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The homogeneous, isochoric and adiabatic autoignition of rich methanol mixtures is analysed using algorithmic tools of  Computational Singular Perturbation . It is shown that ignition delay decreases as the equivalence ratio  ϕ  increases, due to the faster production of OH radicals via the reactions CHOH + HOCHOH + HOand HO(+M)OH + OH (+M). After ignition and for sufficiently rich mixtures the phenomenon of super-adiabatic temperature (SAT) is observed; i.e. the temperature after ignition decreases with time. This feature is accompanied by the appearance of an explosive mode. With increasing values of  ϕ , SAT becomes more pronounced and the explosive mode becomes faster; i.e. its time scale is shortened. SAT is due to the fact that as  ϕ  increases the role of hydrogen chemistry diminishes and the explosive character of the process is basically generated by endothermic dissociation reactions of carbon-containing species that cause an increase in number of molecules and a temperature decrease.

Chemical dynamics of the autoignition of near-stoichiometric and rich methanol/air mixtures