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Thermodynamic Study of Heptane + Silicone Mixtures. Excess Volumes and Enthalpies at 298.15 K

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CNR-IPCF, Consiglio Nazionale delle Ricerche, Istituto per i Processi Chimico Fisici, UOS di Pisa, Area della Ricerca, via G. Moruzzi 1, 56124 Pisa, Italy
Cite this: J. Chem. Eng. Data 2011, 56, 12, 5019–5027
Publication Date (Web):November 9, 2011
https://doi.org/10.1021/je2007378
Copyright © 2011 American Chemical Society

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    Abstract

    Excess molar volumes VE and partial molar enthalpies and excess enthalpies HE of binary mixtures of heptane + linear (hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane) and cyclic (octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane) silicone oligomers have been determined at 298.15 K. Both excess properties have small values (|VE| < 0.13 cm3·mol–1, HE < 0.23 kJ·mol–1) for linear silicones, exhibiting a monotonic increase with an increasing number of dimethylsiloxane units. Higher VE and HE data are instead observed in the case of cyclic molecules, with a larger value exhibited by octamethylcyclotetrasiloxane. Partial molar volumes at infinite dilution of silicones in heptane are markedly larger than those of n-alkanes of the same size. Likewise, their enthalpies of solvation in heptane are less negative than those of hydrocarbons. Cyclic silicones display partial molar volumes lower than corresponding linear compounds, and their solvation enthalpies are slightly more negative. Both partial molar volumes and enthalpies of solvation of silicones are found to be additive, thus enabling the prediction of these properties for unstudied molecules. The additivity of partial molar volumes was found to also hold for a short silicone polymer, thus indicating an open structure of the polymeric chain in hydrocarbon solution, that is, equally exposed to the solvent as the shorter oligomers.

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    Calorimetric experimental data. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Cited By

    This article is cited by 5 publications.

    1. Monika Thol, Frithjof H. Dubberke, Elmar Baumhögger, Jadran Vrabec, and Roland Span . Speed of Sound Measurements and Fundamental Equations of State for Octamethyltrisiloxane and Decamethyltetrasiloxane. Journal of Chemical & Engineering Data 2017, 62 (9) , 2633-2648. https://doi.org/10.1021/acs.jced.7b00092
    2. M. Thol, F.H. Dubberke, G. Rutkai, T. Windmann, A. Köster, R. Span, J. Vrabec. Fundamental equation of state correlation for hexamethyldisiloxane based on experimental and molecular simulation data. Fluid Phase Equilibria 2016, 418 , 133-151. https://doi.org/10.1016/j.fluid.2015.09.047
    3. Yindi Zhang, Hong Dong, Chuan Wu, Lijiao Yu, Jing Xu. The mixing properties of 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl) cyclotrisiloxane with various organosilicon compounds at different temperatures. The Journal of Chemical Thermodynamics 2015, 81 , 16-25. https://doi.org/10.1016/j.jct.2014.09.010
    4. Yindi Zhang, Hong Dong, Chuan Wu, Lijiao Yu. Thermophysical properties of binary mixtures of triethoxysilane, methyltriethoxysilane, vinyltriethoxysilane and 3-mercaptopropyltriethoxysilane with ethylbenzene at various temperatures. The Journal of Chemical Thermodynamics 2014, 76 , 45-55. https://doi.org/10.1016/j.jct.2014.03.003
    5. Lijiao Yu, Hong Dong, Chuan Wu, Yindi Zhang. The density, refractive index, and thermodynamic behaviour of binary mixtures of 1,3-Diethenyl-1,1,3,3-tetramethyldisiloxane with aromatic hydrocarbons. The Journal of Chemical Thermodynamics 2014, 72 , 139-151. https://doi.org/10.1016/j.jct.2013.12.025

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