On the resolution of constant isosteric heat of propylene adsorption on graphite in the sub-monolayer coverage region
[Display omitted] •Resolution of isosteric heat versus loading for propylene adsorption on graphite.•Importance of the solid-fluid (SF) interaction with orientation of propylene.•Extensive simulation study of propylene adsorption with various potential models.•The dominance of adsorbate interactions...
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| Published in | Colloids and surfaces. A, Physicochemical and engineering aspects Vol. 512; pp. 101 - 110 |
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| Main Authors | , , , , , |
| Format | Journal Article |
| Language | English |
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Elsevier B.V
01.01.2017
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| Abstract | [Display omitted]
•Resolution of isosteric heat versus loading for propylene adsorption on graphite.•Importance of the solid-fluid (SF) interaction with orientation of propylene.•Extensive simulation study of propylene adsorption with various potential models.•The dominance of adsorbate interactions over the SF interactions.
An early experimental study by Bezus, Dreving and Kiselev [1] on the adsorption of propylene on Spheron-6 carbon black (graphitized at ∼3000C) reported a plot of constant isosteric heat versus loading in the sub-monolayer region. This contrasts with their report of a linear increase in isosteric heat for propane, a similar molecule to propylene. In this paper, we report extensive Grand Canonical Monte Carlo (GCMC) simulations and a high-resolution experimental study of propylene adsorption on Carbopack F, a highly graphitized thermal carbon black, over the same temperature range studied by Bezus et al. From this combined simulation and experimental study we conclude that propylene also shows a linear increase in the isosteric heat versus loading in the sub-monolayer region, indicating that the linear increase in the fluid-fluid interaction in this region more than compensates for the decrease in the solid-fluid interaction that results from the change in orientation of the adsorbate molecules. Our study contradicts the propylene results of Bezus et al., and careful inspection of their isotherm in the sub-monolayer region shows that it does not follow Henry’s law. This calls into question their argument that π-π interactions between propylene molecules are an explanation for the constant heat. |
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| AbstractList | [Display omitted]
•Resolution of isosteric heat versus loading for propylene adsorption on graphite.•Importance of the solid-fluid (SF) interaction with orientation of propylene.•Extensive simulation study of propylene adsorption with various potential models.•The dominance of adsorbate interactions over the SF interactions.
An early experimental study by Bezus, Dreving and Kiselev [1] on the adsorption of propylene on Spheron-6 carbon black (graphitized at ∼3000C) reported a plot of constant isosteric heat versus loading in the sub-monolayer region. This contrasts with their report of a linear increase in isosteric heat for propane, a similar molecule to propylene. In this paper, we report extensive Grand Canonical Monte Carlo (GCMC) simulations and a high-resolution experimental study of propylene adsorption on Carbopack F, a highly graphitized thermal carbon black, over the same temperature range studied by Bezus et al. From this combined simulation and experimental study we conclude that propylene also shows a linear increase in the isosteric heat versus loading in the sub-monolayer region, indicating that the linear increase in the fluid-fluid interaction in this region more than compensates for the decrease in the solid-fluid interaction that results from the change in orientation of the adsorbate molecules. Our study contradicts the propylene results of Bezus et al., and careful inspection of their isotherm in the sub-monolayer region shows that it does not follow Henry’s law. This calls into question their argument that π-π interactions between propylene molecules are an explanation for the constant heat. |
| Author | Nakai, Kazuyuki Do, D.D. Abdul Razak, Mus’ab Horikawa, Toshihide Prasetyo, Luisa Nicholson, D. |
| Author_xml | – sequence: 1 givenname: Luisa surname: Prasetyo fullname: Prasetyo, Luisa organization: School of Chemical Engineering, University of Queensland, St. Lucia, Qld 4072, Australia – sequence: 2 givenname: Mus’ab surname: Abdul Razak fullname: Abdul Razak, Mus’ab organization: Department of Chemical and Environmental Engineering, Universiti Putra Malaysia, 43400 Serdang, Malaysia – sequence: 3 givenname: D.D. surname: Do fullname: Do, D.D. email: d.d.do@uq.edu.au organization: School of Chemical Engineering, University of Queensland, St. Lucia, Qld 4072, Australia – sequence: 4 givenname: Toshihide surname: Horikawa fullname: Horikawa, Toshihide organization: Graduate School of Science and Technology, The University of Tokushima, 2-1 Minamijosanjima, Tokushima 770-8506, Japan – sequence: 5 givenname: Kazuyuki surname: Nakai fullname: Nakai, Kazuyuki organization: MicrotracBEL. Corp., 8-2-52 Nanko-Higashi, Suminoe-ku, Osaka 559-0031, Japan – sequence: 6 givenname: D. surname: Nicholson fullname: Nicholson, D. organization: School of Chemical Engineering, University of Queensland, St. Lucia, Qld 4072, Australia |
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| Cites_doi | 10.1071/CH15134 10.1021/jp012542o 10.1260/0263617054770020 10.1080/08927022.2011.586349 10.1039/B714478D 10.1016/j.colsurfa.2005.11.094 10.1063/1.1343487 10.1016/j.jcis.2016.06.033 10.1063/1.1537245 10.1021/la0486483 10.1016/j.jcis.2008.05.028 10.1021/j100822a004 10.1021/j100308a038 10.1080/00268979909482913 10.1016/0039-6028(73)90264-1 10.1021/jp052448y 10.1080/08927020600622030 10.1021/la052545i 10.1016/j.carbon.2015.08.034 10.1016/j.jcis.2014.10.024 10.1080/08927020601001911 10.1021/ja00334a030 10.1021/jp001044x 10.1021/jp205498p 10.1021/jp057230q 10.1021/ja982453y 10.1021/jp003882x 10.1016/j.ces.2004.12.009 |
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