A comprehensive, semidetailed kinetic scheme, describing hydrocarbon oxidat
ion has been applied to the simulation of a premixed, rich, nearly sooting,
butadiene, laminar dame. The main goal of this work was to understand the
mechanism and to validate a general detailed kinetic model for the predicti
on of both polycyclic aromatic hydrocarbons (PAHs) and soot precursors from
the pyrolysis and oxidation of butadiene. The modeling computations are in
quite good agreement with the experimental measurements. Under these condi
tions, butadiene: undergoes particular pathways involving resonantly stabil
ized radicals. Molecular reactions explain almost all the consumption of bu
tadiene during its pyrolysis, while the additions on double bonds are of gr
eat importance in explaining the formation of the first aromatic rings, and
, consequently, of PAHs. Kinetic analysis allows identification of the radi
cal C4H5 as being the major contributing factor in the initial formation of
benzene and naphthalene. Several combustion byproducts and radicals are qu
ite well simulated by the model, although important discrepancies in the pr
ediction of CH4 were found. To extend the validity of the developed scheme
and to build up a better understanding of the role of different reaction pa
ths, the kinetic model for butadiene was also compared with measurements of
both oxidation in jet-stirred and plug flow reactors at intermediate tempe
ratures, and of pyrolysis ina shock tube at high temperatures. (C) 2000 by
The Combustion Institute.