Chemical Reactor Theory

UNIT 1
1. (a) Define molecularity and order of the reaction.
(b) For an elementary reaction A + B Products, the reaction rate at 500 K is ten times that at 400 K. Calculate
the activation energy for this reaction.
[6+10]
2. (a) Define Activation Energy and write the equation to calculate it.
b) A reaction has E = 400 kJ. By what percentage does the reaction rate change if the temperature is raised (a)
from 300 K to 310 K, (b) from 2000 K to 2010 K
[6+10]
3. a) What is activation energy and discuss its temperature dependency.
b) A 1100 K, n-nonane thermally cracks (breaks down into small molecules 20 times as rapidly as at 1000K.
Find the activation energy for this decomposition
[6+10]
4. a) Differentiate between elementary and non-elementary reactions
b) The pyrolysis of ethane proceeds with an activation energy of about 300kJ. How much faster is the
decomposition at 650 C than at 500 C?
[6+10]
5. (a) The decomposition of nitrous oxide (N2O) is found to be as follows:
N2O N2 + 1/2O2, rN2O = k1[N2O]2 /(1+k2[N2O])
What is the order of this reaction with respect to N2O, and overall?
(b) How can the kinetics of non-elementary reactions be explained? Briefly explain with suitable example.
(c) What are the different types of intermediates formed in non-elementary reactions? Define each type. [4+4+8]
6. a) Define molecularity and order of the reaction
b) A certain reaction has a rate given by rA = 0.005 (CA)2 mol/cm3 min. If the concentration is to be expressed
in mol/liter and time in hours what would be the value and units of the rate constant?
7. a) Define Activation Energy and write the equation to calculate it.
b) Milk is pasteurized if it is heated to 63 C for 30 min, but if it is heated to 74C it only needs 15s for the same
result. Find the activation energy of this sterilization process
[6+10]
8. a) Differentiate between elementary and non-elementary reactions.
b) A human being (75 kg) consumes about 6000 kJ of food per day. Assume that the food is all glucose and that
the overall reaction is: C6H12O6 + 6O2 6CO2 + 6H2O, -Hr = 2816kJ. Find mans metabolic rate in terms of
moles of oxygen used per m3 of person per second. Assume density of man to be 1000kg/m3
[6+10]
9. a) Differentiate between elementary and non-elementary reaction
[6]
b) For a gas reaction at 400K, the rate is reported as dPA/ dT = 3.66 PA2 atm/hr. what are the units of rate
constant?
10. (a) Come up with (guess and then verify) a mechanism that is consistent with the experimentally found rate
equation for the following reaction : 2A + B A2 B with + r = k [A] [B]
(b) A common rule of temperature is that the rate of a reaction doubles for each 10C rise in temperature.
Justify?
(c) Discuss briefly about the activation energy and temperature dependency.
A2B

11. Experiment shows that the homogeneous decomposition of ozone proceeds with a rate,
-rO3 = k[O3]2[O]-1. What is the overall order of reaction? And suggest a two-step mechanism to explain this rate
and state how you would further test this mechanism?
12. (a) The decomposition of nitrous oxide is found to proceed as follows:
N2O N2 +1/2 O2. What is the order of this reaction with respect to N 2O and overall?
(b) At 500 K the rate of a bimolecular reaction is ten times the rate at 400 K. Find the activation energy of this
reaction from Arrhenius law.

13. Phosgene forms and decomposes according to the reaction CO + Cl 2

COCl2
Forward reaction: rCOCl2 = K1 [CO] [Cl2]3/2
Reverse reaction: -r = K2[Cl2]1/2[COCl2]
Determine whether the following mechanism is consistent with experimentally found rates.

Cl2

2 Cl*

Cl* + CO

Fast, at equilibrium
COCl* Fast, at equilibrium

COCl* + Cl2

COCl2 + Cl Slow, rate controlling.

[16]

14. (a) For the reaction 2A+0.5 B C, write the relation between the rate of formation and disappearance of the
three components of the reaction.
[6]
(b) A reaction has the stoichiometric equation 2AR+ S. What is the order of the reaction?
[2]
(c) The reaction with the following stoichiometric equation A+ 1/2 B R has the rate expression
- rA =kCACB0.5. What is the rate expression for the reaction written as 2A + B 2R
[2]
(d) A certain reaction has a rate given by-r A =0.005CA2, mol/cm3.min. If the concentration is to be expressed in
mol/lit and time in hours, what would be the value and units of the reaction rate constant?
[6]
15. For the non-elementary reaction A + 2B R + S if the mechanism suggested is:
A+B

R+X

B+X
S where X is the unstable intermediate compound,
(a) Derive an expression for rate of disappearance of A.
(b) Explain how the rate constants can be evaluated using the rate law.

[8+8]

16. Consider the reaction A + 3B R + 3S for which the mechanism suggested is A + B

B+X

S+X

S+Y

B+Y
R+S
(a) Derive the rate law.
(b) Show how the rate law transforms when each of the mechanism steps controls the rate. [16]
17. (a) What are the variables affecting the reaction rate. List out the different forms of reaction rate.
(b) Derive the Arrhenius law from thermodynamic principles.
(c) Experiment shows that the homogeneous decomposition of ozone proceed with a rate r0 = K[O3]2[O2]1.
Suggest a two step mechanism to explain this rate and explain how would you further test this mechanism?
3

Problems:
18) a)Discuss the temperature dependency of the rate constant from Arrhenius law and also give
Comparison of theories with this law.
b) Give the classifications of reactions. On doubling the concentration of the reactant the rate of
reaction triples. Find the reaction order.
19) a)Explain Arrhenius plot for temperature dependency of reaction rate and how do you find the
activation energy?
b) A 10 minute experimental run shows that 75% of liquid reactant is converted to product by a
order rate. What would be the fraction converted in a half hour run?
20) a)Explain the temperature dependence of rate equation using Arrhenius, collision and Transition
State theory?
b) What is pseudo steady state hypothesis? For the decomposition of Ozone in an inert gas M,the

experimentally observed rate is

-ro3 =k1[o3]2[M]/[o2][M]+k2[o3]
21) a)How does the temperature dependency of reaction by Arrhenius law is adequate in
comparison
With the other expressions derived from theories.
b) The decomposition nitrous oxide is found to proceed as follows:
N2O N2+1/2O2
-rN20 = k1[N2O]2 /1+K2[N2O]
22) a)Discuss temperature dependency of rate constant from Arrhenius law and also give
comparison

Of theories with this law?

b)On doubling the concentration of the reactant the rate of the reaction triples.find the reaction order.
23) a)Explain the salient features of the three theories that are proposed to explain the temperature
dependence of reaction?
0

b)A reaction is carried out at 40 c ,the activation energy of the reaction is 75kJ/mol .Find the
temperature required to make the reaction twice faster .
24) Explain Arrhenius plot for temperature dependency of a reaction rate and how do you find the
activation energy
b) Estimate the activation energy for oxidation of so2 to so3 over the vanadium catalyst if the variation
of reaction rate constant with temperature as given below
0
temperature ( c)
rate constant k, in hr

-1

455

470

490

6.3

12

26.2