Kinetics of the Degradation of Isoamyl Nitrite in Ampuls I. : Nature of Reaction Products and Influence of Temperature, Oxygen, Alcohol, Water, and Acid on the Overall Rate

Results of a kinetics study on the rate of degradation of both laboratory and commercial lots of isoamyl nitrite in sealed ampuls are presented. The reaction appears to be autocatalytic with an effective heat of activation of 20 kcal./mole. Commercial ampuls containing roughly O.33 ml. of the ester explode on developing from 7–12 ml. of by-product gases. Mass spectrometric and gas chromatographic analyses show that these consist largely of nitrogen, nitrous oxide, carbon dioxide, and traces of nitric oxide and carbon monoxide. Results obtained suggest that the first three gases are produced by a secondary reaction between nitric oxide and aldehyde. The liquid products appear to be a mixture consisting of at least twelve components including carboxylic ester, carboxylic acid, isoamyl alcohol, aldehyde, and isoamyl nitrate. The influences of water, acid, alcohol, oxygen, and certain additives on the overall degradative rate are also given.