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Solid state reaction kinetics, mechanisms and catalysis: a retrospective rational review

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Abstract

Kinetic studies are widely used to characterize the factors that control the reactivity and the mechanisms of chemical changes that occur on heating solid reactants. This survey appraises the origins, assumptions and scientific foundations that underlie the theoretical methods that are conventionally, and unquestioningly, used to analyze and to interpret thermal analysis (TA) rate measurements. The extensive TA literature is reviewed in the context of the unusual history of this branch of science, in which TA has effectively superseded the formerly thriving subject of Thermal Decomposition of Solids (TDoS) (also reviewed). Such complete replacement of one scientific discipline by another is unusual, so that reasons for, and consequences of, this eclipse merit detailed consideration. The rapid rise of TA, after about 1970, resulted from the unprecedented advances in instrumental and computational methods which massively accelerated the collection and analysis of accurate rate data for thermal reactions (including solids). Consequently, TA theory initially tended to focus on developing experimental equipment together with facilitation of data interpretation by computer programs. These achievements have enabled each TA study to be completed very rapidly and with relatively much less effort than was usual in the former TDoS methodology. However, much less effort was also invested in developing coherent and soundly-based theory for the interpretation of TA kinetic data, with consequences that are critically appraised here in their historical context.

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Acknowledgement

It is my pleasure to mention the many fruitful discussions with Professor Boris V L’vov that have contributed to the arguments presented here. However, the content of this article expresses my personal opinions about the present unfortunate lack of progress towards acceptance of CDV theory. In this survey, I have also recorded my perceptions about some unresolved issues in this valuable theory that, overall, I regard as offering a ‘new start’ for studies of TDoS.

Academic Auto-Obituary

This is my personal valedictory article, bidding farewell to the scientific arena after six decades of active research. I now retire fully. This explains my attempt here to view the subject in perspective, surveying the literature, including my own small contributions, as objectively as possible. Overall, it is an interesting history which still requires further effort. I express my Sincere Best Wishes to everyone involved with TDoS, together with the inevitable regrets of an elderly researcher who will not see the current (rather serious) conundrums resolved. Let us all hope that worthwhile New Science will prevail very soon.

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  1. Department of Chemistry, Rhodes University, Grahamstown, 6140, South Africa

    Andrew K. Galwey

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  1. Andrew K. Galwey
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Correspondence to Andrew K. Galwey.

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Galwey, A.K. Solid state reaction kinetics, mechanisms and catalysis: a retrospective rational review. Reac Kinet Mech Cat 114, 1–29 (2015). https://doi.org/10.1007/s11144-014-0770-7

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  • DOI: https://doi.org/10.1007/s11144-014-0770-7

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