“Model-free” kinetic analysis?

• Published in: Thermochimica acta 2002-07, Vol.390 (1), p.217-225
• Main Authors: Sewry, Joyce D., Brown, Michael E.
• Format: Article
• Language: English
• Subjects: Chemistry; Exact sciences and technology; General and physical chemistry; Kinetic compensation effect; Model-free methods; Non-parametric kinetics; Theory of reactions, general kinetics; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
• ISSN: 0040-6031; 1872-762X
• DOI: 10.1016/S0040-6031(02)00083-7

All kinetic analyses aim to determine a sufficient number of kinetic parameters, usually at least an apparent Arrhenius activation energy and pre-exponential factor, and a conversion function or kinetic model (making up a ‘kinetic triplet’), so that accurate extrapolations of kinetic behaviour can be made. “Model-free” methods of kinetic analysis postpone the problem of identifying a suitable kinetic model until an estimate of the activation energy has been made. A major reason for doing this is that misidentification of the kinetic model has a marked effect on the values obtained for the Arrhenius parameters in both isothermal and non-isothermal kinetic analyses. Some aspects of this problem are discussed. The non-parametric kinetics (NPK) method [1,2] is a “model-free” method of kinetic analysis that does not seem to have received the attention that it deserves. This is probably because of its mathematical sophistication and the fact that the matrix and non-linear regression calculations involved are not readily automated. The principle of the method appears to be that of “forcing” a set of non-isothermal data into the set which should have been obtained if the experiments had been carried out isothermally. The method deserves wider testing and also raises some interesting aspects of the philosophy behind non-isothermal kinetic analysis.