New Invariant Expressions in Chemical Kinetics

Abstract

This paper presents a review of our original results obtained during the last decade. These results have been found theoretically for classical mass-action-law models of chemical kinetics and justified experimentally. In contrast with the traditional invariances, they relate to a special battery of kinetic experiments, not a single experiment. Two types of invariances are distinguished and described in detail: thermodynamic invariants, i.e., special combinations of kinetic dependences that yield the equilibrium constants, or simple functions of the equilibrium constants; and “mixed” kinetico-thermodynamic invariances, functions both of equilibrium constants and non-thermodynamic ratios of kinetic coefficients.

Perturbed and Unperturbed: Analyzing the Conservatively Perturbed Equilibrium (Linear Case)

“…It was shown [ 1 , 2 ] that in such CPE experiments, the concentration of any unperturbed species first evolves away from its initial value, which equals the equilibrium value, and then back to this value as time tends to infinity, via an unavoidable first extreme value (maximum or minimum), possibly followed by other extreme values. These extreme concentration values and the times of their occurrences present essential information: on the detailed mechanism on the values of the kinetic parameters on the possibility of new regimes with an improved yield and selectivity.…”

“…A new kinetic technique, Conservatively Perturbed Equilibrium (CPE), was analyzed theoretically in previous studies [1,2]. It is formulated within a new paradigm of chemical kinetics, the so-called "Joint Kinetics", which was developed during the last decade (see the papers [3][4][5][6][7][8] and the most recent review [9]).…”