Tutorial Problems, Department of Chemistry

Chemical Kinetics Problems:

Tutorial Sheet 1
(The first five questions are to done by the students as an assignment.)
1. Derive second-order integrated rate law expression for the following reaction:
A + B→ P. Assume i) the initial concentrations of A and B are the same, and ii)
initial concentrations of A and B are not the same.
2. From the general rate law expression derived in the above question, assume that
the concentration of A>>B. Derive the rate expression. Can you see why it is
called a pseudo-first-order reaction?
3. Compare different methods of determining the rate law for a reaction.
4. Why is the method of initial rates the best wayof determining the correct rate law?
5. The isolation method cannot be used to determine the ratelaw by itself. Show how
it can be used in combination with another technique to determine the reaction rate
law.
6. Will the isolation technique give reliable results if the reaction is a composite
reaction, that is, involves several stages?
7. The simple reaction A + 2B →C is of the half-order with respect to substance A
and of the second-order with respect to substance B. Determine the overall order
of the reaction, and write the kinetic equation for the rate of consumption of
substance A, for the rate of formation of substance C, and the relation between the
respective rate constants.
8. The initial rate of a certain reaction depended on the concentration of a substance J
as follows:
[J]/(mmol dm-3) 5.0 10.2 17 30
−7 −3 −1
rate/(10 mol dm s ) 3.6 9.6 41 130
Find the order of the reaction with respect to J and the rate constant.
9. Establish the integrated form of a third-order rate law of the form rate = kr[A]3.
What would it be appropriate to plot to confirm that a reaction is third-order?
2n−1−1
10(a)Show that, for a reaction that is n-order in A, t1/2 is given by t1/2= n−1
( n−1 ) k r [ A ]0
(b)Deduce an expression for the time it takes for the concentration of a substance to
fall to one-third the initial value in an nth-order reaction.
11.The half-life of pyruvic acid in the presence of an aminotransferase enzyme (which
converts it to alanine) was found to be 221 s. How long will it take for the
concentration of pyruvic acid to fall to 1/64 of its initial value in this first-order
reaction?
12.The rate of the reaction A → products is 0.01 mol.dm−3.min−1 at cA = 1 mol.dm−3,
and 0.005 mol.dm−3.min−1 at cA = 0.5 mol.dm−3. Determine the reaction order and the
rate constant.
13. Two simultaneous reactions proceed in a system:
→
Ak 1 R + 2S + B, (1)
→
A + B k 2 M+ S (2)
The reaction (1) is first order. The reaction (2) is second order, i.e. first order with
respect to both A and B. Write the relations for the rate of formation of substances A,
B and S.