Kinetics of oxidation of nitrogen compounds by cerium(IV)

Abstract

The kinetics of oxidation by Ce^IV in sulfuric acid of hydrazine, hydroxylamine, nitrous acid, hydrazoic acid and of an intermediate involved in the nitrite/hydrazine reaction has been examined under a uniform set of conditions. Reaction proceeds through the free base form of the nitrogen substrate, probably by an inner-sphere mechanism, with a reactivity sequence N₂H₄ > NH₂OH > N₃^– > NO₂^–. An intermediate in the hydrazine/nitrous acid reaction, NH₂N[double bond, length half m-dash]NOH, is also oxidised by Ce^IV in a Ce^IV/HNO₂/N₂H₅⁺ system. For the Ce^IV/HNO/HN₃ system there is a much larger consumption of oxidant than can be accounted for by the separate oxidations of nitrite and azide. An additional pathway is proposed, probably involving NNN–O–N[double bond, length half m-dash]O, formed by combination of azide and nitrogen dioxide radicals.

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