Influence of the activation entropy on the change of the isokinetic temperature in the SN2 reactions in solution

Vlasov, V. M.

doi:10.1007/s00706-018-2321-9

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2021

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“…It is a common practice in the chemical kinetics laboratory to study what are known as homologous reaction series, understanding for that term families of closely related chemical processes differing, for instance, either in the structure of one of the reactants (replacing an inert substituent with another) [1][2][3][4] or in the solvent employed [4,5].…”

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confidence: 99%

Interdependence of the Hammett and isokinetic relationships: a numerical simulation approach

Perez‐Benito

Clavero-Masana

2021

Monatsh Chem

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Many homologous reaction series present linear correlations between the enthalpy ( o ,i H   ) and entropy ( o ,i S  ) of activation (kinetic compensation effect), the slope being the isokinetic temperature of the series (T iso ), so that at T = T iso all the reactions of the family share the same value of the rate constant. S   vs. i  plots, are all indicative of false isokinetic relationships, highly contaminated by the statistical correlation between the enthalpy and entropy experimental errors.

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