Variation of Reaction Mechanism with Surface Conditions in the Reduction of Silver Salts by Hydroxylamine

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Abstract
Silver bromide oxidizes hydroxylamine at pH 10.2–10.8 to nitrogen and water. Under comparable conditions, silver thiocyanate yields a mixture of nitrogen and nitrous oxide as the gaseous products. By varying the surface conditions of the thiocyanate, the composition of the reaction product may be varied over a wide range. Small additions of bromide or iodide greatly decrease the nitrous oxide yield. With initial partial coverage of the precipitate surface by gelatin, the nitrous oxide yield increases to a maximum. Further gelatin additions progressively decrease the yield. Aging a fresh precipitate increases the nitrous oxide yield. The results are explained by the effects of adsorption upon the relative rates of two competing reaction mechanisms.