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A simple dynamical system that models the competitive thermokinetics and chemistry of cellulose decomposition is examined, with reference to evidence from experimental studies indicating that char formation is a low activation energy exothermal process and volatilization is a high activation energy endothermal process. The thermohydrolysis chemistry at the core of the primary competition is described. Essentially, the competition is between two nucleophiles, a molecule of water and an -OH group on C 6 of an end glucosyl cation, to form either a reducing chain fragment with the propensity to undergo the bond-forming reactions that ultimately form char or a levoglucosan-end-fragment that depolymerizes to volatile products. The results of this analysis suggest that promotion of char formation under thermal stress can actually increase the production of flammable volatiles. Thus we would like to convey an important safety message in this paper: in some situations where heat and mass transfer is restricted in cellulosic materials, such as furnishings, insulation, and stockpiles, the use of char-promoting treatments for fire retardation may have the effect of increasing the risk of flaming combustion.

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