화학공학소재연구정보센터
Thermochimica Acta, Vol.578, 68-73, 2014
Dispersive kinetic models predict variation of the activation energy with extent of conversion observed experimentally in isoconversional data
Two dispersive kinetic models (DICMs) are used for the first time to precisely simulate the evolution of the activation energy barrier, Delta G double dagger, as a function of the extent of conversion, x, of hypothetical conversions with realistic physical parameters. The simulated Delta G double dagger-x plots closely resemble certain trends reported in the recent experimental literature obtained using so-called isoconversional methods of thermal analysis (TA), thus forging a new link between the experimental results and dispersive kinetics theory. The simulations provide unprecedented mechanistic insight into such data trends. It is easily deduced that the activation energy distributions underpinning the two DKMs are responsible for producing the distinct variations observed in Delta G double dagger. That is because DKMs utilize the concept of a distribution of activation energies to simultaneously treat the kinetics and dynamics that can be observed in elementary conversions and that classical kinetic models (CKMs), which assume a single activation energy to model just the kinetics in the absence of dynamical effects, cannot properly describe (Skrdla, 2013). While the use of DKMs in TA applications remains quite limited, the two DKMs considered herein have been discussed in detail elsewhere and their application to a host of different conversions/phase transformations has been demonstrated under isothermal conditions (Skrdla, 2009). In the present work, those DKMs are used to simulate non-isothermal Delta G double dagger-x trends. Through the course of these investigations, it is found that the simulated data sets also indicate that the heating (cooling) rate can have a dramatic impact on kinetic determinations, whereas current isoconversional methods, relying on classical kinetic theory, predict no such effect. The last finding points to a need to develop new thermal methods, based on the theory underpinning DKMs rather than CKMs, to more rigorously model dispersive kinetic processes that exhibit distributed reactivity. (C) 2014 Elsevier B.V. All rights reserved.