Chain Reaction

TOPIC 3
Chain Reaction
Mechanisms
Chain Reaction Mechanisms
Credit to: Cik Siti Khatijah Jamaludin, FKK UiTM Shah Alam
Chain Reaction Mechanisms
Chain Reaction Definition
A chemical chain reaction is a series of chemical
reactions where the products of the reaction
contribute to the reactants of another reaction. This
transformation of products to reactants allows a
reaction to continue along by itself with minimal or no
outside influence. These chain reactions are generally
triggered by a single initial reaction where an unstable
product from the first reaction becomes the reactant.
This process occurs until the system reaches some
stable state. This stable state often comes running out
of fuel because the different chemicals are in their
lowest energy state (like hydrocarbons becoming water
and CO2).
TOPIC 3
Intro to Chain Reaction Mechanism
Autocatalytic reactions
Pseudo steady state approximation/hypothesis
Generic (linear) chain reaction
Characteristics of Chain Reactions
Initiators
Scavengers
Wall termination reactions
Chain Branching Reactions
Reactor Safety
Thermal & Chemical Autocatalysis
Chain Reactions
Example
CH 3CHO CH 4 CO
3
r kC A 2
Initiation step 3 + =
Propagation step 1 + 3 4 + 3 1 = 1 3
Propagation step 2 3 + 3 2 = 2 3
Termination step 23 2 6 = 3 2
The species circled with GREEN are known as: stable molecules
The species circled with RED are known as: free-radical molecules
FACULTY OF CHEMICAL ENGINEERING 5
Chain Reactions
Propagation steps occur 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 generated by propagation step
Minor products made by initiation and termination
steps.

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:
* j is any species in the chain reaction

Example 1 (Class Activity)
3 + =
+ 3 4 + 3 1 = 1 3
3 + 3 2 = 2 3
23 2 6 = 3 2
Write the mass balance equation on each species for

the mechanism above in a) PFTR and b) CSTR
Mass Balance: PFTR (Batch ( t))
d [ A]
ri rp1 ki [ A] k p1[ A][CH 3 ]
d

=
d [CH 3 ]
ri rp1 rp 2 2rt =1
d
ki [ A] k p1[ A][CH 3 ] k p 2 [CH 3CO] 2kt [CH 3 ]2
d [CH 3CO]
rp1 rp 2 k p1[ A][CH 3 ] k p 2 [CH 3CO]
d
d [CO] d [CH 4 ]
rp 2 k p 2 [CH 3CO] rp1 k p1[ A][CH 3 ]
d d
Mass Balance: CSTR
A A0 k A k ACH
i p1 3
[CH 3 ] [CH 3 0 ]
ri rp1 rp 2 2rt

[CH 3CO] [CH 3CO0 ]

rp1 rp 2 k p1[ A][CH 3 ] k p 2 [CH 3CO]

[CO] [CO0 ] [CH 4 ] [CH 4,0 ]

rp 2 k p 2 [CH 3CO] rp1 k p1[ A][CH 3 ]

When the concentration of the two radicals are low (very
reactive) :
[CH 3CO] [CH 3CO 0 ]

0

k p1[ A][CH 3 ] k p 2 [CH 3CO] 0
To obtain.
k p1[ A][CH 3 ] k p 2 [CH 3CO]
Rates of two propagation steps are exactly equal
CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

When the concentration of the two radicals are low (very
reactive) :
[CH 3 ] [CH 3 0 ] [CH 3CO] [CH 3CO 0 ]

0

Hence adding the two propagation steps:
k p1[ A][CH 3 ] k p 2 [CH 3CO]
ki [ A] 2kt [CH 3 ]2
The initiation and termination step are exactly equal

3 + =
Reaction itself generate its own catalyst (3 ) from initiation
step.
Adding p1 and p2 steps yield:
A CH 3 CH 4 CO CH 3
The overall rate is enhanced by large ki and inhibited by large kt
even though ki, kt << kp
Chain reactions generate major (propagation step) and minor
(initiation & termination steps) products respectively.
4
Kinetic chain length =
2 6

PSS valid when the concentration of the
species is small
In Batch/PFR setting time derivative

equal to zero
In CSTR - Mass balance equations are

developed by assuming steady state, so
that PSS of intermediate species is in
steady state and concentration is small.

[CH 3 ] [CH 3,0 ] [CH 3CO] [CH 3CO0 ]
0


k p1[ A][CH 3 ] k p 2 [CH 3CO]
ki [ A] 2kt [CH 3 ]2 [CH 4 ] [CH 4 o ]

r

ki [ A] k p1[ A][CH 3 ]
[CH 3 ]2
2k t 1/ 2
ki
ki
1/ 2 k p1[ A] [ A]1/ 2
[CH 3 ] [ A]1/ 2 2k t
2k t ki
1/ 2
k p1[ A]
3/ 2

2k t
A BC
The reaction propagates by radical R
ni A R, ri ki C A ni
A R B C R rp k p C A C R
nt R X rt kt C R nt
ni and nt are the number of molecules react in initiation

and termination steps respectively
Derive the mass balance expression for each species.

PSS approximation on CR yield the overall rate expression
r keff C A eff
1
k nt n
k p C A 1 nt
ni
r i
nt kt
1 1
n
ki nt 1 i ki nt ni
r keff [C A ]
neff
k p [C A ] nt
keff k p neff 1
nt kt
, nt kt
, nt
Replacing each k in Effective activation energy

initiation, propagation and has become :
termination with :
Ei Et
E Eeff Ep
k ko exp nt nt
RT

If ni=nt=1 :
ki
r k p [A]2
kt
Hence the new effective rate coefficient :
E
ki
keff p ko eff e RT
kt
Eeff Ei Et E p

Consider the chain reaction in a CSTR (Constant
volume):
A R, ri k i C A
A R B C R, r p k p C A CR
RX rt k t CR
a) Write the mass balance equations for A, B, R and X in a

CSTR assuming constant density.
b) What is the overall reaction rate with respect to CA?
c) Find for 90% conversion of A in CSTR assuming
pseudo steady state if CA0 = 2 moles/liter, 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?

A R,
a Write the mass balance equations for A R B C R,
A, B, R and X in a CSTR assuming
constant density RX
A A0 k A k AR B k AR
i p
p
[ R]
ki A kt R
X k R
t
b What is the overall reaction rate with respect to CA?
First we need to find CR in terms of CA,
ki A kt R 0
[ R]


ki A
so that: R
kt
and exhibits
Therefore the rate becomes: second-order
k p ki kinetics
r k p AR A2
kt
c Find for 90% conversion of A in CSTR assuming pseudo
steady state if CA0 = 2 moles/liter, ki = 0.001 sec-1, kp = 20
liter/mole sec and kt = 0.1 sec-1.
From the stoichiometry, 1 mole of A produce 1 mole of B.

Therefore, with 90% conversion, only
2 moles/liter 0.9 = 1.8 moles/liter of B will be produced.
And the remaining [A] = 2 1.8 = 0.2 moles/liter.

B k p ki A2
kt
20 0.001

1.8
0.22 225s
0.1
d What are CR and Cx for this conversion?
From the above, we obtain the concentrations:
R ki A 0.001 0.2 0.002 X kt R 0.1 0.002 2 104

kt 0.1
X 2 104 225 0.045
Since CB = CC = 1.8 moles/liter from stoichiometry, we see

that CR and CX are indeed small compared to the major
product, as expected.
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 (cont.)
Scavengers (poisons)
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 the elementary reaction step involving scavenger as:
R+S X rtS = 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
Example 3
Q1: Define initiator and scavenger for a chain reaction.
Q2:
Source: Schmidt, page 440

Recall the definition of termination step. Termination step
is the step by which 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. Why??
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 Chapter 1
rt = (area/volume) rt on Catalytic Wall
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 = (ShDDR) / D
Typical graph of reaction involving reactive intermediates (i.e. free-
radicals, R) .
reactant product
Maximum
concentration of
the reactive
intermediate is
achieve when
dCR/dt = 0
Reactive intermediate,
i.e.: free-radicals, R
Source: Davis, McGraw-Hill Company Inc. 2003
TOPIC 3
Intro to Chain Reaction Mechanism
Pseudo steady state approximation/hypothesis
Generic (linear) chain reaction
Initiators
Scavengers
Chain Branching Reactions
Reactor Safety
Thermal & Chemical Autocatalysis
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: k i CA
CR
kt ( 1)k pCA
Clicker question: Can we assume PSSA on CR for chain branching
reaction?
Answer: No. Reason: the minus sign indicates that it is possible that kt 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.
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

Lab safety :
Organic chemicals will react with oxygen in the air

at room temperature in chain reactions
Hence forming organic peroxides (fuel /C & H

atoms in the compounds)
Consequences : spontaneous react, explosion upon

shaking or opening the cap
Organic peroxide have very exothermic heats of

decomposition

The reactions can only occur if oxygen is present
The reaction depends crucially on the initiation steps,

and different molecules have vastly different
capabilities of dissociation
The reaction depends crucially on the initiation steps,

and different molecules have vastly different
capabilities of dissociation
The initiation step can be photoinduced. If a bottle is

sitting in sunlight, UV photons can cause photo
dissociation to initiate the chain reaction much faster
than in the dark

Organic molecule (R-H) where R could be an alkyl or
any fragment containing C, H and O atoms
In the presence of O2, this molecule undergo auto

oxidation reaction :
R H O2 ROOH
The chain reactions proceeds at high temperature to

break the R-H strong bond (>80 kcal/mole)

Consider the chain reaction sequence :
R H C H , initiation
R O2 ROO, oxidation
ROO R H ROOH R, radical transfer
__________________________
R H O2 ROOH

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
FACULTY OF CHEMICAL ENGINEERING

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
423
Schmidt
plane explosion
-Bhopal incident
Flixborough Bhopal
Incident, Disaster,
June 1974 Dec 1984
OCCUPATIONAL SAFETY &
HEALTH ACT 1994
Chemical autocatalysis reactions accelerates
chemically such as in enzyme-promoted fermentation,
or chain branching reaction
Enzyme reaction nearly isothermal but combustion

processes are both chain branching and auto thermal
Autocatalysis reactive intermediate or heat can act

as catalyst to promote the reaction
Catalyst is generated by the reaction, by adding

promoters or heat to initiate the and accelerate the
process

FINAL EXAM: JUNE 2012
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.

Chain Reaction

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TOPIC 3

Chain Reaction Mechanisms

FACULTY OF CHEMICAL ENGINEERING 6

* j is any species in the chain reaction

Write the mass balance equation on each species for

[CH 3CO] [CH 3CO0 ]

[CO] [CO0 ] [CH 4 ] [CH 4,0 ]

[CH 3CO] [CH 3CO 0 ]

k p1[ A][CH 3 ] k p 2 [CH 3CO]

Rates of two propagation steps are exactly equal

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

[CH 3 ] [CH 3 0 ] [CH 3CO] [CH 3CO 0 ]

Hence adding the two propagation steps:

ki [ A] k p1[ A][CH 3 ] k p 2 [CH 3CO] 2kt [CH 3 ]2

k p1[ A][CH 3 ] k p 2 [CH 3CO]

The initiation and termination step are exactly equal

FACULTY OF CHEMICAL ENGINEERING 13

In Batch/PFR setting time derivative

In CSTR - Mass balance equations are

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

ki [ A] k p1[ A][CH 3 ] k p 2 [CH 3CO] 2kt [CH 3 ]2

ki [ A] 2kt [CH 3 ]2 [CH 4 ] [CH 4 o ]

The reaction propagates by radical R

ni and nt are the number of molecules react in initiation

Derive the mass balance expression for each species.

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Replacing each k in Effective activation energy

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Hence the new effective rate coefficient :

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

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

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

b What is the overall reaction rate with respect to CA?

First we need to find CR in terms of CA,

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

From the stoichiometry, 1 mole of A produce 1 mole of B.

And the remaining [A] = 2 1.8 = 0.2 moles/liter.

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

d What are CR and Cx for this conversion?

From the above, we obtain the concentrations:

R ki A 0.001 0.2 0.002 X kt R 0.1 0.002 2 104

Since CB = CC = 1.8 moles/liter from stoichiometry, we see

Can alter the initiation and

Initiators (promoters) and scavengers (poisons)

kiI can be much larger than ki

R+S X rtS = ktSCRCS

ktS can be much

Source: Schmidt, page 440

Wall termination step frequently occurs readily on surfaces (i.e.

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

Source: Schmidt 1998

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

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Organic chemicals will react with oxygen in the air

Hence forming organic peroxides (fuel /C & H

Consequences : spontaneous react, explosion upon

Organic peroxide have very exothermic heats of

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

The reaction depends crucially on the initiation steps,

The reaction depends crucially on the initiation steps,

The initiation step can be photoinduced. If a bottle is

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

In the presence of O2, this molecule undergo auto

The chain reactions proceeds at high temperature to