The atmospheric chemistry of benzene oxide/oxepin, a possible intermed
iate in the atmospheric oxidation of aromatic hydrocarbons, has been i
nvestigated in a large volume photoreactor at 298 K and atmospheric pr
essure using in situ FTIR spectroscopy for the analysis. Rate coeffici
ents of (10.0 +/- 0.4) x 10(-11) and (9.2 +/- 0.3) x 10(-12) cm(3) mol
ecule(-1) s(-1) have been determined for the reaction of benzene oxide
/oxepin with OH and NO3 radicals, respectively. Reaction with OH radic
als produces almost exclusively the (E,Z)- and (E,E)-isomers of hexa-2
,4-dienedial, whereas reaction with NO3 produces (Z,Z)-hexa-2,4-diened
ial and unidentified organic nitrates. Phenol has been observed as a m
ajor product of the thermal decomposition, visible and UV photolysis o
f benzene oxide/oxepin. The results are discussed in conjunction with
the oxidation mechanisms of aromatic hydrocarbons. The major atmospher
ic sinks of benzene oxide/oxepin will be reaction with OH radicals and
photolysis and, under smog chamber conditions with high NO2 concentra
tions, also reaction with NO3.