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Complex Reaction

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

These reactions are generally carried out with a


bath/inert gas (M) for which [M] >> [A] ([A] =
reactant).
At low pressures, the rate law has partial orders with
respect to A and M of 1 each, so an overall order of 2.
At high pressures, first-order kinetics in [A] is
observed.
These observations are both

Lindemann Mechanism

Lindemann Rate Equation


Using Steady State Approximation

Rate Expression for reactant as Bath


gas

d P
k2k1 A

dt k2 k1 A
2

The rate laws for the Lindemann-Hinshelwood


Mechanism are pressure dependent.
High Pressure Case

d P k2k1 A

dt
k1
k A
/

Low Pressure Case

d P
2
k1 A
dt
2
/
k A

Solution for Practical


Application

Example: cis-trans isomerization


of 2-butene at 740K

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

Example of Branched Chain


reaction
Combustion
Water formation from H2 and O2
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

Chain Reactions (Contd)


Retardation Step
HBr + H H2 + Br

Terminations Steps
2 CH3CH2 CH3CH2CH2CH3

Inhibition Steps
R + CH3 RCH3

The H2 + Br2 Reaction


The overall rate for the reaction was
established in 1906 by Bodenstein and
Lind

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

Using the SSA


Using the SSA on the rates of
formation of Br and H
3
k

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

Rate Laws for the


Rice-Herzfeld
Mechanism
The rate laws for the elementary
reactions are as follows.
v 1 k1C2H 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

k1 = rate constant for initiation step


k2 = rate constant for propagation step
kw = rate constant for termination on wall
kg= rate constant for termination in gaseous phase

chain carriers are H , OH , O


Branching: one
chain carrier
becomes two or
more.
Occurence of explosion given by explosion
region (regions of T,p).
If T is low, rate constants are too small.
If p is low, the reaction rates, v, are too low due
to infrequent collisions.

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

Steady state approximation:

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 ]

Then chain carrier production


rate is

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