​

Chemical Kinetics​
XII - PCM/PCB

1.​ How is the rate of reaction related to concentration of the reactants ?

2.​ What is meant by relative rates of reaction ? Write the relative rates expressions for the following
chemical reaction : 4NH(g) + 5O2(g) → 4NO(g) + 6HO(g)
3.​ Differentiate between reaction rate and reaction rate constant.
4.​ What is meant by order and molecularity of a reaction ? Distinguish between order and molecularity.
5.​ Explain with suitable examples how the molecularity of reaction is different from order of reaction.
6.​ The kinetics of the reaction : A + 2B → C + D , obeys the rate equation: Rate = k[A]x[B]y. For it, find
(i) order of the reaction (ii) apparent molecularity of reaction (iii) order of the reaction when B is
present in large excess.
7.​ Show by using rate law, how much rate of reaction: 2NO(g) + O2(g) → 2NO2(g) the volume of the
reaction vessel is reduced to one-third of its initial value.
8.​ Show graphically, how the rate of reaction depends on the concentration of reactant when there is
only one reactant and the reaction is of first order.
9.​ What are pseudo unimolecular reactions ? Give two examples.
10.​Derive integrated rate equation for first order reaction.
11.​ (a) Draw a schematic graph showing how the rate of a first order reaction changes with change in
concentration of the reactant. (b) Rate of a reaction is given by the equation: Rate = k[A]2[B]​
What are the units for the rate and the rate constant for this reaction ?
12.​Write the rate law for the first order reaction and justify the statement that half-life of such a
reaction is independent of its initial concentration.
13.​ (a) Express the relationship between the rate of production of oxygen and the rate of disappearance
of H2 O2 in the following reaction: 2H2O2(l) → 2H2O(l) + O2(g) ​
(b) The rate of formation of a dimer in second order dimerization reaction is ​
6.55 X 10–6 mol L–1 s–1 at 0.01 mol L–1 monomer concentration. Calculate the rate constant.
14.​The rate constant for a first order reaction is 0.005 min–1. Calculate its half-life.
15.​The rate constant of a first order reaction becomes 5 times when the temperature is raised from
350 K to 400 K. Calculate the activation energy for the reaction. ​
(R = 8.314 J K–1 mol–1)
16.​A first order reaction is 30% complete in 50 minutes. Calculate the value of rate constant.
17.​ Show that time required for t99.9% of the reaction is 10 times t1/2 .
18.​ A first order reaction is 20% completed in 10 minutes. How much time does it take for 75%
completion ?
19.​A first order reaction is 20% complete in 20 minutes. Calculate the time it will take the reaction to
complete 80%.
20.​The reaction SO2Cl2 → SO2Cl2 is a first order reaction with half-life 3.15 × 104 s at 320º C. What
percentage of SO2Cl2 would be decomposed on heating at 320º C for 90 minutes ?
21.​What will be the initial rate of reaction if its rate constant is 10–3 s–1 and the concentration of the
reactant is 0.2 mol L–1 ? What fraction of the reactant will be converted into the products in 200
seconds ?
22.​The reaction SO2Cl2 ƒ SO2 + Cl2 is a first order reaction with k = 2.2 × 10–5 s–1 at 575 K. What
percentage of SO2 Cl2 will get decomposed in 80 minutes, when the reaction is carried out at 575 K
?
23.​Rate constant k of a reaction varies with temperature according to the equation: ​
log k = constant - Ea/ 2.303R . 1 /T​
where Ea is the energy of activation for the reaction. When a graph is plotted for log k versus 1/T , a
straight line with a slope – 6670 K is obtained. Calculate energy of activation for this reaction. State
the units. (R = 8.314 J K–1 mol–1)
24.​The specific rate constant for a particular reaction is 2.34 × 10–3 mol L–1 s–1 at 370 K and 7.50 × 10–2
mol L–1 s–1 at 400 K. Calculate the activation energy for the reaction. [R = 8.314 JK–1 mol–1]
25.​The rate of a particular reaction triples when temperature changes from 50ºC to 100ºC. Calculate
the activation energy of the reaction. [log 3 = 0.4771; R = 8.314 JK–1 mol–1]
26.​A certain reaction is 50% complete in 20 minutes at 300 K and the same reaction is again 50%
complete in 5 minutes at 350 K. Calculate the activation energy if it is a first order reaction.
27.​Derive the relationship between half-life of a first order reaction and its rate constant.
28.​What is meant by the ‘rate constant’, k of a reaction ? If the concentration be expressed in mol L–1
units and time in seconds, what would be the units of k ​
(i) for a zero order reaction and ​
(ii) for a first order reaction ?
29.​ (a) A first order reaction is 15% completed in 20 minutes. How long will it take to complete 60%. ​
(b) What is the significance of rate constant in a rate law ?
30.​A first order reaction takes 69.3 minutes for 50% completion. Set up an equation for determining
the time needed for 80% completion of this reaction. (Calculate of result is not required)
31.​The rate constant for a first order reaction is 60 s–1. How much time will it take to reduce the
concentration of the reactant to 1/10th of its initial value ?
32.​ A reaction is first order in A and second order in B. ​
(i) Write a differential rate equation. ​
(ii) How is the rate affected if the concentration of B is tripled ? ​
(iii) How is the rate affected when the concentrations of both A and B are doubled ? What is the
significance of rate constant in the rate expression ?
33.​ (a) How is the half-life period related to initial concentration for a second order reaction ? (b)
Dissociation of SO2Cl2 in the gas phase is a first order reaction with rate constant 2.3 × 10–5 s–1 at
600 K. Calculate the percentage of SO2Cl2 that would remain after 200 minutes of reaction time.
34.​ In general it is observed that the rate of a chemical reaction doubles with every 10º rise in
temperature. If this generalization holds for a reaction in the temperature range 295 K to 305 K,
what would be the value of activation energy for this reaction ? (R = 8.314 JK–1 mol–1)
35.​ If the rate constant of a reaction is 2.0 mol–1 L s–1 at 700 K and 32.0 mol–1 L s> at 800 K, what is the
activation energy ?
36.​ If the slope of line obtained by plot of log k against 1/T is – 5.3 × 103, calculate the activation
energy.
37.​ If slope of line obtained by plot of log [N2O5] vs, time is –2.147 × 10–4 s–1, calculate the value of ‘k’.
38.​The activation energy of a reaction is 75.2 kJ mol–1 in the absence of a catalyst and 50.14 kJ mol–1
with a catalyst. How many times will the rate of reaction grow in the presence of the catalyst if the
reaction proceeds at 25º C ? (R = 8.314 JK–1 mol–1)
39.​Following reaction takes place in one step, 2NO(g) + O2(g) ƒ → 2NO2(g)​
How will the rate of the above reaction change if the volume of the reaction vessel is diminished to
 one third of its original volume ? Will there be any change in the order of the reaction with the
reduced volume ?
40.​ (a) Decomposition of 2N2O5(g) is a first order reaction with a rate constant of 5 × 10–4 sec–1 at 45º
C. i.e. 2 N205 (g) → 4NO2(g) + O2(g) . If the initial concentration of N2O5 is 0.25 M, calculate its
concentration after 2 min. Also calculate half-life for decomposition of N2O5 (g). (b) For an
elementary reaction: 2A + B → 3C the rate of appearance of C at time ‘t’ is 1.3 × 10–4 mol L–1 s–1. ​
Calculate at this time (i) Rate of the reaction. (ii) Rate of disappearance of A.