KINETICS OF BUFFERED

REACTION

Nitramide NO2NH2 decomposes

slowly in aqueous solution
according to the reaction:
NO2NH2 (aq)
N2O (g) + H2O (l)
The experimental kinetic law is as
follows:
+
dt
[H
O
] 2]
d[N2O] = k [NO
3 2NH

a) What

is the apparent
order of this reaction in a
buffered solution?
ANSWER :

In a buffer solution
[H3O+]
is constant and the reaction is
of the first order:
v = kl [NO2NH2]
3

Which of the following

mechanisms is the most
appropriate for the
interpretation of this kinetic
law?
b)

Mechanism 1:
k1
NO2NH2
N2O +H2O

Mechanism 2:
k
NO2NH2 + H3O+ 2
k-2
equilibrium)

NO2NH3+ + H2O

(rapid

k3
NO2NH3+

N2O + H3O+

(rate limiting

step)
5

Mechanism 3:
k4

NO2NH2 + H2O
equilibrium) k-4

NO2NH + H3O+ (rapid

k
NO2NH
step)

H3O+ + OH
reaction)

k6

N2O + OH

(rate limiting

2 H2O your answer. (very fast

Justify

ANSWER :

The rate laws of the three mechanisms

proposed are:
v1 = k1 [NO2NH2]
v2 = k3 [NO2NH3 +] k
=-2k3k2 [NO2NH2] [H3O+]
+ NH ]
v3 = k5 [NO2NH ] =
[NO
k-4k5k4 [H
O
2]
2
3

Thus, it is the third mechanism that is

correct.

c) Show

the relationship between

the experimentally observed
rate constant and the rate
constants
of
the
selected
mechanism.
ANSWER:

k =k-4k5k4

d) Show

that hydroxyl ions catalyze

the decomposition of nitramide.
The decomposition is studied in
a buffered solution of a constant
volume V at a constant
temperature by measuring the
partial pressure of the gas N2O,
considered to be insoluble in
water, in a constant volume of
the same value V above the
solution.
9

t(min)

p(Pa)

10

15

2
0

2
5

6800 12400172002080024000

After a sufficiently long time, the

pressure stabilises at 40000 Pa.

ANSWER:
Noting that [H3O+]= KW /[OH ]
It follows v = k/ KW [NO2NH2] [OH
]
which shows the catalytic role of
OH

e Express the pressure p as

) function of time and the

constant kl such that

kl =
[H3Ok+ ]
ANSWER:
d[N2O] can be expressed by the
change
of pressure dp(N2O)/RT
(according to pV = nRT). We obtain:
dt
RT dt
RT dt
v= d[N+2O] = 1 dp(N2O) = 1
[H3O ]
k[NO2NH2]

dp =
1

We also know that ,

V[NO2NH2]=n(NO2NH2 )-n(N2O)=n(N2O)
-n(N2O)
from which
dp = k RT (n(N2O) )-n(N2O) and
thus
dt [H3O+] V
dp = k

(p-p)= kl (p-p)

Integration gives p= p(1- ekIt)

1

f) Verify graphically that the kinetic

law is confirmed by these

experimental results.
ANSWER:

-0.2
-0.4
-0.6

10

15

20

t(mins)
x
x
x

-0.8

ln(p-p)
p

g Calculate kl giving its units.

)
ANSWER:

The graph of f(x) = ln(1p/p)=-klt

Is a straight line with the slope kl
as shown in previous graph
kl was determined to be 3.7102
min-1.
1

REFERENCES
THE 22ND INTERNATIONAL
CHEMISTRY OLYMPIAD, 1990
(Problem -5).
CHESMISTRY AND CHEMICAL
REACTIVITY by John C. Kotz,
Paul M. Treichel,
John Raymond Townsend,Pg. 720
1