Abstract
High-pressure mass spectrometric measurements were carried out to examine the mechanism of NO 3 − formation in pure gaseous ethyl nitrate and its binary mixtures with various bath gases. A novel reaction: NO 2 − + C 2H 5ONO 2 → NO 3 − + C 2 H 5 ONO occurring with an activation energy has been reported and evidence for collisional deactivation of the intermediate complex [NO 2 ·C 2H 5ONO 2 has been obtained. The calculations performed with semi-empirical MINDO/3 suggest that this reaction proceeds by the nucleopholic displacement mechanism. Attack of NO 2 − on H-atom of the methyl group prefers the formation of clustered ion NO 2 −sd C 2H 5ONO 2, which is experimentally observed.
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