DPP3_CHK_Advanced_ Genetry

PHYSICAL CHEMISTRY
(JEE-ADVANCED)
CHEMICAL KINETICS DPP-3

1. The rate constant is numerically the same for three reactions of first, second and third order
respectively, the unit of concentration being in moles per litre. Which reaction should be the
fastest and is this true for all ranges of concentrations?
2. A first-order gas reaction has k = 1⋅5 × 10– 6 per second at 200°C. If the reaction is allowed to
run for 10 hours, what percentage of the initial concentration would have changed in the
product? What is the half-life of this reaction?
3. For a reaction, the concentration of the reactant C varies with time t as shown by the
following graph:
what do you conclude about the order of the reaction?
4. The rate of a first order reaction is 0⋅04 mole/L/s at 10 minutes and 0⋅03 mole/L/s at 20
minutes after initiation. Find the half-life of the reaction.
5. In the decomposition of H2O2 at 300 K, the energy of activation was found to be 18 kcal/mole,
while it decreased to 6 kcal/mole when the decomposition was carried out in the presence of a
catalyst at 300 K. How many times is the catalysed reaction faster than the uncatalysed one?
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6. In Arrhenius’s equation for a certain reaction, the value of A and E(activation energy) are
4 × 1013 s–1 and 98.6 kJ mol–1 respectively. If the reaction is of first order, at what temperature
will its half-life period be ten minutes?
7. Two reactions proceed at 25°C at the same rate. The temperature coefficient of the rate of the
first reaction is 2 and that of the second is 2.5. Find the ratio of the rates of these reactions at
95°C.
8. In the course of the reaction

CH3COOCH3(g) → C2H4(g) + H2(g) + CO (g)
the initial pressure was found to be 0⋅42 atm while after 6⋅5 minutes, it was 0⋅54 atm. If the
reaction follows first order kinetics, find the rate constant.
9. The decomposition of N2O5 according to the equation

2N2O5(g) → 4NO2(g) + O2(g)
is a first-order reaction. After 30 minutes from the start of the decomposition in a closed
vessel, the total pressure developed is found to be 284.5 mm Hg and on complete
decomposition the total pressure is 584.5 mm Hg. Calculate the rate constant of the reaction.
10. The decomposition of N2O into N2 and O in the presence of argon follows second-order
kinetics with k = (5⋅0 × 1011) e–29000 K/T. Calculate the energy of activation.
11. In a second order reaction when the concentration of both the reactants are equal, the
reaction is 20% completed in 500 seconds. How long will it take the reactionto go to 60%
completion?
12. For the reaction: SO2CL2(g) → SO2(g) + Cl2(g), it is found that a plot of ln [SO2Cl2] versus time
is linear, and that in 240 seconds the [SO2Cl2] decreases from 0.4 M to 0.28 M. What is the
rate constant?
13. A drop (0.05 mL) of a solution contains 3.0 × 10–6 mole of H+ ions. If the rate constant of
disappearance of H+ is 1.0 × 107 mol/L/s, how long would it take for H+ ions in the drop to
disappear?
14. The gas-phase decomposition of NOBr is second order in [NOBr], with k = 0.81
M–1.s–1 at 10ºC. Initial concentration of NOBr in the flask at 10ºC = 4.00 × 10–3 M. In how
many seconds does it take up 1.50 × 10–3 M of this NOBr?
2NOBr → 2NO + Br2

15. A first order reaction is 50% complete in 30 min at 27°C and in 10 min at 47°C. Calculate the
reaction rate constant at 27°C and the energy of activation of there action in kJ/mole.
d(product)
16. The rate law of the reaction A + 2B → Product is given by = k[A]2 .[B] . If A is
dt
taken in large excess, the order of the reaction will be
(A) 0 (B) 1 (C) 2 (D) 3
17. If the volume of a closed vessel in which the equilibrium 2SO2 + O2 2SO3 is set in is
halved, the rate of
(A) forward reaction will remain same as that of backward reaction
(B) forward reaction will become double that of backward reaction
(C) forward reaction will be halved that of backward reaction
(D) all are wrong
18. From different sets of data of t1/2 at different initial concentration say ‘a’ for a given reaction,
the product (t1/2 × a) is found to be constant. The order of the reaction is
(A) 0 (B) 1 (C) 2 (D) 3
19. The temperature coefficient of a reaction is 2. The rate of this reaction, on raising the
temperature by 25º, shall increase by
(A) 4 times (B) 8 times (C) 6 times (D) 5.65 times
20. A plot of reactant concentration versus time for a reaction is a straight line with a negative
slope giving the rate constant, and the intercept, giving the initial concentration of the reactant.
The order of the reaction is
(A) 0 (B) 1 (C) 2 (D) none of these
21. For the first-order reaction, 2N2O5(g) → 4NO2(g) + O2(g)

(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 proceed to 99.6% completion eight half-life duration.

22. For a first-order reaction, A(g) → 2B(g) + C(g) at constant volume and 300 K, the total
pressure at the beginning (t = 0) and at time t are p0 and pt, respectively. Initially, only A is
present with concentration [A]0 and t1/2 is the time required for the partial pressure of A to
1
reach rd of its initial value. The correct option(s) is (are) (Assume that all these gases
3
behave as ideal gases).
23. A 22.4 litre flask contains 0.76 mm of ozone at 25°C. Calculate:

(i) The concentration of oxygen atoms needed so that the reaction O + O3 → 2O2 having rate
constant equal to 1.5 × 107 litre mol–1 sec–1 can proceed with a rate of 0.15 mol litre–1sec–1.
(ii) The rate of formation of oxygen under this condition.
24. On the top of a certain mountain, the atmospheric pressure is 0.7 atm and pure water boils at
363 K. A climber finds that it takes 300 minute to boil an egg as against 3 minute at 373 K.
Calculate:
(a) Ratio of rate constants at 373 K and 363 K,
(b) Energy of activation for the reaction when egg boiled. Assume Arrhenius factor be same.
25. Find out the percentage of the reactant molecules crossing over the energy barrier at 325 K,
given that ∆H325 = 0.12 kcal, Ea(b) = + 0.02 kcal
ANSWER KEY
2. 0.9473, 0.462 × 106s 3. 2
4. 24.086 min 5. 4.8 × 108 6. 311.2 K
–1
7. 4.768 8. 0.0237 min 9. 2.625 × 10–3 min–1
10. 241 kJ/mole 11. 3000 s 12. 1.49 × 10–3s–1
13. 6.0 × 10–9s 14. 92.6s 15. 0.0231 min–1, 43.84 kJ
16. (B) 17. (B) 18. (C)
19. (D) 20. (A) 21. (A,D)
–4 –
22. (A) 23. 2.45 × 10 M, 0.30Ms
24. 100, –124.729 Kcal 25. 80.65%


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PHYSICAL CHEMISTRY

CHEMICAL KINETICS DPP-3

what do you conclude about the order of the reaction?

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8. In the course of the reaction

9. The decomposition of N2O5 according to the equation

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21. For the first-order reaction, 2N2O5(g) → 4NO2(g) + O2(g)

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23. A 22.4 litre flask contains 0.76 mm of ozone at 25°C. Calculate:

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