Study of molecular shape and non-ideality effects on mixture adsorption isotherms of small molecules in carbon nanotubes: A grand canonical Monte Carlo simulation study

• Published in: Chemical engineering science Vol. 57; no. 13; pp. 2439 - 2448
• Main Authors: Heyden, Andreas, Düren, Tina, J. Keil, Frerich
• Format: Journal Article
• Language: English
• Published: Oxford Elsevier Ltd 01.07.2002; Elsevier
• Subjects: Adsorption; Carbon nanotubes; Chemistry; Exact sciences and technology; General and physical chemistry; Monte Carlo; Porous media; Separations; Simulation; Solid-gas interface; Surface physical chemistry; Porous media; Carbon nanotubes; Adsorption; Monte Carlo; Simulation; Separations; Fugacity; Methane; Monte Carlo method; Gas mixture; Hydrocarbon; Organic adsorbate; Carbon tetrafluoride; Adsorption isotherm; Inorganic adsorbent; Fluorocarbon; Ethane; Gas solid adsorption; Grand canonical ensemble; Binary mixture; Gas solid interface; Numerical simulation; Propane
• ISSN: 0009-2509; 1873-4405
• DOI: 10.1016/S0009-2509(02)00131-8

The sorption isotherms for binary mixtures of methane, ethane, propane and tetrafluoromethane have been determined in carbon nanotubes using configurational bias Monte Carlo simulation techniques. At high loadings, a curious maximum for equimolar gas-phase mixtures occurs with increasing pressure in the absolute adsorption isotherm of one or both adsorbing species. It was detected that there exist two fundamentally different reasons for this maximum. First, due to a higher packing efficiency, one component is able to displace the other component at high loadings. Here, it must be stressed that the displaced component is not necessarily the larger molecule. Second, non-ideality effects of the bulk gas phase can be made responsible for this maximum. The acceptance probability of a molecule insertion in a grand canonical Monte Carlo step is proportional to the component fugacity. If, owing to non-ideality effects of the gas phase, the fugacity of one component does not increase as steeply with pressure as the other component, a maximum can occur in the absolute adsorption isotherm of this component. These findings were demonstrated for various binary mixtures of CH 4, CF 4, C 2H 6 and C 3H 8.