Microscopic evidence that the nitromethane aci ion is a rate controlling species in the detonation of liquid nitromethane
We present microscopic evidence that the aci ion (H/sub 2/CNO/sup -//sub 2/) of nitromethane (H/sub 3/CNO/sub 2/) plays an important role in the detonation kinetics of liquid-phase nitromethane. It is known from previous detonation experiments that very minute additions of organic bases (e.g., amines) have a profound effect on the detonation properties of nitromethane; i.e., the explosive is strongly sensitized. Here we show that, under conditions similar to the detonation experiments, the only new chemical species generated in nitromethane by the bases sodium hydroxide (NaOH), diethylenetriamine (NH/sub 2/CH/sub 2/CH/sub 2/NHCH/sub 2/CH/sub 2/NH/sub 2/), and pyridine (C/sub 5/H/sub 5/N) is the aci ion, within the sensitivity of the experiments. The primary tool used to demonstrate this is /sup 13/C NMR spectroscopy. Ab initio quantum-mechanical calculations of the chemical shifts are used to support the experimental interpretation. Qualitative arguments concerning the increased reactivity of the aci ion, relative to normal nitromethane, are given. We review earlier work and relate it to the current findings.
- Research Organization:
- Los Alamos National Laboratory, Los Alamos, New Mexico 87545
- OSTI ID:
- 6344248
- Journal Information:
- J. Chem. Phys.; (United States), Vol. 84:1
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
NITROMETHANE
DETONATIONS
CHEMICAL REACTION KINETICS
LIQUIDS
MOLECULAR IONS
REACTION INTERMEDIATES
REACTIVITY COEFFICIENTS
SENSITIVITY
CHARGED PARTICLES
CHEMICAL EXPLOSIVES
EXPLOSIVES
FLUIDS
IONS
KINETICS
NITRO COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
REACTION KINETICS
450100* - Military Technology
Weaponry
& National Defense- Chemical Explosions & Explosives