Isothermal Vapor−Liquid Equilibrium, Excess Enthalpy Data, and Activity Coefficients at Infinite Dilution for the Binary System Water + Methyl Lactate

Sanz, Marı́a Teresa; Gmehling, Jürgen

doi:10.1021/je049824c

Cited by 10 publications

(4 citation statements)

References 16 publications

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“…The reported properties show a denser fluid as the ML concentration increases with increasing interaction energy and decreasing cohesive energy density. Computed density and derived excess molar volume are reported in Figure , and although no experimental data are available for this system, the remarkable deviations from ideality are in agreement with literature negative excess enthalpy data that also point to strong heteroassociations . The computed excess volume shows a very efficient packing in the mixture, confirming the permeation of water and ML hydrogen bonding networks.…”

Section: Resultssupporting

confidence: 80%

Computational Study on the Properties and Structure of Methyl Lactate

Aparício

2007

J. Phys. Chem. A

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A theoretical study on the properties and molecular level structure of the very important green solvent methyl lactate is carried out in the gas phase and methanol and water solutions, with the solvent treated both explicitly and as a continuum. Torsional barriers giving rise to different conformers by rotation of the hydroxyl and methyl groups were analyzed using density functional theory (DFT) to establish the most stable conformer both in gas phase and solution. DFT computations on lactate dimers were also done to study short-range features, and the effect of the surrounding solvent on intra- and intermolecular hydrogen bonding was analyzed according to the polarizable continuum model approach. We have also studied lactate/water and lactate/methanol small clusters together with the corresponding binding energies. Moreover, classical molecular dynamics simulations (MD) were carried out to study medium- and large-range effects at lower computational cost. MD simulations at different pressure and temperature conditions on pure lactate were carried out, and mixtures with water and methanol of different compositions were also studied. Structural information, analyzed through the radial distribution functions, together with dynamic aspects of pure and mixed fluids were considered. The intramolecular hydrogen bonding ability of methyl lactate together with the possibility of homo- and hetero-intermolecular association determines the behavior of this molecule in pure fluids or in mixed.

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Section: Resultssupporting

confidence: 80%

Computational Study on the Properties and Structure of Methyl Lactate

Aparício

2007

J. Phys. Chem. A

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“…To our knowledge, there is no experimental excess enthalpy data published in the literature for the ethyl lactate + water system, but published values for the closely related system methyl lactate + water point to negative values, exothermic mixing, with minima for water-rich regions at water mole fractions close to those reported in this work for the studied properties reported in Figures and . Therefore, we may infer exothermic mixing values for the ethyl lactate + water system, and thus, pointing again to the development of strong heteroassociation between EL and W molecules for water-rich mixtures.…”

Section: Resultssupporting

confidence: 79%

“…As the pressure increases, a small endothermic contribution to excess enthalpy rises, and thus, hydrogen bonding is partially hindered at high pressures because of the disruptive effect of closer packings at high pressures. Nevertheless, considering the experimental large values of excess enthalpy for the methyl lactate + water system, excess enthalpy for the ethyl lactate + water system should remain negative for the studied pressure range, at least for the lower temperatures. Moreover, as the pressure rises a positive excess entropic contribution appears with maxima for water-rich regions, and thus, for high pressures the disruptive effect of pressure on water hydrogen network is not fully balanced by the development of EL/W heteroassociations.…”

Section: Resultsmentioning

confidence: 99%

Insights into the Ethyl Lactate + Water Mixed Solvent

Aparício

Alcalde

2009

J. Phys. Chem. B

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The mixed green solvent ethyl lactate + water is studied from macro- and microscopic viewpoints using a wide collection of experimental and computational tools. High-pressure thermophysical data, density, and dynamic viscosity provide valuable information on the macroscopic behavior of the mixed fluid, which is of remarkable importance for industrial purposes, and through the analysis of the derived excess and mixing properties lead to relationships with molecular level properties. Large deviations from ideality are obtained, which are related to the development of strong intermolecular hydrogen bonding between both molecules upon mixing. Computational studies, using the density functional theory, both in gas phase and water solution, allow to characterize, from energetic and structural viewpoints, the different ethyl lactate/water association complexes. The use of atoms in a molecule and natural bond orbital methods sheds light into the properties of ethyl lactate/water hydrogen bonding. Classical molecular dynamics simulations are carried out for the whole composition range, and as a function of pressure and temperature. Force field validation is done by comparison of predicted thermophysical properties with measured ones. Structural features are inferred from the analysis of radial distribution functions and their evolution with composition, pressure, and temperature, and dynamic aspects are inferred from the calculated self-diffusion constants and mean square displacements. The whole study points to a highly structured fluid, in which hydrogen bonding is developed both for water-rich and ethyl-lactate-rich solvents, showing a remarkable effect in the fluid structure upon the addition of the second component for both pure compounds, even more important for the effect of ethyl lactate on water hydrogen bonding network.

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“…In a similar situation, the Universal Quasichemical (UNIQUAC) activity model has been chosen on comparable grounds to the NRTL model, as it finds applicability across a diverse range of nonelectrolyte mixtures encompassing both nonpolar and polar fluids, ,,,,− including partially miscible mixtures . The outcomes of molecular dynamic computations have demonstrated that UNIQUAC frequently exhibits a tendency to excessively rectify deviations associated with random mixing due to the significant magnitudes observed in the arguments of the Boltzmann factors.…”

Section: Resultsmentioning

confidence: 99%

Liquid–Liquid Equilibrium for the Binary Mixtures of Butyl l-Lactate + Water and Butyl Lactate + Water at 74.6 kPa

Céspedes,

Betancourt,

Gil

2023

J. Chem. Eng. Data

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This work presents the isobaric liquid−liquid equilibrium (LLE) data for the binary mixtures of butyl L-lactate + water and butyl lactate + water, which were measured at 74.6 kPa in the temperature range from 283 to 343 K. The composition of the samples from LLE experiments was determined by gas chromatography using a Shimadzu 2010 plus with a thermal conductivity detector (TCD). The nonrandom two-liquid (NRTL) and universal quasichemical activity coefficient (UNIQUAC) models were applied to correlate the experimental data and to determine the binary interaction parameters. Both models generate data that correlates well with the observed experimental data and the parameter determination was proved to be consistent through topological analysis of the generated G M /RT function, such that the correlations can be applied to the separation process design for the synthesis of n-butyl lactate via reactive distillation.

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Isothermal Vapor−Liquid Equilibrium, Excess Enthalpy Data, and Activity Coefficients at Infinite Dilution for the Binary System Water + Methyl Lactate

Cited by 10 publications

References 16 publications

Computational Study on the Properties and Structure of Methyl Lactate

Computational Study on the Properties and Structure of Methyl Lactate

Insights into the Ethyl Lactate + Water Mixed Solvent

Liquid–Liquid Equilibrium for the Binary Mixtures of Butyl l-Lactate + Water and Butyl Lactate + Water at 74.6 kPa

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