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Evaluation of the protonation thermochemistry obtained by the extended kinetic method

Authors

  • Guy Bouchoux

    Corresponding author
    1. Département de Chimie, Laboratoire des Mécanismes Réactionnels, Ecole Polytechnique, 91120 Palaiseau, France
    • Département de Chimie, Laboratoire des Mécanismes Réactionnels, Ecole Polytechnique, 91120 Palaiseau, France.
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  • This paper is dedicated to Jean-François Gal on the occasion of his 61st birthday and in recognition of his contribution to proton transfer thermochemistry

Abstract

An evaluation of the results obtained by the extended kinetic method for a series of representative bases is presented here. Analysis of the original experimental data is conducted using the orthogonal distance regression (ODR) statistical treatment. A comparison with the proton affinities and protonation entropies obtained from variable temperature equilibrium constant measurements demonstrate deviations, which may be ascribed to random and systematic errors. Considerable random errors are associated with the extended kinetic method if the number of reference bases and the range of effective temperatures are too low. It is also confirmed that large systematic errors on proton affinities and protonation entropies are obtained when large protonation entropy is associated with the considered system. It is, however, encouraging to note that the gas phase basicities obtained by the extended kinetic method are generally comparable to that obtained by other methods within a few kJ/mol. Copyright © 2006 John Wiley & Sons, Ltd.

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