Issue 13, 2015

Structural properties of methanol–water binary mixtures within the quantum cluster equilibrium model

Abstract

Density functional theory (B3LYP-D3, M06-2X) has been used to calculate the structures, interaction energies and vibrational frequencies of a set of 93 methanol–water clusters of different type (cubic, ring, spiro, lasso, bicyclic), size and composition. These interaction energies have been used within the framework of the Quantum Cluster Equilibrium Theory (QCE) to calculate cluster populations as well as thermodynamic properties of binary methanol–water mixtures spanning the whole range from pure water to pure methanol. The necessary parameters amf and bxv of the QCE model were obtained by fitting to experimental isobars of MeOH–H2O mixtures with different MeOH content. The cubic and spiro motifs dominate the distribution of methanol–water clusters in the mixtures with a maximum of mixed clusters at x(MeOH) = 0.365. Reasonable agreement with experimental data as well as earlier molecular dynamics simulations was found for excess enthalpies HE, entropies SE as well as Gibbs free energies of mixing GE. In contrast, heat capacities Cp and CEp showed only poor agreement with experimental data.

Graphical abstract: Structural properties of methanol–water binary mixtures within the quantum cluster equilibrium model

Supplementary files

Article information

Article type
Paper
Submitted
12 Dez 2014
Accepted
27 Jan 2015
First published
30 Jan 2015
This article is Open Access
Creative Commons BY-NC license

Phys. Chem. Chem. Phys., 2015,17, 8467-8479

Structural properties of methanol–water binary mixtures within the quantum cluster equilibrium model

G. Matisz, A.-M. Kelterer, W. M. F. Fabian and S. Kunsági-Máté, Phys. Chem. Chem. Phys., 2015, 17, 8467 DOI: 10.1039/C4CP05836D

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements