Microscopic evidence that the nitromethane aci ion is a rate controlling species in the detonation of liquid nitromethane

Journal Article · Tue Dec 31 23:00:00 EST 1985 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.450189· OSTI ID:6344248

Engelke, R; Earl, W L; Rohlfing, C M

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), Journal Name: J. Chem. Phys.; (United States) Vol. 84:1; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEFENSE
450100* -- Military Technology
Weaponry
& National Defense-- Chemical Explosions & Explosives
CHARGED PARTICLES
CHEMICAL EXPLOSIVES
CHEMICAL REACTION KINETICS
DETONATIONS
EXPLOSIVES
FLUIDS
IONS
KINETICS
LIQUIDS
MOLECULAR IONS
NITRO COMPOUNDS
NITROMETHANE
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
REACTION INTERMEDIATES
REACTION KINETICS
REACTIVITY COEFFICIENTS
SENSITIVITY