Fourier transform infrared spectroscopic study of the thermal stability of peroxyacetyl nitrate
The unimolecular decomposition of peroxyacetyl nitrate (PAN) to form methyl nitrate and carbon dioxide has been studied over the temperature range 298-338 K by Fourier transform infrared spectroscopy (FTIR). Pure PAN samples (> 98%; 2-30 torr) were found to decompose thermally, nearly quantitatively, to these products, with the only other observed product being nitromethane (< 10%). Both PAN decomposition and methyl nitrate formation rates yielded the Arrhenius equation, k = (2.1 x 10/sup 12/) exp(-24.800 +/- 1800 cal/(K mol/RT)) s/sup -1/. Perdeuterio-PAN was synthesized and observed to decompose to perdeuteriomethyl nitrate and carbon dioxide with no apparent isotope effect. One pathway is a concerted reaction most likely proceeding via a cyclic intermediate, and the other previously identified equilibrium between PAN and the peroxyacetyl radical and nitrogen dioxide. The rate of the PAN decomposition in a large excess of NO was determined to be 2.2 x 10/sup -4/ s/sup -1/ at 298 K. This rate is somewhat slower than previously reported for this pathway. The results are discussed with respect to the atmospheric lifetime of PAN and the potential atmospheric production of methyl nitrate. 24 references, 3 figures, 4 tables.
- Research Organization:
- Brookhaven National Lab., Upton, NY
- DOE Contract Number:
- AC02-76CH00016
- OSTI ID:
- 5815042
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 90:1; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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54 ENVIRONMENTAL SCIENCES
ABSORPTION SPECTROSCOPY
ARRHENIUS EQUATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
DEUTERIUM COMPOUNDS
EQUATIONS
EXPERIMENTAL DATA
FOURIER TRANSFORM SPECTROMETERS
HYDROGEN COMPOUNDS
INFORMATION
INFRARED SPECTRA
ISOTOPE EFFECTS
KINETICS
LIFETIME
MEASURING INSTRUMENTS
MEDIUM TEMPERATURE
NITRATES
NITROGEN COMPOUNDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXYGEN COMPOUNDS
PYROLYSIS
REACTION KINETICS
SPECTRA
SPECTROMETERS
SPECTROSCOPY
THERMOCHEMICAL PROCESSES