Abstract:Variable correlations are usually neglected during parameter estimation. Very frequently these are gross assumptions and may potentially lead to inadequate interpretation of final estimation results. For this reason, variable correlation and model parameters are sometimes estimated simultaneously in certain parameter estimation procedures. It is shown, however, that usually taking variable correlation into consideration during parameter estimation may be inadequate and unnecessary, unless independent experimen… Show more
“…20,23 had shown the existence of strong correlation of kinetic parameters in mathematical models containing more than one temperature-dependent kinetic constant. Such correlation makes the task of precise estimation of different kinetic parameters more onerous 24,25 . In such cases, re-parametrized form of Arrhenius equation is known to significantly reduce computational effort by reducing the correlation between parameters 26 .…”
Epoxidation of high-linolenic perilla oil was carried out in the presence of solid acidic ion-exchange resin at varying reaction temperatures for 8 h. A pseudo two-phase kinetic model that captures the differences in reactivity of double bonds at various positions in the fatty acid of a triglyceride molecule during both epoxy formation and cleavage was developed. The proposed model is based on the Langmuir-Hinshelwood-Hougen-Watson (L-H-H-W) postulates and considers the adsorption of formic acid on the catalyst as the rate-determining step. To estimate the kinetic rate constants of various reactions, genetic algorithm was used to fit experimentally obtained iodine and epoxy values of epoxidized perilla oil. A re-parametrized form of Arrhenius equation was used in the proposed model to facilitate the precise estimation of parameters with least computational effort. The obtainment of the least error between experimentally determined and theoretically predicted iodine and epoxy values indicates the robustness of the proposed model.
“…(21)). The parameters are correlated, thus a maximum likelihood procedure was used, the ESTIMA software (Santos and Pinto, 1998). At this step, no oscillations were considered; therefore the model described the curve inclination, and its proximity to a PFR model.…”
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