INORG. NUCL. CHEM. LETTERS Vol. 13, pp. 37-40, 1977. Pergamon Press. Printed in Great Britain.

THE M E C H A N I S M OF T H E S U L P H A M I C ACID - NITRIC ACID R E A C T I O N

by M a r t i n N. Hughes and James R. L u s t y

Chemistry Department, Queen E l i z a b e t h College, Campden Hill, London W8 7AH

(Received 20 September 1976)

Nitric acid reacts w i t h s u l p h a m i c acid (I) to give dinitrogen oxide and sulphate.

Nitramide may be i s o l a t e d (2) from t h e - ~ e a c t i o n at -50°C implying that it m a y be

an intermediate. Attwood and S t e d m a n (3) have s u g g e s t e d a mechanism involving

+ +
a rate-determining displacement of SO3H by NO 2 to give nitramide which de-

composes to d i n i t r o g e n oxide. We have studied the reaction at up to 15 mol dm -3

nitric acid over the temperature range 41-79°C and have shown that several steps

m u s t be involved.

T h e reaction was f o l l o w e d by m e a s u r i n g the loss of sulphamic acid, w h i c h was

monitored by p i p e t t i n g known volumes of the reaction mixture into excess dilute

s o d i u m nitrite solution at O°C. Sulphamic acid and nitrous acid react (4) in

i:i ratio, and so s u b t r a c t i o n of the residual nitrous acid (determined by the ab-

sorption at 372 nm) from the initial concentration gives the a m o u n t of sulphamic

acid in the reaction sample. Unexpected results of some interest w e r e obtained.

It was a n t i c i p a t e d that in the early stages of the reaction the residual nitrous

acid c o n c e n t r a t i o n in the analytical operation w o u l d be low and w o u l d increase

for successive samples. Such a situation was found by A t t w o o d and Stedman.

However, we o b s e r v e d different behaviour in the early stages of the reaction,

particularly at h i g h e r acidities. The first reaction sample left a high nitrous

acid level, which decreased for successive samples and then i n c r e a s e d again as

shown in the Figure. Possibly Stedman and A t t w o o d did not take samples until

after the first stage of the reaction was complete. It is clear though that they
+
were not m e a s u r i n g the kinetics of d i s p l a c e m e n t by NO 2 , but rather the kinetics

37
38 Sulphamic Acid - Nitric Acid Reaction

of decomposition of an intermediate species which was able to react with nitrous

acid. It appears that sulphamic acid reacts very rapidly with nitric acid to

give a species which cannot be nitrosated and which rearranges to another species

(X) which may be nitrosated and which possibly decomposes to nitramide and

sulphate.

Residual nitrous acid levels i n th e analysis for sul~hamate in kinetic runs at

75°C

08

0"7 ~ l~dn~3HNO3
>-
I-
0.6

..J 0.4
0
~ 0.3
0
0.2 9.20 mol dm-3 HNO3
6.57 mol dm- 3 HNO3
0.1
! ! !

10 20 3O
TIME (minutes)

Apart from these complications in the first stage of the reaction, our

results agree with those of Attwood and Stedman. The reaction is of first

order in sulphamic acid, approximately second order (1"8) in H (indicative

O
+
of NO 2 involvement), and we have confirmed a first order-dependence on

nitrate by studying the reaction in perchloric acid solutions with varied

2-
amounts of sodium nitrate. Results obtained using analysis for SO 4 and N20

agreed well with the nitrite method, except that these could not be used in

the very early stages of the reaction. It appears that the production of

sulphate and N20 and the decay of intermediate X occur at the same rate, in

accord with the instability of nitramide under these conditions (5). Any
 Sulphamic Acid - Nitric Acid Reaction 39

scheme involving consecutive reactions must still allow for the involvement
+
of NO 2 in the rate determining step, either directly or by a series of

equilibria,

+ + +
H + HNO3~=~ H2NO 3 ~ NO 2 + H20
+ + +
NO 2 + NH2SO3H ~ O2N NH2SO3H ~ 02NNHSO3H + H
slow
O2NNHSO3H ~ X H 2 ~O NH2NO 2 + H2SO 4

NH2NO 2 v . ~ f a s t N20 + H20

An alternative approach is to assume that nitramide is not an intermediate

at the elevated temperatures under study and that a different pathway holds, or

that nitramide is the product of a side reaction and can only be isolated at

-50°C. One scheme involves rapid oxygen atom transfer from nitric acid to

sulphamic acid giving NH2OSO3H , with production of an equivalent amount of nitrous

acid, so accounting for the initial non-consumption of nitrous acid in the

analytical reaction (assuming that this only reacts with NH2OSO3H when diluted).

However, as the nitrous acid thus produced will decompose rapidly at 70 ° , some

nitrous acid will be consumed for later samples in the analytical procedure to

allow for this. Further reactions have to be postulated to give the products.

However, we have been unable to confirm the existence of any intermediates by

U.V. difference spectroscopy (on the reaction solution and on a water diluted

reaction sample) and by chemical testing of reaction samples. No evidence

could be found for the production of nitrite in the early stages of the reaction.

Accordingly, it is not possible to write detailed reaction schemes , but it

seems clear that the direct displacement mechanism is incorrect.

We are grateful to Dr. G. Stedman for discussion and suggestions.

References
_ L

i. K. W. C. BURTON and G. NICKLESS, Inorganic Sulphur Chemistry, 607 (1968),

Elsevier.

2. S. TELLIER-POLLON and J. HENBAL, Rev. Chim. Minerale, 4, 413 (1967).

40 Sulphamic Acid - Nitric Acid Reaction

3. D. ATTWOOD and G. STEDMAN, J.C.S. Dalton, 508 (1976).

4. M.N. HUGHES, J. Chem. Soo. (A), 902 (1967)

5. M.N. HUGHES and J. R. LUSTY, in preparation.