A General Exploratory Chemometrics Methodology For Catalytic System Identification

The system identification of unknown catalytic phenomena is often fraught with complications, and it is difficult to obtain quantitative kinetics and thermodynamic understanding of such chemical systems. Quantitative descriptions of catalytic phenomena constitute part of the inverse problem in chemistry and chemical engineering. In this paper, a novel chemometrics numerical methodology for general exploratory studies of complex catalytic systems is presented. Through the systematic implementation of various chemometrics techniques and logical rationalization, important chemical knowledge of little known or totally unknown catalytic systems can be elucidated. The chemical knowledge includes: (i) pure component spectra of observable species, (ii) chemical species identities and algebraic atom-free stoichiometries, (iii) postulated catalytic mechanism, (iv) algebraic reaction stoichiometries and corresponding extents of reaction matrices, (v) observable differential rate laws and activation kinetics, and (vi) observable activation and equilibrium thermodynamics parameters. This method was successfully applied to the complicated catalytic system of unmodified Rh4(CO)12 catalyzed 1,3cyclohexadiene hydroformylation, and is proven to be efficacious for obtaining coherent quantitative and qualitative answers for the aforesaid inverse problem.