Prediction of CL-20 chemical degradation pathways, theoretical and experimental evidence for dependence on competing modes of reaction.
Highest occupied and lowest unoccupied molecular orbital energies, formation energies, bond lengths and FTIR spectra all suggest competing CL-20 degradation mechanisms. This second of two studies investigates recalcitrant, toxic, aromatic CL-20 intermediates that absorb from 370 to 430 nm. Our earlier study (Struct. Chem., 15, 2004) revealed that these intermediates were formed at high OH(-) concentrations via the chemically preferred pathway of breaking the C-C bond between the two cyclopentanes, thereby eliminating nitro groups, forming conjugated pi bonds, and resulting in a pyrazine three-ring aromatic intermediate. In attempting to find and make dominant a more benign CL-20 transformation pathway, this current research validates hydroxylation results from both studies and examines CL-20 transformations via photo-induced free radical reactions. This article discusses CL-20 competing modes of degradation revealed through: computational calculation; UV/VIS and SF spectroscopy following alkaline hydrolysis; and photochemical irradiation to degrade CL-20 and its byproducts at their respective wavelengths of maximum absorption.
Qasim
M
M
U.S. Army ERDC, 3909 Halls Ferry Road, Vicksburg, MS 39180, USA. Mohammad.M.Qasim@erdc.usace.army.mil
Fredrickson
H
H
Honea
P
P
Furey
J
J
Leszczynski
J
J
Okovytyy
S
S
Szecsody
J
J
Kholod
Y
Y
D001372:Aza Compounds / Q000737:chemistry* / Q000378:metabolism*; D006571:Heterocyclic Compounds / Q000737:chemistry* / Q000378:metabolism*; D006868:Hydrolysis; D006900:Hydroxylation; D008962:Models, Theoretical; D010777:Photochemistry / Q000379:methods; D011237:Predictive Value of Tests; D013056:Spectrophotometry, Ultraviolet; D017550:Spectroscopy, Fourier Transform Infrared
C482139:2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaaza-isowurtzitane; D001372:Aza Compounds; D006571:Heterocyclic Compounds