NATIONAL INSTITUTE OF TECHNOLOGY, ROURKELA

MID SEMESTER EXAMINATION, SPRING 2018, OPEN ELECTIVE PAPER

CY-232: Chemical Kinetics
Duration of Examination: 02.00 hours. This question paper contains 2 pages
Full marks: 60
Answer all questions. Figures in the right hand margin indicate marks. Show all derivation
for full credit (wherever applicable). Numerical answers must be with correct unit.
No. Question Marks
1. k1 k2
B C
i) A
Assuming both the consecutive reactions are of first order as shown above
and initial concentration of A is 0.025 M, what is the rate of formation of C at
2
100 seconds (k1=10-5 s-1 & k2=105 s-1)?

ii) What is the dimension of the rate constant of a second order reaction?
2
iii) Draw conc. vs time plot for a zero order reaction.
2
k
iv) 2B → B2 Express the rate of this single step reaction in terms of –dB/dt.
2
v) The gas phase formation of HBr is an ideal example of chain reaction.
4
Applying steady state approximation it can be shown that:
1/2 1/2
d[HBr] = 2k2(k1/k5) [H2][Br2]
dt k4 [HBr]
1+
k3 [Br2]

What experimental procedure would you follow to measure the constant

2k2(k1/k5)1/2?

2. Consider the gas phase decomposition of acetaldehyde into methane and 6

carbon monoxide. The decomposition follows a free radical chain mechanism
as given below:
k1
(i) CH3CHO CH3 + CHO
k2
(ii) CH3 + CH3CHO CH4 + CH3CO
k3
(iii) CH3CO CO + CH3
k4
(iv) CH3 + CH3 C2H6

Applying the concept of steady state show that the rate of formation of
methane follows a 3/2 order kinetics.

[please turn over]

3. Draw qualitative plots of concentration vs time for the two cases given below 6+6
in the consecutive reaction as shown (no derivation or equation is required):
k1 k2
A B C
Case i) k1 >> k2
Case ii) k1 << k2

4. k1
B 6
A
k-1

The value of equilibrium constant (K) is 1.0 for the above opposing reaction
(first order in both ways). The reaction starts with reactant A with an initial
concentration of 1.0 M. If the concentration of B after 100 second is 0.25 M,
calculate k1 (rate constant of the forward reaction).

5. Find out the rate constant in the decomposition of a gas which is of 3/2 order,
when 84% decomposition took place in 2 hours when initial pressure is 1 atm. 6

6. Derive the integrated rate equation for a second order chemical kinetics in
terms of appearance of products. 6

7. In an industrial reaction, the desired product B is decayed into unwanted

product in the following reaction scheme. Find the time point where [B] 6
would be maximum. Given k1 = 100 h-1 and k2 = 10h-1
k1 k2
A B C
[each step is first order]

Decomposition of ozone gas follows the mechanism given below. Applying

8.
the concept of steady state, prove that the reaction follows first order kinetics
6
at an extremely high concentration of ozone.