There has been evidence lately that several endophytic fungi can
convert lignocellulosic biomass into ketones among other oxygenated
compounds. Such compounds could prove useful as biofuels for internal
combustion engines. Therefore, their combustion properties are of
high interest. Cyclohexanone was identified as an interesting second-generation
biofuel (Boot, M.; et al. Cyclic Oxygenates:
A New Class of Second-Generation Biofuels for Diesel Engines? Energy Fuels 2009, 23, 1808−1817; Klein-Douwel, R. J. H.; et al. Soot and Chemiluminescence
in Diesel Combustion of Bio-Derived, Oxygenated and Reference Fuels. Proc. Combust. Inst. 2009, 32, 2817–2825). However, until recently (Serinyel, Z.; et al. Kinetics of Oxidation of Cyclohexanone in a Jet- Stirred Reactor:
Experimental and Modeling. Proc. Combust.
Inst. 2014; DOI: 10.1016/j.proci.2014.06.150), no previous studies on the kinetics of oxidation of that fuel
could be found in the literature. In this work, we present the first
theoretical kinetic study of the unimolecular decomposition pathways
of cyclohexanone, a cyclic ketone that could demonstrate important
fuel potential. Using the quantum composite G3B3 method, we identified
six
different decomposition pathways for cyclohexanone and computed the
corresponding rate constants. The rate constants were calculated using
the G3B3 method coupled with Rice–Ramsperger–Kassel–Marcus
theory in the temperature range of 800–2000 K. Our calculations
show that the kinetically more favorable channel for thermal decomposition
is pathway 2 that produces 1,3-butadien-2-ol, which in turn can isomerize
easily to methyl vinyl ketone through a small barrier. The results
presented here can be used in a future kinetic combustion mechanism