Anomalous Thermodynamics of Nonideal Gas Physisorption on Nanostructured Carbons

Citation

Murialdo, Maxwell Robert (2017) Anomalous Thermodynamics of Nonideal Gas Physisorption on Nanostructured Carbons. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/Z9GH9FXM. https://resolver.caltech.edu/CaltechTHESIS:08292016-233907648

Abstract

Mesoporous and microporous adsorbents play critical roles in gas storage and separation applications. This thesis describes previously unexplored anomalous thermodynamics in the field of gas physisorption and their impact on energy relevant gases including methane, ethane, krypton and carbon dioxide. Physisorption occurs when an adsorbent induces gas molecules to form a locally densified layer at its surface due to physical interactions. This increases gas storage capacity over pure compression and its efficacy is dependent on the surface area of the adsorbent and the isosteric heat of adsorption. The isosteric heat of adsorption is the molar change in the enthalpy of the adsorptive species upon adsorption and serves as a measure of adsorbent-adsorbate binding strength.

Unlike conventional adsorbate-adsorbent systems, which have isosteric heats of adsorption that decrease with surface loading, zeolite-templated carbon is shown to have isosteric heats of methane, ethane and krypton adsorption that increase with surface loading. This is a largely beneficial effect that can enhance gas storage and separation. The unique nanostructure and uniform pore periodicity of the zeolite-templated carbon promote lateral interactions among the adsorbed molecules that cause the isosteric heats of adsorption to increase with loading. These results have been tested and corroborated by developing robust fitting techniques and thermodynamics analyses. The anomalous thermodynamics are shown to result from cooperative adsorbate-adsorbate interactions among the nonideal species and are modeled with an Ising-type model.

As a second theme of this thesis, the study of nonideal gas adsorption has enabled the development of a Generalized Law of Corresponding States for Physisorption. A predictive understanding of high-pressure physisorption on a variety of adsorbents would facilitate the further development of tailored adsorbents and adsorption analysis. Prior attempts at developing a predictive understanding, however, have been hindered by nonideal gas effects.

By approaching physisorption from both empirical and fundamental perspectives, a Generalized Law of Corresponding States for Physisorption was established that accounts for a number of nonideal effects. This new Law of Corresponding States allows one to predict adsorption isotherms for a variety of classical gases from data measured with a single gas. In brief: "At corresponding conditions on the same adsorbent, classical gases physisorb to the same fractional occupancy."

Corresponding conditions are met when the reduced variables of each nonideal gas are equivalent, and fractional occupancy gives the fraction of occupied adsorption sites. This Law of Corresponding States for Physisorption is determined using monolayer, BET and Dubinin-Polanyi adsorption theories along with measured adsorption isotherms across a number of conditions and adsorbents. Furthermore, the anomalous cooperative adsorbate-adsorbate interactions discussed in this thesis are shown to be consistent with the Generalized Law of Corresponding States for Physisorption.

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