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A1 A2 ( E1 E2 E1' ) / RT
e
A1'
Thus the composite rate constant also has an Arrhenius-like form
with activation energy,
E = E1 + E2 – E1’
• Solution:
Chain reactions
• Chain reactions: a reaction intermediate produced in one
step generates an intermediate in a subsequent step, then that
intermediate generates another intermediate, and so on.
• Initiation step:
• Propagation steps:
• Termination steps:
23.1 The rate laws of chain
reactions
• Consider the thermal decomposition of acetaldehyde
CH3CHO(g) → CH4(g) + CO(g)
v = k[CH3CHO]3/2
it indeed goes through the following steps:
1. Initiation: CH3CHO → . CH3 + .CHO ki
v = ki [CH3CHO]
2. Propagation: CH3CHO + . CH3 → CH4 + CH3CO. kp
Propagation: CH3CO. → .CH3 + CO k’p
3. Termination: .CH3 + .CH3 → CH CH kt
3 3
The following mechanism has been proposed to account for the above
rate law.
1. Initiation: Br2 + M → Br. + Br. + M ki
2. Propagation: Br. + H2 → HBr + H. kp1
H. + Br2 → HBr + Br. kp2
3. Retardation: H. + HBr → H2 + Br. kr
4. Termination: Br. + Br. + M → Br2 + M* kt
derive the rate law based on the above mechanism.
• 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
• The above results has the same form as the empirical rate law, and
the two empirical rate constants can be identified as
1/ 2
k kr
k 2k p i k,
kt k p2
• Effects of HBr, H2, and Br2 on the reaction rate based on the
equation
1/ 2 3/ 2
d [ HBr] 2k p1 (k i / k t ) [ H 2 ][ Br2 ]
dt [ Br2 ] (k r / k p 2 )[ HBr]
• Self-test 23.1 Deduce the rate law for the
production of HBr when the initiation step
is the photolysis, or light-induced
decomposition, of Br2 into two bromine
atoms, Br.. Let the photolysis rate be v =
Iabs, where Iabs is the intensity of absorbed
radiation.
• Hint: the initiation rate of Br. ?
Exercises 23.1b: On the basis of the
following proposed mechanism, account
for the experimental fact that the rate law
for the decomposition
2N2O5(g) → 4NO2(g) + O2(g)
is v = k[N2O5].
d[ H . ]
v init k p [ .OH ][ H 2 ] kb1[ H . ][O2 ] k[O][ H 2 ] k t 1[ H . ] k t 2 [ H . ][O2 ][ M ]
dt
d[ .OH ]
k p [ .OH ][ H 2 ] kb1[ H . ][O2 ] kb 2 [O][ H 2 ]
dt
d [ .O]
kb1[ H . ][O2 ] kb 2 [ .O][ H 2 ]
dt
k b1 [ H . ][O2 ] k b 2 [O ][ H 2 ] 0
kb1[ H . ][O2 ]
[ .O]
kb 2 [ H 2 ]
2kb1[ H . ][O2 ]
[ OH ]
.
k p[ H 2 ]
Therefore, d[ H . ]
v init (2k b1 [O2 ] k t 1 k t 2 [O2 ][ M ])[ H . ]
dt
we write kbranch = 2kb1[O2] and kterm = kt1 + kt2[O2][M], then
d[ H . ]
v init (k branch k term )[ H . ]
dt
At low O2 concentrations, termination dominates branching, so kterm >
v init
kbranch. Then [ H . ] (1 e ( kterm kbranch ) t ) this solution corresponds
k term kbranch
d[ H . ]
vinit
dt
The integrated solution is [H.] = vinit t