Physical Chemistry 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 way of determining the correct rate
law?
5. The isolation method cannot be used to determine the rate law 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)𝑘 𝑛−1
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:
 A→ R + 2S + B, (1)
𝑘1
A + B → M+ S (2)
𝑘2
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).
𝑑[𝐶𝑆2 ] 1
If the rate law for the reaction can be written as − = (3.07 × 10−4 )[𝐶𝑆2 ]2
𝑑𝑡 𝑀.𝑠
how long will it take for the concentration of CS2 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
𝑘1 𝑘2
𝐴 → 𝐵 → 𝐶 has been done in the class. In this case, both the first (A→ 𝐵) and second
step (𝐵 → 𝐶) were first order. Derive the relevant integrated rate law expressions for
[B] and [C], where the first step (A→ 𝐵) is first order but the second step (𝐵 → 𝐶) 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
𝑡1⁄ ,1 𝑡1⁄ ,2
210 2 210 2
206
83𝐵𝑖 → 84𝑃𝑜 → 82𝑃𝑏
which are the last two steps in the radioactive decay series starting with 238
92𝑈 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, 𝑡1⁄ ,1 , 𝑡1⁄ ,2 are 5.01days and 138.4 days, respectively.
2 2
210
Comment on the relative amounts of Bi, 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

Photochemistry
Tutorial Sheet IV Problems
Q1a) Define quantum yield.
1b) A certain system absorbs 2 × 1016 quanta of light per second. At the end of 20
minutes it is observed that 0.002 mole of irradiated substance has reacted. What is the
quantum yield of the process?
Q2) In the photochemical combination of H2 (g) and Cl2 (g) a quantum efficiency of
1 × 106 is obtained with a wavelength of 4800A. How many moles of HCl would be
produced under these conditions per calorie of radiant energy absorbed?

Q3. Label each of the following processes in the Jablonsky diagram below with the
following letters.
A) “allowed absorption” (D) Phosphorescence
B) Forbidden absorption (E) Internal conversion (IC)
C) Fluorescence (F) Intersystem Crossing (ISC)