{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,15]],"date-time":"2026-09-15T10:49:26Z","timestamp":1789469366151,"version":"build-2803163510"},"reference-count":40,"publisher":"Wiley","issue":"10","license":[{"start":{"date-parts":[[2025,10,29]],"date-time":"2025-10-29T00:00:00Z","timestamp":1761696000000},"content-version":"vor","delay-in-days":28,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["analyticalsciencejournals.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["J of Separation Science"],"published-print":{"date-parts":[[2025,10]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    The minor\u2010disturbance method is a convenient route to adsorption isotherms, but the thermodynamic void volume extracted from its data is often taken\u2014sometimes uncritically\u2014to be the column's geometrical void. Here, we investigate the thermodynamic void volume using an adsorption\u2010dividing\u2010plane framework. This framework clarifies that the choice of any hold\u2010up volume implicitly defines a Gibbs\u2010like dividing surface, which in turn determines the thermodynamic meaning of the resulting isotherm. Experiments were performed on two contrasting media: a cyano\u2010silica normal phase with\n                    <jats:italic>C<\/jats:italic>\n                    <jats:sub>2<\/jats:sub>\n                    \u2013\n                    <jats:italic>C<\/jats:italic>\n                    <jats:sub>4<\/jats:sub>\n                    alcohols and acetone, and an octyl\u2010bonded reversed phase with acetonitrile, methanol, and acetone, each probed at 15 or more bulk concentrations. On the cyano column, all solutes yielded an identical thermodynamic void volume (\u22482.98\u00a0mL), indicating the dividing plane aligns with the silica surface and the resulting isotherms represent true surface excess. In contrast, the thermodynamic void volume on the octyl\u2010bonded column was solute\u2010dependent (acetonitrile\u00a0&gt;\u00a0acetone &gt;\u00a0methanol), reflecting probe\u2010specific penetration into the bonded phase rather than the physical void volume. Negative branches observed in the high\u2010concentration excess isotherms of acetonitrile and acetone are rationalized by a conceptual three\u2010zone concentration profile in which brush\u2010induced depletion exceeds interfacial adsorption. Reprocessing the reversed\u2010phase data with a single, fixed void volume shifted the excess isotherms as predicted while leaving the total\u2010uptake isotherms unchanged, demonstrating that total adsorption is independent of the definition of the excess dividing plane when the saturation point is used to define the dividing surface. The study clarifies the physical meaning of the thermodynamic void volume: it equals the geometrical void only for phases with negligible bonded layers, but becomes probe\u2010specific on densely bonded reversed\u2010phase materials, where it serves as a quantitative indicator of brush penetration. A fixed dividing plane is therefore essential for meaningful cross\u2010solute comparison of excess isotherms and for reliable interpretation of minor\u2010disturbance data.\n                  <\/jats:p>","DOI":"10.1002\/jssc.70301","type":"journal-article","created":{"date-parts":[[2025,10,29]],"date-time":"2025-10-29T18:20:18Z","timestamp":1761762018000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Unmasking the Thermodynamic Void Volume in the Minor\u2010Disturbance Method: Clarifying Its Physical Meaning and Relation to the Geometrical Void"],"prefix":"10.1002","volume":"48","author":[{"given":"Hung\u2010Wei","family":"Tsui","sequence":"first","affiliation":[{"name":"Department of Chemical Engineering National Taiwan University  Taipei Taiwan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Feng\u2010Ji","family":"Dai","sequence":"additional","affiliation":[{"name":"Department of Chemical Engineering and Biotechnology National Taipei University of Technology  Taipei Taiwan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chun\u2010Cheng","family":"Yang","sequence":"additional","affiliation":[{"name":"Department of Chemical Engineering and Biotechnology National Taipei University of Technology  Taipei Taiwan"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,10,29]]},"reference":[{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chroma.2024.465383"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chroma.2013.12.078"},{"key":"e_1_2_9_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chroma.2021.462736"},{"key":"e_1_2_9_5_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chroma.2023.464140"},{"key":"e_1_2_9_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/jssc.202000905"},{"key":"e_1_2_9_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0021-9673(01)96399-X"},{"key":"e_1_2_9_8_1","doi-asserted-by":"publisher","DOI":"10.1016\/0021\u20109673(94)80116\u20109"},{"key":"e_1_2_9_9_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0021\u20109673(00)81964\u20100"},{"key":"e_1_2_9_10_1","doi-asserted-by":"publisher","DOI":"10.1081\/SPM\u2010200042081"},{"key":"e_1_2_9_11_1","doi-asserted-by":"publisher","DOI":"10.1002\/aic.690441206"},{"key":"e_1_2_9_12_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0021\u20109673(00)88734\u20108"},{"key":"e_1_2_9_13_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chroma.2006.05.022"},{"key":"e_1_2_9_14_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0021-9673(99)00920-6"},{"key":"e_1_2_9_15_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0021-9673(03)00213-9"},{"key":"e_1_2_9_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/jssc.200800425"},{"key":"e_1_2_9_17_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chroma.2008.12.021"},{"key":"e_1_2_9_18_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chroma.2013.03.023"},{"key":"e_1_2_9_19_1","doi-asserted-by":"publisher","DOI":"10.1093\/chromsci\/33.6.321"},{"key":"e_1_2_9_20_1","doi-asserted-by":"publisher","DOI":"10.1093\/chromsci\/31.8.317"},{"key":"e_1_2_9_21_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0021\u20109673(00)01239\u20105"},{"key":"e_1_2_9_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/ac9005759"},{"key":"e_1_2_9_23_1","doi-asserted-by":"publisher","DOI":"10.1007\/s10450\u2010010\u20109236\u2010z"},{"key":"e_1_2_9_24_1","doi-asserted-by":"publisher","DOI":"10.1365\/s10337\u2010010\u20101522\u20100"},{"key":"e_1_2_9_25_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chroma.2013.11.019"},{"key":"e_1_2_9_26_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0021\u20109673(02)00730\u20106"},{"key":"e_1_2_9_27_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chroma.2007.10.032"},{"key":"e_1_2_9_28_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chroma.2005.08.029"},{"key":"e_1_2_9_29_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chroma.2024.465627"},{"key":"e_1_2_9_30_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0021\u20109673(01)83779\u20101"},{"key":"e_1_2_9_31_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chroma.2025.465952"},{"key":"e_1_2_9_32_1","doi-asserted-by":"publisher","DOI":"10.1016\/0021\u20109797(78)90196\u20100"},{"key":"e_1_2_9_33_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chroma.2025.465660"},{"key":"e_1_2_9_34_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0021\u20109673(00)01076\u20101"},{"key":"e_1_2_9_35_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chroma.2007.04.024"},{"key":"e_1_2_9_36_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chroma.2007.05.102"},{"key":"e_1_2_9_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.7b04746"},{"key":"e_1_2_9_38_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chroma.2021.461958"},{"key":"e_1_2_9_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcb.2c06871"},{"key":"e_1_2_9_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/ac049789c"},{"key":"e_1_2_9_41_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chroma.2007.11.074"}],"container-title":["Journal 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