The Reaction of Nitrous Acid with Hydroxylamine
1952; American Institute of Physics; Volume: 20; Issue: 3 Linguagem: Inglês
10.1063/1.1700442
ISSN1520-9032
AutoresAksel A. Bothner‐By, L. Friedman,
Tópico(s)Analytical Chemistry and Sensors
ResumoApproximately equal quantities of N14N15O16 and N15N14O16 are produced by reaction of hydroxylamine hydrochloride and N15-enriched sodium nitrite in solution in O18-enriched water. The same reaction when carried out in a solution brought to a pH of 1 with gaseous HCl produces an excess of N14N15O16. In both experiments the concentration of N15N15O16 was accounted for on the basis of the reaction of nitrous acid with hydroxylamine to yield nitrous oxide molecules containing one nitrogen atom from each source. O18 exchange occurred to a greater extent in acid medium and the double tagged N2O so produced was mainly N14N15O18 rather than a mixture of the isomers N14N15O18+N15N14O18. These observations lead to the following conclusions concerning the reaction mechanisms. In neutral solution most of the nitrous oxide produced is formed by dehydration of a symmetrical intermediate, probably hyponitrous acid. In acid medium a competitive dehydration of an unsymmetrical intermediate plays an important role. Mechanisms involving nitroxyl as an intermediate are untenable. Oxygen exchange is acid catalyzed and occurs exclusively with nitrous acid or with an unsymmetrical intermediate formed in the course of this reaction. Oxygen atoms from either nitrous acid or hydroxylamine appear in the product nitrous oxide.
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