A Gibbs energy minimization procedure is used to predict the flammability envelopes of alkanes, carboxylic acids, and acetates. In addition to providing the calculated adiabatic flame temperature (CAFT), the product profiles reveal regions of incomplete combustion products and the onset of methane formation above 0.0001 mole fraction. Temperatures at the predicted onset of methane production appear to be closely related to the temperature at the upper flammability limit (UH). Although a fixed CAFT value could be related to the lower flammability limit (LFL), it was found that this was not the case with the UH and only for acetic acid could a single CAFT value of 1200K be used to conservatively predict the flammable region. Rather, in general, a single CAFT value could not conservatively predict the upper flammable region. The predictions also reveal local maxima and minima in the concentrations of reaction products. These maps of incomplete combustion products for the flammability region predict that incomplete combustion products are produced at fuel/oxygen ratios significantly below the fuel/oxygen stoichiometric ratio. This region decreases as the limiting oxygen concentration is approached. (c) 2006 American Institute of Chemical Engineers.