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Understanding the azeotropic diethyl carbonate–water mixture by structural and energetic characterization of DEC(H2O) n heteroclusters

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Abstract

Diethyl carbonate (DEC) is an oxygenated fuel additive. During its synthesis through a promising green process, a DEC-water azeotrope is formed, which decreases DEC production efficiency in the gas phase. Molecular information about this system is scarce but could be of benefit in understanding (and potentially improving) the synthetic process. Therefore, we report a detailed computational study of the conformers of DEC, and their microsolvation with up to four water molecules, with the goal of understanding the observed 1:3 DEC:H2O molar ratio. The most stable DEC conformers (with mutual energy differences < 1.5 kcal mol−1) contribute to the energetic and structural properties of the complexes. An exhaustive stochastic exploration of each potential energy surface of DEC-(H2O) n , (where n = 1, 2, 3, 4) heteroclusters discovered 3, 8, 7, and 4 heterodimers, heterotrimers, heterotetramers, and heteropentamers, respectively, at the MP2/6-311++G(d,p) level of theory. DEC conformers and energies of the most stable structures at each heterocluster size were refined using CCSD(T)/6-311++G(d,p). Energy decomposition, electron density topology, and cooperative effects analyses were carried out to determine the relationship between the geometrical features of the heteroclusters and the non-covalent interaction types responsible for their stabilization. Our findings show that electrostatic and exchange energies are responsible for heterocluster stabilization, and also suggest a mutual weakening among hydrogen bonds when more than three water molecules are present. All described results are complementary and suggest a structural and energetic explanation at the molecular level for the experimental molar ratio of 1:3 (DEC:H2O) for the DEC-water azeotrope.

Molecular understanding of the DEC-Water system: energy and structural data

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Acknowledgments

The authors would like to thank the Universidad de Antioquia (Sustainability Strategy 2013-2014) and the Pontifica Universidad Javeriana for financial support of this work. J.D.R. thanks “Colciencias” and the Universidad de Antioquia for his PhD scholarship. Additionally, great gratitude is due to Professor Albeiro Restrepo for permission to use the ASCEC program.

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Authors and Affiliations

  1. Environmental Catalysis Research Group, Chemical Engineering Department, Engineering Faculty, Universidad de Antioquia, Calle 70 No. 52-21, Medellin, Colombia

    Juan D. Ripoll & Aída L. Villa

  2. Grupo de Investigación Fitoquímica Universidad Javeriana (GIFUJ), Departamento de Química, Facultad de Ciencias, Pontificia Universidad Javeriana, Carrera 7 No. 40-62, Bogotá, D. C., Colombia

    Sol M. Mejía

  3. Deconstruction Division, Joint BioEnergy Institute, Emeryville, CA, USA

    Matthew J. L. Mills

  4. Biomass Science and Conversion Technology Department, Sandia National Laboratories, Livermore, CA, USA

    Matthew J. L. Mills

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  1. Juan D. Ripoll
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Correspondence to Sol M. Mejía.

Electronic supplementary material

Bidimensional relaxed potential energy surface scan to locate the minimum energy conformation of DEC molecule, comparison of vibrational wavenumbers of the DEC isolated molecule (experimental-computational data), performance of ASCEC algorithm to obtain candidate structures of DEC-(H2O) n , n = 1, 2, 3, 4, heteroclusters, depictions of critical points of electron density obtained by both AIM and NCI methodologies of the most stable heteroclusters.

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Ripoll, J.D., Mejía, S.M., Mills, M.J.L. et al. Understanding the azeotropic diethyl carbonate–water mixture by structural and energetic characterization of DEC(H2O) n heteroclusters. J Mol Model 21, 93 (2015). https://doi.org/10.1007/s00894-015-2593-5

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