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While interferometry has been widely used for diffusion measurements in liquid mixtures, it was hardly applied so far to vapour-gas mixtures. The present work aims to bridge this gap. Using an improved Mach–Zehnder interferometer, we investigate the evaporation of acetone and HFE-7100 in ambient air. Our observations build on complete evaporation of a thin liquid layer in a cell with open end, at ambient temperature varying between 283.15 and 313.15 K. Monitoring the evolution of the refractive index change allows us to determine the evaporation rate and vapour-in-air diffusion coefficients. The spatial distribution of the refractive index reveals that the purely diffusive mode of transport is perturbed at both ends of the cell. Interferometric images facilitate isolating these regions, determining the true diffusion path, and hence, the correct diffusion coefficients. Besides, we illustrate the possibility of calculating the optical contrast factors, which we find in excellent agreement with current experiments.

Thermodiffusion in ternary mixtures is considered prototypic for the Soret effect of truly multicomponent systems. We discuss ground-based measurements of the Soret coefficient along the binary borders of the Gibbs triangle of the highly polar and hydrogen bonding ternary DCMIX3-system water/ethanol/triethylene glycol. All three Soret coefficients decay with increasing concentration, irrespective of the choice of the independent component, and show a characteristic sign change as a function of temperature and/or composition. With the exception of triethylene glycol/ethanol at high temperatures, the minority component always migrates toward the cold side. All three binaries exhibit temperature-independent fixed points of the Soret coefficient. The decay of the Soret coefficient with concentration can be related to negative excess volumes of mixing. The sign changes of the Soret coefficients of the binaries allow to draw far-reaching conclusions about the signs of the Soret coefficients of the corresponding ternary mixtures. In particular, we show that at least one ternary composition must exist, where all three Soret coefficients vanish simultaneously and no steady-state separation is observable.

The density and refractive index were experimentally determined for binary mixtures of water + ionic liquid 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate throughout the ionic liquid mass frac- tion range, at atmospheric pressure and various temperatures between 293.15 K and 323.15 K. The refractive index was measured at five wavelengths between 589.2 nm and 935 nm. From the experimen- tal data on density, volumetric properties such as the excess molar volume and thermal expansion coef- ficient were calculated. The excess molar volume was negative throughout the ionic liquid mass fraction range and its magnitude decreased with temperature. From the experimental data on the refractive index, the deviation in the refractive index and its coefficients of concentration, temperature and chro- matic dispersion were obtained. The values of the deviation in the refractive index were positive and decreased with temperature. In order to simultaneously investigate the dependence of the refractive index on concentration, temperature and wavelength, we correlated the experimental data with a two-term Cauchy equation. Furthermore, a comparative study of 11 refractive index mixing rules was performed to assess their prediction ability. More advanced mixing rules do not lead to any improvement in comparison with the simple linear mixing rule (Arago-Biot) for estimating refractive index and the concentration contrast factor of the mixture studied. The results are expected to be useful for tuning the properties of an ionic liquid by adding water or selecting the temperature or optical region., Peer Reviewed, Postprint (author's final draft)

This study aims at contributing to quinine extraction using supercritical CO2 and ethanol as a co-solvent. The diffusion coefficients of quinine in supercritical CO2 are measured using the Taylor dispersion technique when quinine is pre-dissolved in ethanol. First, the diffusion coefficients of pure ethanol in the supercritical state of CO2 were investigated in order to get a basis for seeing a relative change in the diffusion coefficient with the addition of quinine. We report measurements of the diffusion coefficients of ethanol in scCO2 in the temperature range from 304.3 to 343 K and pressures of 9.5, 10 and 12 MPa. Next, the diffusion coefficients of different amounts of quinine dissolved in ethanol and injected into supercritical CO2 were measured in the same range of temperatures at p = 12 Mpa. At the pressure p = 9.5 MPa, which is close to the critical pressure, the diffusion coefficients were measured at the temperature, T = 343 K, far from the critical value. It was found that the diffusion coefficients are significantly dependent on the amount of quinine in a small range of its content, less than 0.1%. It is quite likely that this behavior is associated with a change in the spatial structure, that is, the formation of clusters or compounds, and a subsequent increase in the molecular weight of the diffusive substance.

Mutual diffusion coefficients of a binary mixture of water + ionic liquid 1-(2-hydroxyethyl)-3- methylimidazolium tetrafluoroborate have been investigated by means of experimental and predictive ap- proaches. Optical digital interferometry has been employed to determine the mutual diffusion coefficients over the full ionic liquid mass fraction range and at four temperatures between 298.15 and 313.15 K. Moreover, the prediction ability of four different models has been tested. The influence of using different excess Gibbs energy (gE) models to calculate the relevant thermodynamics properties was also addressed. The mutual diffusion coef- ficient has a strong dependence on concentration and varies from 2 × 10-10 to 1.27 × 10-9 m2 s-1. The concen- tration and temperature dependencies of the present experimental diffusion coefficients were correlated using empirical and predictive equations. The use of binary interaction parameter regressed from diffusion data instead of vapor-liquid equilibria improves considerably the prediction ability of the employed predictive models. Among the studied predictive models, the modified group contribution model provides the best results with an absolute relative deviation of 2.1%. Throughout the paper, thermodynamic and kinetic behavior of the mixture are analyzed for establishing an appropriate criterion for the screening of ionic liquids as working fluids for ab- sorption refrigeration systems., Peer Reviewed, Postprint (author's final draft)