Further developments and applications of the Green’s function method of sensitivity analysis in chemical kinetics

Abstract

A numerical procedure is presented for implementing the Green’s function method of sensitivity analysis in chemical kinetics. The procedure is applied to three sets of chemical reactions: the Chapman mechanism for ozone kinetics, a mechanism for methane combustion and a model for formaldehyde oxidation in the presence of carbon monoxide. Whenever possible, comparisons with alternative methods of sensitivity analysis are made. It is shown that carefully analyzed sensitivity profiles can be used in conjunction with experiments and/or models to obtain useful information about chemical kinetic behavior. By using methods from multivariable calculus an entire family of sensitivity coefficients may be derived from the elementary sensitivities obtained by solving differential equations. Each elementary or derived sensitivity coefficient has a unique physical interpretation in terms of an experiment or modeling calculation. A simple nonlinear interpolation formula is suggested for easily estimating higher‐order sensitivity information. Finally the overall computational efficacy of the Green’s function method of sensitivity analysis is assessed.