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Title: Grand Canonical Monte Carlo studies of CO2 and CH4 adsorption in p-tert-butylcalix[4]arene

Abstract

Grand Canonical Monte Carlo (GCMC) simulations were performed for single component isotherms of CO2 and CH4 in the p-tert-butylcalix[4]arene (TBC4) structure. Comparison with literature data for adsorption used the Peng-Robinson equation of state to map simulated fugacities to experimentally determined pressures. CO2 binding in the high-pressure structure of TBC4 (TBC4-H) occurs in two distinct waves. The cage sites in TBC4 completely fill, followed by the filling of interstitial sites, resulting in the sum of two Langmuir isotherms being the best way to describe the total absorption isotherms. Our simulation results capture the essential experimental feature that the cage sites are the major contributor to the absorption isotherms, and the contribution of interstitial sites are significantly less. We found that CH4 does not exhibit the same two site binding characteristic and has a smaller temperature dependence, which arises from a smaller negative entropy change upon absorption compared with CO2. Our calculations give higher binding than observed experimentally for the cage site but lower binding for the interstitial site. We also demonstrate that by rescaling the interaction between CO2 and the lattice, the results can reproduce the experimental data well. This work was performed at the Pacific Northwest National Laboratory (PNNL) andmore » was supported by the Division of Chemical Sciences, Office of Basic Energy Sciences, U.S. Department of Energy (DOE). PNNL is operated by Battelle for the DOE.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
982290
Report Number(s):
PNNL-SA-67808
Journal ID: ISSN 1520-6106; ISSN 1520-5207; KC0301020; TRN: US201013%%970
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry B, 114(17):5764-5768
Additional Journal Information:
Journal Volume: 114; Journal Issue: 17; Journal ID: ISSN 1520-6106
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; ADSORPTION; BASIC; CAPTURE; DATA; ENERGY; ENTROPY; EQUATIONS; EXHIBITS; EXPERIMENTAL DATA; INTERACTIONS; INTERSTITIALS; ISOTHERMS; MAPS; PRESSURE RANGE MEGA PA 10-100; SIMULATION; TEMPERATURE DEPENDENCE; WORK

Citation Formats

Daschbach, John L, Sun, Xiuquan, Thallapally, Praveen K, McGrail, B Peter, and Dang, Liem X. Grand Canonical Monte Carlo studies of CO2 and CH4 adsorption in p-tert-butylcalix[4]arene. United States: N. p., 2010. Web. doi:10.1021/jp9101465.
Daschbach, John L, Sun, Xiuquan, Thallapally, Praveen K, McGrail, B Peter, & Dang, Liem X. Grand Canonical Monte Carlo studies of CO2 and CH4 adsorption in p-tert-butylcalix[4]arene. United States. https://doi.org/10.1021/jp9101465
Daschbach, John L, Sun, Xiuquan, Thallapally, Praveen K, McGrail, B Peter, and Dang, Liem X. 2010. "Grand Canonical Monte Carlo studies of CO2 and CH4 adsorption in p-tert-butylcalix[4]arene". United States. https://doi.org/10.1021/jp9101465.
@article{osti_982290,
title = {Grand Canonical Monte Carlo studies of CO2 and CH4 adsorption in p-tert-butylcalix[4]arene},
author = {Daschbach, John L and Sun, Xiuquan and Thallapally, Praveen K and McGrail, B Peter and Dang, Liem X},
abstractNote = {Grand Canonical Monte Carlo (GCMC) simulations were performed for single component isotherms of CO2 and CH4 in the p-tert-butylcalix[4]arene (TBC4) structure. Comparison with literature data for adsorption used the Peng-Robinson equation of state to map simulated fugacities to experimentally determined pressures. CO2 binding in the high-pressure structure of TBC4 (TBC4-H) occurs in two distinct waves. The cage sites in TBC4 completely fill, followed by the filling of interstitial sites, resulting in the sum of two Langmuir isotherms being the best way to describe the total absorption isotherms. Our simulation results capture the essential experimental feature that the cage sites are the major contributor to the absorption isotherms, and the contribution of interstitial sites are significantly less. We found that CH4 does not exhibit the same two site binding characteristic and has a smaller temperature dependence, which arises from a smaller negative entropy change upon absorption compared with CO2. Our calculations give higher binding than observed experimentally for the cage site but lower binding for the interstitial site. We also demonstrate that by rescaling the interaction between CO2 and the lattice, the results can reproduce the experimental data well. This work was performed at the Pacific Northwest National Laboratory (PNNL) and was supported by the Division of Chemical Sciences, Office of Basic Energy Sciences, U.S. Department of Energy (DOE). PNNL is operated by Battelle for the DOE.},
doi = {10.1021/jp9101465},
url = {https://www.osti.gov/biblio/982290}, journal = {Journal of Physical Chemistry B, 114(17):5764-5768},
issn = {1520-6106},
number = 17,
volume = 114,
place = {United States},
year = {Thu May 06 00:00:00 EDT 2010},
month = {Thu May 06 00:00:00 EDT 2010}
}