TOPIC WISE REVIEW CPP-IV-CK

Q.1 The approach to the following equilibrium was observed kinetically from both directions:
PtCl42 + H2O l [Pt(H2O)Cl3] + Cl at 25°C, it was found that

 [PtCl 24 ]  [3.9 10 5 sec 1 ][PtCl 24 ]  [2.110 3 L.mol 1 sec 1 ]  [Pt (H 2O)Cl 3 ] [Cl  ]
t 
What is the value of equilibrium constant for the complexation of the fourth Cl by Pt(II)?

Q.2 The oxidation of certain metals is found to obey the equation 2 = t + where  is the thickness of the oxide film at
time t,  and are contants. What is the order of this reaction?

Q.3 The complex [Co(NH3)5F]2+ reacts with water according to the equation.
[Co(NH3)5F]2+ + H2O  [Co(NH3)5(H2O)]3+ + F
The rate of the reaction = rate const. x[complex]ax[H+]b. The reaction is acid catalysed i.e. [H+] does not change during the
reaction. Thus rate = k[Complex]a where k’ = k[H+]b, calculate ‘a’ and ‘b’ given the following data at 250C.
[Complex]M [H+]M T1/2hr T3/4hr

0.1 0.01 1 2
0.2 0.02 0.5 1
Q.4 A flask containing a solution a solution of N2O5 in CCl4 was placed in a thermostat at 40°C. The N2O5 began to decompose
by a firstorder reaction, forming NO2 and N2O4, which remained in the solution, and oxygen, which defined pressure. The
measurements were started (t = 0) when 10.75ml gas had collected. At t = 2400 sec., 29.65ml was measured. After a very long
time, (t = )45.50ml was measured. Find the (a) rate constant, (b) halflife time for reaction at 40°C in CCl4 solution.
(c) What volume of gas should have collected after 4800 sec?

Q.5 An optically active compound A upon acid catalysed hydrolysis yield two optically active compound B and C by pseudo
first order kinetics. The observed rotation of the mixture after 20 min was 5° while after completion of the reaction it was –
20°. If optical rotation per mole of A, B & C are 60°, 40° & – 80°. Calculate half life and average life of the reaction.

Q.6 A bacterial preparation was inactivated in a chemical bath. The inactivation process was found to be first order in bacterial
concentration having rate constant 1.7×10–2 sec–1. Meanwhile the multiplication of bacteria (1bacterium  2 bacteria) which
also follows first order kinetics with rate constant
1.5×10–3 sec–1 also continued. Calculate the number of bacteria left after 2 minutes if the initial number of bacteria is 103.

Q.7 The formation in water of dpotassium chromooxalate from its lform is reversible reaction which is first order in both
directions, the racemate being the equilibrium product. A polarimeter experiment at 22°C showed that, after 506 sec, 12 mole
% of the lisomer was converted to the dform. Find the rate constant for the forward and the reverse reactions.

Q.8 For a reversible firstorder reaction A B

k1 = 10 2 s 1 and [B]eq /[A] eq = 4. If [A]0 = 0.01 mole L 1 and [B]0 = 0, what will be the concentration of B after 30 s ?

3k
Q.9 For the mechanism A+B C C  D
(a) Derive the rate law using the steady-state approximation to eliminate the concentration of C.
(b) Assuming that k3 << k2, express the pre-exponential factor A and Ea for the apparent second-rder rate constant in
terms of A1, A2 and A3 and Ea1, Ea2 and Ea3 for the three steps.
Q.10 The following kinetic data have been obtained at 250 °C, for the reaction
CO (g) + Cl2 (g)  COCl2(g)
SET – 1 SET – 2
Initial Pressure CO = 400 Pa Initial Pressure CO = 1600 × 103 Pa
3
Cl2 = 800 × 10 Pa Cl2 = 400 Pa
Time(sec) Pressure of COCl2 (Pa) Time(sec) Pressure of COCl2 (Pa)
0 0 0 0
2072 200 2070 300
4140 300 4140 375
10280 375 infinity 400
infinity 400
(i) Determine the order of reaction with respect to CO and Cl2.
(ii) Calculate the rate constant, when pressure in pascal and time in seconds.

Q.11(a) The equilibrium between two isomers ‘A’ and ‘B’ can be represented as follow .

A B
 Where k1 and k2 are first order rate constants for forward and reverse reactions respectively. Starting with a non equilibrium
mixture of conc. [A]0 = a and [B]0 = b, it was found that ‘x’ mole of ‘A’ has reacted after time ‘t’. Give an expression for rate,
dx  P   k1a  k 2 b 
, and hence show that integerated rate expression is ln   = (k1 + k2) t where P =  
dt Px  k1  k 2 
P
(b) After 69.3 minute x = . Calculate k1 and k2 if equilibrium constant K = 4.
2
(Given : log2 = 0.3010)
Q.12 The gaseous reaction : n1A(g)  n2B(g) is first order with respect to A. It is studied at a constant pressure, with a0 as the
initial amount of A. Show that the volume of system at the concentration of A at time ‘t’ are given by the expressions
 n 2   n 2  
V = V0      1 exp (  n1kt )  ; [A]  [A]  exp (n1kt ) 
n n t 0 
 1   1    n 2 n1   n 2 n1  1 exp (n1kt ) 
Q.13 For the following first order gaseous reaction

The initial pressure in a container of capacity V litres is 1 atm. Pressure at time t = 10 sec is 1.4 atm and after infinite time it
becomes 1.5 atmosphere. Find the rate constant k1 and k2 for the appropriate reactions.

Q.14 In a nature decay chain series starts with 90Th232 and finally terminates at 82Pb208. A thorium ore sample was found to contain
8 × 105 ml of helium at STP and 5 × 107 gm of Th232. Find the age of ore sample assuming that source of He to be only due
to decay of Th232. Also assume complete retention of helium within the ore. (Halflife of Th232 = 1.39 × 1010Y)

3
Q.15 A 0.20 mL sample of a solution containing 1.0 ×107Ci of 1 H is injected into the blood stream of a laboratory animal. After
sfficient time for circulatory equilibrium to be established, 0.10 mL blood is found to have an activity of 20 dis/min. Calculate
the blood volume of the animal.

Q.16 A sample of 131

53 I
, as iodine ion, was administered to a patient in a carrier consisting of 0.10 mg of stable iodide ion. After 4.00
days, 67.7% of the initial radioactivity was detected in the thyroid gland of the patient. What mass of the stable iodide ion had
migrated to the thyroid gland? ( t½ = 8 days.)

Q.17 Potassium having atomic mass=39.1u contains 93.10 atom % 39K, having atomic mass 38.96371 u; 0.0118 atom % 40K, which
has mass of 40.0 u and is radioactive with t½ = 1.3 ×109y and 6.88 atom % 41K having a mass of 40.96184 u. Calculate the
specific activity of naturally occurring potassium.

Q.18 A mixture of 239Pu and 240Pu has a specific activity of 6 ×109 dis/s/g. The half lives of the isotopes are 2.44 ×104 y and 6.08 ×103
y respectively. calculate the isotopic composition of this sample.

Q.19 238 by successive radioactive decays changes to 82Pb206. A sample of uranium ore was analyzed and found to contain
92U
1.0g of U238 and 0.1g of Pb206. Assuming that all the Pb206 had accumulated due to decay of U238, find out the age of the ore.
(Half life of U238 = 4.5 ×109 years).

Q.20 Fallout from nuclear explosions contains 131I and 90Sr. Calculate the time required for the activity of each of these isotopes to
fall to 1.0 % of its initial value. Radioiodine and radiostrontium tend to concentrate in the thyroid and the bones, respectively,
of mammals which ingest them. Which isotope is likely to produce the more serious long-term effects? Half-life of 131I = 8
days, 90Sr = 19.9 yrs.

Q.21 218 (t = 3.05 min) decay to 82Pb214 (t1/2 = 2.68 min) by -emission, while Pb214 is a -emitter. In an experiment starting
84Po /12
with 1 gm atom of Pure Po218, how much time would be required for the number of nuclei of 82Pb214 to reach maximum.

Q.22 A sample pitch blende is found to contain 50% Uranium and 2.425% Lead. Of this Lead only 93% was Pb206 isotope, if the
disintegration contant is 1.52 × 10–10 yr–1. How old could be the pitch blende deposit.

Q.23 A sample of Uraninite, a Uranium containing mineral was found on analysis to contain 0.214 gm of Pb206 for every gram of Uranium.
Assuming that the lead all resulted from the radioactive disintegration of the Uranium since the geological formation of the
Uraninite and all isotopes of Uranium other than 238U can be neglected. Estimate the day when the mineral was formed in the Earth’s
crust. [t1/2 of 238U = 4.5 × 109 years]
Q.24 The rate of a reaction is expressed in different ways as follows :
1 d[C] 1 d[ D] 1 d[ A] d[ B]
   
2 dt 3 dt 4 dt dt
The reaction is:
(A) 4 A + B  2C + 3D (B) B + 3 D  4 A + 2 C
(C) A + B  C + D (D) B + D A + C

Q.25 Units of rate constant for first and zero order reactions in terms of molarity M unit are respectively
(A) sec–1, M sec–1 (B) sec–1, M (C) M sec–1, sec –1 (D) M, sec–1

Q.26 The rate constant for the forward reaction A (g) l 2B(g) is 1.5 × 10–3 s–1 at 100 K. If 10–5 moles of A and 100 moles of B are
present in a 10 litre vessel at equilibrium then rate constant for the backward reaction at this temperature is
(A) 1.50× 104 L mol–1 s–1 (B) 1.5 × 1011 L mol–1 s–1
(C) 1.5 × 1010 L mol–1 s–1 (D) 1.5 × 10–11
1 1

Q.27 Reaction A + B  C + D follow's following rate law : rate = k  [ A] 2 [ B] 2 . Starting with initial conc. of one mole of A and

B each, what is the time taken for amount of A of become 0.25 mole. Given k = 2.31 × 10–3 sec–1.
(A) 300 sec. (B) 600 sec. (C) 900 sec. (D) none of these
Q.28 Consider the following first order competing reactions:
k k2
X  1 A + B and Y  C+D
if 50% of the reaction of X was completed when 96% of the reaction of Y was completed, the ratio of their rate constants (k2/
k1) is
(A) 4.06 (B) 0.215 (C) 1.1 (D) 4.65
Q.29 A first order reaction is 50% completed in 20 minutes at 27°C and in 5 min at 47°C. The energy of activation of the reaction is
(A) 43.85 kJ/mol (B) 55.14 kJ/mol (C) 11.97 kJ/mol (D) 6.65 kJ/mol
Q.30 For the first order reaction A — B + C, carried out at 27 ºC if 3.8 × 10–16 % of the reactant molecules exists in the activated
state, the Ea (activation energy) of the reaction is
(A) 12 kJ/mole (B) 831.4 kJ/mole (C) 100 kJ/mole (D) 88.57 kJ/mole
Q.31 The reactions of higher order are rare because
(A) many body collisions involve very high activation energy
(B) many body collisions have a very low probability
(C) many body collisions are not energetically favoured.
(D) many body collisions can take place only in the gaseous phase.
Q.32 The following mechanism has been proposed for the exothermic catalyzed complex reaction.
1k k
A+B I AB  AB + I  2 P+ A
If k1 is much smaller than k2. The most suitable qualitative plot of potential energy (P.E.) versus reaction coordinate for the
above reaction.

(A) (B) (C) (D)

Question No. 10 to 11 (2 questions)

Oxidation of metals is generally a slow electrochemical reaction involving many steps. These steps involve electron transfer
reactions. A particular type of oxidation involve overall first order kinetics with respect to fraction of unoxidised metal (1– f
) surface thickness relative to maximum thickness (T) of oxidised surface, when metal surface is exposed to air for considerable
period of time
df
Rate law : = k(1 – f ), where f = x/T,,
dt
x = thickness of oxide film at time 't'

& T = thickness of oxide film at t = 

A graph of ln(1 – f ) vs t is shown in the adjacent figure.
Q.33 The time taken for thickness to grow 50% of 'T' is
(A) 23.1 hrs (B) 46.2 hrs (C) 100 hrs (D) 92.4 hrs

Q.34 The exponential variation of 'f' with t(hrs) is given by

(A) [1  e 3 t / 200 ] (B) e 3t / 200  1 (C) e 3t / 200 (D) e3t / 200
Question No. 12 to 13 ( 2 questions)

k1 1
For a hypothetical elementary reaction where 
k2 2
Initially only 2 moles of A are present.
Q.35 The total number of moles of A, B & C at the end of 50% reaction are
(A) 2 (B) 3 (C) 5 (D) None

Q.36 Number of moles of B are

(A) 2 (B) 1 (C) 0.666 (D) 0.333

Q.37 Two radioactive nuclides A and B have half lives of 50 min and 10 min respectively. A fresh sample contains the nuclides of
B to be eight time that of A. How much time should elapse so that the number of nuclides of A becomes double of B
(A) 30 (B) 40 (C) 50 (D) None

Q.38 Give the correct order of initials T (true) or F (false) for following statements.
(i) On bombarding 7N14 Nuclei with -particle, the nuclei of the product formed after release of proton would be 8O17.

(ii) 228 and Th 229 belong respectively to Actinium and Neptunium series.
89Ac 90
(iii) Nuclide and it's decay product after -emission are called isodiaphers.
(iv) Half life of radium is 1580 years. Its average life will be 1097.22 years.
(A) TFTF (B) TTTF (C) FFTT (D) TFFF
ANSWERS KEY
TOPIC WISE REVIEW CPP-IV-CK
Q.1 53.84 Q.2 (d/dt) =  /2, –1 order
Q.3 a=b=1
Q.4 (a) 3.27 · 104sec1; (b) 2120 sec; (c) 38.27 (measured : 55.00ml)
Q.5 20 min, 28.66 min
Q.6 156 Q.7 Kf = Kb = 0.00027 sec–1 Q.8 0.0025 m
d(D) k 1 k 3 (A)(B) A1 A 3
Q.9 (a)  ; (b) E = E + E – E . A =
dt k2  k3 a a1 a3 a2 A2
Q.10 Set – I : 3.5 × 10–4S–1; Set – II : 6.7 ×10–4S–1
Q.11 k2 = 2 × 10–3 sec–1 ,k1 = 8 × 10–3 sec–1
Q.13 0.805

Q.14 t = 4.89 × 109 years Q.15 V = 1.1 L Q.16 0.0958 mg

Q.17 Specific activity = 30.69 dis. g-1s-1 Q.18 239Pu = 45.1%, 240Pu = 54.9%
Q.19 t = 7.1 × 108 years Q.20 53.1 days, 132 yrs, 90Sr is likely to be serious, the iodine will soon be gone
Q.21 4.125 min Q.22 3.3 × 108 years Q.23 1.4 × 109 yrs
Q.24 B Q.25 A Q.26 D Q.27 B Q.28 D Q.29 B Q.30 C
Q.31 B Q.32 A Q.33 B Q.34 A Q.35 B Q.36 C Q.37 C
Q.38 A
 ANSWERS KEY
TOPIC WISE REVIEW CPP-IV-CK
Q.1 53.84 Q.2 (d/dt) =  /2, –1 order
Q.3 a=b=1
Q.4 (a) 3.27 · 104sec1; (b) 2120 sec; (c) 38.27 (measured : 55.00ml)
Q.5 20 min, 28.66 min
Q.6 156 Q.7 Kf = Kb = 0.00027 sec–1 Q.8 0.0025 m
d(D) k 1 k 3 (A)(B) A1 A 3
Q.9 (a)  ; (b) E = E + E – E . A =
dt k2  k3 a a1 a3 a2 A2
Q.10 Set – I : 3.5 × 10–4S–1; Set – II : 6.7 ×10–4S–1
Q.11 k2 = 2 × 10–3 sec–1 ,k1 = 8 × 10–3 sec–1
Q.13 0.805

Q.14 t = 4.89 × 109 years Q.15 V = 1.1 L Q.16 0.0958 mg

Q.17 Specific activity = 30.69 dis. g-1s-1 Q.18 239Pu = 45.1%, 240Pu = 54.9%
Q.19 t = 7.1 × 108 years Q.20 53.1 days, 132 yrs, 90Sr is likely to be serious, the iodine will soon be gone
Q.21 4.125 min Q.22 3.3 × 108 years Q.23 1.4 × 109 yrs
Q.24 B Q.25 A Q.26 D Q.27 B Q.28 D Q.29 B Q.30 C
Q.31 B Q.32 A Q.33 B Q.34 A Q.35 B Q.36 C Q.37 C
Q.38 A
 ANSWERS KEY
TOPIC WISE REVIEW CPP-IV-CK
Q.1 53.84 Q.2 (d/dt) =  /2, –1 order
Q.3 a=b=1
Q.4 (a) 3.27 · 104sec1; (b) 2120 sec; (c) 38.27 (measured : 55.00ml)
Q.5 20 min, 28.66 min
Q.6 156 Q.7 Kf = Kb = 0.00027 sec–1 Q.8 0.0025 m
d(D) k 1 k 3 (A)(B) A1 A 3
Q.9 (a)  ; (b) E = E + E – E . A =
dt k2  k3 a a1 a3 a2 A2
Q.10 Set – I : 3.5 × 10–4S–1; Set – II : 6.7 ×10–4S–1
Q.11 k2 = 2 × 10–3 sec–1 ,k1 = 8 × 10–3 sec–1
Q.13 0.805

Q.14 t = 4.89 × 109 years Q.15 V = 1.1 L Q.16 0.0958 mg

Q.17 Specific activity = 30.69 dis. g-1s-1 Q.18 239Pu = 45.1%, 240Pu = 54.9%
Q.19 t = 7.1 × 108 years Q.20 53.1 days, 132 yrs, 90Sr is likely to be serious, the iodine will soon be gone
Q.21 4.125 min Q.22 3.3 × 108 years Q.23 1.4 × 109 yrs
Q.24 B Q.25 A Q.26 D Q.27 B Q.28 D Q.29 B Q.30 C
Q.31 B Q.32 A Q.33 B Q.34 A Q.35 B Q.36 C Q.37 C
Q.38 A

ANSWERS KEY
TOPIC WISE REVIEW CPP-IV-CK
Q.1 53.84 Q.2 (d/dt) =  /2, –1 order
Q.3 a=b=1
Q.4 (a) 3.27 · 104sec1; (b) 2120 sec; (c) 38.27 (measured : 55.00ml)
Q.5 20 min, 28.66 min
Q.6 156 Q.7 Kf = Kb = 0.00027 sec–1 Q.8 0.0025 m
d(D) k 1 k 3 (A)(B) A1 A 3
Q.9 (a)  ; (b) E = E + E – E . A =
dt k2  k3 a a1 a3 a2 A2
Q.10 Set – I : 3.5 × 10–4S–1; Set – II : 6.7 ×10–4S–1
Q.11 k2 = 2 × 10–3 sec–1 ,k1 = 8 × 10–3 sec–1
Q.13 0.805

Q.14 t = 4.89 × 109 years Q.15 V = 1.1 L Q.16 0.0958 mg

Q.17 Specific activity = 30.69 dis. g-1s-1 Q.18 239Pu = 45.1%, 240Pu = 54.9%
Q.19 t = 7.1 × 108 years Q.20 53.1 days, 132 yrs, 90Sr is likely to be serious, the iodine will soon be gone
Q.21 4.125 min Q.22 3.3 × 108 years Q.23 1.4 × 109 yrs
Q.24 B Q.25 A Q.26 D Q.27 B Q.28 D Q.29 B Q.30 C
Q.31 B Q.32 A Q.33 B Q.34 A Q.35 B Q.36 C Q.37 C
Q.38 A