Wa0031.
Wa0031.
Wa0031.
Question 2.
Express the relation between conductivity and molar conductivity of a solution held
in a cell. (Delhi 2011)
Answer:
Λ = KC= Conductivity Concentration
m
Question 3.
What is the effect of catalyst on:
(i) Gibbs energy (ΔG) and
(ii) activation energy of a reaction? (Delhi 2017)
Answer:
(i) There will be no effect of catalyst on Gibbs .energy.
(ii) The catalyst provides an alternative pathway by decreasing the activation energy
of a reaction.
Question 4.
What is the effect of adding a catalyst on
(a) Activation energy (Ea), and
(b) Gibbs energy (AG) of a reaction? (All India 2017)
Answer:
(a) On adding catalyst in a reaction, the activation energy reduces and rate of
reaction is fastened.
(b) A catalyst does not alter Gibbs energy (AG) of a reaction.
Construct the redox equation from the two half cell reactions and predict if this
reaction favours formation of reactants or product shown in the equation. (All India
2009)
Answer:
The reactions can be represented at anode and at cathode in the following ways :
At anode (oxidation) :
Sn → = Sn (aq) + 2e ] × 5 E° = + 0.15 V
2+ 4+ –
At cathode (reduction) :
MnO (aq) + 8H (aq) + 5e → Mn (aq) + 4H O (I)] × 2 E° = + 1.51 V
–
4
+ – 2+
2
Question 6.
Express the relation among the cell constant, the resistance of the solution in the cell
and the conductivity of the solution. How is the conductivity of a solution related to
its molar conductivity? (All India 2010)
Answer:
1R×1a = Conductance (C) × Cell constant
Molar conductance : (Λ ) = K×1000c. m
Question 7.
Given that the standard electrode potentials (E°) of metals are :
K /K = -2.93 V, Ag /Ag = 0.80 V, Cu /Cu = 0.34 V,
+ + 2+
Arrange these metals in increasing order of their reducing power. (All India 2010)
Answer:
Ag /Ag < Cu /Cu < Fe /Fe < Cr /Cr < Mg / Mg < K /K
+ 2+ 2+ 3+ 2+ +
More negative the value of standard electrode potentials of metals is, more will be
the reducing power.
Question 8.
Two half-reactions of an electrochemical cell are given below :
MnO (aq) + 8H (aq) + 5e → Mn (aq) + 4H O (I), E° = 1.51 V
–
4
+ – 2+
2
Construct the redox reaction equation from the two half-reactions and calculate the
cell potential from the standard potentials and predict if the reaction is reactant or
product favoured. (All India 2010)
Answer:
The reactions can be represented at anode and at cathode in the following ways :
At anode (oxidation) :
Sn → Sn (aq) + 2e ] × 5 E° = + 0.15 V
2+ 4+ –
Af cathode (reduction) :
MnO (aq) + 8H (aq) + 5e → Mn (aq) + 4H O (I)] × 2 E° = + 1.51 V
–
4
+ – 2+
2
H CO ⇌2H + CO
2 3
+
2
2-
H O ⇌ H + OH
2
+ –
H + e → H
+ –
4H + O → 2H O 2 2
Question 10.
Determine the values of equilibrium constant (K ) and ΔG° for the following reaction : c
E° = 1.05 V
(1F = 96500 C mol ) (Delhi 2011) -1
Answer:
According to the formula
ΔG° = -nFE° = – 2 × 96500 ×1.05
or ΔG° = -202650 J mol = -202.65 KJ mol -1 -1
Question 11.
Two half-reactions of an electrochemical cell are given below :
MnO (aq) + 8H (aq) + 5e → Mn (aq) + 4H O (I), E° = 1.51 V
–
4
+ – 2+
2
Construct the redox equation from the standard potential of the cell and predict if the
reaction is reactant favoured or product favoured. (Delhi 2011)
Answer:
The reactions can be represented at anode and at cathode in the following ways :
At anode (oxidation) :
Sn → = Sn (aq) + 2e ] × 5 E° = + 0.15 V
2+ 4+ –
At cathode (reduction) :
MnO (aq) + 8H (aq) + 5e → Mn (aq) + 4H O (I)] × 2 E° = + 1.51 V
–
4
+ – 2+
2
Now E° = E° – E°
cell cathode anode
Question 12.
Express the relation among cell constant, resistance of the solution in the cell and
conductivity of the solution. How is molar conductivity of a solution related to its
conductivity? (All India 2012)
Answer:
GG* = K
where Q is conductance;
G * is cell constant;
K is conductivity
G* × 1R = K ⇒ G* = RK
∴ Λ = K×1000C S cm mol
m
2 -1
Question 13.
The molar conductivity of a 1.5 M solution of an electrolyte is found to be 138.9 S
cm2 mol-1. Calculate the conductivity of this solution. (All India 2012)
Answer:
C = 1.5 M, Λ = 138.9 S cm mol
m
2 -1
Λ = K×1000c
m
∴K = Λm×C1000=138.9×1.51000 = 0.20835 S cm -1
Question 14.
A zinc rod is dipped in 0.1 M solution of ZnSO . The salt is 95% dissociated at this 4
Answer:
The electode reaction is given as
Zn + 2e → Zn
+2
Question 15.
Write the reactions taking place at cathode and anode in lead storage battery when
the battery is in use. What happens on charging the battery ? (Comptt. All India 2012)
Answer:
At Anode: Pb + SO → PbSO + 2e
4
-2
4
On charging the battery, the reaction is reversed and PbSO on anode and cathode is 4
Question 16.
The conductivity of 0.20 M solution of KCl at 298 K is 0.025 S cm . Calculate its -1
Question 17.
The standard electrode potential (E°) for Daniel cell is +1.1 V. Calculate the ΔG° for
the reaction
Zn(s) + Cu (aq) → Zn (aq) + Cu(s)
2+ 2+
Answer:
We know, ΔG° = -nF E°cell
Given : E°cell = 1.1 volt
∴ ΔG° = -2 × 96500 C mol × 1.1 volt -1
= -212300 CV mol -1
Question 18.
The conductivity of 0.001 M acetic acid is 4 × 10 S/cm. Calculate the dissociation -5
constant of acetic acid, if molar conductivity at infinite dilution for acetic acid is 390
S cm /mol. (Comptt. Delhi 2013)
2
Answer:
Given : K = 4 × 10 S/cm, M = 0.001 M
-5
Answer:
Given : E° = 1.1V, F = 96,500 C mol , n = 2 -5
Zn + Cu ⇌ Cu + Zn
2 2+
Question 20.
State Kohlrausch law of independent migration of ions. Why does the conductivity of
a solution decrease with dilution? (All India 2014)
Answer:
Kohlrausch law of independent migration of ions: The limiting molar conductivity of
an electrolyte (i.e. molar conductivity at infinite dilution) is the sum of the limiting
ionic conductivities of the cation and the anion each multiplied with the number of
ions present in one formula unit of the electrolyte
Λ°m for A B = xλ° + yλ°
x y + –
Question 21.
Define the following terms :
(i) Fuel cell
(ii) Limiting molar conductivity (Λ ) (All India 2014)
°
m
Answer:
(i) Fuel cells : These cells are the devices which convert the energy produced during
combustion of fuels like H , CH , etc. directly into electrical energy.
2 4
(ii) The molar conductivity of a solution at infinite dilution is called limiting molar
conductivity and is represented by the symbol Λ .°
m
Question 22.
Define the following terms :
(i) Molar conductivity (Λ ) m
Λ = KAl I = 1 and A = V
m
∴ Λ = KV Unit = S cm mol
m
2 -1
Answer:
(i) Rate constant (k): It is a proportionality constant and is equal to the rate of
reaction when the molar concentration of each of the reactants is unity.
(ii) Activation energy (E ): The minimum extra amount of energy absorbed by the
a
Question 24.
Set up Nemst equation for the standard dry cell. Using this equation show that the
voltage of a dry cell has to decrease with use. (Comptt. All India 2014)
Answer:
Cell reaction of a dry cell can be represented as
Zn + Hg → Zn + Hg (n = 2)
2+ 2+
Nemst equation
E = E° – 0.05912log[Zn2+]Hg2+
cell cell
The voltage of dry cell has to decrease because the concentration of electrolyte
decreases in the reactions.
Question 25.
Define conductivity and molar conductivity for the solution of an electrolyte. Discuss
their Variation with change in temperature. (Comptt. All India 2014)
Answer:
Conductivity: 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. It is represented by
K.
Its unit is S cm -1
electrodes is so large that the whole of the solution is contained between them. It is
represented by Λ . m
Question 26.
(a) Following reactions occur at cathode during the electrolysis of aqueous silver
chloride solution :
Ag (aq) + e → Ag(s) E° = +0.80 V
+ –
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? (Delhi 2015)
Answer:
(a) At the cathode Ag (aq) + e → Ag(s) + –
reaction is feasible, because Ag+ ion has higher reduction potential i.e. higher E°
value.
(b) Limiting molar conductivity or the molar conductivity of solution at infinite
dilution is the sum of molar conductivity cations and anions.
Conductivity of an electrolyte solution decreases on dilution because number of ions
per unit volume decreases.
Question 27.
Calculate the time to deposit 1.27 g of copper at cathode when a current of 2A was
passed through the solution of CuSO . 4
Answer:
CuSO → Cu+ + SO
4 4
2-
Cu + 2e → Cu
2+ –
39.05 S cm mol . 2 -1
Given: λ°(H ) = 349.6 S cm mol and λ°(CH3COO ) = 40.9 S cm mol (Delhi 2017)
+ 2 -1 – 2 -1
Answer:
Λ (HAC) = λ° + λ°
°
m H
+
AC
–
= λ° COOH = λ° + λ° COO
CH3 H
+
CH3
–
= 390.5 S cm mol 2 -1
Question 30.
Write the name of the cell which is generally used in hearing aids. Write the reactions
taking place at the anode and the cathode of this cell. (All India 2017)
Answer:
Mercury cells are used in hearing aids.
Reaction at anode:
Zn (Hg) + 2OH → ZnO (s) + H O + 2e–
2
–
Reaction at cathode:
HgO + H O + 2e → Hg (l) + 2OH
2
– –
Question 31.
Write the name of the cell which is generally used in transistors. Write the reactions
taking place at the anode and the cathode of this cell. (All India 2017)
Answer:
Leclanche cells (Dry cell) is used in transistors.
Reaction at Anode:
Zn(s) → Zn + 2e 2+ –
At Cathode:
MnO + NH+4 + e → MnO(OH) + NH
2
–
3
Question 32.
Write the name of the cell which is generally used in inverters. Write the reactions
taking place at the anode and the cathode of this cell. (Delhi 2017)
Answer:
Lead storage battery is used in inverters.
At Anode:
Pb(s) + SO2−4(aq) → PbSO (s) + 2e 4
–
At Cathode:
PbO (s) + SO2−4(aq) + 4H (aq) + 2e
2
+ –
PbSO (s) + 2H O
4 2
Question 33.
Following reactions can occur at cathode during the electrolysis of aqueous silver
nitrate solution using Pt electrodes :
On the basis of their standard electrode potential values, which reaction is feasible at
cathode and why? (Comptt. All India 2017)
Answer:
As the standard electrode potential of silver is greater than that of the other
hydrogen electrode, so reduction of silver takes place and reaction (i) will be feasible
i.e., Ag+(aq) + e → Ag
–
(s)
Question 34.
Following reactions may occur at cathode during the electrolysis of aqueous silver
nitrate solution using silver electrodes :
On the basis of their standard electrode potential values, which reaction is feasible at
cathode and why? (Comptt. All India 2017)
Answer:
The value of E0cell is positive due to higher standard electrode potential (E° = +0.80
V) of Ag+ than that of H+ so reaction (i) will be feasible at cathode
i.e. Ag+(aq) + e → Ag(s). Silver has higher reduction potential.
–
Question 35.
Following reactions may occur at cathode during the electrolysis of aqueous
CuCl solution using Pt electrodes:
2
On the basis of their standard electrode potential values, which reaction is feasible at
cathode and why? (Comptt. All India 2017)
Answer:
Since the standard electrode potential of Cu is greater than that of H , so reaction (i)
2+ +
Answer:
The reaction takes place at anode and cathode in the following ways :
At anode (oxidation) :
Cu(s) → Cu (aq) + 2e
2+ –
At cathode (reduction) :
Cu(s) + 2Ag (aq) → Cu (aq) + 2Ag(s)
2+ 2+
Question 37.
The electrical resistance of a column of 0.05 M NaOH solution of diameter 1 cm and
length 50 cm is 5.55 × 10 ohm. Calculate its resistivity, conductivity and molar
3
Question 38.
A voltaic cell is set up at 25°C with the following half cells :
Al/Al (0.001 M) and Ni/Ni (0.50 M)
3+ 2+
Write an equation for the reaction that occurs when the cell generates an electric
current and determine the cell potential.
E0Ni2+/Ni=−0.25V and E0Al3+/Al=−1.66V
(Log 8 × 10 = -0.54) (All India 2012)
-6
Answer:
Half cell reactions and overall cell reaction are
Question 39.
A solution containing 30 g of non-volatile solute exactly in 90 g of water has a vapour
pressure of 2.8 kPa at 298 K. Further 18 g of water is added to this solution. The new
vapour pressure becomes 2.9 kPa at 298 K. Calculate
(i) the molecular mass of solute and
(ii) vapour pressure of water at 298 K. (Comptt. Delhi 2012)
Answer:
For a very dilute solution
Electrons released at anodic spot move through the metal and go to another spot on
the metal and reduce oxygen in presence of H . This spot behaves as cathode +
At Cathode : O + 4H + 4e- 2
+
Question 41.
When a certain conductance cell was filled with 0.1 M KCl, it has a resistance of 85
ohms at 25°C. When the same cell was filled with an aqueous solution of 0.052 M
unknown electrolyte, the resistance was 96 ohms. Calculate the molar conductance
of the electrolyte at this concentration.
[Specific conductance of 0.1 M KCl = 1.29 × 10 ohm cm ] (Comptt. All India 2012) -2 -1 -1
Answer:
Cell contant = Conductivity × Resistance
G* = K × R
= 1.29 × 10 Ω × 85
-2 -1
= 109.65 × 10 Ω -2 -1
= 1.0965 cm -1
Question 42.
(a) How many coulombs are required to reduce 1 mole Cr O to Cr ? 2 7
2- 3+
(b) The conductivity of 0.001 M acetic acid is 4 × 10 S/m. Calculate the dissociation -5
constant of acetic acid if Λ0m,for acetic acid is 390 S cm mol . (Comptt. All India 2 -1
2012)
Answer:
(a) Cr O + 14H + 6e → 2Cr + 7H O
2 7
-2 + -3
2
Question 43.
The cell in which the following reaction occurs :
2Fe (aq) + 2I (aq) → 2Fe (aq) + I (s) has E = 0.236V at 298K. Calculate the
3+ – 2+
2
0
cell
standard Gibbs energy and the equilibrium constant of the cell reaction.
(Antilog of 6.5 = 3.162 × 10 ; of 8.0 = 10 × 10 ; of 8.5 = 3.162 × 10 ) (Comptt. All India
6 8 8
2012)
Answer:
log K = nE0 cell 0.0591=2×0.2360.0591 = 8
C
K = antilog 8 = 1 × 10
C
8
= -45548 J/mol -1
= -45.548 kJ/mol -1
Question 44.
Calculate the emf of the following cell at 298 K: Fe(s) | Fe (0.001 M) || H (1M) | H (g) 2+ +
2
Answer:
As Fe + 2H → Fe + H (n = 2)
+ 2+
2
Question 45.
Calculate the emf of the following cell at 25°C : Ag(s) | Ag (10 M) || Cu (10 M) | + -3 2+ -1
Answer:
Given: Cell notation is incorrect. Correct cell formula is
Cu (10 m) | Cu || Ag (10 M) | Ag
2+ -1
(5)
+ -3
(s)
Question 46.
(a) What are fuel cells? Explain the electrode reactions involved in the working of
H – O fuel cell.
2 2
2013)
Answer:
(a) Fuel cells : These cells are the devices which convert the energy produced during
combustion of fuels like H , CH , etc. directly into electrical energy.
2 4
(b) The galvanic cell may be represented as Zn (s) | Zn (1M) || Cu (1M) | Cu (s) 2+ 2+
Question 47.
(a) State and explain Kohlrausch law.
(b) How much electricity in terms of Faradays is required to produce 20 g of calcium
from molten CaCl ? (Comptt. Delhi 2013) 2
Answer:
(a) Corrosion is an electrochemical phenomenon. At a particular spot of iron j
oxidation it takes place and the spot behaves j as anode and the reaction will be: i
At anode :
2Fe(s) → 2Fe + 4e 2+ –
Electrons released above move through the metal to another spot and reduce
oxygen in presence of H and the spot behaves as cathode with the reaction.
+
At cathode :
O (g) + 4H (aq) + 4e → 2H O(I)
2
+ –
2
Overall reaction :
2Fe(s) + O (g) + H (aq) → 2Fe (aq) + 2H O (l)
2
+ 2+
2
The ferrous ions are further oxidised by atmospheric oxygen to form hydrated ferric
oxide (Fe O xH O) as rust.
2 3 2
(b) Ca2 + 2e → Ca
2+ –
Thus, 1 mole of Ca i.e. 40 g of Ca requires electricity = 2F
∴ 20 g of Ca will require electricity = 1F
Question 48.
Silver is uniformly electro-deposited on a metallic vessel of surface area of 900
cm by passing a current of 0.5 ampere for 2 hours. Calculate the thickness of silver
2
deposited.
[Given: the density of silver is 10.5 g cm and atomic mass of Ag = 108 amu.]
-3
Question 49.
A current was passed for 5 hours through two electrolytic cells connected in series.
The first cell contains AuCl and second cell CuSO solution. If 9.85 g of gold was
3 4
deposited in the first cell, what amount of copper gets deposited in the second cell?
Also calculate magnitude of current in ampere.
Given: Atomic mass of Au = 197 amu and Cu = 63.5 amu. (Comptt. All India 2013)
Answer:
Question 50.
(a) Calculate Δ G for the reaction
r
0
(b) Name the type of cell which was used in Apollo space programme for providing
electrical power. (All India 2014)
Answer:
(a) Δ G = – nFE
r
0 0
= -2 × 96500 × 2.71 (∵ n = 2)
= -523,030 J mol = -523.03 KJ mol -1 -1
(b) Fuel cell was used in Apollo space programme for providing electrical power.
Question 51.
The resistance of 0.01 M NaCl solution at 25° C is 200 Ω. The cell constant of the
conductivity cell used is unity. Calculate the molar conductivity of the
solution.(Comptt. All India 2014)
Answer:
For 0.01 M NaCl solution,
R = 200 Ω, cell constant is unity.
∴ Conductivity (K) = Cell constant Resistance
= 1200 = 0.005 Sm -1
Question 52.
Calculate emf of the following cell at 25°C :
Fe | Fe (0.001 M) || H (0.01 M) | H (g) (1 bar) | Pt(s)
2+ +
2
Answer:
Fe | Fe (0.001 M) || H (0.01 M) | H (g) (1 bar) | Pt(s)
2+ +
2
= 0.4105 Volts
Question 53.
Conductivity of 2.5 × 10 M methanoic acid is 5.25 × 10 S cm . Calculate its molar
-4 -5 -1
Answer:
Concentration is 2.5 x 10 M -4
K = 5.25 × 10 Scm . -5 -1
Λcm=K×1000 Concentration
Question 54.
Calculate e.m.f. of the following cell at 298 K: 2Cr(s) + 3Fe (0.1 M) → 2Cr (0.01 M) 2+ 3+
+ 3 Fe(s)
Given: E (Cr | Cr) = -0.74 V E (Fe | Fe) = -0.44 V (Delhi 2016)
0 3+ 0 2+
Answer:
Cell reaction: 2Cr(s) + 3Fe (0.1 M) → 2Cr (0.01 M) + 3Fe(s) 2+ 3+
Given: E (Cr /Cr) = -0.74
0 3+
Question 55.
(i) Calculate the mass of Ag deposited at cathode when a current of 2 amperes was
passed through a solution of AgNO for 15 minutes. 3
has Eo Cell = 0.236 V at 298 K. Calculate the standard Gibbs energy of the cell
reaction. (Given: 1F = 96,500 C mol ) -1
(b) How many electrons flow through a metallic wire if a current of 0.5 A is passed
for 2 hours? (Given: 1F = 96,500 C mol ) (All India 2017) -1
Answer:
(a) 2Fe (aq) + 2I (aq) → 2Fe (aq) + I (s)
3+ – 2+
2
(b) Given:
I = 0.5 A
t = 2 hrs. = 2 × 60 ×60 s = 7,200 s
Q = I × t = 0.5 × 7200 = 3,600 C
96,500 C electricity flows to produce
= 6.022 × 10 electrons 23
Question 57.
Why an electrochemical cell stop working after some time? The reduction potential
of an electrode depends upon the concentration of solution with which it is in
contact. (All India 2017)
Answer:
As the cell works, the concentration of reactants decrease. Then according to Le
chatelier’s pri¬nciple it will shift the equilibrium in backward direction. On the other
hand if the concentration is more on the reactant side then it will shift the equilibrium
in forward direction. When cell works concentration in anodic compartment in
cathodic compartment decreases and hence E° cathode will decrease. Now EMF of
cell is
E = E
0
cell
0
– E
cathode
0
anode
Question 58.
Calculate Δ G° and log K for the following reaction at 298 K.
r c
2Cr(s)+3Cd2+(aq) 2Cr3+raq+3Cd(s)
[Given : E0Cell = +0.34 V, IF = 96500 C mol ] (Comptt. All India 2017)
-1
Answer:
Question 59.
Calculate Δ G° and log K. for the following reaction at 298 K. (Comptt. All India 2017)
r
Answer:
Answer:
(a) Molar conductivity: Molar conductivity of a solution at a given concentration is
tire conductance of the volume ‘V’ of a solution containing one mole of electrolyte
kept between two electrodes with area of cross section ‘A’ and distance of unit
length. It is represented by Λ (lamda).
m
Λ = KAl ∴ l = 1 and A = V
m
∴ Λ = KV Unit = S cm mol
m
2 -1
= 0.46 – 0.0592 × 5
= 0.46 – 0.1475 = 0.3125
Question 61.
(a) State the relationship amongst cell constant of a cell, resistance of the solution in
the cell and conductivity of the solution. How is molar conductivity of a solute
related to conductivity of its solution?
(b) A voltaic cell is set up at 25°C with the following half-cells :
Al | Al (0.001 M) and Ni | Ni (0.50 M)
3+ 2+
is given by
Λ = KC
m
E cell = E – E
0 0
R
0
L
Question 62.
(a) What type of a cell is the lead storage battery? Write the anode and the cathode
reactions and the overall reaction occurring in a lead storage battery while operating.
(Delhi, All India 2009)
(b) A voltaic cell is set up at 25 °C with the half-cells, Al | Al (0.001 M) and Ni |
3+
Ni (0.50 M). Write the equation for the reaction that occurs when the cell generates
2+
E cell = E – E
0 0
R
0
L
is given by
Λ = KC
m
Question 64.
(a) Define the term molar conductivity. How is it related to conductivity of the related
solution?
(b) One half-cell in a voltaic cell is constructed from a silver wire dipped in silver
nitrate solution of unknown concentration. Its other half-cell consists of a zinc
electrode dipping in 1.0 M solution of Zn(NO ) . A voltage of 1.48 V is measured for
3 2
this cell. Use this information to calculate the concentration of silver nitrate solution
used.
(E0Zn2+/Zn=−0.76V,E0Ag+/Ag = + 0.80 V) (Delhi 2009)
Answer:
(b) Half cell reactions :
Question 65.
(a) Corrosion is essentially an electrochemical phenomenon. Explain the reactions ;
occurring during corrosion of iron kept in j an open atmosphere.
(b) Calculate the equilibrium constant for the equilibrium reaction
Fe(s) + Cd (aq) ⇌ Fe (aq) + Cd(s)
2+ 2+
Electrons released above move through the metal to another spot and reduce
oxygen in presence of H and the spot behaves as cathode with the reaction.
+
At cathode :
O (g) + 4H (aq) + 4e → 2H O(I)
2
+ –
2
Overall reaction :
2Fe(s) + O (g) + H (aq) → 2Fe (aq) + 2H O (l)
2
+ 2+
2
The ferrous ions are further oxidized by atmospheric oxygen to form hydrated ferric
oxide (Fe O xH O) as rust
2 3 2
Question 66.
(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 Λ for acetic acid.
°
m
Answer:
(a) Kohlrausch law of independent migration of ions : The limiting molar conductivity
of an electrolyte (i.e. molar conductivity at infinite dilution) is the sum of the limiting
ionic conductivities of the cation and the anion each multiplied with the number of
ions present in one formula unit of the electrolyte
Question 67.
(a) Write the anode and cathode reactions and the overall reaction occuring in a lead
storage battery.
(b) A copper-silver cell is set up. The copper ion concentration is 0.10 M. The
concen¬tration of silver ion is not known. The cell potential when measured was
0.422 V. Determine the concentration of silver ions in the cell. (Delhi 2010)
Answer:
(b) The reaction takes place at anode and cathode in the following ways :
At anode (oxidation) :
Cu(s) → Cu (aq) + 2e
2+ –
At cathode (reduction) :
Cu(s) + 2Ag (aq) → Cu (aq) + 2Ag(s)
2+ 2+
and the standard electrode potential is given as E = 1.33 V. (All India 2011)
0
Answer:
(a) The lead storage battery is a secondary cell (rechargeable). During discharging
the electrode reaction occurs as follows :
At anode :
(b) E = ? E = 1.33 V
0
E = 1.33 – 0.05916log[Cr+3]2[Cr2O2−7][H+]14
0
cell
Question 69.
(a) How many moles of mercury will be produced by electrolysing 1.0 M
Hg(NO ) solution with a current of 2.00 A for 3 hours? [Hg(NO ) = 200.6 g mol ]
3 2 3 2
-1
(b) A voltaic cell is set up at 25 °C with the following half-cells Al (0.001 M) and
2+
Ni (0.50 M). Write an equation for the reaction that occurs when the cell generates
2+
Question 70.
(a) What type of a battery is the lead storage battery? Write the anode and the
cathode reactions and the overall reaction occurring in a lead storage battery when
current is drawn from it
(b) In the button cell, widely used in watches, the following reaction takes place
Zn + Ag O → Zn + 2Ag + 2OH O
(s) 2 (s)
2+
(aq) (s)
–
(aq)
Question 71.
(a) Define molar conductivity of a solution and explain how molar conductivity
changes with change in concentration of solution for a weak and a strong
electrolyte.
(b) The resistance of a conductivity cell containing 0.001 M KCl solution at 298 K is
1500 Ω. What is the cell constant if the conductivity of 0.001 M KCl solution at 298 K
is 0.146 × 10 S cm ? (Delhi 2011)
-3 -1
Answer:
(a) Molar conductivity: Conductivity of 1 M electrolytic solution placed between two
electrodes 1 cm apart and have enough area of cross-section to hold the entire
volume is known as molar conductivity or conductivity observed for one molar
solution of electrolyte. Molar condctivity increases with decrease in concentration of
solute for both weak and strong electrolytes.
(b) R = ρ (l/a)
Cell constant la=Rρ = R K
Question 72.
(a) Define the following terms :
(i) Limiting molar conductivity (ii) Fuel cell
(b) Resistance of a conductivity cell filled with 0.1 mol L KCl solution is 100 Ω. If the -1
resistance of the same cell when filled with 0.02 mol L KCl solution is 520 Ω, -1
calculate the conductivity and molar conductivity of 0.02 mol L KCl solution. The -1
Answer:
(a) (i) Fuel cells : These cells are the devices which convert the energy produced
during combustion of fuels like H , CH , etc. directly into electrical energy.
2 4
(ii) The molar conductivity of a solution at infinite dilution is called limiting molar
conductivity and is represented by the symbol Λ . °
m
Question 73.
(a) State Faraday’s first law of electrolysis. How much charge in terms of Faraday is
required for the reduction of 1 mol of Cu to Cu. 2+
(b) Calculate emf of the following cell at 298 K : Mg(s) | Mg (0.1 M) || Cu (0.01) | Cu
2+ 2+
(s)
[Given E = +2.71 V, 1 F = 96500 C mol ] (Delhi 2014)
0
cell
-1
Answer:
According to first law of Faraday’s “the amount of chemical reaction and hence the
mass of any substance deposited/liberated at any electrode is directly proportional
to the quantity of electricity passed through the electrolyte.”
The quantity of charge required for reduction of 1 mol of Cu 2+
= 2 faradays (∵ Cu + 2e → Cu)
2+ –
= 2 × 96500 C = 193000 C
Cell reaction : Mg + Cu Mg + Cu(n = 2)
2+ 2+
Question 74.
(a) Define the terms conductivity and molar conductivity for the solution of an
electrolyte. Comment on their variation with temperature.
The measured resistance of a conductance cell was 100 ohms. Calculate (i) the
specific conductance and (ii) the molar conductance of the solution.
(KC1 = 74.5 g mol and cell constant = 1.25 cm ) (Comptt. Delhi 2014)
-1 -1
Answer:
(a) Conductivity : Reciprocal of resistivity is called conductivity
k = 1R×lA
Molar conductivity : It is defined as the conductivity of solution containing 1 mole
solute dissolved per litre when placed between two electrodes of unit area separated
by 1 cm.
Molar conductivity and conductivity of solution increase on increasing the
temperature.
(b) Given : R = 100 Ω Cell constant = 1.25 cm
-1
Question 75.
(a) Predict the products of electrolysis in each of the following:
(i) An aqueous solution of AgNO with platinum electrodes.
3
(b) Estimate the minimum potential difference needed to reduce Al O at 500°C. The
2 3
Gibbs energy change for the decomposition reaction 23 Al O → 43 Al + O is 960 kJ
2 3 2
Answer:
Question 76.
(a) Define the following terms :
(i) Molar conductivity (Λ )
m
(b) (i) Faraday first law of electrolysis : According to this law the mass of the
substance deposited or liberated at any electrode during electrolysis is directly
proportional to the quantity of charge passed through the electrolyte.
ω ∝ Q (∵ Q = I × t)
ω = = ZIt
(ii) Kohlrausch’s law of independent migration of ions : According to this law limiting
molar conductivity of an electrolyte can be represented as the sum of the limiting
ionic conductivities of the cation and the anion each multiplied with the number of
ions present in one formula unit of electrolyte.
Λom for AxBy=xλo++yλo−
Question 77.
(a) Define the term degree of dissociation. Write an expression that relates the molar
conductivity of a weak electrolyte to its degree of dissociation.
(b) For the cell reaction
Ni | Ni || Ag | Ag
(s)
2+
(aq)
+
(aq) (s)
Calculate the equilibrium constant at 25 °C. How much maximum work would be
obtained by operation of this cell?
EoNi2/Ni = 0.25 V and EoAg+/Ag = 0.80 V (Comptt. Delhi 2014)
Answer:
(a) Degree of dissociation: It is the measure of the extent to which an electrolyte
gets dissociated into its constitutent ions.
Thus higher the degree of dissociation, higher will be its molar conductance.
Mathematically it can be expressed as :
Question 78.
Calculate Δ G° and e.m.f. (E) that can be obtained from the following cell under the
r
Answer:
Question 79.
(a) Define conductivity and molar conductivity for the solution of an electrolyte.
Discuss their variation with concentration.
(b) Calculate the standard cell potential of the galvanic cell in which the following
reaction takes place :
Fe (aq) + Ag (aq) → Fe (aq) + Ag (s) Calculate the Δ G° and equilibrium constant of
2+ + 3+
r
Given: E = 1.98 V
cell
(b) Using the E values of A and B, predict which is better for coating the surface of
0
Answer:
(a) For the reaction
2Al(s) + 3Cu (0.01M) → 2Al (0.01M) + 3Cu(s)
2+ 3+
Given: E = 1.98 V E = ?
cell
0
cell
(b) Element A will be better for coating the surface of iron than element B because
its E° value is more negative.
Question 81.
(a) The conductivity of 0.001 mol L solution of CH COOH is 3.905 × 10 S cm .
-1
3
-5 -1
(b) Define electrochemical cell. What happens if external potential applied becomes
greater than E of electrochemical cell? (All India 2016)
0
cell
Answer:
(a) Concentration = 0.001 mol L -1
(b) Electrochemical cell: It is a device which converts chemical energy into electrical
energy i.e., produced as a result of redox reaction taking place in the electrolyte.
The reaction gets reversed and it becomes non-spontaneous. It starts acting as an
electrolytic cell.
Question 82.
(a) Define the following :
(i) Molar conductivity
(ii) Fuel cell
(b) The molar conductivity of a 1.5 M solution of an electrolyte is found to be 138.9 S
cm mol Calculate the conductivity of the solution. (Comptt. Delhi 2016)
2
-1
answer:
(a) (i) Molar conductivity Λ ): Molar conductivity can be defined as the conductance
m
138.9 = k×10001.5
k = 0.208 S cm -1
Question 83.
(a) Define the following terms :
(i) Primary batteries
(ii) Corrosion
(b) The resistance of a conductivity cell containing 0.001 M KCl solution at 298 K is
1500 Ω. What is the cell constant if conductivity of 0.001 M KCl solution at 298 K is
0.146 × 10 S cm ? (Comptt. Delhi 2016)
-3 -1
Answer:
(a) (i) Primary batteries : Batteries which can’t be rechared/reused.
(ii) Corrosion : Loss of useful metals due to oxidation on exposure to atmospheric
gases and moisture.
(b) k = 1R(lA)
lA = k × R = 0.146 × 10 S cm × 1500 Ω
-3 -1
lA = 0.219 cm -1
Question 84.
(a) What are the two classifications of batteries? What is the difference between
them?
(b) The resistance of 0.01 M NaCl solution at 25°C is 200 Ω. The cell constant of the
conductivity cell is unity. Calculate the molar conductivity of the solution. (Comptt.
All India 2016)
Answer:
(a) Two types of batteries are Primary batteries and Secondary batteries. Primary
batteries are non-chargeable whereas secondary batteries are rechargeable.
Question 85.
(a) What are fuel cells? Give an example of a fuel cell.
(b) Calculate the equilibrium constant (log K ) and Δ G° for the following reaction at
c r
298 K.
Cu (s) + 2Ag (aq) ⇌ Cu (aq) + 2Ag (s)
+ 2+
Answer:
(a) Cell which converts energy of combustion of fuel directly into electricity.
Example : H – O fuel cell.
2 2
Or
Those cells which convert fuel energy directly into electrical energy.
Example : H – O fuel cell
2 2
Question 86.
(a) When a bright silver object is placed in the solution of gold chloride, it acquires a
golden tinge but nothing happens when it is placed in a solution of copper chloride.
Explain this behaviour of silver.
[Given : E0Cu2+/Cu =+0.34V,E0Ag+/Ag =+0.80V, E0Au3+/Au = +1.40V]
(b) Consider the figure given and answer the following questions :
(i) What is the direction of flow of electrons?
(ii) Which is anode and which is cathode?
(iii) What will happen if the salt bridge is removed?
(iv) How will concentration of Zn2+ and Ag+ ions be affected when the cell
functions?
(v) How will concentration of these ions be affected when the cell becomes dead?
(Comptt. Delhi 2017)
Answer:
(a) The standard electrode potential, E° for silver is 0.80 V and that of gold is 1.5 V,
hence silver can displace gold from its solution. The replaced gold is deposited on
silver object due to which golden tinge is obtained. On the other hand E° for Cu is
0.34 V which is lower than that of silver, thus silver cannot replace copper from its
solution.
(b)
(i) Electrons flow from anode (Zinc plate) to cathode (Silver plate).
(ii) Zinc plate where oxidation occurs acts as anode and silver plate where reduction
occurs acts as cathode.
(iii) If the salt bridge is removed then electrons from zinc electrode will flow to the
silver electrode where they will neutralize some of Ag ions and the SO2−4 ions will
+
be left and the solution will acquire a negative charge. Secondly the Zn ions from
2+
zinc plate will enter into ZnSO solution producing positive charge. Thus due to
4
accumulation of charges in two solutions, further flow of electrons will stop and
hence the current stops flowing and the cell will stop functioning.
(iv) As silver from silver sulphate solution is deposited on the silver electrode and
sulphate ions migrate to the other side, the concentration of AgSO solution
4
(v) When the cell becomes dead, the concentration of these ions become equal due
to attainment of equilibrium and zero EMF.
Question 87.
(a) What is limiting molar conductivity? Why there is steep rise in the molar
conductivity of weak electrolyte on dilution?
(b) Calculate the emf of the following cell at 298 K :
Mg (s) | Mg (0.1 M) || Cu (1.0 × 10 M) | Cu (s)
2+ 2+ -3