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 , initiation

R O2 ROO, oxidation

ROO R H ROOH R, radical transfer

__________________________
R H O2 ROOH
 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
1. Burning of wood and coal
2. Pyrolysis
3. Coke and charcoal
4. The campfire / charcoal grill
5. Coal combustion
 ie : Decomposition of acetaldehyde

CH 3CHO CH 4 CO

r" kC A3 / 2 experimentally

A CH 3 CHO ,
 Major steps chain reaction mechanism
Initiation (i) : A CH 3 CHO , ri ki [ A]

Propagation 1 (p1) :
A CH 3 CH 4 CH 3CO , rp1 k P1[ A][CH 3 ]

Propagation 2 (p2) :
CH 3CO CO CH 3 , rp 2 k p 2 [CH 3CO]

2
Termination (t) : 2CH 3 C 2 H 6 , rt k t [CH 3 ]
 Propagations step producing major
product:

Propagation 1 (P1) :
A CH 3 CH 4 CH 3CO

Propagation 2 (P2) :

CH 3CO CO CH 3

A CH 4 CO
 PFTR/Batch : Time derivative, dC A
dt

CSTR : Concentration gradient, C Ao C A r

Mass balance = - reactant + product
d [ A]
ri rp1 ki [ A] k p1[ A][CH 3 ]
d
d [ CH 3 ]
ri r p 1 r p 2 2 rt
d
k i [ A ] k p 1 [ A ][ CH 3 ] k p 2 [ CH 3 CO ] 2 kt [ CH 3 ] 2

d [ CH 3 CO ]
r p 1 r p 2 k p 1 [ A ][ CH 3 ] k p 2 [ CH 3 CO ]
d
d [CO]
rp 2 k p 2 [CH 3CO]
d
d [CH 4 ]
rp1 k p1[ A][CH 3 ]
d
 [ CH 3 CO ] [ CH 3 CO o ]
0

k p 1 [ A ][ CH 3 ] k p 2 [ CH 3 CO ] 0

Hence :

k p 1 [ A ][ CH 3 ] k p 2 [ CH 3 CO ]

Rates of two propagation steps are

exactly equal
[ CH 3 ] [ CH 3 o ] [ CH 3 CO ] [ CH 3 CO o ]
0

Hence :
k i [ A ] k p 1 [ A ][ CH 3 ] k p 2 [ CH 3 CO ] 2 kt [ CH 3 ] 2

k p 1 [ A ][ CH 3 ] k p 2 [ CH 3 CO ]

k i [ A ] 2 kt [ CH 3 ] 2

The initiation and termination

step are exactly equal
 Autocatalytic initiation step generates
catalyst , concentration of catalyst not
changed by the propagation steps
Reaction generating catalyst that
promotes reaction
Large ki and inhibited by large kt
Kinetic chain length = [CH 4 ] rp
[C2 H 6 ] rt
[ CH 3 ] [ CH 3 o ] [ CH 3 CO ] [ CH 3 CO o ]
0

Hence :
k i [ A ] k p 1 [ A ][ CH 3 ] k p 2 [ CH 3 CO ] 2 kt [ CH 3 ] 2

k p 1 [ A ][ CH 3 ] k p 2 [ CH 3 CO ]

k i [ A ] 2 kt [ CH 3 ] 2 r
[CH 4 ] [CH 4 ]

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

k p1[ A]
2 kt
A B C

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 [CR ]nt

ni & nt = number of molecules that react in the

initiation & termination step.
Show that by PSS approximation,
1
ni
ki nt 1
r k p [C A ] nt
nt k t
 1 1
ni
n k nt 1 ki nt ni
r keff [CA ] eff i k p[CA ] nt keff neff 1
nt kt
, nt kt
, nt

Replacing each k in initiation,

propagation and termination with :
E
k ko exp
RT
Effective activation energy has become :
Ei Et
E eff Ep
nt nt
If ni=nt=1 :

ki
r k p [ A]2
kt
Hence the new effective rate coefficient :

E
ki
k eff p k o eff e RT
kt

E eff E i E t E p
 Initiation (promoters)
ni A R , ri ki C Ani (i )
I R , riI kiI C Ini (iI ) ki I ki

Scavengers (poisons)
nt R X , rt kt C Rnt (t )

R S X , rts kt C R CS (t s )
s
R S X , rt s kt C R CS
s

area " " "

rt rt , rt kt C RS k m (C Rb C Rs )
vol
" ShD DA
k km
t Mass transfer controlling
D

area " area

kt *k * km Process control by
vol vol surface termination
 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
A B C
A R , ri ki C A
A R B C R , rp k p C A C R
R X , rt kt CR

dC R
ki C A ( 1)k p C AC R kt C R 0
dt

kiC A For linear ki C A

CR CR
k t ( 1) k p C A chain : kt
 Denominator : kt ( 1) k p C A
If the propagation term is large
compares to others:
dC R
( 1) k p C A C R
dt
kt
C R ( t ) C Ro e