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Thermodynamics and Kinetics of the Thermal Decomposition of N,N,N-trimethylmethanaminium and 1-methylpyridinium Halides

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Abstract

The decomposition of the quaternary salts mentioned in the title was examined at the quantum mechanical Hartree-Fock level of theory employing pseudopotentials combined with a SBKJ** basis set. This enabled identification of intermediate and transition state species on the reaction pathway and prediction of the thermodynamic and kinetic barriers to the dissociation of the compounds in the gaseous phase. Application of classical methods permitted the lattice energies of salts, whose crystal structures had been established earlier, to be predicted. Combination of these latter characteristics with the heats of formation of gaseous halide ions (available from the literature) and the relevant cations (obtained at the density functional (B 3LYP)/6-31G**level of theory) provided heats of formation of the salts. On the basis of these values, the thermodynamic and kinetic barriers to the dissociation of the compounds were predicted. The characteristics thus obtained compare quite well with those available in the literature or determined in this work on the basis of TG or DSC measurements. These investigations have shed more light on the mechanism of the thermal dissociation of quaternary salts, and more generally on thermal processes involving solids.

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Authors and Affiliations

  1. Department of Chemistry, University of Gdańsk, J. Sobieskiego 18, 80-952, Gdańsk, Poland

    J. Błażejowski, K. Krzymiński, P. Storoniak & J. Rak

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  1. J. Błażejowski
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  3. P. Storoniak
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Błażejowski, J., Krzymiński, K., Storoniak, P. et al. Thermodynamics and Kinetics of the Thermal Decomposition of N,N,N-trimethylmethanaminium and 1-methylpyridinium Halides. Journal of Thermal Analysis and Calorimetry 60, 927–941 (2000). https://doi.org/10.1023/A:1010120027248

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