Thermodynamic stability of chemical species in multiple reaction systems.
A general thermodynamic and stoichiometric method, recently developed by us to study subtle forms of stability/instability relations among chemical species, such as resonance and strain energies (Fishtik, I.; Datta, R. J. Phys. Chem. A 2004, 108, 5727-5739), is extended to stability relations in multiple chemical reaction systems. Namely, a new definition as well as a new algorithm of evaluation of the stabilities of chemical species, referred to as the overall stabilities, is proposed. It is further shown that the overall stabilities may be partitioned into a sum of contributions associated with a complete set of stoichiometrically unique response reactions (RERs). This finding reveals that the conventional stability analysis is stoichiometrically and thermodynamically inconsistent in that it involves only a part of RERs.
Fishtik
Ilie
I
Department of Chemical Engineering, Worcester Polytechnic Institute, Worcester, Massachusetts 01609-2280, USA. ifishtik@wpi.edu