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Single Quality Factor for Enthalpy‐Entropy Compensation, Isoequilibrium and Isokinetic Relationships

Enthalpy‐entropy compensation (EEC) is very often encountered in chemistry, biology and physics. Its origin is widely discussed since it would allow, for example, a very accurate tuning of the thermodynamic properties as a function of the reactants. However, EEC is often discarded as a statistical a...

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Autores principales: Griessen, Ronald, Boelsma, Christiaan, Schreuders, Herman, Broedersz, Chase P., Gremaud, Robin, Dam, Bernard
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7522686/
https://www.ncbi.nlm.nih.gov/pubmed/32573925
http://dx.doi.org/10.1002/cphc.202000390
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author Griessen, Ronald
Boelsma, Christiaan
Schreuders, Herman
Broedersz, Chase P.
Gremaud, Robin
Dam, Bernard
author_facet Griessen, Ronald
Boelsma, Christiaan
Schreuders, Herman
Broedersz, Chase P.
Gremaud, Robin
Dam, Bernard
author_sort Griessen, Ronald
collection PubMed
description Enthalpy‐entropy compensation (EEC) is very often encountered in chemistry, biology and physics. Its origin is widely discussed since it would allow, for example, a very accurate tuning of the thermodynamic properties as a function of the reactants. However, EEC is often discarded as a statistical artefact, especially when only a limited temperature range is considered. We show that the likeliness of a statistical origin of an EEC can be established with a compensation quality factor (CQF) that depends only on the measured enthalpies and entropies and the experimental temperature range. This is directly derived from a comparison of the CQF with threshold values obtained from a large number of simulations with randomly generated Van ‘t Hoff plots. The value of CQF is furthermore a direct measure of the existence of a genuine isoequilibrium or isokinetic relationship.
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spelling pubmed-75226862020-10-02 Single Quality Factor for Enthalpy‐Entropy Compensation, Isoequilibrium and Isokinetic Relationships Griessen, Ronald Boelsma, Christiaan Schreuders, Herman Broedersz, Chase P. Gremaud, Robin Dam, Bernard Chemphyschem Articles Enthalpy‐entropy compensation (EEC) is very often encountered in chemistry, biology and physics. Its origin is widely discussed since it would allow, for example, a very accurate tuning of the thermodynamic properties as a function of the reactants. However, EEC is often discarded as a statistical artefact, especially when only a limited temperature range is considered. We show that the likeliness of a statistical origin of an EEC can be established with a compensation quality factor (CQF) that depends only on the measured enthalpies and entropies and the experimental temperature range. This is directly derived from a comparison of the CQF with threshold values obtained from a large number of simulations with randomly generated Van ‘t Hoff plots. The value of CQF is furthermore a direct measure of the existence of a genuine isoequilibrium or isokinetic relationship. John Wiley and Sons Inc. 2020-07-10 2020-08-04 /pmc/articles/PMC7522686/ /pubmed/32573925 http://dx.doi.org/10.1002/cphc.202000390 Text en © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Articles
Griessen, Ronald
Boelsma, Christiaan
Schreuders, Herman
Broedersz, Chase P.
Gremaud, Robin
Dam, Bernard
Single Quality Factor for Enthalpy‐Entropy Compensation, Isoequilibrium and Isokinetic Relationships
title Single Quality Factor for Enthalpy‐Entropy Compensation, Isoequilibrium and Isokinetic Relationships
title_full Single Quality Factor for Enthalpy‐Entropy Compensation, Isoequilibrium and Isokinetic Relationships
title_fullStr Single Quality Factor for Enthalpy‐Entropy Compensation, Isoequilibrium and Isokinetic Relationships
title_full_unstemmed Single Quality Factor for Enthalpy‐Entropy Compensation, Isoequilibrium and Isokinetic Relationships
title_short Single Quality Factor for Enthalpy‐Entropy Compensation, Isoequilibrium and Isokinetic Relationships
title_sort single quality factor for enthalpy‐entropy compensation, isoequilibrium and isokinetic relationships
topic Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7522686/
https://www.ncbi.nlm.nih.gov/pubmed/32573925
http://dx.doi.org/10.1002/cphc.202000390
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