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On the way from the activation model of solid decomposition to the thermochemical model

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Abstract

The development of the technology and the theory of electrothermal atomization, which began in atomic absorption spectrometry about 60 years ago, led to a confrontation between the two alternative models used in the kinetics of heterogeneous chemical reactions: the activation model proposed by Arrhenius (Z Phys Chem 4:226–248, 1889) and based on the effect of activation, and the thermochemical model (TM) proposed by Langmuir (Phys Rev 2:329–342, 1913), which excludes the existence of this effect. An analysis of the events surrounding the creation and evolution of both models and a comparison of their fundamental principles and their application to the solution of actual problems show the shortcomings of the activation model and fundamental limitations in its applicability. The TM for the first time in the history of these studies allowed a quantitative estimation and a prediction of the lifetime for substances depending on the environment and temperature of their storage. It allows the calculation of the rate of reaction and the Arrhenius parameters taking into account the composition, stoichiometry and thermochemical characteristics of the reaction, the excess pressure of the gaseous product in the reactor and the physical properties of the reactant (sample size and the density of the reactant). Within the TM, it was possible to solve many of the accumulated problems, including the physical nature of the parameters of the Arrhenius equation, the effect of autocatalysis, the kinetic compensation effect and the Topley–Smith effect. To overcome the lasting crisis in the kinetics of heterogeneous reactions, it is necessary to advance the public discussion of the current situation and search for appropriate ways to replace the activation model by the TM.

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Acknowledgments

The author is indebted to Dr. Andrew Galwey (Belfast) and Dr. Valery Ugolkov (St Petersburg) for fruitful cooperation in some of these studies and Dr. Gábor Lente, the Managing Editor of the journal “Reaction Kinetics, Mechanism and Catalysis”, for his careful consideration of this work, including valuable comments which greatly helped in the presentation of this manuscript. The author thanks also his grandson Nikita L’vov (Princeton University, USA) for linguistic corrections to the text.

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  1. Department of Physical Chemistry, St Petersburg State Polytechnic University, St Petersburg, 195251, Russia

    Boris V. L’vov

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Correspondence to Boris V. L’vov.

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L’vov, B.V. On the way from the activation model of solid decomposition to the thermochemical model. Reac Kinet Mech Cat 116, 1–18 (2015). https://doi.org/10.1007/s11144-015-0886-4

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