Class Practice 11 - The Steady-State Approximation Solution:

A proposed mechanism for the formation of N2O5 from NO2 and O3 NO3 is the intermediate.
(2NO2 + O3  N2O5 + O2) is Apply steady-state approximation,
NO 2  O3 
k1
 NO3  O 2
NO3  NO 2  M 
k2
 N 2 O5  M d [ NO3 ]
 k1[ NO2 ][O3 ]  k 2 [ NO2 ][ NO3 ]  0
dt
Determine the rate law expression for the production of N2O5 given this
mechanism using steady-state approximation.
The net rate of formation of [N2O5] is
Methods:
d  N 2 O5 
• First identify the intermediate(s) and write expression(s) for their net  k2  NO 2  NO3 
dt
rate(s) of formation.
• Set all net rates of change of [I] = 0.
Substitute the first equation above into the second one.
• Write the expression for the rate of production of N2O5. Any
intermediate concentration involved is then expressed in terms of
reactant concentration.
• Solve the resulting equation algebraically.
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Class Practice 12 - The Steady-State Approximation

d  NO3 
 0  k1  NO 2  O3   k2  NO 2  NO3  Using the steady-state approximation, derive the rate law for the
dt following reaction on the basis of the proposed mechanism given
k2  NO 2  NO3   k1  NO 2  O3  below.
2N2O5 (g)  4NO2 (g) + O2 (g)
k
 NO3   1 O3  Proposed mechanism:
k2
N2O5  NO2 + NO3 ka
NO2 + NO3  N2O5 ka’
d  N 2 O5  NO2 + NO3  NO2 + O2 + NO kb
 k2  NO 2  NO3  NO + N2O5  3NO2 kc
dt
k 
 k2  NO2   1  O3  
 k2 
 k1  NO2  O3 
The mechanism predicts that the reaction is first order in NO2 and O3,
second order overall.
3 4
Solutions: From 2 , k a [ N 2O5 ]
[ NO2 ][ NO3 ]  4
NO and NO3 are intermediates k a ' kb
Apply steady-state approximation,
d [ NO ]
 kb [ NO2 ][ NO3 ]  kc [ NO ][ N 2O5 ]  0 1 Substitute 4 into 3 ,
dt
d [O2 ]
d [ NO3 ]  kb [ NO2 ][ NO3 ] 3
 k a [ N 2O5 ]  k a '[ NO2 ][ NO3 ]  kb [ NO2 ][ NO3 ]  0 2 dt
dt k k [N O ]
 a b 2 5
k a ' kb
The net rate of change of [O2] is

d [O2 ] kk Resultant
d [O2 ]
 kb [ NO2 ][ NO3 ] 3 Since rate   ( a b )[ N 2O5 ]
dt dt k a ' kb rate law

5 6

Or
The net rate of change of [N2O5] is Substitute 4 into 5 , k a kb
[ NO ]  6
d [ N 2O5 ] (k a ' kb )kc
 k a [ N 2O5 ]  k a '[ NO2 ][ NO3 ]  kc [ NO ][ N 2O5 ] 3
dt
Replace the intermediate concentrations in 3 by using 1 & 2 Substitute 4 and 6 into 3 ,
in terms of [N2O5] d [ N 2O5 ]  2k a kb
( )[ N 2O5 ]
From 2 , k a [ N 2O5 ] dt k a ' kb
[ NO2 ][ NO3 ]  4
k a ' kb
1 d [ N 2O5 ] kk Resultant
Since rate    ( a b )[ N 2O5 ]
From 1 , kb [ NO2 ][ NO3 ] 2 dt k a ' kb rate law
[ NO ]  5
kc [ N 2O5 ]

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