26 The kinetics of complex reactions

26.1 The rate laws of chain reactions

The thermal decomposition of acetaldehyde

CH3CHO(g) → CH4(g) + CO(g)

v = k[CH3CHO]3/2 26.1.1

Initiation: CH3CHO → . CH3+ .CHO

v = ki[CH3CHO]
Propagation: CH3CHO + . CH3 → CH4 + CH3CO. kp
Propagation: CH3CO. → .CH3 + CO k’p
Termination: .CH3 + .CH3 → CH3CH3 kt

The net rates of change of the intermediates are:

d [ .CH 3 ]
= k i [CH 3CHO ] − k p [ .CH 3 ][CH 3CHO ] + k ,p [CH 3CO . ] − 2k t [ .CH 3 ]2
dt
d [CH 3 CO . ]
= k p [ .CH 3 ][CH 3 CHO ] − k ,p [CH 3 CO . ]
dt
Applying the steady state approximation to the above two equations
0 = k i [CH 3 CHO ] − k p [ .CH 3 ][CH 3 CHO ] + k ,p [CH 3 CO . ] − 2k t [ .CH 3 ]2
0 = k p [ .CH 3 ][CH 3CHO ] − k ,p [CH 3 CO . ]

The sum of the above two equations is:

ki [CH 3CHO ] - 2kt [.CH 3 ]2 = 0

thus the steady state concentration of [.CH3] is:

1/ 2
 k 
[ CH3] =  i
.
 [CH 3 CHO ]1 / 2
 2k t 
The rate of formation of CH4 is:
1/ 2
d [CH 4 ]  k 
= k p [ .CH 3 ][CH 3 CHO ] = k p  i  [CH 3 CHO ]3 / 2 26.1.2
dt  2k t 

Equation 26.1.2 is in agreement with the three-halves order observed

experimentally.
 We have discussed earlier that hydrogen-bromine reaction has
complicated rate law rather than the second order reaction as anticipated.
Now we examine why
H2(g) + Br2(g) → 2HBr(g)

Yield
k[ H 2 ][ Br2 ] 3 / 2
v= 26.1.3
[ Br2 ] + k '[ HBr ]

The following mechanism has been proposed to account for the above
rate law.

Initiation: Br2 + M → Br. + Br. + M ki

Propagation: Br. + H2 → HBr + H. kp1
H. + Br2 → HBr + Br. kp2
Retardation: H. + HBr → H2 + Br. kr
Termination: Br. + Br. + M → Br2 + M* kt

The net rates of formation of the two intermediates are

d[ H . ]
= k p1 [ Br . ][ H 2] − k p 2 [ H . ][ Br2 ] − k r [ H . ][ HBr ]
dt
d [ Br . ]
= 2k i [ Br2 ][ M ] − k p1 [ Br . ][ H 2 ] + k p 2 [ H . ][ Br2 ] + k r [ H . ][ HBr ] − 2k t [ Br . ]2 [ M ]
dt

The steady-state concentrations of the above two intermediates can be

obtained by solving the following two equations:
k p1 [ Br . ][ H 2] − k p 2 [ H . ][ Br2 ] − k r [ H . ][ HBr ] = 0
2k i [ Br2 ][ M ] − k p1 [ Br . ][ H 2 ] + k p 2 [ H . ][ Br2 ] + k r [ H . ][ HBr ] − 2k t [ Br . ] 2 [ M ] = 0

1/ 2
k  .
[Br ] =  i  [Br2 ]1 / 2
 kt 
. k p1 (k i / k t )1 / 2 [ H 2 ][ Br2 ]1 / 2
[H ] =
k p 2 [ Br2 ] + k r [ HBr ]
substitute the above results to the rate law of [HBr]
 d [ HBr ]
= k p1 [ Br . ][ H 2 ] + k p 2 [ H . ][ Br2 ] − k r [ H . ][ HBr ]
dt
1/ 2 3/ 2
d [ HBr ] 2k p1 (k i / k t ) [ H 2 ][ Br2 ]
= 26.1.4
dt [ Br2 ] + (k r / k p 2 )[ HBr ]
Equation 26.1.4 has the same form as the empirical rate law 26.1.4, so
the two empirical rate constants can be identified as
1/ 2
k 
k = 2k p  i 
 kt 
k
k’ = r
k p2
analyzing the effects of HBr, H2, and Br2 on the reaction rate based on
equation 26.1.4.

26.2 Explosions
A thermal explosion is a very rapid reaction arising from a rapid
increase of reaction rate with increasing temperature.

A chain-branching explosion occurs when the number of chain

centres grows exponentially.

An example of both types of explosion is the following reaction

2H2(g) + O2(g) → 2H2O(g)

Initiation: H2 → H. + H.
Propagation H2 + .OH → H. + H2O kp
Branching: O2 + .H → O + .OH kb1
O + H2 → .OH + H. kb2
Termination H. + Wall → ½ H2 kt1
H. + O2 + M → HO2. + M* kt2
 Analyzing the above reaction and show that an explosion occurs when
the rate of chain branching exceeds that of chain termination.