| Résumé | Hexanitrohexaazaisowurtzitane (HNIW) or CL-20 is a caged structure polycyclic nitramine that may replace RDX and HMX as a common use energetic chemical. To provide insight into the environmental fate of CL-20 we photolyzed the chemical in a Rayonet photoreactor (254-350 nm) and with sunlight in aqueous solutions. Previously, we found that initial photodenitration of the monocyclic nitramine RDX leads to ring cleavage and decomposition. Presently, we found that photolysis of the rigid molecule CL-20 produced NO2-, NO3-, NH3, HCOOH, N2 and N2O. Using LC/MS (ES-) we detected several key intermediates carrying important information on the initial steps involved in the degradation of CL-20. The identities of the intermediates were confirmed using a uniformly ring labeled15 N-(CL-20). When CL-20 was photolyzed in the presence of H218O, D2O or18 O2 we obtained a product distribution suggesting that the energetic chemical degraded via at least two initial routes; one involved sequential homolysis of N-NO2 bond(s) and another involved photorearrangement prior to hydrolytic ring cleavage and decomposition in water. Copyright 2004 Elsevier Ltd. All rights reserved. |
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