Detailed Primary Mechanism

The general rules of the generation
In the primary mechanism (only the initial organic molecules contained in the initial mixture and oxygen are considered as reactants), the rules which govern the reaction generation are those which are currently used to write alkanes oxidation mechanisms in the literature. A summary of theses rules is given in the figure below. Each time that a free radical °R is created by an initiation reaction, it is systematically submitted to all the generic propagation reactions considered. If a new radical °R', with respect to the preceding ones, is created, it is submitted in its turn to all the generic propagation reactions. Finally, termination reactions between all the pairs of radicals are also considered. The systematic application of the generic propagation reactions to each free radical which is created either by an initiation or by a propagation reaction ensures the primary mechanism generated to be comprehensive.

ui : Unimolecular initiation   bi : Bimolecular initiation   ad : Addition of a free radical on an unsaturated molecule   adox : Addition of a free radical on oxygen   is : Isomerization of a free radical   bs : Unimolecular decomposition of a free radical by beta-scission   or : Unimolecular decomposition of a free radical to an oxygenated ring (cycloether)   ox : H-abstraction of a free radical by oxygen   me : H-abstraction of a molecule by a free radical   co : Combination of two free radicals   dis : Disproportionation of two free radicals

Generic propagation reactions considered

Rules governing the primary mechanism

The rules for the primary mechanism simplification
With the purpose of avoiding the generation of unnecessary long reaction mechanisms, the following simplifying rules can be activated by the kineticist. Three classes of free radicals have been discriminated:

		The beta free radicals cannot decompose by unimolecular process (typical beta free radicals are H, OH, :O and CH3)
		The mu free radicals can easily decompose by unimolecular process involving a (C-C) or a (C-O) bond scission (typical m free radicals are n-C3H7 and s-C4H9)
		The beta-mu free radicals have a beta behaviour at "low" temperature and a mu behaviour at "high" temperature (typical beta-mu free radicals are OOH, CHO, CH2(OH), OCH3, OOCH3, C2H5, i-C3H7 and t-C4H9). Therefore according to these classes, the free radicals involved into termination steps, metathesis and oxidation reactions, which are bimolecular ones, can be choosen