Mention its one merit over the lead storage cell.
ANS: Nickel-cadmium cell: It is another type of secondary cell which has longer life than lead
storage cell but more expensive to manufacture. The overall reaction during discharge is
Cd(s) + 2Ni(OH)3(s) → CdO(s) + 2Ni(OH)2(s) + H2O (l). Its merit over the lead storage cell
is its longer life as compared to lead storage battery.
17 Mention the reactions occurring at (i) anode, (ii) cathode, during working of a mercury cell. Why
2
does the voltage of a mercury cell remain constant during its operation?
ANS: Mercury cell: It consists of zinc mercury amalgam as anode, a paste of HgO and carbon
as the cathode. The electrolyte is a paste of KOH and ZnO. The reaction of the cell is
At anode: Zn (amalgam) + 2OH– → ZnO(s) + H2O + 2e–
At cathode: HgO(s) + H2O + 2e– → Hg(l) + 2OH–
The net reaction: Zn (amalgam) + HgO(s) → ZnO(s) + Hg(l)
It gives constancy in voltage over long period because no ions are involved in net cell reaction. It
is used in watches and hearing aids.
18 The conductivity of 0.20 M KCl at 298 K is 0.025 S cm –1. Calculate its molar conductivity. 2
ANS:
19 The conductivity of 0.001 M acetic acid is 4 × 10 –5 S cm–1. Calculate the dissociation constant of
2
an acid, if molar conductivity at infinite dilution for acetic acid is 390 S cm 2 mol–1.
ANS:
20 Calculate the time to deposit 1.27 g of copper at cathode when a current of 2 A was passed
through the solution of CuSO4. 2
(Molar mass of Cu = 63.5 g mol–1, 1 F = 96500 C mol–1)
3
ANS:
21 In the electrolysis of aqueous sodium bromide, there are two possible anodic reactions:
2H2O(l) → O2(g) + 4H+(aq) + 4e–, E° = 1.23 V
2
2Br–(aq) → Br2(g) + 2e–, E° = 1.08 V
Which reaction occurs at anode and why?
ANS: 2Br–(aq) → Br2 + 2e– occurs at anode because it has lower reduction potential. Liberation
of O2 requires over voltage.
ANS:
23 The specific conductivity of 0.40 M solution of KCl at 258 K in 4.96 × 10 –2 Scm–1. Calculate its
2
molar conductivity.
ANS:
ANS: (a)
(b) H2—
O2 Fuel Cell was used in Apollo space programme for providing electrical power.
4
ANS:
26 A strip of nickel metal is placed in a 1 molar solution of Ni(NO 3)2 and a strip of silver metal is
placed in a 1-molar solution of AgNO3. An electrochemical cell is created when the two solutions
are connected by a salt bridge and the two strips are connected by wires to a voltmeter.
(i) Write the balanced equation for the overall reaction occurring in the cell and calculate the cell
potential. 3
(ii) Calculate the cell potential, E, at 25 °C for the cell if the initial concentration of Ni(NO 3)2 is
0.100 molar and the initial concentration of AgNO3 is 1.00 molar.
ANS:
27 Conductivity of 2.5 × 10–4 M methanoic acid is 5.25 × 10–5 S cm–1. Calculate its molar conductivity
and degree of dissociation. 3
–1 – –1
Given: λ0(H ) = 349.5 S cm mol and λ0(HCOO ) = 50.5 S cm2 mol .
+ 2
ANS:
5
28 When a certain electrolytic cell was filled with 0.1 M KCl, it has resistance of 85 ohms at 25 °C.
When the same cell was filled with an aqueous solution of 0.052 M unknown electrolyte, the
3
resistance was 96 ohms. Calculate the molar conductance of the electrolyte at this concentration.
[Specific conductance of 0.1 M KCl = 1.29 × 10 –2 ohm–1 cm–1]
ANS:
29 The electrical resistance of a column of 0.05 mol L–1 NaOH solution of diameter 1 cm and length
3
50 cm is 5.55 × 103 ohm. Calculate its resistivity, conductivity and molar conductivity.
ANS:
30 An aqueous solution of copper sulphate, CuSO4 was electrolysed between platinum electrodes
using a current of 0.1287 ampere for 50 minutes. (Atomic mass of Cu = 63.5 g mol –1]
(a) Write the cathodic reaction.
(b) Calculate: 3
(i) Electric charge passed during electrolysis
(ii) Mass of copper deposited at the cathode
[Given: 1F = 96,500 C mol–1]
ANS:
31 Calculate the emf of the following cell at 25 °C: Zn | Zn 2+ (0.001 M) || H+ (0.01 M) | H2(g) (1 bar) |
3
Pt(s)
6
ANS:
32 Estimate potential difference needed to reduce Al2O3 at 500 °C and equilibrium constant ‘K’.
3
ANS:
ANS:
7
34 Limiting molar conductivities of NH4Cl, NaOH and NaCl are respectively 129.8, 217.4 and 108.9 S
cm2 and the molar conductivity of 10–2 M solution of NH4OH is 9.33 S cm2 mol–1. Calculate the 3
degree of dissociation of NH4OH.
ANS:
35 How long a current of 3 amperes has to be passed through a solution of silver nitrate to coat a
metal surface of 80 cm2 with a 0.005 mm thick layer? Density of Ag is 10.5 g cm –3. At. Wt. of Ag = 3
108.0 u.
ANS:
ANS:
8
ANS:
38 Consider the cell: Mg(s) | Mg2+ (0.13 M) || Ag+ (1.0 × 10–4) M | Ag(s)
Its emf is 2.96 V. Calculate E°cell. 3
(R = 8.314 JK–1 mol–1, 1F = 96500 C mol–1)
ANS:
39 A conductivity cell was filled with 0.1 M NaCl solution at 25 °C. Its resistance was found to be
176.6 ohms. The conductivity of the solution is 9.2 × 10 –3 S cm–1. The cross-sectional area of the
3
electrode used was 4 cm2. What must be distance between the electrodes and calculate molar
conductivity.
ANS:
40 How long will it take an electric current of 0.15 A to deposit all the copper from 500 mL of 0.15 M
3
copper sulphate solution?
9
ANS:
ANS: (a) (i) Limiting molar conductivity: It is defined as the maximum molar conductance of an
electrolyte when solution is infinitely dilute, i.e. concentration approaches zero when electrolyte
solution is kept in cell, unit distance apart having large area of cross-section to hold enough
electrolyte.
(ii) Fuel cell is a cell in which chemical energy of a fuel is converted into electrical energy.
(b) R = 100 ohms, M = 0.1 mol L –1 of KCl
42 (a) State Faraday’s first law of electrolysis. How much charge in terms of Faraday is required for
the reduction of 1 mol of Cu2+ to Cu?
(b) Calculate emf of the following cell at 298 K: 5
Mg(s) | Mg2+ (0.1 M) || Cu2+ (0.01) | Cu(s) [Given E°cell = + 2.71 V, 1 F = 96500 C mol–1]
ANS: (a) It states that the mass of the substance deposited is directly proportional to charge
passed through electrolyte.
10
Cu2+ + 2e– → Cu(s) 2 Faraday of charge is required to deposite 1 mole of copper, i.e.
63.5 g of Cu. (b)
43 (a) State Kohlrausch law of independent migration of ions. Write an expression for the molar
conductivity of acetic acid at infinite dilution according to Kohlrausch law.
(b) Calculate for acetic acid.
5
Given that (HCl) = 426 S cm2 mol–1
(NaCl) = 126 S cm2 mol–1
(CH3COONa) = 91 S cm2 mol–1
ANS:
44 (a) What type of a battery is lead storage battery ? Write the anode and cathode reactions and the
overall cell reaction occurring in the operation of a lead storage battery.
(b) Calculate the potential for half-cell containing 0.10 M K2Cr2O7(aq), 0.20 M Cr3+(aq) and 1.0 × 5
10–4 M H+(aq)
The half-cell reaction is
11
Cr2O72–(aq) + 14 H+(aq) + 6e– → 2Cr3+(aq) + 7H2O(l) and the standard electrode potential
is given as E° = 1.33 V.
ANS: (a) Lead storage battery: It is a secondary cell. It consists of a lead anode and a grid of
lead packed with lead dioxide as cathode. A solution of sulphuric acid (38% by mass) is used as
electrolyte.
The cell reactions when the battery is in use are given below:
The overall
cell reaction consisting of cathode and anode reactions is:
On recharging the
battery, the reaction is reversed.
(b)
45 (a) How many moles of mercury will be produced by electrolysing 1.0 M Hg(NO 3)2 solution with a
current of 2.00 A for 3 hours ? [Hg(NO3)2 = 200.6 g mol–1]
(b) A voltaic cell is set up at 25° C with the following half-cells Al3+ (0.001 M) and Ni2+ (0.50 M).
Write an equation for the reaction that occurs when the cell generates an electric current and 5
determine the cell potential.
ANS:
12
46 (a) Define the term conductivity and molar conductivity of the solution of an electrolyte. Comment
on its variation with temperature.
(b) The measured resistance of conductivity cell was 100 ohms. If 7.45 g of KCl is dissolved per
5
litre of solution. Calculate (i) specific conductance (ii) molar conductance. [ = 1.25 cm–1, Molar
mass of KCl is 74.5 g mol–1]
(b)
47 A new galvanic cell of E°cell more than E°cell of Daniel cell is connected to Daniel cell in a manner
that new cell gives electrons to cathode, what will happen
(a) Ecell will increase
(b) Ecell will decrease 1
(c) No change will take place
(d) Daniel cell will work as electrolytic cell where Zn will be deposite on zinc rod and copper will
dissolve from copper rod.
ANS:
49 Which of the following expression is correct for ‘Ka’ in terms of Λ° and Λ, where ‘C’ is molarity.
ANS:
13
50
1
ANS:
51 X(s) + 2Y+(aq) X2+(aq) + 2Y(s); (E°cell = 0.059 V ) What is the value of ‘K’ for above reaction?
(a) 1 × 10 (b) 1 × 102
8 1
(c) 4 × 103 (d) 3 × 104
ANS:
ANS: (c) E°cell depends upon concentration (amount) of substance therefore, intensive property
but ∆G is extensive property.
ANS: (b) It is because = 0.77 V, it means Fe3+ can gain electron early to form Fe 2+.
55 Λm of M/32 solution of weak acid is 8 S cm 2 mol–1 and limiting molar conductivity is 400 S cm 2
mol–1. Ka for acid is (a) 1.25 × 10–6 (b) 6.25 × 10–4 1
(c) 1.25 × 10–4 (d) 1.25 × 10–5
14
ANS:
56 The positive value of the standard electrode potential of Cu 2+/Cu indicates that ____________. (a)
this redox couple is a stronger reducing agent than the H+/H2 couple.
(b) this redox couple is a stronger oxidising agent than H +/H2. 1
(c) Cu can displace H2 from acid.
(d) Cu cannot displace H2 from acid.
57 E°cell for some half cell reactions are given below. On the basis of these mark the correct answer.
(d) In dilute sulphuric acid solution, ion will be oxidised to tetrathionate ion at anode.
ANS:
58
= 1.1V for Daniel cell. Which of the following expressions are correct description of state of
ANS:
15
59
ANS:
60 Match the terms given in Column I with the units given in Column II.
Column I Column II
(d) G* (iv) V
61 Match the terms given in Column I with the items given in Column II.
Column I Column II
Column I Column II
1
(a) Lead storage battery (i) maximum efficiency
16
(c) Fuel cell (iii) gives steady potential
ANS: (a) Assertion and reason both are correct statements and reason is correct explanation
for assertion.
ANS: (a) Assertion and reason both are correct statements and reason is correct explanation
for assertion.
66 1
for weak electrolyte is determined by _________.
17
ANS: Kohlrausch law
ANS: 3F
68
1
number of moles of electrons gained or lost = _________.
ANS: n=4
69 1
If is –ve, cell will not work. [True/False]
ANS: True.
70 If external emf opposing Daniel cell is less than 1.10 V, cell will keep in working. [True/False] 1
ANS: True.
71 Salt bridge completes internal circuit and prevents accumulation of charges. [True/False] 1
ANS: True.
72 Inert electrolyte in salt bridge reacts with solution of half cells. [True/False] 1
ANS: False, (Inert electrolyte does not react with any of the electrolyte present in half cell).
73 Calculate the time in hours for collecting 24g of Mg from MgCl 2 using 10 amp current? (Mg = 2 hr)
(a) 2 hrs (b) 4 hrs 1
(c) 5 hrs (d) 5.36 hour
ANS:
74
18
75
76
ANS:
ANS:
19
78 What will happen during the electrolysis of aqueous solution of CuSO4 by using platinum
electrodes? [NCERT Exemplar Problem]
(a) Copper will deposit at cathode.
1
(b) Copper will deposit at anode.
(c) Oxygen will be released at anode.
(d) Copper will dissolve at anode.
ANS:
79 What will happen during the electrolysis of aqueous solution of CuSO 4 in the presence of Cu
electrodes?
(a) Copper will deposit at cathode.
1
(b) Copper will dissolve at anode.
(c) Oxygen will be released at anode.
(d) Copper will deposit at anode.
ANS:
ANS:
Column I Column II
1
(a) Lechlanche (i) cell reaction
cell 2H2 + O2 → 2H2O
20
(ii) does not involve any ion in solution and is used in
(b) Ni–Cd cell
hearing aids.
83 Match the items of Column I and Column II on the basis of data given below:
Column I Column II
ANS: (a) (iii) (b) (i) (c) (vii) (d) (v) (e) (iv) (f) (ii) (g) (vi)
ANS: (e) Assertion and reason both are correct statements but reason is not correct
explanation of assertion.
85
number of Faradays required = _________. 1
21
ANS: 6F
ANS: O2
87 Agar – Agar is gum like substance which holds inert electrolyte. [True/False] 1
ANS: True
88 KCl is used in salt bridge because K+ and Cl– have almost equal mobility. [True/False] 1
ANS: True.
89 Anode is on left side and cathode is on right side of galvanic cell. [True/False] 1
ANS: True.
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