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CHEMISTRY

Class

II IIT- JEE Achiever 2016-17


Solutions to Worksheet 14

Topic

Chemical Kinetics and Nuclear Chemistry


Redox Reactions and Electrochemistry

Date

20-12-2016

Multiple choice questions with one correct alternative

1. Nuclear volume of an element is directly proportional to


(A) atomic number.
(B) mass number.
(C) number of electrons.
(D) the number of isotopes of the element.
Ans (B)
2. Under the action of cosmic neutrons, the
(A)

12
6 C

Ans (B)
14
1
7 N +0 n

(B)
14
6 C

14
7

N present in the atmosphere changes to

14
6 C

(C)

13
6 C

(D) none of these

+ 11 H

3. Suppose that the number of neutrons is plotted against the number of protons for nuclides of all
elements. It is found that stable nuclides are generally located in a zone of stability. A certain light
nuclide is located at the left of this zone. Which of the following statements is true for this nuclide?
(A) Its N/P ratio is less than unity.
(B) It is a positron emitter.
(C) Its N/P ratio is greater than unity, which stabilizes itself by -decay.
(D) It is an -emitter.
Ans (C)
14
14
0
6 C 7 N + 1 e +
4. The rate of a nuclear decay reaction can be increased by
(A) increasing the temperature.
(B) increasing the pressure.
(C) decreasing the pressure.
(D) increasing the mass of sample.
Ans (D)
It depends only on and N and we know that dN/dt = N
5. The rate of a zero order reaction can be altered by
(A) change of temperature.
(C) increasing the reactant concentration.
Ans (A)

(B) decreasing the reactant concentration


(D) any of these methods.

4
6. It is given that log 2 = 0.3, log 3 = 0.5 and log 5 = 0.7. Also for 14
6 C is about 10 per year. The activity
1
of a sample of dry fossil wood per gram is about th of the activity of freshly cut and dried wood per
5
gram. The age of the fossil is
(A) about 7000 years.
(B) about 11500 years
(C) about 16000 years
(D) none of these
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Ans (C)
2 .3
a 2.3
2 .3
7
=
log =
log 5 =
0.7, t = 2.3 4
a
t
t
t
10
5
7. Choose the incorrect statement among the following
(A) rate constants are never negative
(B) the pre-exponential factor A, is independent of temperature
(C) the rate of a reaction becomes independent of temperature if Ea = 0
(D) the value of Boltzmann factor decreases as the temperature increases
Ans (D)
8. The rate law for a reaction is, r = k[A]2[B]2. If the concentration of A is halved and that of B is doubled,
the rate of the reaction will
1
(A) be 2r
(B) be r
(C) be 4r
(D) remain the same
2
Ans (D)
Rate r = k[A]2[B]2
2

1
1
New rate r = k A [2B]2 = k [A]2 4[B]2
4
2
2
2
= k[A] [B] which is the same as the old rate
9. The rate constant of a reaction is given by k = p Z e Ea / RT . Which factor should register a decrease for

the reaction to proceed more rapidly?


(A) T
(B) Z
Ans (C)
k = p Z e Ea / RT

(C) Ea

(D) p

= const. e Ea /RT
Thus, as the Ea value decreases, the reaction would proceed more rapidly.
10. The activation energy of a certain reaction is 65.7 kJ/mol. How many times faster will the reaction occur
at 50 C than at 0 C?
(A) 22 times
(B) 66 times
(C) 110 times
(D) 88 times
Ans (D)
E a T2 T1
k
log 2 =

k1 2.303 R T1 T2
65.7 1000 50
2.303 8.314 273 323
3431.3 50
=
1.9456
88179

k2
= antilog 1.9456 = 88
k1
11. E (reduction) of three species of cations X, Y and Z are respectively 0.5, 3 and 1.2 V. The decreasing
order of reducing powers of the corresponding metals is
(A) Y > Z > X
(B) X > Y > Z
(C) Z > Y > X
(D) Z > X > Y
Ans (A)
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12. If the pH of a 1 M solution of potassium permanganate in dilute sulfuric acid at 25C is changed by
further addition of a small amount of dilute sulfuric acid, electrode potentials of the system suggest that
(A) the oxidizing power of potassium permanganate increases.
(B) the oxidizing power of potassium permanganate decreases.
(C) the oxidizing power of potassium permanganate remains unaffected.
(D) a brown precipitate of manganous hydroxide separates out.
Ans (A)
MnO 4 + 8H+ + 5e Mn2+ + 4H2O.
E (MnO 4 | Mn 2 + ) = E(MnO 4 | Mn 2 + ) +

[MnO 4 ][H + ]8
0.0591
log
.
5
[Mn 2 + ][H 2 O] 4

With the addition of further amounts of acid, [H+] increases and E (MnO 4 | Mn 2 + ) increases.
It means that reduction of MnO 4 becomes easier, implying that the oxidizing power of potassium
permanganate further increases.
13. When an aqueous solution containing an equimolar mixture of potassium bromide and potassium iodide
is electrolyzed between inert platinum electrodes with increasing applied voltage
(A) elemental potassium is generated at the cathode.
(B) iodine is initially released followed by liberation of bromine, both occurring at the anode.
(C) bromine is initially released at the anode followed by iodine, also at the anode.
(D) bromine and iodine are simultaneously released at the anode.
Ans (B)
14. A molten binary compound yields hydrogen at the anode upon electrolysis. Which of the following is
correct?
(A) The binary compound is a saline hydride.
(B) Hydrogen is less electropositive than the other element in the binary compound.
(C) Oxidation has occurred at the anode.
(D) All these statements are correct.
Ans (D)
Consider a saline (or salt-like) hydride such as Li+ H. Lithium must be more electropositive compared to
hydrogen. H loses its electrons by oxidation to the positively charged anode.
All these are reactive elements located high in the activity series. Hydrogen is released in the place of
these metals at the corresponding cathodes during electrolysis.
15. Which statement is true about a galvanic cell employing Pb, Cu, Pb2+ and Cu+?
Electrode reaction
E
2+

Pb (aq) + 2e Pb(s)
0.127 V
+

Cu (aq) + e Cu(s)
+0.518 V
(A) The cell potential increases when the Cu+ solution is diluted
(B) Anions flow from the lead half-cell to the copper half-cell through the salt bridge
(C) The concentration of the cation in the cathode compartment changes faster than the cation
concentration in the anode compartment.
(D) Cations flow from the copper half-cell to the lead half-cell through the salt bridge.
Ans (C)
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16. Which of the following statements is incorrect?


A salt bridge
(A) allows the ions of the electrolyte to migrate but the solutions in the two half cells do not mix
(B) is used to maintain the electrical neutrality of two solutions by intermigration of ions into two half
cells
(C) is made up of an inert electrolyte in which cation and anion have a large difference of ionic
mobilities
(D) helps to nullify or minimize the liquid junction potential
Ans (C)
17. A current of 3 A is passed for 6h between nickel electrodes in 0.5 L of 2 M solution of nickel nitrate. The
molarity of the solution at the end of electrolysis is
(A) 2 M
(B) 1 M
(C) 0.5 M
(D) 0.2 M
Ans (A)
Because, some nickel dissolves from anode into the solution by oxidation.
However, an equivalent amount of nickel from the solution will be deposited on the cathode.
Hence no change in the molarity.
19 g
18. Consider the following statements: When a direct current is passed through an aqueous concentrated
solution of NaCl,
(i) pH of the solution decreases
(ii) metallic sodium will be deposited at the cathode
(iii) chlorine gas will be liberated at the anode.
(iv) pH of the solution increases
Which of the statements given above are correct?
(A) (i) and (ii)
(B) (ii) and (iii)
(C) (iii) and (iv)
(D) (i) and (iii)
Ans (C)
On electrolysis, NaOH solution is produced, which makes pH of the solution increased. Chlorine gas is
evolved at anode.
19. For the cell
Au(s) | Au3+ (aq), 0.025 M || Au3+ (aq), 0.50 m | Au(s), E = .... V
(A) 0.077 V
(B) 0.026 V
(C) 0.0111 V
Ans (B)
It is a concentration cell w.r.t [Au3+]
0.06
0.5
0.06
C
log
= 0.02 1.3 = 0.026 V
E=
log 2 where C 2 > C1 =
n
C1
3
0.025

(D) 0.077 V

Multiple choice questions with one or more than one correct alternatives

20. For the first order reaction 2N2O5 4NO2 + O2,


(A) the concentration of the reactant decreases exponentially with time
(B) the half-life of the reaction decreases with increasing temperature
(C) the half-life of the reaction depends on the initial concentration of the reactant
(D) the reaction proceeds to 99.6 % completion in eight half-lives duration
Ans (A), (B) and (D)
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21. Which of the following is/are not formed when a very dilute sulfuric acid solution is electrolysed
between inert platinum electrodes?
(A) SO2
(B) S
(C) H2S2O8
(D) O3
Ans (A), (B), (C) and (D)
Electrolysis of acidified water produces oxygen and hydrogen.
22. Which of the following is/are correct for a spontaneous galvanic cell?
(A) E ocell = E o (reduction potential at cathode + E (oxidation potential at anode)
(B) E ocell > 0
(C) E ocell = E o (oxidation potential at cathode + E (reduction potential at anode)
(D) G ocell < 0

Ans (A), (B) and (D)


Read the passage given below and answer the questions by choosing the correct
alternative

Consider the energy profile diagram for the reaction A + B


M + N , given below and answer the
questions that follow:
A+B
Energy

x
y
M+N
z

Reaction co-ordinate

23. The enthalpy change for the reaction A + B


M + N is
(A) x
Ans (B)

(B) y

(C) z

(D) x + z

24. The activation energy for the reaction M + N


A + B is represented by the value
(A) x
Ans (C)

(B) y

(C) x + y

(D) y x

25. In the presence of a catalyst, the activation energy for the conversion A + B
M + N , is
(A) x
(B) y
(C) z
(D) none of these
Ans (D)
The catalyst speeds up the reaction, which means that more molecules have sufficient energy to react.
Thus, the activation energy must have been lowered.
Read the passage given below and answer the questions by choosing the correct
alternative

Faradays investigations on the relationship between the quantity of electricity passing through a solution
and the amount of metal, or other substance, liberated at the electrodes, resulted in the form of the two
following laws.
I. The amount of chemical decomposition produced by a current is proportional to the quantity of
electricity passing through the electrolytic solution (w Q)
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II. The amounts of different substances liberated by the same quantity of electricity are proportional to their
chemical equivalent weights (w E).
Both the laws are followed rigidly, and apply to molten electrolytes as well as to electrolyte solutions. These
laws are independent of temperature, pressure, concentration of electrolyte and nature of solvent. It is
assumed that the solvent aids ionization of the electrolyte.
26. For how long a current of 3A has to be passed through a solution of AgNO3 to coat a metal surface of
80 cm2 area with 0.005 mm thick layer? Density of silver is 10.5 g cm3 and atomic weight of Ag is
108 g mol.
(A) 1250 s
(B) 125 s
(C) 1.25 h
(D) 1250 min
Ans (B)
mass
mass
Density =
=
volume area thickness
mass
10.5 =
0.005
80
10
Mass = 0.42 g
E
We know that, w = I t
F
108
0.42 =
3 t
96500
t = 125 s

27. Select the correct statement/s, if 9.65 A is passed for 1 h through the cell Ag|Ag+ (1 M) || Cu2+ (1 M)|Cu
(A) Ag will be oxidized Ag+ and new [Ag+] = 1.36 M
(B) Ag+ will be reduced to Ag and new [Ag+] = 0.64 M
(C) Cu2+ will be reduced to Cu and new [Cu2+] = 0.82 M
(D) Cu will be oxidized to Cu2+ and new [Cu2+] = 0.82 M
Ans (A) and (C)
Oxidation occurs at anode and reduction occurs at cathode
E
108 9.65 60 60
It =
= 38.8g
F
96500
w=NVE
38.8 = N 1 108
N = 0.36 or 0.36 M
+
Thus, the new [Ag ] = 1 + 0.36 = 1.36 M

(A) w =

E
31.8 9.65 60 60
It =
= 11.448g
F
96500
w = M V AW
11.448 = M 1 63.54
M = 0.18 M
Thus, the new [Cu++] = 1.0 0.18 = 0.82 M

(C) w =

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Numerical problems

28. In the gas phase reaction A + B product, rate = k[A][B]2. If the volume of the container is reduced to
1/3rd, find the change in the rate of the reaction.
Solution
Given rate = k[A][B]2
(1)
rd
When volume is reduced to1/3 , the concentration of reactants A and B will increase by 3 times.
(2)
New rate = k[3A][3B]2
2
= k 3 9 [A][B]
= 27.k[A][B]2
(3)
27k[A][B]2
= 27
(3) (1) gives
k[A][B]2
29. It is required to deposit a 0.1 mm thick copper film on one side of a 100 cm2 iron lamina by making it the
cathode in an electrolytic cell using an aqueous solution of potassium tetracyanocuprate K3[Cu(CN)4] as
a source of copper. Atomic weight and specific gravity of copper are respectively 63 and 9.45. Calculate
(in minutes) the duration of electrolysis using 9.65 amperes.
Solution
Copper exists as Cu+ in K3 [Cu(CN)4]. The equivalent weight of copper = 63/1 = 63.
Volume of copper = thickness area = 0.01 cm 100 cm2 = 1 cm3.
Mass of copper = volume density = 1 9.45 = 9.45 g = 9.45 / 63 = 0.15 equivalent.
Charge required = 0.15 F = 0.15 96500 C. Time current = charge.
0.15 96500
Time =
= 1500 seconds = 25 minutes
9.65
M
solution of a weak monobasic acid is 80 mho cm2/eq and is
32
400 mho cm2/eq. Calculate the dissociation constant of the acid.
Solution

8
Degree of dissociation = c =
= 0.02
400

30. Equivalent conductance of

Dissociation constant K a =

c 2
c 2
1
1
= (0.02) 2 = 1.25 10 5
32

31. 4.5 g of Al(Atomic mass 27) is deposited at cathode from Al3+ solution by a certain quantity of electric
charge. The volume of hydrogen produced at STP from H+ ions in the solution by the same quantity of
electric charge will be ..............
Solution
Al3 + + 3e Al
3F

1 mol ( = 27 g )

1 mol (27 g) of Al is deposited by 3F of electricity


4.5 of Al is deposited by..?
3 4 .5
= 0 .5 F
27
2H+ + 2e H2
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2F gives 22.4 L
0.5F gives 5.6 L at STP.
32. A hydrogen electrode is prepared by dipping the electrode in a solution of pH = 3. Calculate the potential
2.303 RT

= 0.059
of the electrode at this pH.
f

Solution
1
H + + e H 2
2
n = 1 ; pH = 3 or [H+] = 103
0.059
E = Eo +
log[H + ]
1
= 0 + 0.059 log 103 = 0.059 (3) = 0.177 V
Alternatively, E = 0.059 pH
= 0.059 3 = 0.177 V

Column II
(P) May be negative or fraction
(Q) Rate determining step
(R) Integer except zero
(S) Half life 1
a
(v) Zero order
(T) Single step
(vi) Second order
(U) Rate = Rate constant
Ans (i) (R) ; (ii) (P) ; (iii) (T) ; (iv) (Q) ; (v) (U) ; (vi) (S)

33.

Column I
(i) Molecularity
(ii) Order
(iii) Elementary reaction
(iv) Slow reaction

34.
(i)
(ii)

Column I
Reversible cell
Irreversible cell

(P)
(Q)

(iii) Galvanic cell without transference


(iv) Electrolytic cell

(R)
(S)

(v)

(T)

Galvanic cell with transference

Column II
Zn|H2SO4 |Cu
Electrochemical cell
Hoffmanns voltmeter
Zn|Zn2+|| Cu2+ |Cu
Zn | Zn 2+ Cu 2+ | Cu

(U) Copper coulometer


Ans (i) (S) ; (ii) (P) ; (iii) (P), (S), (Q) ; (iv) (Q), (R), (U), (v) (T)

***

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