Tutorial 1 Solutions

Chemical Kinetics Problems:
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?
7. The initial rate of a certain reaction depended on 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.
10(a) Show that, for a reaction that is n-order in A, t1/2 is given by t1/2 = ( ) [ ]
(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.
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?
6. Will the isolation technique give reliable results, if the reaction is a composite reaction,
that is, involves a number of stages?
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:
A R + 2S + B, (1)
A+B 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.
Chemical Kinetics IInd Tutorial Sheet:
14. The oxidation-reduction reaction between iron metal and aqueous permanganate ions in
acidic solution is 16H+ (aq) + 5Fe (s) + 2MnO4- (aq) →2Mn2+ (aq) 5Fe2- + 4H2O(l). At some
temperature, the reaction proceeds at such a rate that 1.00 millimole of H+ is consumed in 2
minutes 33.8 seconds. What is the (invariant) rate of this reaction in units of moles per
second?
15. For a general reaction “aA bB → products,” the following initial rates are determined
experimentally when reactions are set up with the initial amounts indicated in units of
molarity, M.
[A] (M) [B](M) Initial rate (M/s)
1.44 0.35 5.37 10-3
1.44 0.70 2.15 10-2
2.89 0.35 2.69 10-3
Assuming that the rate law can be written as rate = k [A]m.[B]n, determine the values of m, n,
and k.
16. One example of a first-order reaction is the isomerization of hydrogen isocyanide to

hydrogen cyanide: HNC (g) → HCN (g)
If the rate constant at a particular temperature is 4.403 ×10-4 s-1, what mass of HNC remains
after 1.50 hr if a 1.000-gram sample of HNC was present at the beginning of the reaction?
17. Consider the following reaction: CS2 (g) + 3O2 (g) CO2 (g) + 2SO2 (g).
[ ]
If the rate law for the reaction can be written as ( )[ ]
how long will it take for the concentration of CS 2 to drop to half of the initial concentration
for the initial concentrations a. 0.05000 mol/L b. 0.00500 mol/L?
18. The derivation of the integrated rate law expressions for the consecutive reaction
has been done in the class. In this case, both the first (A ) and second step
( ) were first order. Derive the relevant integrated rate law expressions for [B] and [C],
where the first step (A ) is first order but the second step ( ) is zero order.
19. Kinetics of consecutive reactions are easily applicable to nuclear decay processes, in
which a parent isotope produces a radioactive daughter isotope that also decays. (In fact, in
the early twentieth century, such sequential processes were a major complicating factor in
trying to understand this new phenomenon.) One such example is
⁄ ⁄
→ →
which are the last two steps in the radioactive decay series starting with and ending in
the nonradioactive isotope of Pb. (It is sometimes called the 4n+2 series because all of the
mass numbers of the isotopes involved can be represented by that general equation.) The
half-lives, ⁄ ⁄ are 5.01days and 138.4 days, respectively. Comment on the relative
amounts of 210Bi, 210Po, and 206Pb over time.
Chemical Kinetics IIIrd Sheet
20. Consider the reaction:
NO2(g)+CO(g)→NO(g)+CO2(g) (1)
which occurs in two elementary steps:
NO2+NO2→NO+NO3 (slow) (2)
NO3+CO→NO2+CO2 (fast) (3)
Derive the rate law.
21. A reaction between NO and H2 occurs in the following three-step process:

NO+NO→N2O2 (fast)
N2O2+H2→N2O+H2O (slow)
N2O+H2→N2+H2O (fast)
a) What is the rate determining step?
b) Write the balanced equation for the overall reaction.
c) Derive the rate law for this mechanism.
22. If the rate law for the reaction 2 NO(g) + Cl2(g)  2 NOCl(g), is rate = k[NO][Cl2], is the
mechanism that follows consistent with this? Why?
NO(g) + Cl2(g)  NOCl2(g) slow
NO(g) + NOCl2(g)  2 NOCl(g) fast
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Chemical Kinetics Problems:

16. One example of a first-order reaction is the isomerization of hydrogen isocyanide to

21. A reaction between NO and H2 occurs in the following three-step process:

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