Abstract
The nature of the overall reaction and its activation energy are investigated for both competitive and multiple reactions resulting from a one-step, irreversible, first-order reaction. For the competitive reaction model, the overall reaction is a function of the rates of the individual reactions in the reaction mixture. The rate constant of the competitive reaction in most cases can be represented satisfactorily by the Arrhenius equation. If the ratios of the individual reaction rates vary significantly with temperature, then the activation energy of the competitive reaction may vary with temperature and becomes a function of the activation energy of the most dominating reaction. The nature of the multiple reaction is a strong function of the individual reaction rates and the initial composition of the reaction mixture. It is demonstrated that a set of independent first-order reactions cannot be approximated by a single first-order multiple reaction having a lower activation energy than any of the reactions in the set. Possible reasons for previously reported “ low” activation energies observed in coal and biomass pyrolysis studies are briefly discussed.
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