Chain Reactions

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Example : Decomposition of acetaldehyde

CH3CHO CH 4 + CO
Initiation step
Propagation #1
Propagation #2
Termination step

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r = kCA2

A CH3 +CHO,

r i = k i [ A]

A + CH3 CH 4 + CH3CO

rp1 = k p1[ A][CH3 ]

CH3CO CO + CH3

rp2 = k p2 [CH3CO]

CH

2CH3 C2H6

rt = kt [CH3 ]

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Propagation steps occur faster than initiation

and termination steps
Radical species are very reactive and
concentrations are always very low.
Major products generated by propagation step
Minor products made by initiation and
termination steps.
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Mass balance
PFTR/Batch : Time derivative,

CSTR : Concentration gradient,

Mass balance = - reactant + product

dC A
dt

r = C A C A

Mass balance : PFTR

d [ A]
= ri rp1 = ki [ A] k p1[ A][CH 3 ]
d
d [CH 3 ]
= ri rp1 + rp 2 2rt
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]
= rp 2 = k p 2 [CH 3CO]
d
d [CH 4 ]
= rp1 = k p1[ A][CH 3 ]
d

Recall:

A CH3 +CHO,

r i = k i [ A]

A + CH3 CH 4 + CH3CO

rp1 = k p1[ A][CH3 ]

CH3CO CO + CH3

rp2 = k p2 [CH3CO]

2CH3 C2H6

rt = kt [CH3 ]2

Activity in Class :
Write mass balance for CSTR

When the concentration of the two radicals are low

(very reactive) :
[CH 3CO] [CH 3CO o ]

=0

k p1[ A][CH 3 ] k p 2 [CH 3CO] = 0

Hence :

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

Rates of two propagation steps are
exactly equal

[CH 3 ] [CH 3 o ]

[CH 3CO] [CH 3CO o ]

=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]
ki [ A] = 2kt[CH 3 ]2

The initiation and termination step

are exactly equal

The major processes are the propagation steps

Adding p1 and p2 steps yield:

A + CH3 CH 4 + CO + CH3
Autocatalytic the reaction generates the catalyst
that promotes the reaction.
The overall rate is enhanced by large ki and inhibited
by large kt even though ki, kt << kp
Kinetic chain length ratio of rp to rt.

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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.

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[CH 3 ] [CH 3 o ]

[CH 3CO] [CH 3CO o ]

=0

Hence :

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]
ki [ A] = 2kt[CH 3 ]2
[CH 3 ]2 =

= k p1[ A][CH 3]

ki [ A]
2kt

ki
[CH 3 ] =
2kt

1/ 2

r=

[CH 4 ] [CH 4 o ]

[ A]1/ 2

k
= k p1[ A] i
2kt

1/ 2

[ A]1/ 2

3 / 2 ki
= k p1[ A]
2kt

1/ 2

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A B +C

The reaction propagates by radical R.

ni A R ,

ri = k i [C A ]

A + R B + C + R ,
nt R X

r p = k p [C A ][CR ]

ni

nt

rt = k t [CR ]

ni and nt are the number of molecules react in

initiation and termination steps respectively.
PSS approximation on CR yield the overall rate
expression

CPE624

k i
r =
n k
t t

1
nt

1+

k p [C A ]

ni
nt

neff

r = keff [CA ]

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Generic Chain Reaction

neff

r = keff [C A ]

1
nt

ni
1+
nt

ki
k p [C A ]
=
nt kt

ki
k p
keff =
nt kt

Replacing each k in initiation, propagation

and termination with :
Effective activation energy has become :

Eeff

Ei Et
=

+ Ep
nt
nt

1
nt

ni
neff = 1 +
nt

E
k = ko exp

RT

Generic Chain Reaction

If ni=nt=1 :

ki
2

r = k p [A]
kt
Hence the new effective rate coefficient :

keff

ki
=
p = ko eff e RT
kt

Eeff = Ei Et + E p

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Example 10-1 (Schmidt pg 404)

Consider the chain reaction in a CSTR:

A R,
A + R B + C + R,
RX

ri = k i [C A ]
r p = k p [C A ][CR ]
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?
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Exercise in class

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Large temperature dependences.

Sensitive to trace impurities that can alter the initiation and
termination rates
Initiators and Scavengers (promoters and poisons) have large
influences.
Initiators
Initiated by adding species I that easily forms radical
Initiate the reaction faster than reactant.

Scavengers
Termination step - radical species decomposed /reacted with other
radical species to form an inactive species X
Adding scavengers S
X is important in determining overall reaction rate
CPE624

R + S X , rts = ktsCRCS

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Example: Briefly explain the terms initiator

and scavenger for a chain reaction
Initiator: Species (I) that can easily form radicals in a
chain reaction and can initiate the reaction faster than
the reactant.

Scavenger: Species (S) added into a chain reaction

that can readily scavenge the chain propagator to
terminate the reaction.

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Surface reaction steps important in

controlling chain reactions.
Wall termination reactions introduce a
complexity to all chain reactions the
overall reaction rate as a function of the size
of reactor.
In a small reactor, termination reactions on
surface keep the radical intermediate small
and inhibit chain reaction.
In large reactor, the termination rate is
smaller.
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Wall termination reactions

R + S X , rts = kt CRCS
s

area " "

"
rt =
rt , rt = kt CRS = k m (CRb CRs )
vol

S hD DA
k = km =
D
"
t

area " area

kt =
*k =
* km
vol
vol

Mass transfer controlling

Process control by surface

termination

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Example
Consider the chain reaction in a CSTR:
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 98% conversion of A in CSTR assuming pseudo
steady state if CA0 = 2 moles/liter, ki = 0.002 sec-1, kp = 10 liter/
mole sec and kt = 0.05 sec-1.
d) What are CR and Cx for this conversion?

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(a)

Initiation:
Propagation:
Termination:

A R ; ri = kiCA
A + R B + C + R; ri = kpCA CR
R X; rt = ktCR

(b) Overall reaction rate:

CR/ = kiCA ktCR = 0
CR = ki/kt x CA
r = kpCACR
= kikp/kt CA2
(c) Solving CSTR equation:
r = CAo CA
= (CAo CA)/r = (CAo CA )/CA2 x kt/kikp
= [2 moles/L - 2(1-0.98)]/(0.04)2 x 0.05/ s/0.002/s

x 10 l/s

= 1225 x 2.5 = 3062.5 s

=
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51 min
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Q#1 Test 2 Oct 2012

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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 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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 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 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 ,
R +O2 ROO,
ROO + R H ROOH + R,
__________________________
R H + O2 ROOH

initiation
oxidation
radical transfer

Thermal and chemical

autocatalysis
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

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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:

ROOH R +O +OH

Rapid rise in the concentration of radical species can

accelerate the reaction and possibly a chain-branching
explosion.

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 Produce two reactive free radicals from one

Propagation steps produce more radical species that
start with. ie:

H + O2 OOH OH + O
The hydroperoxy radical .OOH reacts immediately at high
temperature

Most combustion reactions involve chain branching

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Consider the reaction of :

A B +C
The mechanisms are:
A R,
A + R B + C + R,
RX

derive
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ri = k i C A
r p = k pC ACR
rt = k t CR

k i CA
CR =
k t ( 1)k pCA
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 For > 1 and CA is large enough and not in SS :

kt = ( 1)k p C A
If the propagation term is large compares to others:

dC R
= +( 1)k p C AC R
dt
C R( t ) = C Ro e kt
Sample of chain branching reaction :
Combustion of Hydrogen to form water

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Exercise in Class : Problem 10-16

(Schmidt) pg 440

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36

Chemical industry is the safer industry compare to the risk if

you drive on the road
Some example of disaster
-Texas City disaster I and II
-Flixborough & Philips polyethylene plane explosion
-Bhopal incident

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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.

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A B+C
A R , ri = ki C A
A + R B + C + R , rp = k pC A CR

R X , rt = kt CR
dC R
= ki C A + ( 1)k p C ACR kt CR = 0
dt

ki C A
CR =
kt ( 1)k pC A

For linear
chain :

CR =

ki C A
kt

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Exam Q#1-June 2012

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