Transition to the Most Probable Kinetic State in a Pre-Steady State System

Abstract

A system containing a pre-steady state standard (non-autocatalytic) reaction, with multiple paths, evolves toward a kinetic state with the minimum attainable activation free energy. Displacement of the path frequency distribution in this transition was shown to minimise the affinity linked to this change in activation free energy. In damping this scalar force, a standard system is driven along a path of least action, as previously established for a system of competing autocatalytic reactions. A kinetic source of time asymmetry arises within the system, as the activation affinity moves the system toward the most probable distribution of reaction paths. As the functions of state are not changed by path displacement, a change of kinetic state cannot produce chemical work. This generalises the notion of force to a scalar quantity responsible for a displacement that does not yield work or heat. Spectrophotometric observations reported on the transition to steady state kinetics during dinitrophenyl phosphate phosphorolysis confirmed that time variations in the activation affinity are non-positive.