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26 The Kinetics of Complex Reactions: V K (CH

The document summarizes reaction kinetics for complex chain reactions involving acetaldehyde decomposition and hydrogen bromine reaction. It also discusses conditions for thermal explosions in reactions involving hydrogen and oxygen. 1) Acetaldehyde decomposition follows a three-halves order rate law due to radical chain reactions involving CH3 and CH3CO intermediates. Applying a steady state approximation derives the observed rate law. 2) The hydrogen-bromine reaction has a more complex rate law than second order due to radical chain reactions involving H and Br intermediates. Applying a steady state approximation derives the empirical rate law. 3) Thermal explosions can occur when the rate of chain branching reactions exceeds the rate of chain terminating reactions, as

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652 views4 pages

26 The Kinetics of Complex Reactions: V K (CH

The document summarizes reaction kinetics for complex chain reactions involving acetaldehyde decomposition and hydrogen bromine reaction. It also discusses conditions for thermal explosions in reactions involving hydrogen and oxygen. 1) Acetaldehyde decomposition follows a three-halves order rate law due to radical chain reactions involving CH3 and CH3CO intermediates. Applying a steady state approximation derives the observed rate law. 2) The hydrogen-bromine reaction has a more complex rate law than second order due to radical chain reactions involving H and Br intermediates. Applying a steady state approximation derives the empirical rate law. 3) Thermal explosions can occur when the rate of chain branching reactions exceeds the rate of chain terminating reactions, as

Uploaded by

Lukman Hakim
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

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.

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