Algorithmic criteria for the validity of quasi-steady state and partial equilibrium models: the Michaelis-Menten reaction mechanism.

Abstract

We present "on the fly" algorithmic criteria for the accuracy and stability (non-stiffness) of reduced models constructed with the quasi-steady state and partial equilibrium approximations. The criteria comprise those introduced in Goussis (Combust Theor Model 16:869-926, 2012) that addressed the case where each fast time scale is due to one reaction and a new one that addresses the case where a fast time scale is due to more than one reactions. The development of these criteria is based on the ability to approximate accurately the fast and slow subspaces of the tangent space. Their validity is assessed on the basis of the Michaelis-Menten reaction mechanism, for which extensive literature is available regarding the validity of the existing various reduced models. The criteria predict correctly the regions in both the parameter and phase spaces where each of these models is valid. The findings are supported by numerical computations at indicative points in the parameter space. Due to their algorithmic character, these criteria can be readily employed for the reduction of large and complex mathematical models.