Shimizu, Seishi orcid.org/0000-0002-7853-1683 and Matubayasi, Nobuyuki (2022) Surface Area Estimation:Replacing the BET Model with the Statistical Thermodynamic Fluctuation Theory. Langmuir. 7989–8002. ISSN 1520-5827
Abstract
Surface area estimation using the BET analysis has been beset by difficulties. The BET model has been applied routinely to the systems that break its basic assumptions. Even though unphysical results arising from force-fitting can be eliminated by the consistency criteria, such a practice, in turn, complicated the simplicity of the linearized BET plot. We have derived a general isotherm from the statistical thermodynamic fluctuation theory, leading to facile isotherm fitting, because our isotherm is free of the BET assumptions. The reinterpretation of the monolayer capacity and the BET constant has led to a statistical thermodynamic generalization of the BET analysis. The key is Point M, which is defined as the activity at which the sorbate-sorbate excess number at the interface takes minimum (i.e., the point of strongest sorbate-sorbate exclusion). The straightforwardness of identifying Point M and the ease of fitting by the statistical thermodynamic isotherm has been demonstrated using Zeolite 13X and a Portland cement paste. The adsorption at Point M is an alternative for the BET monolayer capacity, making the BET model and its consistency criteria unnecessary. The excess number (i) replaces the BET constant as the measure of knee sharpness and monolayer coverage, (ii) links macroscopic (isotherms) to microscopic (simulation) and (iii) serves as a measure of sorbate-sorbate interaction as a signature of sorption cooperativity in porous materials. Thus, interpretive clarity and ease of analysis have been achieved by a statistical thermodynamic generalization of the BET analysis.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2022 The Authors |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Depositing User: | Pure (York) |
Date Deposited: | 30 May 2022 13:40 |
Last Modified: | 02 Apr 2025 23:22 |
Published Version: | https://doi.org/10.1021/acs.langmuir.2c00753 |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1021/acs.langmuir.2c00753 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:187448 |
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Description: Surface Area Estimation: Replacing the Brunauer−Emmett−Teller Model with the Statistical Thermodynamic Fluctuation Theory
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