Cross diffusion governs an oscillatory instability in a ternary mixture with the Soret effect.

In a ternary mixture with the Soret effect, the interplay between cross-diffusion, thermodiffusion, and convection can lead to rich and complex dynamics including spatial patterns and oscillations. We present an experimental and three-dimensional numerical study of dynamic regimes in the toluene-methanol-cyclohexane ternary mixture with the Soret effect in the geometry of a thermogravitational column. An important feature of the system is that for the first component, toluene, the Soret and thermodiffusion coefficients have opposite signs, which triggers the oscillatory instability. Our experiments and numerical analysis show that the primary long-wave instability manifests itself in the form of a standing wave, and the secondary one emerges in the form of a swinging pattern. The computational model provides insight into the role of cross-diffusion coefficient D12 in the emergence and development of oscillatory instability. This study demonstrates that the long-wave oscillatory instability in transverse direction occurs only within a limited range of the D12 values and outside of this range it decays to a stationary pattern of either Turing-like or monotonic instability.

Measurement of Diffusion of Atmospheric Gases in a Liquid Perfluoro Compound by Means of an Optical Technique.

We report on accurate measurements of Fickian diffusion coefficients in binary mixtures consisting of hydrofluoroether (a perfluoro compound of methoxy-nonafluorobutane or HFE-7100) with dissolved atmospheric gases CO2, N2, and O2 in the limit of an infinite dilution of the gas. We show that the use of optical digital interferometry (ODI) allows the determination of diffusion coefficients of dissolved gases with relatively small standard uncertainties for this class of experiments. In addition, we illustrate the ability of an optical approach to determine the gas concentration. We compare the capacity of four mathematical models, singly used in the literature, to obtain diffusion coefficients by applying them to the processing of a large amount of experimental data. We quantify their systematic errors and standard uncertainties. The temperature behavior of the diffusion coefficients measured in the range of 10 to 40 °C is consistent with the behavior of the same gases in other solvents available in the literature.

Soret vector for description of multicomponent mixtures.

The Soret effect describes the transport of constituent species in multicomponent mixtures that occurs due to a temperature gradient. This cross-coupling effect of heat and mass transfer has been successfully examined in binary liquid mixtures, while experiments with ternary mixtures are rare as they impose significant difficulties. We introduce a new and innovative concept, the Soret vector, for the characterization of Soret driven separation in ternary mixtures. The presentation of the component separation in the vector form offers several advantages: (i) to predict the Soret sign of a ternary mixture from knowledge of the Soret coefficients in binary subsystems; (ii) to control consistency of measured coefficients, this is especially important when results are obtained using different instruments and methods; (iii) to determine in which regions and which components cause the greatest separation; (iv) to identify the regions where the Soret separation is inaccessible for optical techniques or gravitationally unstable. We demonstrate these features by exploring ternary mixtures of different origins: (a) nearly ideal mixture composed by THN-IBB-nC12 when Soret coefficients in binary subsystems ([Formula: see text]) are positive, (b) non-ideal mixture containing water and ethanol TEG-Wat-EtOH when [Formula: see text] are positive and negative and (c) Tol-MeOH-Ch mixture containing demixing zone with positive and negative [Formula: see text]. Our approach provides a promising systematic framework for the future research of an important and challenging problem of thermodiffusion in multicomponent liquids.

A ternary mixture at the border of Soret separation stability.

Ternary mixtures with the Soret effect are prone to triple-diffusive convection in a thermal field. The Soret coefficients of the toluene-methanol-cyclohexane mixture, measured in microgravity at a given composition [0.62-0.31-0.07] in mass fractions, showed that the net separation ratio, Ψ, the parameter responsible for the hydrodynamic stability in a gravity field is close to zero. Furthermore, the large cross-diffusion of toluene leads to a curious situation: the Soret coefficient ST1 is positive while the thermodiffusion coefficient DT1 is negative. The behavior of this ternary mixture on the border of stability, when Ψ is slightly negative or positive, is examined experimentally and numerically. The mixture is placed in an elongated cell between the differently heated walls. Depending on Ψ and the initial temperature of the liquid (mean temperature, linear profile or cold one), the evolution of concentration patterns are classified by four regimes. We observe the emergence of motionless, metastable, and convective patterns. In the case of Ψ > 0, it was found that cross-diffusion fluxes cause a temporarily unstable density pattern. The initially cold mixture at either Ψ sign shows dissimilar Soret separation in the upper and lower parts of the cell. It leads to the formation of a long-lived inverse density gradient at the upper part of the cell, which finally results in a motionless (Ψ > 0) or convective (Ψ < 0) pattern.

Diffusion of Quinine with Ethanol as a Co-Solvent in Supercritical CO2.

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.

Results of the DCMIX1 experiment on measurement of Soret coefficients in ternary mixtures of hydrocarbons under microgravity conditions on the ISS.

The Soret coefficients of a set of ternary systems of 1,2,3,4-tetrahydronaphthalene (THN), isobutylbenzene (IBB), and n-dodecane (nC12) at 298.15 K were measured under microgravity condition aboard the International Space Station in the frame of the DCMIX1 experiment. The present work includes a comprehensive study of possible data processing sequences for the interpretation of interferometric Soret experiments in ternary systems. Several data processing methodologies are discussed. A significant concentration dependence of the Soret coefficients is observed. In the present study, we have obtained large and positive values for THN and negative ones for IBB in all investigated systems. A linear relation between the Soret coefficients of two components is derived for each system and allows validating experimentally the coefficients measured in other experiments.

Diffusion of methane in supercritical carbon dioxide across the Widom line.

Diffusion of methane diluted in supercritical carbon dioxide is studied by experiment and molecular simulation in the temperature range from 292.55 to 332.85 K along the isobars 9.0, 12.5 and 14.7 MPa. Measurements of the Fick diffusion coefficient are carried out with the Taylor dispersion technique. Molecular dynamics simulation and the Green-Kubo formalism are employed to obtain Fick, Maxwell-Stefan and intradiffusion coefficients as well as shear viscosity. The obtained diffusion coefficients are on the order of 10-8 m2/s. The composition, temperature and density dependence of diffusion is analyzed. The Fick diffusion coefficient of methane in carbon dioxide shows an anomaly in the near-critical region. This behavior can be attributed to the crossing of the so-called Widom line, where the supercritical fluid goes through a transition between liquid-like and gas-like states. Further, several classical equations are tested on their ability to predict this behavior and it is found that equations that explicitly include the density are better suited to predict the sharp variation of the diffusion coefficient near the critical region predicted by molecular simulation.

Interplay of structure and diffusion in ternary liquid mixtures of benzene + acetone + varying alcohols.

The Fick diffusion coefficient matrix of ternary mixtures containing benzene + acetone + three different alcohols, i.e., methanol, ethanol, and 2-propanol, is studied by molecular dynamics simulation and Taylor dispersion experiments. Aiming to identify common features of these mixtures, it is found that one of the main diffusion coefficients and the smaller eigenvalue do not depend on the type of alcohol along the studied composition path. Two mechanisms that are responsible for this invariant behavior are discussed in detail, i.e., the interplay between kinetic and thermodynamic contributions to Fick diffusion coefficients and the presence of microscopic heterogeneities caused by hydrogen bonding. Experimental work alone cannot explain these mechanisms, while present simulations on the molecular level indicate structural changes and uniform intermolecular interactions between benzene and acetone molecules in the three ternary mixtures. The main diffusion coefficients of these ternary mixtures exhibit similarities with their binary subsystems. Analyses of radial distribution functions and hydrogen bonding statistics quantitatively evidence alcohol self-association and cluster formation, as well as component segregation. Furthermore, the excess volume of the mixtures is analyzed in the light of intermolecular interactions, further demonstrating the benefits of the simultaneous use of experiment and simulation. The proposed framework for studying diffusion coefficients of a set of ternary mixtures, where only one component varies, opens the way for further investigations and a better understanding of multicomponent diffusion. The presented numerical results may also give an impulse to the development of predictive approaches for multicomponent diffusion.

The effect of alcohols as the third component on diffusion in mixtures of aromatics and ketones.

With laboratory and numerical work, we demonstrate that one of the main diffusion coefficients and the smaller eigenvalue of the Fick diffusion matrix are invariant to the number of methylene groups of the alcohol in ternary mixtures composed of an aromatic (benzene), a ketone (acetone) and one of three different alcohols (methanol, ethanol or 2-propanol). A critical analysis of the relationship between the kinetic and thermodynamic contributions to the diffusion coefficients allows us to explain this intriguing behaviour of this class of mixture. These findings are reflected by the diffusive behaviour of the according binary subsystems. Our approach provides a promising systematic framework for future investigations into the important and challenging problem of transport diffusion in multicomponent liquids.

Mutual diffusion governed by kinetics and thermodynamics in the partially miscible mixture methanol + cyclohexane.

To gain an understanding of the transport and thermodynamic behavior of the highly non-ideal mixture methanol + cyclohexane, three complementary approaches, i.e. experiment, molecular simulation and predictive equations, are employed. The temperature and composition dependence of different diffusion coefficients is studied around the miscibility gap at ambient pressure. On the one hand Fick diffusion coefficients are measured experimentally by interferometric probing and on the other hand Maxwell-Stefan diffusion coefficients and intradiffusion coefficients are sampled by equilibrium molecular dynamics simulation at five temperatures below the upper critical temperature of ∼319 K. The spinodal curve is determined from extrapolation of the experimental Fick diffusion coefficient data and compared to predictions from excess Gibbs energy models. It is found that these models are not capable to correctly describe the activity coefficients over the whole composition range of the studied mixture. Thus, different parameter sets for a modified Wilson model are used for calculations of the thermodynamic factor, which is needed to transform Maxwell-Stefan into Fick diffusion coefficients and vice versa. Further, predictive equations for the Maxwell-Stefan diffusion coefficient, which are based on intradiffusion coefficients, are compared to simulation results. Using different approaches provides a clearer understanding of the relations between kinetic and thermodynamic properties contributing to the diffusion behavior of partially miscible mixtures.

Wall-generated pattern on a periodically excited miscible liquid/liquid interface.

We present a new generic type of pattern generated by bounding walls on the interface between miscible liquids in a horizontally vibrated cell. The pattern is observed in laboratory experiments and numerical simulations below and above the frozen-wave instability threshold. At the threshold, a competition develops between the new "fish-spine" pattern and frozen waves, while above the threshold these two kinds of patterns may coexist in spatially separated domains. We propose a theoretical model for the formation mechanism of the fish-spine pattern and its spreading along the interface.

Communication: New approach for analysis of thermodiffusion coefficients in ternary mixtures.

A new approach is proposed to cross-check conflicting measured values of the thermodiffusion coefficients in ternary mixtures. The results of recent measurements performed in ternary mixture of hydrocarbons 1,2,3,4-tetrahydronaphthalene, isobutylbenzene, and dodecane by thermogravitational column [P. Blanco, M. M. Bou-Ali, J. K. Platten, D. A. de Mezquia, J. A. Madariaga, and C. Santamaría, J. Chem. Phys. 132, 114506 (2010)] and optical beam deflection [A. Königer, H. Wunderlich, and W. Köhler, J. Chem. Phys. 132, 174506 (2010)] are critically analyzed. A way of matching them into a unique value is reported. The accuracy of the integrated value should significantly exceed that of the original results. Two diagnostics are required to determine thermodiffusion coefficients in ternary mixture, e.g., two different wavelengths or density and refractive index. It is shown that by attributing a reliability weight for each pair of diagnostics among the available techniques the best combination can be selected. The true values of thermodiffusion coefficients are extremely sensitive to the knowledge of precise values of mass diffusion coefficients and contrast factors.