Fick diffusion coefficients probed by the shadowgraph method considering confinement and advection.

The present work contributes to the development of the shadowgraph method for its routine application for an accurate determination of the Fick diffusion coefficient D11 of binary fluid mixtures. In this context, measurement and data evaluation strategies for thermodiffusion experiments where confinement and advection are potentially present are elaborated by studying two binary liquid mixtures with positive and negative Soret coefficients, i.e., 1,2,3,4-tetrahydronaphthalene/n-dodecane and acetone/cyclohexane. For obtaining accurate D11 data, the dynamics of non-equilibrium fluctuations in concentration is analyzed considering recent theory by data evaluation procedures that are demonstrated to be suitable for different experimental configurations.

Determination of diffusivities in binary fluid mixtures with various Lewis numbers as well as positive and negative Soret coefficients by the shadowgraph method.

The present work demonstrates the accessibility of the Fick diffusion coefficient D11 and/or the thermal diffusivity a of the binary mixtures dicyclohexylmethane/diphenylmethane, n-hexane/carbon dioxide, 1-hexanol/carbon dioxide, and methane/propane by the analysis of the dynamics of non-equilibrium fluctuations using the shadowgraph method. It is evidenced that D11 and a can be simultaneously determined for binary mixtures with Lewis numbers Le = a/D11 ranging over two orders of magnitude down to Le ≈ 5 or in the presence of minor advection for binary mixtures possessing a negative Soret coefficient in the investigated temperature and pressure ranges from (298.15 to 473.15) K and from about (0.5 to 25) MPa. The determined diffusivities are compared with those measured by heterodyne dynamic light scattering or obtained from the literature, with a focus on achievable uncertainties. By this comparison, it is shown that the determination of a by the shadowgraph method was hindered by mode-coupling effects for Le ≈ 5, whereas a determination of D11 was always possible for mixtures with Le ≥ 5. Furthermore, it is demonstrated that even in the presence of solutal advection, the description of the purely diffusive behavior of non-equilibrium fluctuations in concentration remains valid.

Simultaneous determination of multiple transport properties over a wide range of temperatures and pressures from the analysis of non-equilibrium fluctuations by the shadowgraph method.

The present work demonstrates that by the analysis of the dynamics of non-equilibrium fluctuations using the shadowgraph method, the thermal diffusivity, the Fick diffusion coefficient, the kinematic viscosity, and the Soret coefficient of a binary mixture can be determined from a single thermodiffusion experiment. The study was performed for a mixture consisting of equal masses of 1,2,3,4-tetrahydronaphthalene and n-dodecane in a newly developed shadowgraph apparatus at temperatures up to 373 K and pressures up to 40 MPa. The obtained results are mainly discussed in the light of their uncertainties at varying thermodynamic states for evaluating the benefits, drawbacks, and potentials of the apparatus. The Fick diffusion coefficient and the thermal diffusivity obtained with average expanded uncertainties of 2.8% and 6.6% agree with literature data and measurements for the same mixture taken by heterodyne dynamic light scattering. Current limitations of the method are reflected by the distinctly larger uncertainties of the kinematic viscosity and the Soret coefficient. Corresponding reasons and potential measures to overcome the limitations are discussed.