A detailed study of the effects of forcing a hydrocarbon oxidation reaction

The Gray-Yang thermokinetic or chain-thermal model of hydrocarbon oxidation is able to explain many of the experimentally observed phenomena in hydrocarbon oxidation. The model incorporates initiation, branching and termination processes where the rates of both the branching and one of the termination processes are governed by Arrhenius kinetics with different activation energies. The solutions to the governing equations yield the temperature in the vessel and the concentration of the intermediate chemical species. Under certain circumstances, these solutions can exhibit oscillatory behaviour. In this paper, we investigate the scenario in which the Gray-Yang model is subjected to additional external oscillations by varying the ambient temperature sinusoidally. We show the presence of primary, super and subharmonic resonances, as well as period-doubled solutions and even deterministic chaos for appropriate parameter values. More importantly, particularly from the industrial point of view, we study the effects of such external forcing on the gains in selectivity and yield of a desired product.