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Kinetic parameters of CaCO3 decomposition in vacuum, air and CO2 calculated theoretically by means of the thermochemical approach

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Abstract

Fundamental advantages of the thermochemical approach compared with the activation approach were supported in this work by the results of theoretical calculations of the A and E kinetic parameters of CaCO3 decomposition in vacuum, air and CO2 and their comparison with experimental data. The temperature of the reaction in CO2 increases from 800 K (in vacuum) up to 1,200 K at equal rates of decomposition. This effect (unexplained in the framework of the activation approach) is of tremendous importance for estimating the thermal stability and lifetime of materials. It has been shown that the pre-exponential factor A in the Arrhenius equation is related to the entropy change of decomposition reaction and, in the isobaric mode, additionally, to the pressure of the external gaseous product. The mysterious effect of “variable activation energy” observed in many non-isothermal studies of solid decompositions, in particular, for CaCO3, was explained by the change of the reaction regime from the isobaric mode at low temperature (and decomposition degree) to the equimolar mode at higher temperatures (and higher decomposition degrees). This effect manifests itself for reactions related to the evolution of O2, H2O and CO2 gaseous products, which can be present in the reactor media as impurities.

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Acknowledgments

The author is indebted to Dr. Andrew Galwey (Belfast) and Dr. Valery Ugolkov (St Petersburg) for fruitful cooperation in these studies. The author thanks also his grandson Nikita L’vov (Princeton University, USA) for a stylistic improvement of the manuscript.

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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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  1. Boris V. L’vov
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Correspondence to Boris V. L’vov.

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L’vov, B.V. Kinetic parameters of CaCO3 decomposition in vacuum, air and CO2 calculated theoretically by means of the thermochemical approach. Reac Kinet Mech Cat 114, 31–40 (2015). https://doi.org/10.1007/s11144-014-0767-2

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