CYL 101 Structure, Reactivity and Dynamics

Physical Chemistry

Tutorial – 1 (03.09.14)

(1) Write the units of the rate constants for a (i) zeroth-order (ii) half-order (iii) first-order (iv) 3/2
order (v) second order (vi) 5/2 order and (vii) third order reaction.

(2) Nitrous oxide, N2O, decomposes into N2 and O2. If the reaction is first-order, develop
expression for the rate constant as a function of time, initial pressure and total pressure.

(3) From the following data for the decomposition of ammonium nitrite in aqueous solution, show
that the reaction is first-order.

Time (min) 10 15 20 15 Infinite

Volume of N2 (cc) 6.25 9.00 11.40 13.65 35.05

(4) Show that for a first order reaction, the time required for 99.9% completion of the reaction is
10 times that required for 50% completion.

(5) The following results were obtained for the saponification of ethyl acetate using equal
concentrations of ester and alkali. Show that the reaction is second-order.

Time (min) 0 4.89 10.07 23.66 Infinite

Acid used (cc) 47.65 38.92 32.62 22.58 11.84

(6) The half-life of the homogeneous gaseous reaction, SO2Cl2  SO2 + Cl2, which obeys first-
order kinetics, is 8.0 minutes. How long will it take for the concentration of SO2Cl2 to be
reduced to 1% of the initial values?

(7) In an enzyme solution, sucrose undergoes fermentation. If 0.1M solution of sucrose is reduced
to 0.05M in 10 hours and to 0.025 M in 20 hours, what is the order of the reaction and what is
the rate constant?

(8) The radioactive decay of elements such as thorium and radon emitting alpha particles follows
first-order kinetics. Calculate the number of alpha particles emitted per second by one gram of
pure ThO2 if the half-life of Th232 is 1.39X1010 years. The molar mass of ThO2 is 264 gmol-1.

(9) Derive an expression for the half-life of an nth-order reaction where n>=2.

(10) Show that the ratio t1/2/t3/4 for an nth-order reaction is a function of n alone.
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(11) The t1/2 of a reaction is halved as the initial concentration of the reactant is doubled.
What is the order of the reaction?

(12) The following data were obtained for the decomposition of a compound at 580oC:

ao (mol/l) 0.50 1.10 2.48

t1/2(s) 4280 885 174

Determine the order of the reaction and the rate constant.

(13) The activation energy of a non-catalyzed reaction at 37oC is 83.68 kJ mol-1 and activation
energy for the same reaction catalyzed by an enzyme is 25.1 kJ mol -1. Calculate the ratio of
the rate constants of the enzyme-catalyzed and the non-catalyzed reactions.

(14) The rate constant of a second-order reaction is 5.70X10-5 dm3 mol-1 s-1 at 25oC and
1.64X10-4 dm3 mol-1 s-1 at 40oC. Calculate the activation energy and the Arrhenius pre-
exponential factor.

(15) The rate constant for the second order decomposition of N2O follows the following
equation: k= (5.00X1011) exp(-29000K/T). Calculate the activation energy of the reaction.

(16) For the first-order isomerization of an organic compound at 130oC, the activation energy
is 108.4 kJ mol-1 and the rate constant is 9.12X10-4 s-1. Calculate the standard entropy of
activation for this reaction.

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