Assignments 01-04-24

QUESTION 1
(a) Outline the collision theory and transition state theory on chemical
reaction [10]
(b) The initial rate of a reaction depended on concentration of a substance J
as follows:
[J]o/(mmoldm-3) 5.0 8.2 17 30
Rate/(10-7moldm-3s- 3.6 9.6 41 130
1)

Determine the order of the reaction with respect to J and calculate the rate
constant. [8]
(c) The rate of the second-order decomposition of acetaldehyde (ethanal,
CH3CHO) was measured over the temperature range 700-1000 K, and
the rate constants are reported below. Determine the activation energy
and the pre-exponential factor. [7]

Temperature/K 700 730 760 790 810 840 910 1000

k/(dm3mol-1s-1 0.011 0.035 0.105 0.343 0.789 2.17 20 145

QUESTION 2
a. (i) Suppose that in an industrial batch process a substance A produces
the desired compound I which goes on to decay to a worthless product C,
each step of the reaction being first -order. At what time will I be present
in greatest concentration? [7]
(i) Calculate the maximum concentration of and justify [4]

b. Devise the rate law for the decomposition of N205

2 N 2O5  4 NO2 ( g )  NO2( g )

1
 on the basis of the following mechanism:
N 2O5( g )  NO2( g )  NO3( g ) ka

NO2  NO3  NO2  O2  NO kb

NO  N 2O5  NO2  NO2  NO2 kc

NO2  NO3  N 2 O5 k’a [14]

08-03-24
QUESTION 3
(a) Compare heterogeneous catalysis with homogeneous catalysis [4]
(b) With the aid of and example, illustrate the importance of catalysis [3]
(c)Sketch and illustrate the designs of the following reactors
i) Fluidised bed reactor [4]
ii) Fixed bed reactor [4]
iii) Slurry reactor [4]

(d) With reference to a two phase packed bed reactor, outline the catalytic
process steps, clearly showing the actual catalytic steps [6]

QUESTION 4
a) Outline the principal features of enzyme catalyzed reactions [3]
b) Show that the Michaelis-Menten mechanism accounts for the
features in (a) above and leads to the Michaelis-Menten equation
kb [ E ]0
v
1 KM
[ S ]0
E  S  ES
ka / k’a

ES  P  E kb [9]
c) Examine the Michaelis-Menten relationship under the following
conditions

2
 i) Very high [S]0 [2]
ii) KM is equal to [S]0 [2]
d) The enzyme carbonic anhydrase catalyses the hydration of CO2 in
red blood cells to give bicarbonate (hydrogencarbonate) ion:

CO2( g )  H 2O(l )  HCO3 ( aq )  H  ( aq )

The following data were obtained for the reaction at pH = 7.1, 273.5 K, and an
enzyme concentration of 2.3 nmol dm-3:
[CO2]/mmoldm-3 1.25 2.5 5 20
Rate/mmoldm-3s-1 2.78 x 10-2 5 x 10-2 8.33 x 10-2 1.67 x 10-1

Determine the catalytic efficiency of carbonic anhydrase at 273.5 K [9]

15-03-24
QUESTION 5

a) As proposed by the Lindemann theory, the following mechanism applies

to first order gaseous reaction kinetics:
A + B  Products
Mechanism:

A + B  K 1
K1
[ AB

[AB # ] 
k2
Pr oducts

(i) Derive an expression for the rate of formation of products. [5]

(ii) State the effects of high and low pressures on the overall rate of
reaction. [5]
(iii) State the limitations of the Lindemann theory. [5]
b) Using the following bimolecular reaction equation:
3
 k1
k1
A+B [AB]# P
k-1

(i) Show that the equilibrium constant,

Keq# = (e∆S#/R)(e∆H#/RT). [5]
(ii) Using the data in the Table below, deduce the values
of ∆S# and ∆H#.
[5]

T/K 345 295 275 240 223

Keq# 1.55 1.80 1.92 2.24 2.66

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