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Mechanism
Complex Reactions
Complex reaction mechanism
involves multiple step and/or
multiple intermediates in the
reaction.
Examples include
Unimolecular Reaction
Chain Reactions and Explosion reactions
Catalysis
Biocatalysis
Unimolecular Reactions
Lindemann Mechanism
d P
k2k1 A
dt k2 k1 A
2
d P k2k1 A
dt
k1
k A
/
d P
2
k1 A
dt
2
/
k A
Chain reactions
The steps involved in a chain
reaction may be non-cyclic or cyclic
steps.
A chain reactions can further be
treated as
Linear chain reaction or
Branched chain reaction
Example of Chain
Reaction
Halogenation of alkane
Decomposition of alkanes
Decomposition of acetaldehyde
Ozone depletion
Smog formation
Nuclear fission
Chain Reactions
Classifying steps in a chain reaction.
Initiation
C2H6 (g) 2 CH3
Propagation Steps
C2H6 + CH3 C2H5 + CH4
Branching Steps
H2O + O 2 OH
Terminations Steps
2 CH3CH2 CH3CH2CH2CH3
Inhibition Steps
R + CH3 RCH3
d HBr
k H 2 Br2 2
/
Br2 k HBr
dt
3
The Mechanism
The mechanism was proposed independently by
Christiansen and Herzfeld and by Michael Polyani.
Mechanism
Rate Laws
Br2 2Br
v 1 k1 Br2
Br H 2 HBr H
v 2 k 2 Br H 2
H Br2 HBr Br
v 2 k 2 Br2 H
H HBr H 2 Br
v 3 k 3 H HBr
Br Br Br2
v 4 k 4 Br
2k 2 1 H 2 Br2 2
k4
d HBr
k3
dt
Br2 k / HBr
2
Hydrogenation of
Ethane
The Rice-Herzfeld Mechanism
Mechanism
C2H 6 2CH 3
C2H 6 CH 3 CH 3CH 2 CH 4
CH 3CH 2 CH 2CH 2 H
CH 3CH 3 H CH 3CH 2 H 2
CH 3CH 2 H C2H 6
v 2 k 2 C2H 6 CH 3
v 2 k 2 CH 3CH 2
v 2 / k 2 / H CH 3CH 3
v 3 k 3 H CH 3CH 2
Decomposition of
Acetaldehyde
Example.
v k[ HBr ( g )][O2 ( g )]
Explosion Reaction
An explosion is a rapidly accelerating
reaction arising from a rapid increase in
reaction rate with increasing temperature
Inititation
R.
Propogation
R.
P + R.
Termination
R. Destruction
General Expression
Example
Show that an explosion
happens when rate of chain
branching
exceeds that of chain
termination.
H
Answer:
Focus only on the rate of prod
of
d
[H
] vini
k p [ Has
HO] kb [ H ][O2 ]
2 ][important.
chain
carrier
dt
Rate
change
of chain
kb '[O
][ H 2 ]of
k
t [ H ] k 't [ H ][ M ][O2 ]
carrier:
Example
d
[OH ] k p [OH ][ H 2 ] kb [O2 ][ H ] k 'b [O][ H 2 ] 0
dt
d
[O] kb [O2 ][ H ] k 'b [O][ H 2 ] 0
dt
k
[OH ] 2 b [O2 ][ H ] /[ H 2 ]
kp
[O] k b [O2 ][ H ] / k 'b [ H 2 ]
d
[ H ] vini ( 2kb [O2 ] kt k 't [ M ][O2 ])[ H ]
dt
Example
write:
kbranch 2kb [O2 ] measuring chain branching rate.
kterm kt kt' [O2 ][ M ] measuring termination rate.
Then chain carrier production rate is
d
[ H ] vini ( kbranch kterm )[ H ]
dt
vinit
a ) [ H ]
(1 e ( kterm kbranch ) t ) kbranch kterm
kterm kbranch
vinit
b) [ H ]
(e ( kbranch kterm ) t 1) kbranch kterm
kbranch kterm