Quasi-chemical approximation for polyatomic mixtures

Literature Information

Publication Date 2016-08-02
DOI 10.1039/C6CP03548E
Impact Factor 3.676
Authors

M. V. Dávila, P. M. Pasinetti, A. J. Ramirez-Pastor


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Abstract

The statistical thermodynamics of binary mixtures of polyatomic species was developed based on a generalization in the spirit of the lattice-gas model and the quasi-chemical approximation (QCA). The new theoretical framework is obtained by combining: (i) the exact analytical expression for the partition function of non-interacting mixtures of linear k-mers and l-mers (species occupying k sites and l sites, respectively) adsorbed in one dimension, and its extension to higher dimensions; and (ii) a generalization of the classical QCA for multicomponent adsorbates and multisite-occupancy adsorption. This process is analyzed using the partial adsorption isotherms corresponding to both species of the mixture. Comparisons with analytical data from Bragg–Williams approximation (BWA) and Monte Carlo simulations are performed in order to test the validity of the theoretical model. Even though a good fitting is obtained from BWA, it is found that QCA provides a more accurate description of the phenomenon of adsorption of interacting polyatomic mixtures.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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