https://chemical.eng.usm.my/bassim/PDF/adsorption%20isotherm.pdf

Insights into the modeling of adsorption isotherm systems

Metal–Organic Frameworks for Separations

Kenji Sumida, David L. Rogow, Jarad A. Mason, Thomas M. McDonald, Eric D. Bloch, Zoey R. Herm, Tae-Hyun Bae, Jeffrey R. Long

Carbon Dioxide Capture in Metal–Organic Frameworks

New materials capable of storing hydrogen at high gravimetric and volumetric densities are required if hydrogen is to be widely employed as a clean alternative to hydrocarbon fuels in cars and other mobile applications. With exceptionally high surface areas and chemically-tunable structures, microporous metal–organic frameworks have recently emerged as some of the most promising candidate materials. In this critical review we provide an overview of the current status of hydrogen storage within such compounds. Particular emphasis is given to the relationships between structural features and the enthalpy of hydrogen adsorption, spectroscopic methods for probing framework–H2 interactions, and strategies for improving storage capacity (188 references).

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Hydrogen storage in metal–organic frameworks

Hydrogen Storage in Metal–Organic Frameworks

A simple technique is described for calculating the adsorption equilibria for components in a gaseous mixture, using only data for the pure-component adsorption equilibria at the same temperature and on the same adsorbent. The proposed technique is based on the concept of an ideal adsorbed solution and, using classical surface thermodynamics, an expression analogous to Raoult's law is obtained. The essential idea of the calculation lies in the recognition that in an ideal solution the partial pressure of an adsorbed component is given by the product of its mole fraction in the adsorbed phase and the pressure which it would exert as a pure adsorbed component at the same temperature and spreading pressure as those of the mixture. Predicted isotherms give excellent agreement with experimental data for methane-ethane and ethylene-carbon dioxide on activated carbon and for carbon monoxide-oxygen and propane-propylene on silica gel. The simplicity of the calculation, which requires no data for the mixture, makes it especially useful for engineering applications.

Thermodynamics of mixed‐gas adsorption

The storage of gases in porous adsorbents, such as activated carbon and carbon nanotubes, is examined here thermodynamically from a systems viewpoint, considering the entire adsorption-desorption cycle. The results provide concrete objective criteria to guide the search for the "Holy Grail" adsorbent, for which the adsorptive delivery is maximized. It is shown that, for ambient temperature storage of hydrogen and delivery between 30 and 1.5 bar pressure, for the optimum adsorbent the adsorption enthalpy change is 15.1 kJ/mol. For carbons, for which the average enthalpy change is typically 5.8 kJ/mol, an optimum operating temperature of about 115 K is predicted. For methane, an optimum enthalpy change of 18.8 kJ/mol is found, with the optimum temperature for carbons being 254 K. It is also demonstrated that for maximum delivery of the gas the optimum adsorbent must be homogeneous, and that introduction of heterogeneity, such as by ball milling, irradiation, and other means, can only provide small increases in physisorption-related delivery for hydrogen. For methane, heterogeneity is always detrimental, at any value of average adsorption enthalpy change. These results are confirmed with the help of experimental data from the literature, as well as extensive Monte Carlo simulations conducted here using slit pore models of activated carbons as well as atomistic models of carbon nanotubes. The simulations also demonstrate that carbon nanotubes offer little or no advantage over activated carbons in terms of enhanced delivery, when used as storage media for either hydrogen or methane.

/pdf/optimum-conditions-for-adsorptive-storage-26opq4h9wj.pdf

Optimum conditions for adsorptive storage.

Isosteric heats of adsorption and adsorption isotherms have been measured simultaneously in a calorimeter for a series of gases of increasing size and magnitude of quadrupole moment (Ar, O2, N2, CH4, C2H6, SF6, CO2) on adsorbents of varying pore structure and ion type (NaX, H-ZSM-5, Na-ZSM-5). Adsorption isotherms have been checked for reversibility by desorption experiments. The average experimental error in loading is ±0.6%; the average uncertainty in the isosteric heat of adsorption is ±0.5 kJ/mol. Heats of adsorption of nonpolar molecules (CH4, C2H6, SF6) increase in the order NaX, silicalite, H-ZSM-5, Na-ZSM-5 at low coverage. Heats of adsorption of nonpolar molecules are almost identical on silicalite, H-ZSM-5, and Na-ZSM-5 at high coverage. Heats of adsorption of the quadrupolar molecule CO2 increase in the order silicalite, H-ZSM-5, Na-ZSM-5, NaX. The electric field adjacent to Na+ sites is 6.2 V/nm, on the basis of the difference between the heat of adsorption of CO2 in Na-ZSM-5 and the heat of a...

Calorimetric Heats of Adsorption and Adsorption Isotherms. 2. O2, N2, Ar, CO2, CH4, C2H6, and SF6 on NaX, H-ZSM-5, and Na-ZSM-5 Zeolites

A Tian−Calvet type calorimeter is applied to the simultaneous determination of adsorption isotherms and heats of adsorption This is the first of a series of studies of the effect of adsorbate size and polarity on the energetics of adsorption in zeolites The adsorbate gases used in this study are quadrupolar (N2 and CO2) and nonpolar (Ar, O2, CH4, C2H6, and SF6) The heats of adsorption of both polar and nonpolar gases are either constant or increase with coverage, so silicalite may be classified as a relatively homogeneous adsorbent compared to X type zeolite Reversibility was established by comparing adsorption and desorption isotherms Reproducibility was studied by comparing runs for different samples of the same adsorbent The average experimental error in loading is ±06% The error in the isosteric heat of adsorption is ±2% for heats larger than 20 kJ/mol and ±5% for heats smaller than 20 kJ/mol

Alan L. Myers

Papers

Thermodynamics of mixed‐gas adsorption

Optimum conditions for adsorptive storage.

Calorimetric Heats of Adsorption and Adsorption Isotherms. 2. O2, N2, Ar, CO2, CH4, C2H6, and SF6 on NaX, H-ZSM-5, and Na-ZSM-5 Zeolites

Calorimetric Heats of Adsorption and Adsorption Isotherms. 1. O2, N2, Ar, CO2, CH4, C2H6, and SF6 on Silicalite

Storage of natural gas by adsorption on activated carbon