Software for the computer generation of kinetic models was exploited to con
struct a mechanistic kinetic model for alcohol oxidation in high temperatur
e (300 less than or equal to T/degrees C less than or equal to 380) water.
The complexities of the oxidation mechanism were captured by a detailed mec
hanism consisting of eight reaction families. These included hydrogen abstr
action by oxygen, hydrogen abstraction by radical, beta-scission, non-termi
nating radical reactions, isomerizations, decomposition, molecular addition
and termination steps. The mechanistic model was generated computationally
, using the graph theory notions where the molecules and radicals are repre
sented as atomic connectivity matrices and the reactions as matrix operator
s. The free-radical kinetics of C1-C4 alcohols exhibited features of both g
as-phase combustion and liquid-phase oxidation chemistry. The imposition of
Evans-Polyanyi relationships for the associated rate constants provided a
significant reduction in model parameters with little loss of predictive ca
pability. Kinetic parameter vectors, one for each reaction family, obtained
by optimizing the model predictions to pure-component ethanol data provide
d a very good fit to pure component kinetics of other alcohols, as well as
mixture kinetics.