Production of the nitromethane aci ion by static high pressure

Journal Article · Wed Nov 16 23:00:00 EST 1988 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100334a062· OSTI ID:6188513

Engelke, R; Schiferl, D; Storm, C B; Earl, W L

The authors present experimental evidence that static high pressure (/approximately/2 GPa) produces an increased concentration of the aci ion (CH/sub 2/NO/sub 2//sup /minus//) of nitromethane (CH/sub 3/NO/sub 2/). The presence of this form is inferred from hydrogen/deuterium isotope exchange between CH/sub 3/NO/sub 2/ and CD/sub 3/NO/sub 2/ induced by pressure. Control experiments in which isotope exchange is produced chemically and in which it is shown that temperature alone does not produce the exchange are described. The Raman spectral diagnostic used to identify the isotope-exchange process at high pressure is analyzed by use of ab initio calculations of the vibrational spectra of the four H/D nitromethane isotopomers. Ambient-pressure /sup 13/C NMR was used to establish the chemistry involved in the isotope-exchange process. Their observation that pressure causes an increased aci ion concentration provides an explanation of nitromethane's observed pressure-dependent self-explosion behavior.

• Research Organization: Los Alamos National Lab., NM (USA)
• OSTI ID: 6188513
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 92:23; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALCOHOLS
ANIONS
CARBON 13
CARBON ISOTOPES
CHARGED PARTICLES
CHEMICAL EXPLOSIVES
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
DATA
DEUTERIUM
ENOLS
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
EXPLOSIVES
FLUIDS
HYDROGEN ISOTOPES
HYDROXY COMPOUNDS
INFORMATION
IONS
ISOTOPES
ISOTOPIC EXCHANGE
LASER SPECTROSCOPY
LIGHT NUCLEI
LIQUIDS
MAGNETIC RESONANCE
NITRO COMPOUNDS
NITROMETHANE
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PRESSURE DEPENDENCE
RAMAN SPECTROSCOPY
REACTION INTERMEDIATES
RESONANCE
SPECTRA
SPECTROSCOPY
STABLE ISOTOPES
VERY HIGH PRESSURE
YIELDS