Thermodynamic properties of solutions of alcohols and carbon tetrachloride. Part 1.—Free energies and volumes of mixing

Paraskevopoulos, G.; Missen, R. W.

doi:10.1039/tf9625800869

Cited by 82 publications

(25 citation statements)

References 5 publications

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“…For the methanol rich mixtures we see that the excess volumes are substantially reduced by taking into account the polarizability of CCl 4 . This complements the discussion Paraskevopoulos et al 13 on the total volume change of mixing. They found that increasing the chain length of the alcohol, lead to a decrease of the partial excess volume of CCl 4 ͑at infinite dilution͒.…”

Section: Thermodynamic Propertiessupporting

confidence: 82%

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Molecular dynamics study of the thermodynamic and structural properties of methanol and polarizable/non-polarizable carbon tetrachloride mixtures

Veldhuizen

Leeuw

1996

The Journal of Chemical Physics

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Molecular dynamics simulations have been performed for methanol/carbon tetrachloride mixtures over the whole composition range at 323 K and zero pressure. The OPLS ͑optimized potentials for liquid simulation͒ potential energy parameters by Jorgensen were used to model the methanol potential. Both a non-polarizable carbon tetrachloride model taken from McDonald, Bounds, and Klein ͓Mol. Phys. 45, 521 ͑1982͔͒ as well as a polarizable model were used. The latter model was devised by combining the model of McDonald, Bounds, and Klein with the atomic polarizabilities proposed by Applequist, Carl, and Fung ͓J. Am. Chem. Soc. 94, 2952 ͑1972͔͒. We show that the role of the methanol-carbon tetrachloride interactions are very important in discussing the thermodynamic mixing properties. In order to reproduce the asymmetric behavior of the excess enthalpies with respect to composition it is necessary to include the non-additive polarization interaction. The structure and especially hydrogen bonding properties are discussed. Radial distribution functions show a strong tendency of methanol to preserve the local order similar to the one in the pure fluid. The deviations from random mixing are more pronounced at the lower mole fractions. This is explained by a frustration model. At low methanol concentrations the molecules get more freedom to align themselves in energetically favorable ͑hydrogen bonded͒ configurations. Throughout the composition range, the majority of the methanol molecules is found to be engaged in two hydrogen bond, As in the pure fluid, this leads to the pattern of hydrogen bonded winding chains. Upon dilution the degree of cross-linking between the chains diminishes whereas the free monomer fraction rises. Furthermore a significant number of the remaining chains close to form cyclic polymers.

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Section: Thermodynamic Propertiessupporting

confidence: 82%

“…The methanol-methanol interactions are described by Jorgensens OPLS model. 11 Otterstedt and Misssen 12 and Paraskevopoulos and Missen 13 performed an extensive experimental study on the thermodynamic properties of alcohol/carbon tetrachloride mixtures. Exothermic mixing was observed at high alcohol mole fractions.…”

Section: Introductionmentioning

confidence: 99%

Molecular dynamics study of the thermodynamic and structural properties of methanol and polarizable/non-polarizable carbon tetrachloride mixtures

Veldhuizen

Leeuw

1996

The Journal of Chemical Physics

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“…The excess volume of a mixture is also the resultant of a number of competing effects (29,30). For the present system, the breakup of the structures of both cyclopentanol and pdioxane will contribute positive terms to V E ; heterogeneous complex formation and the fitting of one solvent into the structure of the other will make negative contributions.…”

Section: Discussionmentioning

confidence: 86%

Thermodynamic Properties of Cyclopentanol + p-Dioxane Mixtures at 25 °C

Anand¹,

Grolier²,

Kiyohara³

et al. 1973

Can. J. Chem.

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Excess enthalpies, excess volumes, and total vapor pressures were measured for cyclopentanol + pdioxane mixtures at 25 "C. The method of Barker was used to calculate vapor-liquid equilibria and excess Gibbs free energies from the vapor pressure results. apparaitre que les proprietes thermodynamiques d'exces des melanges cyclopentanol + p-dioxane resultent principalement de la rupture de la structure du solvant p-dioxane, dans ces melanges.

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“…Changes in the self-association of the alcohol or interactions between like molecules lead to an increased V E ; negative contributions to V E arise from interactions between unlike molecules, or structural effects as changes in free volume, or interstitial accommodation. [70][71][72][73]. In the case of (1-alkanol + given alkane), these contributions are sensitive to the lengths of the component molecules [72].…”

Section: Molar Excess Volumesmentioning

confidence: 99%