Table of Contents
Laser Chemistry
Volume 13, Issue 2, Pages 101-111
http://dx.doi.org/10.1155/1993/68637

IR Laser Chemistry of Dimethylnitramine and Diethylnitramine

Department of Chemistry, University of Crete, and Institute of Electronic Structure and Laser, F.O.R.T.H., Heraklion, Crete 71409, Greece

Received 30 September 1992

Copyright © 1993 Hindawi Publishing Corporation. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

The infrared multiphoton decomposition of dimethylnitramine and diethylnitramine in the gas phase under almost collisionless conditions has been studied with a tunable CO2 laser. The steady state rate coefficient for their unimolecular decomposition were found to be kDENA(st) = 105.5 ± 0.1(I/MW cm–2) s–1, and kDENA(st) = 105.2 ± 0.1(I/MW cm–2) s–1, for laser intensities in the range 3–15 MW cm –2. The dependence of rate constants and product yields on laser fluence have indicated that the unimolecular dissociation of both nitramines occurs via scission of the N-NO2 bond, and the main secondary reaction leading to the final photolysis products (nitrosamine and nitroxide) is the oxidation reaction of nascent dialkylamino radical with parent nitramine or NO2 product.