DEDAN KIMATHI UNIVERSITY OF TECHNOLOGY

UNIVERSITY EXAMINATIONS 2015/2016

YEAR THREE SEMESTER ONE EXAMINATION FOR THE DEGREE OF
BACHELOR OF SCIENCE IN INDUSTRIAL CHEMISTRY and BACHELOR OF
SCIENCE IN LEATHER TECHNOLOGY
SCH 2360: CHEMICAL KINETICS AND PHOTOCHEMISTRY
DATE: 8TH SEPTEMBER 2015 TIME: 8.30AM-10.30AM

INSTRUCTIONS: Answer question ONE and any other TWO questions

Useful data.
R= 8.3145 J mol K .,
-1 -1

QUESTION ONE (30 MARKS)

a) Derive the integrated law for the 3rd order kinetics for the reaction
A Products [4 Marks]
+ - N2(g) + H2O (l)
b) Consider the following reaction at 25°C NH 4 (aq) + NO2 (aq)
and the data given in table below;

[NH4+](in M) [NO2] (in M) Initial Rates (in M/s)

0.24 0.10 7.2×10-6
0.12 0.10 3.6×10-6
0.12 0.15 5.4×10-6

Determine the rate law and rate constant for the reaction [6 Marks]

c) Define or explain the following terms;

i. Catalytic promoter
ii. Parallel reaction
iii. Grotthus-Draper law
iv. Chemical Kinetics:
v. Singlet state
vi. Molecularity

[6 Marks]
d) The activation energy of one of the reactions in a biochemical process is 87 kJ mol−1.
What is the change in rate constant when the temperature falls from 37°C to 15°C??
[4 Marks]

1
 e) State the limitations of Beer-Lambert’s law [2Marks]

f) Distinguish between fluorescence and phosphorescence. [4 Marks]

g) List four applications of fluorescence [2 Marks]
h) Distinguish between photoluminescence and triboluminesence [2 Marks]

QUESTION TWO (20 MARKS)

a) Eplain the steps involved in heterogeneous catalysis [8 Marks]

b) Explain how temperature and pH affect enzyme catalysis [4 Marks]

c) For the reaction between nitric oxide and hydrogen

It may proceed via the following mechanism:

Fast

slow

Using steady state approximation, derive the rate law for the disappearance of hydrogen
[8 Marks]

QUESTION THREE (20 MARKS)

a) With a suitable diagram illustrate how phosphorescence takes place [5 Marks]

b) List three photophysical processes.

[3Marks]

c) What is a laser? What are their advantage over conventional light in photochemical
reaction?
[2 Marks]
d) List two types of radiationless transitions:
[2Marks]
e) Define or explain the following terms;
i. Reaction mechanism:
ii. Chemiluminescence:
[2 Marks]
f) List four characteristics of enzyme catalysts

[4 Marks]

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g) Explain the intermediate theory of catalysis [2 Mark]

QUESTION FOUR (20 MARKS)

a) The rate of the second-order decomposition of acetaldehyde (ethanal, CH3CHO) was

measured over the range 700–1000 K, and the rate constants that were found are reported
below. Determine the activation energy and the pre-exponential factor. [8Marks]

T/K 700 730 760 790 810 840 910 1000

Kf/(mol- 0.011 0.035 0.105 0.343 0.789 2.17 20.0 145
1
dm3s-1)

b) Describe an experiment that onecan use to monitor the rate of decomposition of H2O2 in
the presence of KMnO4in H2O
[4 Marks]

c) When irradiated with light of 5000 Å wavelength, 1 × 10–4 mole of a substance is

decomposed. How many photons are absorbed during the reaction if its quantum
efficiency is 10.00. (Avogadro number N = 6.02 × 1023). [4 Marks]

d) Derive an expression for the half-life of a second-order reaction in terms of the rate
constant k.? [4 Marks]

QUESTION FIVE (20 MARKS)

a) For the thermal decomposition of Ozone to oxygen, the following mechanism has been
suggested.
k1
O3 k-1 O2 + O
K2
O3 + O 2O2
Use the steady state approximation and other suitable approximationsto account for
observed rate law:
rate= -k [O3]2/ [O2]
[6Marks]
b) A certain substance in a cell of length 1 absorbs 10% of the incident light. What fraction
of the incident light will be absorbed in a cell which is five times long? [4 Marks]

c) The variation in the partial pressure PA of azomethane with time was followed at 460 K,
with the results given below. Confirm that the decomposition CH3N2CH3(g) →

3
 CH3CH3(g) + N2(g) is first-order in CH3N2CH3, and findthe rate constant at this
temperature.

t/s 0 1000 2000 30000 40000

PA/(10-2 10.20 5.72 3.99 2.78 1.94
Torr

[6 Marks]
d) Calculate the energy associated with (a) one photon; (b) one einstein of radiation of
wavelength 4000 Å. h = 6.62 × 10–27 erg-sec; c = 3 × 1010 cm sec–1 [4 Marks]