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Accuracy of Enthalpy and Entropy Determination Using the Kinetic Method: Are We Approaching a Consensus? by László Drahos; Csaba Peltz; Károly Vékey is a Chemistry article available to read on EtoBox.

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## Abstract There is an emerging consensus regarding the applicability of the kinetic method. All parties acknowledge that it is an approximate quantitative technique, capable of yielding not only enthalpy, but also entropy values. Opinions differ mainly on the accuracy of the results but it is agreed that the energy (effective temperature) dependence of kinetic method plots needs to be checked in all but the simplest of cases. When the ‘apparent basicity’ is found to depend on collision energy (and hence effective temperature), the extended kinetic method __must__ be used. We have performed a large‐scale modeling study, involving thousands of randomly selected molecular systems and a variety of experimental conditions, using exact calculations and realistic data sets. The results show that when the measured entropy difference between the two competing reaction channels is less than ∼35 J mol^−1^ K^−1^, overall errors (standard deviations) of Δ__H__~298~ determined by the kinetic method are ±5 kJ mol^−1^; those of Δ__S__~298~ are ±10 J mol^−1^ K^−1^. These include not only inherent errors of the kinetic method, but also errors in ion abundance measurement (5%) and inaccurate knowle

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Author

László Drahos; Csaba Peltz; Károly Vékey

Publisher

John Wiley and Sons; Wiley (John Wiley & Sons); Wiley-Blackwell; Wiley-Liss Inc; John Wiley & Sons Inc.; Wiley; Heyden And Son (ISSN 1076-5174)

Published

2004

Language

EN

Field

Chemistry (Physical Sciences)