Kinetics and mechanism of acylhydrazine hydrolysis in sulfuric acid-water mixtures.

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概要

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• The rates of acid-catalyzed hydrolysis of formylhydrazine, acetylhydrazine, chloroacetylhydrazine, propionylhydrazine, butyrylhydrazine, and octanoylhydrazine in sulfuric acid–water mixtures have been investigated over a wide range of acidities (about 1–18 M H<SUB>2</SUB>SO<SUB>4</SUB>) by means of spectrophotometric methods. First-order kinetics were obtained in all cases, and the pseudo-first-order rate constants showed one of two types of acidity dependences: (i) a rate maximum at intermediate acidities, followed by slow hydrolysis in highly concentrated acids; (ii) a rate maximum at intermediate acidities, followed by a sharp increase in rate at high acidities. This result was treated as a function of the Hammett acidity function, the water activity, and the total concentration of hydrogen ion to yield reaction parameters which are explicable in terms of a change in mechanism at a high acidity from A-2 to A-1. The mechanism change also was deduced from a criterion based on the values of activation entropies.

• 公益社団法人 日本化学会の論文

著者

• Mashima Mitsuo

  Department of Chemistry, Faculty of Science and Engineering, Saga University

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• Kinetics and mechanism of acylhydrazine hydrolysis in sulfuric acid-water mixtures.

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