Chapter 4

Reaction Mechanism
in Chain
Reaction
and

Biological
Part 1
Reaction
Chain Reaction Mechanism

By: Cik Siti Khatijah Jamaludin, FKK UiTM Shah Alam

 Subtopic covered in Chapter 3 (Part 1)
Intro to Chain Reaction Mechanism
(Chapter 10 Schmidt, page 399-406)
Autocatalytic reactions
Pseudo steady state approximation/hypothesis
Generic (linear) chain reaction
Characteristics of Chain Reactions
(Chapter 10 Schmidt, page 406-408)
Initiators
Scavengers
Wall termination reactions
Chain Branching Reactions (Chapter 10 Schmidt, page 416-418)
Reactor Safety (Chapter 10 Schmidt, page 434-436)
Thermal & Chemical Autocatalysis
(Chapter 10 Schmidt, page 422-432)
 Chain Reactions
Example
3
CH 3CHO CH 4 CO r kC A 2

Initiation step A CH 3 CHO, ri k i [ A]

Propagation step 1 A CH 3 CH 4CH CH 3CO r p1 k p1[ A][CH 3 ]
Propagation step 2 CH 3CO CO CH 3 r p 2 k p 2 [CH 3CO]
Termination step 2CH 3 C2H 6 rt k t [CH 3 ]2

The species circled with green are stable molecules

known as:
The species circled with red are free-radical molecules
known as:
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 Chain Reactions

Propagation steps occur much faster than initiation and

termination steps
Radical species are very reactive and concentrations
are always very low.
Chain carriers: the intermediates in a chain reaction. It
could be radicals (species with unpaired electrons),
ions, etc.
Major products generate by propagation step
Minor products made by initiation and termination
steps.
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 Autocatalytic reactions
The major processes are the propagation steps
Adding p1 and p2 steps yield:

A CH 3 CH 4 CO CH 3

Autocatalytic the reaction generates the catalyst that

promotes the reaction.
The overall rate is initiated by large ki and inhibited by large
kt even though ki, kt << kp
Kinetic chain length ratio of rp to ri or rt.

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 Mass balance of species in
PFTR/Batch and CSTR
So, from the mechanism, you can write the mass
balance on each species and solve them in batch
reactor or continuous reactors (PFTR or CSTR) and
find the species concentrations as a function of
residence time.
General mass balance:
PFTR:

Batch reactor :

CSTR:
 Class activity 1
A CH 3 CHO, ri k i [ A]
A CH 3 CH 4 CH 3CO r p1 k p1[ A][CH 3 ]
CH 3CO CO CH 3 rp 2 k p 2 [CH 3CO]
2CH 3 C2H 6 rt k t [CH 3 ]2
Write the mass balance equation on each
species for the mechanism above in a)
PFTR and b) CSTR
Solution:
In a PFTR In a CSTR
Pseudo steady state approximation
(PSSA)
PSSA is used when one tries to approximate a set of reactions by a simpler
single reaction by invoking the pseudo steady state on suitable intermediate
species.

PSSA is valid when the concentration of the intermediate species is

small.
i.e., in the acetaldehyde decomposition example, [CH3] and [CH3CO] are small
because they are radicals and reactive.

PSSA is done by setting the time derivative of the species with the small
concentration (usually the radical species) to 0:

PFTR/Batch

CSTR

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 Subtopic covered in Chapter 3 (Part 1)
Intro to Chain Reaction Mechanism
(Chapter 10 Schmidt, page 399-406)
Autocatalytic reactions
Pseudo steady state approximation/hypothesis
Generic (linear) chain reaction
Characteristics of Chain Reactions
(Chapter 10 Schmidt, page 406-408)
Initiators
Scavengers
Wall termination reactions
Chain Branching Reactions (Chapter 10 Schmidt, page 416-418)
Reactor Safety (Chapter 10 Schmidt, page 434-436)
Thermal & Chemical Autocatalysis
(Chapter 10 Schmidt, page 422-432)
Generic chain reaction
A B C
The reaction propagates by radical R.
ni A R , ri k i C A
ni

A R B C R , r p k p C A CR
nt R X rt k t CR
nt

ni and nt are the number of molecules react in initiation

and termination steps respectively.
PSS approximation on CR yield the overall rate r=
expression: rp
1
r k eff C A
nt
ki ni neff
k p C A
1
r nt
nt k t
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 Example 10-1 (page 405 Schmidt)

Consider the following chain reaction, which is conducted in a

CSTR (assuming constant density):

a) Write the mass balance equations for A, B, R and X.

b) Determine the overall reaction rate in terms of CA, and the
possible order of the reaction with respect to CA.
c) Find for 90% conversion of A in CSTR assuming pseudo
steady state. Given CAo = 2 moles/l, ki = 0.001 sec-1, kp =
20
liter/mole sec and kt = 0.1 sec-1.
d) What are CR and CX for this conversion?
 Characteristics of Chain
Reactions
Have very complicated kinetics.
Have extremely large dependency on
temperature.
- Rxn is : negligible (slow) at low T
: very fast at high T
Very sensitive to traces of impurities.
Can alter the
initiation and
termination rates,
up to the level that
they can control the
overall reaction rate
Initiators (promoters) and scavengers
(poisons) can have large influence on chain
reactions.
 Initiators & Scavengers
Initiators (promoters)
Chain reaction can also be initiated by intentionally
adding initiator, I, that easily forms radicals.
Initiator acts to initiate reaction faster than the reactant.
We write the elementary reaction step involving initiator
as:
I R riI =
kiICI
Example of chain reaction mechanism involving initiator:

kiI can be much larger

than ki
 Initiators & Scavengers
Scavengers (poisons) (cont.)
Just like the initiation step, the termination step in a
chain reaction can be speed up by intentionally
adding scavenger, S, that readily scavenge the chain
propagator or chain carrier, R.
We write theRelementary
+ S X reactionrtS = step involving
scavenger as:
ktSCRCS

Scavenger helps to terminate the chain reaction

faster than natural termination. ktS > kt
Example of chain reaction mechanism involving
scavenger: ktS can be
much larger
than kt
 Clicker questions
Q1: Define initiator and scavenger for a chain
reaction.

Q2:

Source: Schmidt, page 440

 Wall termination reactions
Recall the definition of termination step.
the step by
Termination which
step is radical R is removed or
the chain carrier R is deactivated.
Often, this occurs through radical-radical recombination,
reaction with another molecule to create an inactive
product, or through reaction with walls. Our
focus!!

Wall termination step frequently occurs readily on

surfaces (i.e. surfaces of reactor wall) by adsorption.
surface area, wall termination rate
In small reactor: chain reaction easily terminates
(termination rate is high). Why??
In large reactor: chain reaction not easily terminate
(termination rate is low), hence always proceed.
 Wall termination reactions (cont.)
Since the termination reaction happens at surface of reactors wall, the
rate of reaction involve is rt: Recall what we
learnt in
rt = (area/volume) Chapter 1 on
Catalytic Wall
rt Reactor

If surface area is very large, the surface reaction rate is also very large.
rate of termination at reactor wall will most frequently limited by
mass transfer rate.
Recall that at steady state,
rt = ktCRs = km (CRb
CRs)

if we are only looking at what happen at the wall, concentration of

radical at bulk (CRb) can be omitted from the above equation.
kt = km =
(Sh D ) / D
 Source: Schmidt, page 439
Wall termination reactions (cont.)
Problem 10.12 page 439
Schmidt
Consider the chain reaction A B + C, which proceeds by the
steps:

The first termination step occurs homogeneously, while the

second occurs by adsorption of R on the walls of reactor. The
reaction happens in a tube of diameter D with laminar flow and
a diffusion coefficient DR.
a) Formulate the rate expression for this reaction.
b) Determine the effective rate expressions obtained when:
i) homogeneous termination dominates the reaction
ii) reaction at the wall dominates the reaction
iii) mass transfer to the wall dominates the reaction
Typical graph of reaction involving reactive
intermediates (i.e. free-radicals, R) .
reactant product

Maximum
concentrati
on of the
reactive
intermediat
e is
achieved
when dCR/d
= 0 (for PFR
system) or
CR/ = 0 (for
CSTR
system)

Reactive
intermediate, i.e.:
free-radicals, R Source: Davis, McGraw-Hill
 Chain branching reaction
Produce more than one free radical species in propagation step. Thus, the
propagation steps increase the concentration of radical species and
destabilize the kinetics.
Example: Hydrogen oxidation (a simple prototype of combustion reaction):

mechanism:

Chain
branching
reaction

Rapid rise in the concentration of radical species can accelerate the reaction
and possibly a chain-branching explosion.
Chain branching reaction
(cont.)

Source: Schmidt 1998

 Model of chain branching reaction
Consider the reaction of : A B C
The mechanisms are: A R, ri k i C A
A R B C R, r p k pC ACR
RX rt k t CR

If we assume PSSA (means we assume steady state) on CR, we will

get CR as: kiCA
CR
k t ( 1)k pC A
Clicker question: Can we assume PSSA on CR for chain branching
reaction?
Answer: No. Reason: the minus sign indicates that it is possible that k t can
become equal to (-1)kpCA, since >1.
if kt = (-1)kpCA), CR .This indicates the branching chain reaction is not
as steady state. PSSA cannot be applied. Integrate
this
To get CR, we integrate the mass balance for R: equation
dCR/d = kiCA + ( - 1) kpCACR - to gt CRR
 Chain branching reaction
Problem 10.16 page 440
(cont.)
Schmidt
 Combustion
Fast and exothermic that proceeds by free radical chain
reactions
Chains reactions, once ignited, process proceeds very
quickly and becomes very non-isothermal
Release large amounts of energy
Applications in the production of power, heat in
incineration
Involve multiphases: oxidants is air, fuel is liquids/solids
Example is oxidation of H2 and alkanes

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 Autooxidation

Autooxidation autocatalytic process and it is

an oxidation that converts alkanes into alkyl
peroxides.
R H O2 ROOH
R H R H ,
R O2 ROO
ROO R H ROOH R

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 Reactor Safety
Chemical industry is the safer industry
compare to the risk if you drive on the
road. Nevertheless, loss can be
catastrophic if happens.
Some example of disaster
-Texas City disaster I and II
Read
-Flixborough & Philips polyethylene page
434
Schmi
plane explosion dt

-Bhopal incident
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Flixboroug Bhopal
h Incident, Disaster,
June 1974 Dec 1984
OCCUPATIONAL
SAFETY & HEALTH ACT
1994
 References
Schmidt, L.D. (2005). The Engineering of Chemical Reactions,
2nd edition, New York: Oxford University Press.
Fogler, H.S. (2006). Elements of Chemical Reaction
Engineering, 4th Edition, New Jersey: Prentice Hall.
Levenspiel, O. (1999). Chemical Reaction Engineering, 3rd
Edition, New York: John Wiley.
Pn. Hasyimi Rahmat, FKK UiTM Shah Alam.
Pn. Sharmeela Matali, FKK UiTM Shah Alam.

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