Abstract
AbstractMeasurements of chemiluminescence (CL) during heating of nitrate esters (PETN and NC) have been conducted in the temperature range between 40 °C and 90 °C in an inert atmosphere. Faint light was emitted from the condensed‐phase in steady‐state fashion. This new finding implies that the thermal decomposition of nitrate esters is accompanied by some oxidation reactions. Spectral analysis of the CL showed that the light‐emitting species will be the first excited triplet of carbonyl‐containing products and singlet oxygen. The low‐temperature CL phenomena observed for PETN and NC are represented by Arrhenius law, providing the activation energy of 63 kJ/mol (= 15 kcal/mol). Kinetic analysis of the CL has led to the result that the formation of peroxy radicals, which can be produced by oxidation of the primary products of nitrate ester bond (RONO2) cleavage, predominates a consecutive series of radical reactions of the CL.
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