ChemInform Abstract: Measurements and Calculations of Oscillations and Phase Relations in the Driven Gas-Phase Combustion of Acetaldehyde

Abstract

Oscillations in light emission and species concentrations, are measured as periodic perturbations are simultaneously applied to the input rates of acetaldehyde and oxygen in the gas‐phase combustion of acetaldehyde in a continuous‐flow stirred tank reactor for conditions where the autonomous reaction itself is oscillatory. The experimental results are compared with the predictions of a five‐variable thermokinetic model. We measure periodic responses in the fundamental entrainment band (ratio of frequency of perturbation to frequency of response equal to unity) for four different values of phase shift between the acetaldehyde and oxygen perturbation wave forms as we vary the frequency and amplitude of the external periodic perturbations. Outside of the entrainment bands we find quasiperiodic response. We determine the phases of the light emission and six species concentrations, as measured with a mass spectrometer, with respect to the periodic perturbation, the variation of these phases across the fundamental entrainment band for different values of reactant phase shift and for different amplitudes of perturbation, and the effects of the phase shift between the two input perturbations on the light emission response of the system for different frequencies of perturbation. Both the experiments and calculations predict a widening of the entrainment band with an increase in perturbation amplitude, and the same variation in bandwidths for the four values of reactant phase shift studied. The experiments and calculations also predict the same general trends in light phase and species phases (difference between the light emission and species concentrations with respect to the perturbing wave form) as the band is traversed for different amplitudes of perturbation and for different values of reactant phase shift. Some discrepancies in the species phases exist; however, the similarities which exist between the experiments and the calculations provide further substantiation for the model. We find that changing the phase shift between reactant inflows from 0° to 360° produces a sharp change in light phase near 180°, in both the experiments and calculations. In general, we also find that the light emission remains entrained near the total flux minimum of the perturbing wave form, and we attribute this correlation to the net heat loss which arises from the reactant flux through the reactor.