Cooperativity in Sorption Isotherms

[Image: see text] We present a general theory of cooperativity in sorption isotherms that can be applied to sorbent/gas and sorbent/solution isotherms and is valid even when sorbates dissolve into or penetrate the sorbent. Our universal foundation, based on the principles of statistical thermodynami...

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Autores principales: Shimizu, Seishi, Matubayasi, Nobuyuki
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10552535/
https://www.ncbi.nlm.nih.gov/pubmed/37738037
http://dx.doi.org/10.1021/acs.langmuir.3c01243
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author Shimizu, Seishi
Matubayasi, Nobuyuki
author_facet Shimizu, Seishi
Matubayasi, Nobuyuki
author_sort Shimizu, Seishi
collection PubMed
description [Image: see text] We present a general theory of cooperativity in sorption isotherms that can be applied to sorbent/gas and sorbent/solution isotherms and is valid even when sorbates dissolve into or penetrate the sorbent. Our universal foundation, based on the principles of statistical thermodynamics, is the excess number of sorbates (around a probe sorbate), which can capture the cooperativities of sigmoidal and divergent isotherms alike via the ln–ln gradient of an isotherm (the excess number relationship). The excess number relationship plays a central role in deriving isotherm equations. Its combination with the characteristic relationship (i.e., a succinct summary of the sorption mechanism via the dependence of excess number on interfacial coverage or sorbate activity) yields a differential equation whose solution is an isotherm equation. The cooperative isotherm equations for convergent and divergent cooperativities derived from this novel method can be applied to fit experimental data traditionally fitted via various isotherm models, with a clear statistical thermodynamic interpretation of their parameters..
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spelling pubmed-105525352023-10-06 Cooperativity in Sorption Isotherms Shimizu, Seishi Matubayasi, Nobuyuki Langmuir [Image: see text] We present a general theory of cooperativity in sorption isotherms that can be applied to sorbent/gas and sorbent/solution isotherms and is valid even when sorbates dissolve into or penetrate the sorbent. Our universal foundation, based on the principles of statistical thermodynamics, is the excess number of sorbates (around a probe sorbate), which can capture the cooperativities of sigmoidal and divergent isotherms alike via the ln–ln gradient of an isotherm (the excess number relationship). The excess number relationship plays a central role in deriving isotherm equations. Its combination with the characteristic relationship (i.e., a succinct summary of the sorption mechanism via the dependence of excess number on interfacial coverage or sorbate activity) yields a differential equation whose solution is an isotherm equation. The cooperative isotherm equations for convergent and divergent cooperativities derived from this novel method can be applied to fit experimental data traditionally fitted via various isotherm models, with a clear statistical thermodynamic interpretation of their parameters.. American Chemical Society 2023-09-22 /pmc/articles/PMC10552535/ /pubmed/37738037 http://dx.doi.org/10.1021/acs.langmuir.3c01243 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Shimizu, Seishi
Matubayasi, Nobuyuki
Cooperativity in Sorption Isotherms
title Cooperativity in Sorption Isotherms
title_full Cooperativity in Sorption Isotherms
title_fullStr Cooperativity in Sorption Isotherms
title_full_unstemmed Cooperativity in Sorption Isotherms
title_short Cooperativity in Sorption Isotherms
title_sort cooperativity in sorption isotherms
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10552535/
https://www.ncbi.nlm.nih.gov/pubmed/37738037
http://dx.doi.org/10.1021/acs.langmuir.3c01243
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