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The reactions of phenylacetylenes with O({sup 3}P) in the gas phase

Book ·
OSTI ID:93233
; ; ; ;  [1]
  1. Univ. Goettingen (Germany). Inst. fuer Physikalische Chemie

For the understanding of combustion chemistry and soot formation, it is necessary to know the elementary reactions of the phenylacetylenes. In this paper, the authors present kinetic data and results of product analyses of the reactions of oxygen atoms (O({sup 3}P)) with (1) phenylacetylene (C{sub 6}H{sub 5}{single_bond}C{triple_bond}C{single_bond}H), (2) phenyldeuteroacetylene (C{sub 6}H{sub 5}{single_bond}C{triple_bond}C{single_bond}D), and (3) 1-phenylpropyne (methylphenylacetylene, C{sub 6}H{sub 5}{single_bond}C{triple_bond}C{single_bond}CH{sub 3}). A continuous-flow reactor was used with molecular-beam sampling and mass spectrometric detection. Oxygen atoms were produced by chopped microwave discharges in a mixture of oxygen and helium as carrier gas; in all cases the reactions took place under pseudo-first-order conditions in oxygen atom excess. The kinetic measurements were carried out in the temperature range between 298 and 873 K. The kinetic investigations show that for all three compounds, two main reaction centers have to be considered: the phenyl group and the side chain. The electrophilic addition of O({sup 3}P) to the aromatic ring of these compounds is only important at high temperatures (above 500 K). The production analyses at room temperature show that in the case of the reactions of phenylacetylene and phenyldeuteroacetylene with O({sup 3}P), the main stable products formed are benzene (C{sub 6}H{sub 6}) and deutero benzene (C{sub 6}H{sub 5}D). Toluene was not detected in the reaction of methylphenylacetylene with oxygen atoms.

OSTI ID:
93233
Report Number(s):
CONF-940711--
Country of Publication:
United States
Language:
English

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