Obtaining reliable phenomenological chemical kinetic models for real-world applications

• Heating rates need to vary at least a tenfold to give accurate kinetic parameters.
• Replicate measurements at the highest and lowest heating rates most important.
• Mathematical methods for handling arbitrary thermal histories are available.

The derivation of chemical kinetics by the thermal analysis community has a checkered past, with numerous papers published using substandard methodology. The ICTAC kinetics committee has taken on the task of upgrading the quality of thermal analysis kinetics through a series of workshops and publications. However, the resulting publications from those efforts by design do not cover all important aspects in detail. This paper explores two issues in greater depth—the optimum selection of heating rates for kinetic determination based on statistical error considerations and the importance of using a diverse set of thermal histories, including but not limited to isothermal and linear heating, to better constrain and validate global models.