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A universal, model-independent framework is developed by generalizing traditional sorption parameters into partitioning and association coefficients based on sorbate–sorbate and sorbate–surface interactions, enabling consistent interpretation across isotherm types and resolving contradictions.",{"@graph":14,"@context":73},[15,34,56],{"@type":16,"itemListElement":17},"BreadcrumbList",[18,23,27,31],{"item":19,"name":20,"@type":21,"position":22},"https://docshare.wps.com","Home","ListItem",1,{"item":24,"name":25,"@type":21,"position":26},"https://docshare.wps.com/document/","Document",2,{"item":28,"name":29,"@type":21,"position":30},"https://docshare.wps.com/document/research-report/","Research & 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](eprints@whiterose.ac.uk)[https://eprints.whiterose.ac.uk](https://eprints.whiterose.ac.uk)  \nUniversities of Leeds, Sheffield and York  \nDeposited via The University of York.  \nWhite Rose Research Online URL for this paper:  \n[https://eprints.whiterose.ac.uk/id/eprint/198025/](https://eprints.whiterose.ac.uk/id/eprint/198025/)  \nVersion: Published Version  \nArticle:  \nShimizu, Seishi and Matubayasi, N (2023) Understanding Sorption Mechanisms Directly from Isotherms. Langmuir. 6113–6125. ISSN: 1520-5827  \n[https://doi.org/10.1021/acs.langmuir.3c00256](https://doi.org/10.1021/acs.langmuir.3c00256)  \nReuse  \nThis article is distributed under the terms of the Creative Commons Attribution (CC BY) licence. This licence allows you to distribute, remix, tweak, and build upon the work, even commercially, as long as you credit the authors for the original work. More information and the full terms of the licence here: [https://creativecommons.org/licenses/](https://creativecommons.org/licenses/)  \nTakedown  \nIf you consider content in White Rose Research Online to be in breach of UK law, please notify us by  \nemailing [eprints@whiterose.ac.uk](eprints@whiterose.ac.uk) including the URL of the record and the reason for the withdrawal request.  \n[pubs.acs.org/Langmuir](pubs.acs.org/Langmuir)  Article   \nUnderstanding Sorption Mechanisms Directly from Isotherms  \n􀀁􀀂􀀃􀀄􀀅􀀃 􀀁􀀅􀀃􀀆􀀃􀀇􀀈* 􀀉􀀊􀀋 􀀌􀀍􀀎􀀈􀀏􀀈􀀐􀀃 􀀑􀀉􀀒􀀈􀀎􀀉􀀏􀀉􀀄􀀃  \n Cite This: Langmuir 2023, 39, 6113−6125  \nRead Online  \n\n| ACCESS |  Metrics & More |  Article Recommendations |\n| --- | --- | --- |\n\nDownloaded via 2 17.155.106.162 on May 3, 2023 at 1 1 :46 :09 (UTC) . See [https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles](https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles) .  \nABSTRACT: Currently, more than 100 isotherm models coexist for the six IUPAC isotherm types. However, no mechanistic insights can be reached when several models, each claiming a different mechanism, fit an experimental isotherm equally well. More frequently, popular isotherm models [such as the site-specific models like Langmuir, Brunauer−Emmett−Teller (BET), and Guggenheim−Anderson−de Boer (GAB)] have been applied to real and complex systems that break their basic assumptions. To overcome such conundrums, we establish a universal approach to model all isotherm  \ntypes, attributing the difference to the sorbate−sorbate and sorbate−surface interactions in a systematic manner. We have generalized the language of the traditional sorption models (such as the monolayer capacity and the BET constant) to the model-free concepts of partitioning and association coefficients that can be applied across the isotherm types. Through such a generalization, the apparent contradictions, caused by applying the site-specific models alongside with cross-sectional area of sorbates for the purpose of surface area determination, can be eliminated straightforwardly.  \n■ INTRODUCTION  \nCan the mechanism of sorption be revealed by analyzing experimental isotherms? Various isotherm models have been developed to answer this question.1,2 However, the difficulty comes from the diverse functional shapes that isotherms exhibit;3−6 the six types of isotherms, according to the IUPAC classification,3−6 have been analyzed using more than 100 isotherm models proposed so far.7−13 Such a practice, unfortunately, has made this simple question even more complicated for the following reasons. First, multiple isotherm models, each assuming a different adsorption mechanism (or even none), are capable of fitting the same data with comparable R2 values. 14−17 Second, the most popular isotherm models, such as the Brunauer−Emmett−Teller (BET)18, 19 and Guggenheim−Anderson−de Boer (GAB),20−22 have been applied routinely to real systems (e.g., food samples23−25 and construction materials26) that do not satisfy their original assum","cbCairSbmGqCWYnh","https://ap.wps.com/l/cbCairSbmGqCWYnh","pdf",1416840,14,"English","# Abstract\n# Introduction\n## Can sorption mechanism be revealed from experimental isotherms?\n## Limits of existing isotherm models\n## Statistical thermodynamics approach for model-independent identification","[{\"question\":\"Why can mechanistic insights be difficult when analyzing experimental isotherms?\",\"answer\":\"Because several different isotherm models can fit the same experimental data with comparable goodness-of-fit, despite assuming different or even absent mechanisms.\"},{\"question\":\"What assumption limitations affect common isotherm models like Langmuir, BET, and GAB?\",\"answer\":\"These models are site-specific and assume idealized adsorption behavior, but they are often applied to real complex systems (e.g., food samples or construction materials) that do not meet the original assumptions.\"},{\"question\":\"How does the proposed approach enable mechanistic identification without choosing a specific isotherm model?\",\"answer\":\"It generalizes traditional sorption-model language into partitioning and association coefficients, attributing differences to sorbate–sorbate and sorbate–surface interactions and quantifying them directly from isotherm shape using statistical thermodynamics concepts.\"}]","Understanding Sorption Mechanisms Directly from Isotherms - Article | PDF",1790001180,35]