Kinetic-isotope effects in thermal explosions

• Published in: Thermochimica acta 1982-01, Vol.59 (3), p.287-298
• Main Authors: Rogers, R.N., Janney, J.L., Ebinger, M.H.
• Format: Article
• Language: English
• ISSN: 0040-6031; 1872-762X
• DOI: 10.1016/0040-6031(82)87151-7

Kinetic-isotope effects can be used to detect the specific functional groups involved in the elementary reactions of complex explosives decomposition processes. Isothermal kinetics methods must be used to correlate component reactions with specific reaction regimes. When component reactions can be identified at different temperatures, kinetics constants can be determined. Conditions for self heating to explosion can be calculated from the kinetics constants, and predictions can be tested against independent time-to-explosion measurements. The sign of the volume of activation can be predicted from the magnitude of the kinetic-isotope effect. When the sign of the volume of activation is known, it is possible qualitatively to predict pressure effects on chemical reaction rates. An ability to predict pressure effects on rates is important in predicting the relative sensitivities of different explosives. Kinetic-isotope effects can be observed with time-to-explosion experiments, and the specific component reaction responsible for thermal explosion can be identified.