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.