Deduction of chemical mechanisms from the linear response around steady state

The determination of abstract models of complex chemical mechanisms from th e analysis of the experimental time series of the concentration of species is a topic of undoubted interest. Doing so from time series in the linear r egime offers certain advantages because the equations of evolution can be e asily retrieved. This contrasts with the much greater ambiguity associated to the corresponding process in the nonlinear regime. However, until presen tly, the procedure has not been formalized, and known methods of inference of the mechanism still rely too much on guess. The aim of the present artic le is to remedy to this problem by offering a systematic procedure for carr ying out the deduction of the mechanism within the framework of the law of mass action. The number of independent steps and actual values of both the stoichiometric coefficients and of the rate constants are calculated from t he linear equations governing the time response of chemical species to a sm all pulse perturbation of the steady state. Also, the deduction of these li near equations from that same response is outlined.