Supercritical Fluid Adsorption to Weakly Attractive Solids: Universal Scaling Laws

Gruszkiewicz, Miroslaw S.; Rother, Gernot; Vlcek, Lukas; Distefano, Victoria H.

doi:10.1021/acs.jpcc.8b04390

Title: Supercritical Fluid Adsorption to Weakly Attractive Solids: Universal Scaling Laws

Abstract

In this study, adsorption of light hydrocarbons (C1–C3) confined in the pores of silica aerogel (nominal density 0.2 g/cm³) was studied experimentally and by computer simulation. Five isotherms of ethane (25.0, 32.0, 32.3, 33.0, and 35.0 °C) were obtained over a temperature range including the critical temperature of the bulk fluid (T_c = 32.18 °C) to ~220 bar by the vibrating tube densimetry (VTD) method, which yields unique information impossible to obtain by excess sorption measurements. Two isotherms (35 and 50 °C) of methane adsorption in SiO₂ aerogel were measured far above its critical temperature, T_c = -82.59 °C, at 0–150 bar using a gravimetric method. The experimental pore fluid properties of methane, ethane, propane, and CO₂ (obtained earlier by VTD for the same SiO₂ aerogel sample) show behavior conforming to the principle of corresponding states over the entire covered reduced temperature ranges from T_r = 0.976 to T_r = 1.696. The magnitudes of the excess adsorption maxima and the reduced fluid densities where the maxima occur for C1–C3 hydrocarbons and CO₂ are similar functions of the reduced temperature. This behavior indicates that, at least under the conditions covered in this work, the differences in molecular size and shape havemore »« less

Authors:

^[1];

^[2]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division ; Univ. of Tennessee, Knoxville, TN (United States). Bredesen Center

Publication Date:: 2018-06-18

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

OSTI Identifier:: 1474592

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 122; Journal Issue: 27; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Gruszkiewicz, Miroslaw S., Rother, Gernot, Vlcek, Lukas, and Distefano, Victoria H.. Supercritical Fluid Adsorption to Weakly Attractive Solids: Universal Scaling Laws.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpcc.8b04390.

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                    Gruszkiewicz, Miroslaw S., Rother, Gernot, Vlcek, Lukas, & Distefano, Victoria H.. Supercritical Fluid Adsorption to Weakly Attractive Solids: Universal Scaling Laws.  United States.  https://doi.org/10.1021/acs.jpcc.8b04390

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                    Gruszkiewicz, Miroslaw S., Rother, Gernot, Vlcek, Lukas, and Distefano, Victoria H.. Mon .  
"Supercritical Fluid Adsorption to Weakly Attractive Solids: Universal Scaling Laws".  United States.  https://doi.org/10.1021/acs.jpcc.8b04390.  https://www.osti.gov/servlets/purl/1474592.

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@article{osti_1474592,

  title        = {Supercritical Fluid Adsorption to Weakly Attractive Solids: Universal Scaling Laws},

  author       = {Gruszkiewicz, Miroslaw S. and Rother, Gernot and Vlcek, Lukas and Distefano, Victoria H.},

  abstractNote = {In this study, adsorption of light hydrocarbons (C1–C3) confined in the pores of silica aerogel (nominal density 0.2 g/cm3) was studied experimentally and by computer simulation. Five isotherms of ethane (25.0, 32.0, 32.3, 33.0, and 35.0 °C) were obtained over a temperature range including the critical temperature of the bulk fluid (Tc = 32.18 °C) to ~220 bar by the vibrating tube densimetry (VTD) method, which yields unique information impossible to obtain by excess sorption measurements. Two isotherms (35 and 50 °C) of methane adsorption in SiO2 aerogel were measured far above its critical temperature, Tc = -82.59 °C, at 0–150 bar using a gravimetric method. The experimental pore fluid properties of methane, ethane, propane, and CO2 (obtained earlier by VTD for the same SiO2 aerogel sample) show behavior conforming to the principle of corresponding states over the entire covered reduced temperature ranges from Tr = 0.976 to Tr = 1.696. The magnitudes of the excess adsorption maxima and the reduced fluid densities where the maxima occur for C1–C3 hydrocarbons and CO2 are similar functions of the reduced temperature. This behavior indicates that, at least under the conditions covered in this work, the differences in molecular size and shape have only minor impacts on the solid–fluid interactions underlying the adsorption behavior. Lastly, these findings are supported by large-scale GCMC simulations of a lattice gas confined in the pores of a computer representation of the SiO2 aerogel framework, yielding excess adsorption isotherms in good agreement with experimental measurements, as well as the underlying microstructures of the adsorbed fluids.},

  doi          = {10.1021/acs.jpcc.8b04390},

  journal      = {Journal of Physical Chemistry. C},

  number       = 27,

  volume       = 122,

  place        = {United States},

  year         = {2018},

  month        = {6}

}

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Figures / Tables:

Figure 1: Isotherms of density of pore ethane measured using the vibrating tube method and those of bulk ethane calculated from the equation of state. The density difference (along the vertical axis) between these isotherms, caused by a pressure shift (along the horizontal axis), represents the excess adsorption, shown belowmore »

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