Abstract
The development of a method for the prediction of the amounts adsorbed on a surface is of interest due to its application in various areas such as the recovery of gases and the transport thereof in porous beds. Various scientific contributions have been carried out on the adsorption under equilibrium conditions of gas mixtures. In the present work, a theoretical cluster approximation (CA) is analyzed against the experimental and simulation behavior of the adsorbed phase of a binary mixture of gases. The substrate is modeled as an heterogeneous surface and a combination of repulsive lateral interactions between adsorbed particles of the same species is considered. Under these conditions, a rich variety of structural orderings were observed in the adlayer. CA results were compared with Monte Carlo simulations, showing a very well agreement over the range of parameters investigated. Finally, the theoretical formalism was used to model experimental data of CO–O2 mixtures on a template-synthesized 5A zeolite. The study presented here has shown that CA model is a good one considering the complexity of the physical situation, which is intended to be described, and could be more useful in interpreting experimental data of adsorption of interacting binary mixtures on heterogeneous surfaces.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Notes
In this paper, we focus on the case of repulsive lateral interactions among adsorbed particles (\(w_{xx}> 0\)) since, as we shall see, different structures appear in the adsorbed phase. In addition, since the critical interaction for the appearance of a \(c(2 \times 2)\) ordered phase in a standard lattice-gas model is given by \(w_c =1.763668 k_BT\) (Hill 1962), we will use \(w_{xx}=4 k_BT > w_c\) to ensure the formation of the ordered phases.
Similar results can be obtained from b-partial and total adsorption isotherms. The data are not shown here for brevity.
A intermediate degree of heterogeneity (surface with a fraction of impurities \(\rho\)) can be modeled by a cluster with \(f_1 = 1 -\rho\) and \(f_2 = \rho\).
References
Ayache, K., Jalili, S.E., Dunne, L.J., Manos, G., Du, Z.: Monte-carlo simulation and mean-field theory interpretation of adsorption preference reversal in isotherms of alkane binary mixtures in zeolites at elevated pressures. Chem. Phys. Lett. 362, 414 (2002). https://doi.org/10.1016/S0009-2614(02)01031-X
Belardinelli, R., Manzi, S., Ramirez-Pastor, A.J., Pereyra, V.D.: Study of the adsorption of interacting dimers on square lattices by using a cluster-exact approximation. Surf. Sci. 540, 207 (2003). https://doi.org/10.1016/s0039-6028(03)00743-x
Binder, K.: Monte Carlo Methods in Statistical Physics, vol. 7. Springer, Berlin (1979)
Binder, K., Heermann, D.W.: Monte Carlo Simulation in Statistical Physics: An Introduction. Springer, Berlin (1988)
Chen, J., Loo, L.S., Wang, K.: An ideal absorbed solution theory (iast) study of adsorption equilibria of binary mixtures of methane and ethane on a templated carbon. J. Chem. Eng. Data 56, 1209 (2011). https://doi.org/10.1021/je101099c
Danner, R.P., Wenzel, L.A.: Adsorption of carbon monoxide-nitrogen, carbon monoxide-oxygen, and oxygen-nitrogen mixtures on synthetic zeolites. AIChE J. 15, 515 (1969). https://doi.org/10.1002/aic.690150410
Dunne, L.J., Manos, G., Du, Z.: Exact statistical mechanical one-dimensional lattice model of alkane binary mixture adsorption in zeolites and comparision with monte-carlo simulations. Chem. Phys. Lett. 377, 551 (2003). https://doi.org/10.1016/s0009-2614(03)01175-8
Fefelov, V.F., Stishenko, P.V., Kutanov, V.M., Myshlyavtsev, A.V., Myshlyavtseva, M.D.: Monte Carlo study of adsorption of additive gas mixture. Adsorption 22, 673 (2016). https://doi.org/10.1007/s10450-015-9753-x
Fefelov, V.F., Myshlyavtsev, A.V., Myshlyavtseva, M.D.: Phase diversity in an adsorption model of an additive binary gas mixture for all sets of lateral interactions. Phys. Chem. Chem. Phys. 20, 10359 (2018). https://doi.org/10.1039/C7CP08426A
Fishlock, T.W., Pethica, J.B., Egdell, R.G.: Observation of a nanoscale chessboard superstructure in the Br-Cu(100) adsorbate system. Surf. Sci. 445, L47 (2000). https://doi.org/10.1016/S0039-6028(99)01103-6
García, G.D., Sanchez-Varretti, F.O., Bulnes, F., Ramirez-Pastor, A.J.: Monte Carlo study of binary mixtures adsorbed on square lattices. Surf. Sci. 606, 83 (2012). https://doi.org/10.1016/j.susc.2011.09.002
Hill, T.L.: An Introduction to Statistical Thermodynamics. Addison-Wesley, Reading (1962)
Lopinski, G.P., Wayner, D.D.M., Wolkow, R.A.: Self-directed growth of molecular nanostructures on silicon. Nature 406, 48 (2000). https://doi.org/10.1038/35017519
Metropolis, N., Rosenbluth, A.W., Rosenbluth, M.N., Teller, A.H., Teller, E.: Equation of state calculations by fast computing machines. J. Chem. Phys. 21, 1087 (1953). https://doi.org/10.1063/1.1699114
Myers, A.L., Prausnitz, J.M.: Thermodynamics of mixed-gas adsorption. AIChE J. 11, 121 (1965). https://doi.org/10.1002/aic.690110125
Nicholson, D., Parsonage, N.G.: Computer Simulation and the Statistical Mechanics of Adsorption. Academic Press, New York (1982)
Nitta, T., Kuro-Oka, M., Katayama, T.: An adsorption isotherm of multi-site occupancy model for heterogeneous surface. J. Chem. Eng. Jpn. 17, 45 (1984). https://doi.org/10.1252/jcej.17.45
Press, W.H.: Numerical Recipes in C: The Art of Scientific Computing. Cambridge University Press, New York (1992)
Ramirez-Pastor, A.J., Nazzarro, M.S., Riccardo, J.L., Zgrablich, G.: Dimer physisorption on heterogeneous substrates. Surf. Sci. 341, 249 (1995). https://doi.org/10.1016/0039-6028(95)00665-6
Razmus, D.M., Hall, C.K.: Prediction of gas adsorption in 5A zeolites using Monte Carlo simulation. AIChE J. 37, 769 (1991). https://doi.org/10.1002/aic.690370514
Romá, F., Ramirez-Pastor, A.J., Riccardo, J.L.: Critical behavior of repulsive linear k-mers on square lattices at half coverage: theory and Monte Carlo simulations. Phys. Rev. B 68, 205407 (2003). https://doi.org/10.1103/physrevb.68.205407
Rudzinski, W., Everett, D.H.: Adsorption of Gases on Heterogeneous Surfaces. Elsevier, Amsterdam (2012)
Sanchez-Varretti, F.O., García, G.D., Pasinetti, P.M., Ramirez-Pastor, A.J.: Adsorption of binary mixtures on two-dimensional surfaces: theory and Monte Carlo simulations. Adsorption 20, 855 (2014). https://doi.org/10.1007/s10450-014-9627-7
Sanchez-Varretti, F.O., Bulnes, F.M., Ramirez-Pastor, A.J.: A cluster-exact approximation study of the adsorption of binary mixtures on heterogeneous surfaces. Appl. Surf. Sci. 387, 268 (2016). https://doi.org/10.1016/j.apsusc.2016.06.112
Sanchez-Varretti, F.O., Pasinetti, P.M., Bulnes, F.M., Ramirez-Pastor, A.J.: Adsorption of laterally interacting gas mixtures on homogeneous surfaces. Adsorption 23, 651 (2017). https://doi.org/10.1007/s10450-017-9885-2
Sanchez-Varretti, F.O., Bulnes, F.M., Ramirez-Pastor, A.J.: Cluster-exact approximation applied to adsorption with non-additive lateral interactions. Physica A 518, 145 (2019). https://doi.org/10.1016/j.physa.2018.11.067
Sircar, S.: Role of adsorbent heterogeneity on mixed gas adsorption. Ind. Eng. Chem. Res. 30, 1032 (1991). https://doi.org/10.1021/ie00053a027
Sircar, S.: Influence of adsorbate size and adsorbent heterogeneity of IAST. AIChE J. 41, 1135 (1995). https://doi.org/10.1002/aic.690410509
Smit, B., Maesen, T.L.M.: Molecular simulations of zeolites: adsorption, diffusion, and shape selectivity. Chem. Rev. 108, 4125 (2008). https://doi.org/10.1021/cr8002642
Steele, W.A.: The supersite approach to adsorption on heterogeneous surfaces. Langmuir 15, 6083 (1999). https://doi.org/10.1021/la981483b
Tang, X., Ripepi, N., Stadie, N.P., Yu, L., Hall, M.R.: A dual-site langmuir equation for accurate estimation of high pressure deep shale gas resources. Fuel 185, 10 (2016). https://doi.org/10.1016/j.fuel.2016.07.088
Ungerer, P., Tavitian, B., Boutin, A., Montel, F.S.: Applications of Molecular Simulation in the Oil and Gas Industry: Monte Carlo Methods. Editions TECHNIP, Paris (2005)
Yang, R.T.: Gas Separation by Adsorption Processes. Imperial College Press, London (2008)
Acknowledgements
This work was supported in part by CONICET (Argentina) under Project PIP 112-201101-00615; Universidad Nacional de San Luis (Argentina) under Project 322000; Universidad Tecnológica Nacional, Facultad Regional San Rafael (Argentina) under Project PID UTN 3542 and the National Agency of Scientific and Technological Promotion (Argentina) under Project PICT-2013-1678.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Sanchez-Varretti, F.O., Bulnes, F.M. & Ramirez-Pastor, A.J. Adsorption of interacting binary mixtures on heterogeneous surfaces: theory, Monte Carlo simulations and experimental results. Adsorption 25, 1317–1328 (2019). https://doi.org/10.1007/s10450-019-00093-7
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10450-019-00093-7