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Fundamental restrictions of the second-law and Arrhenius plot methods used in the determination of reaction enthalpies in decomposition kinetics

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Abstract

The apparent increase of the reaction enthalpy ΔH with temperature due to the self-cooling and condensation effects is responsible for the fundamental restrictions of the second-law and Arrhenius plot methods related to determination of this parameter. Theoretical analysis and a comparison with the experimental data indicate that the systematic underestimation of ΔH magnitudes determined by the second-law method equals 10–25% for the reactants decomposed to gaseous products and 15–50% for reactants decomposed to solids. Therefore, the use of these methods in decomposition kinetics is hardly acceptable. The replacement of the Arrhenius plot and second-law methods to the much more precise and accurate third-law method is desirable or even obligatory.

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

    B. V. L’vov

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  1. B. V. L’vov
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L’vov, B.V. Fundamental restrictions of the second-law and Arrhenius plot methods used in the determination of reaction enthalpies in decomposition kinetics. J Therm Anal Calorim 92, 639–642 (2008). https://doi.org/10.1007/s10973-007-8693-4

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  • DOI: https://doi.org/10.1007/s10973-007-8693-4

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