Tutorial Chapter 3 : CPE624 (Chain Reactions)

Question 1
Consider the preceding reaction of a general reaction process,

A BC

which is propogated by a single radical R . The mechanism is:

ni A R,

ri k i C A i

A R B C R,
nt R X

rt k t C R t

rp k p C A C R
n

where ni and nt are the number of molecules react in the initiation and termination steps.
By writing the appropriate mass balance for each species involved in the reaction and using
pseudo-steady state approximation on free radical, prove that:

k
r i
nt kt

nt

k p C A

ni
nt

Question 2
Phosgene, an intermediate in polyurethane monomer, is made by the homogeneous reaction

CO Cl 2 COCl2
The elementary steps of this reaction are

Cl 2 2Cl

Cl CO COCl
COCl Cl 2 COCl2 Cl
where all reactions are reversible.
(a) Identify initiation, propagation, and termination steps.
(b) Show that the rate of this reaction could be

r k[CO][Cl 2 ]3 2
(c) Find an expression for the reverse reaction rate.

Question 3
Dimethyl ether decomposes to methane and formaldehyde. It is assumed that the reaction
proceeds according to the elementary steps:

CH 3OCH 3 CH 3 OCH 3

CH 3 CH 3OCH 3 CH 4 CH 2 OCH 3
CH 2 OCH 3 CH 3 HCHO
CH 3 CH 2 OCH 3 CH 3CH 2 OCH 3
where the first is the initiation step, the second and third are propagation steps, and the
fourth is the termination step. Derive a rate expression for this reaction r = k[CH3OCH3]n
assuming pseudo steady state on radical intermediates.

Question 4
Consider the chain reaction A B + C, which proceeds by the steps

IR
A R,
A R BC R
RX

riI k iI C I
ri k i C A

rp k p C A C R
rt k t C R

The first initiation step occurs by reaction of an initiator I whose initial concentration is CI0,
while the second occurs by decomposition of A whose initial concentration is CA0.
(a) Formulate an expression for the rate of this reaction in terms of CA and CI, assuming
CR is small. What are the possible orders of this reaction with respect to CA?
(b) Repeat part (a) assuming the termination step is 2R X, rt k t C R2
(c) For the rate in part (a) calculate CA, CB, and CI versus in a CSTR assuming kiI = 0.
What is the conversion when if kil = 0?
Question 5
Consider the chain reaction A B + C, which proceeds by the steps

A R,
A R BC R
RX

ri k i C A

rp k p C A C R
rt k t C R

with ki = 0.001 sec-1, kp = 200 liter/mole sec, kt = 0.01s-1, and CA0 = 2 moles/liter.
(a) Find r(CA) assuming the pseudo-steady-state approximation.
(b) What residence time will be required in a CSTR for 90% conversion for these kinetics?
(c) What residence time will be required in a PFTR for 90% conversion for these kinetics?