Cross phenomena, representing responses of a system to external stimuli, are ubiquitous from quantum to macro scales. The Onsager theorem is often used to describe them, stating that the coefficient matrix of cross phenomena connecting the driving forces and the fluxes of internal processes is symmetric. Here we show that this matrix is intrinsically diagonal when the driving forces are chosen from the gradients of potentials that drive the fluxes of their respective conjugate molar quantities in the combined law of thermodynamics including the contributions from internal processes. Various cross phenomena are discussed in terms of the present theory. IMPACT STATEMENT Through flux equations based on the combined law of thermodynamics, theory of cross phenomena is developed and applied to thermoelectricity, thermodiffusion, diffusion, electromigration, electrocaloric and electromechanical effects, and thermal expansion.

Theory of cross phenomena and their coefficients beyond Onsager theorem

The investigation of the transport properties of binary fluid mixtures remains a topic of interest in relation to the more challenging studies of ternary mixtures. In fact, the study of the phase boundary limits of the Gibbs composition triangle can be the initial step for a more complete analysis of ternary mixtures. In this paper, we apply the dynamic shadowgraphy optical technique to study non-equilibrium fluctuations induced by the presence of a gradient of temperature and/or concentration in the triethylene glycol (TEG)/water system. These thermodiffusion and free-diffusion experiments aim at measuring the transport properties of samples of the studied system at different experimental conditions. We scan both the average temperature and the TEG concentration, which allows us investigating both positive and negative thermodiffusive behaviours. The obtained values of mass diffusion coefficient are consistent with data available in the literature in the range of temperature investigated in this study. The mass diffusion coefficient of the sample prepared at 0.7 w/w TEG concentration are characterised by shadowgraphy following the two proposed methods, exhibiting consistent results. An increase of the mass diffusion coefficient as a function of the average temperature is highlighted. On the other hand, the thermodiffusion coefficient appears to be independent of the average temperature of the sample at 0.3 w/w TEG concentration. 

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Mass diffusion and Soret coefficient measurements of triethylene glycol/water binary mixtures by dynamic shadowgraphy

Giant thermal and solutal non-equilibrium fluctuations are observed in shadowgraphy experiments on liquid mixtures subjected to a temperature gradient. For large temperature differences, both the temperature and the composition dependence of the relevant thermophysical parameters and the nonlinear terms in the diffusion equation need to be taken into account, leading to a nonlinear concentration profile. For temperature differences exceeding the inverse of the Soret coefficient, in our example approximately 10 K, the usual data evaluation yields increasingly wrong diffusion and Soret coefficients that are off by almost a factor of two for a temperature difference of 50 K. A local model that treats the measured shadowgraph signal as a superposition of the contributions from every layer of the sample is able to capture the essential trend and yields a good agreement with experimental data. The results are important for the application of shadowgraphy as a tool for the measurement of Soret and diffusion coefficients, where large temperature gradients promise a good signal-to-noise ratio. 

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Nonlinearities in shadowgraphy experiments on non-equilibrium fluctuations in polymer solutions

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We investigate numerically the Soret effect on the linear instability properties in convection due to viscous dissipation in a horizontal channel filled with a binary fluid mixture. Two sets of boundary conditions of experimental interest are considered. Both have no-slip boundaries for the velocity and no mass flux through them. The lower boundary is considered adiabatic, while the upper boundary is isothermal for case A and inversely for case B. As no external temperature or concentration difference is imposed on the layer, the cause of thermal instability is the flow rate through the volumetric heating induced by the viscous dissipation and the Soret effect inherent to binary mixtures. It is found that longitudinal rolls (LR) represent the preferred mode for the onset of convection. For case A, both oscillatory and steady-state LR may develop depending on the value of the separation ratio $\psi$ which represents the ratio between the mass contribution and the temperature contribution to buoyancy forces. The dependence of the instability thresholds on the separation ratio is discussed near and far from the codimension-two bifurcation point. For case B, the basic state remains stable for positive separation ratios, while it loses its stability via a stationary bifurcation with zero wave number for negative values of the separation ratio. The relevance of the theoretical results for the observability of such instability in real systems is discussed. Finally, we suggest a protocol to determine Soret coefficients by using the stability diagrams obtained in the current paper.

Soret effect on the onset of viscous dissipation thermal instability for Poiseuille flows in binary mixtures

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.

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P. Möckel

Papers

The Soret coefficients of the ternary system water/ethanol/triethylene glycol and its corresponding binary mixtures.