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CHEM. 204

Consecutive Reactions –
General and Special Cases

Consecutive Reactions
• Consider the reaction scheme:
A 
ka
I 
kb
P
• Rate of decomposition of the reactant A:
d [ A]
 ka [ A] [ A]  [ A]0 e kat
dt
• Net rate of formation of the intermediate I:

d[I ]
 ka [ A]  kb [ I ]  ka [ A]0 e kat  kb [ I ]
dt

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d[I ]
 kb [ I ]  ka [ A]0 e kat
dt
– Homogeneous part:
d[I ]
 kb [ I ]  0 Solution: [I] = aest
dt
– Non-homogeneous part:
d[I ]
 kb [ I ]  ka [ A]0 e kat Solution: [I] = Me kat
dt
– General solution:
[ I ]  aest  Me ka t
• Rate of product (P) formation: d [ P ]
 kb [ I ]
dt

Solution

[ A]  [ A]0 e kat

[I ] 
ka
kb  k a
 
ekat  e kbt [ A]0

 k a e  kb t  kb e  k a t 
[ P]  1   [ A]0
 k b  k a 

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Rate-determining step
A 
ka
I 
kb
P
SLOW FAST kb  ka
0
 k a e  kb t  kb e  k a t 
[ P]  1   [ A]0
 kb  k a 
0
Kinetics of product

[ P]  1  e  ka t
[ A]
0
formation depends
solely on the slow step!

The slow step is called the rate-determining step.

Steady-state Approximation
• Again assume kb >> ka:

[I ] 
ka
kb  k a

ekat  e kbt [ A]0 
0
0 [ A]
k ka ka t
 a [ A]  e [A]0
kb kb
• Over a long time, [I] remains low
and constant.
• Virtually constant concentration of the
d[I ]
reactive intermediate. 0
Steady-state Approximation dt

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Application
• Apply for the scheme of consecutive reactions:
d[ I ]
 k a [ A]  kb [ I ]  0
dt
• Substitute in the rate of product formation:
ka
[I ]  [ A]
kb
• Integrate:
d [ P]
dt
k
 kb [ I ]  kb  a [ A]
kb
 
[ P]  1  e kat [ A]0
Same result as before!

Other typical application of SSA

• The pyrolysis of acetaldehyde at 520C is
believed to proceed through the mechanism:
CH 3CHO 
k1
CH 3  CHO
CH 3  CH 3CHO 
k2
CH 4  CH 3CO
CH 3CO 
k3
CO  CH 3
CH 3  CH 3 
k4
C2 H 6

• Show that this mechanism is consistent with

the rate law: d [CH 4 ]
 k [CH 3CHO] 3 / 2
dt

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Pre-equilibrium
• Consider the following reaction, in which an
intermediate I reaches a fast equilibrium with the
reactants A and B:
Pre-equilibrium ka
A B ka’
I 
bk
P
• The rate of formation of I and its decay back into
reactants is much faster than the rate of product
formation.
• Rate of product formation:
d [ P] ka
 kb K [ A][ B ] where: K
dt ka

Pre-equilibrium
• Alternative approach: Using SSA, show that:

d [ P] k a kb
 k [ A][ B ] where: k  kb K
dt 
k a  kb

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Mechanism II
• Consider the gaseous reaction:

2 NO + O2 k 2 NO2
• Experimentally the reaction is third order, with rate law:
d [ NO2 ]
 k [ NO]2 [O2 ]
dt
• But, the reaction is unlikely to consist of a single
termolecular step:
– The simultaneous collision of three molecules is a
rare event.
– The rate would increase with increasing T. But the
opposite is actually observed!

Investigate:
K
NO  NO N 2O2
N 2O2  O 2 
kb
2 NO2
Can show that:
d [ NO2 ]
 2kb K [ NO]2 [O2 ]
dt
Rate is third order 
k: Third order
rate constant
The dimerization of NO is known to be exothermic, hence K
decreases as T increases. This effect is dominant over
the rate constant kb
Net result is that k decreases as T increases.