Thermal decomposition of alkyl peroxynitrates
- Bergische Universitaet Gesamthochschule Wuppertal (Germany, F.R.)
The thermal decomposition of methyl peroxynitrate and ethyl peroxynitrate was studied in a temperature-controlled 420 L glass chamber at temperatures between -28 and 0{degree}C and total pressures from 10 to 800 mbar (M = N{sub 2}). The reactions proceed via OO-N bond fission. The unmolecular decay of the peroxynitrates was followed in situ by long-path IR absorption using a Fourier transform spectrometer. In Troe's notation, the data are represented by the following limiting low- and high-pressure first-order rate constants k{sub 0} and k{sub {infinity}} and the falloff curvature parameters F{sub c}: for R = CH{sub 3}, k{sub 0}/(N{sub 2}) = 9.0 {times} 10{sup {minus}5} exp(-80.6 kJ mol{sup {minus}1}/RT) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}, k{sub {infinity}} = 1.1 {times} 10{sup 16} exp(-87.8 kJ mol{sup {minus}1}/RT) s{sup {minus}1}, F{sub c} = 0.4; for R = C{sub 2}H{sub 5}, k{sub 0}/(N{sub 2}) = 4.8 {times} 10{sup {minus}4} exp(-77.2 kJ mol{sup {minus}1}/RT) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}, k{sub {infinity}} = 8.8 {times} 10{sup 15} exp(-86.8 kJ mol{sup {minus}1}/RT) s{sup {minus}1}, F{sub c} = 0.3. Combining the present results for R = CH{sub 3} with literature data on the corresponding recombination reaction, K{sub c} = 1.94 {times} 10{sup 27} exp(-10766 K/T) molecule cm{sup {minus}3} s obtained for the equilibrium CH{sub 3}OONO{sub 2} {l equilibrium} CH{sub 3}OO + NO{sub 2}. Some experiments were performed on the thermal decomposition of isomeric mixtures of butyl, hexyl, and octyl peroxynitrate at 253 K and in 800 mbar of N{sub 2}. Atmospheric implications of the thermal stability of alkyl peroxynitrates are briefly discussed.
- OSTI ID:
- 6972109
- Journal Information:
- Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 93:14; ISSN 0022-3654; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400000* -- Chemistry
400201 -- Chemical & Physicochemical Properties
54 ENVIRONMENTAL SCIENCES
540110
ATMOSPHERIC CHEMISTRY
CHEMICAL REACTIONS
CHEMISTRY
DATA
DATA ANALYSIS
DECOMPOSITION
EARTH ATMOSPHERE
EXPERIMENTAL DATA
INFORMATION
LOW PRESSURE
LOW TEMPERATURE
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
PEROXY RADICALS
RADICALS
THERMAL DEGRADATION
TROPOSPHERE