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S Vyazovkin

Publications and source records attributed to S Vyazovkin.

2 recordsLinked to original sources

Estimating realistic confidence intervals for the activation energy determined from thermoanalytical measurements

A statistical procedure is proposed for estimating realistic confidence intervals for the activation energy determined by using an advanced isoconversional method. Nine sets of five thermogravimetric measurements have been produced for the process of gassification of ammonium nitrate at five different heating rates. Independent estimates of the confidence intervals for the activation energy have been obtained from these data sets. Agreement with these independent estimates demonstrates that the proposed statistical procedure is capable of adequately estimating the actual uncertainty in the activation energy determined from a small number of measurements. The resulting averaged relative errors in the activation energy were found to be 26, 21, and 17% for three, four, and five heating rate estimates, respectively.

Journal Article↗

Kinetics in solids.

The kinetics of solid state reactions generally cannot be assumed to follow simple rate laws that are applicable to gas-phase reactions. Nevertheless, a widely practiced method for extracting Arrhenius parameters from thermal analysis experiments involves force fitting of experimental data to simple reaction-order kinetic models. This method can produce significant errors in predicted rates outside the experimental range of temperatures, and it is of limited utility for drawing mechanistic conclusions about reactions. In this review, we discuss how an alternative "model-free" approach to kinetic analysis, which is based on the isoconversional method, can overcome some of these limitations.

Journal Article↗