Thermodiffusion, also called thermal diffusion or the Ludwig–Soret effect, describes the coupling between a temperature gradient and a resulting mass flux in a multicomponent system. Although Ludwig and Soret discovered the effect in the 19th century, there is so far no molecular understanding of thermodiffusion in liquids. In the past decade the Ludwig–Soret effect has attracted growing interest due to improved experimental techniques, especially modern optical methods, which will be discussed and compared. On the basis of theoretical models, simulations and recent experiments we elucidate some properties and mechanisms contributing to the Soret effect.

An expression for the single-particle thermal diffusion coefficient of a charged colloidal sphere is derived on the basis of force balance on the Brownian time scale in combination with thermodynamics. It is shown that the single-particle thermal diffusion coefficient is related to the temperature dependence of the reversible work necessary to build the colloidal particle, including the core, the solvation layer, and the electrical double layer. From this general expression, an explicit expression for the contribution of the electrical double layer to the single-particle thermal diffusion coefficient is derived in terms of the surface charge density of the colloidal sphere, the electrostatic screening length, and its core radius, to within the Debye-Hückel approximation. This result is shown to explain experimental data, for both thin and thick double layers. In addition, a comparison with other theories is made.

Soret coefficients of the ternary system of poly(ethylene oxide) in mixed water/ethanol solvent were measured over a wide solvent composition range by means of thermal diffusion forced Rayleigh scattering. The Soret coefficient S(T) of the polymer was found to change sign as the water content of the solvent increases with the sign change taking place at a water mass fraction of 0.83 at a temperature of 22 degrees C. For high water concentrations, the value of S(T) of poly(ethylene oxide) is positive, i.e., the polymer migrates to the cooler regions of the fluid, as is typical for polymers in good solvents. For low water content, on the other hand, the Soret coefficient of the polymer is negative, i.e., the polymer migrates to the warmer regions of the fluid. Measurements for two different polymer concentrations showed a larger magnitude of the Soret coefficient for the smaller polymer concentration. The temperature dependence of the Soret coefficient was investigated for water-rich polymer solutions and revealed a sign change from negative to positive as the temperature is increased. Thermodiffusion experiments were also performed on the binary mixture water/ethanol. For the binary mixtures, the Soret coefficient of water was observed to change sign at a water mass fraction of 0.71. This is in agreement with experimental results from the literature. Our results show that specific interactions (hydrogen bonds) between solvent molecules and between polymer and solvent molecules play an important role in thermodiffusion for this system.

We report an extensive analysis of the non-equilibrium response of alkali halide aqueous solutions (Na(+)/K(+)-Cl(-)) to thermal gradients using state of the art non-equilibrium molecular dynamics simulations and thermal diffusion forced Rayleigh scattering experiments. The coupling between the thermal gradient and the resulting ionic salt mass flux is quantified through the Soret coefficient. We find the Soret coefficient is of the order of 10(-3) K(-1) for a wide range of concentrations. These relatively simple solutions feature a very rich behavior. The Soret coefficient decreases with concentration at high temperatures (higher than T ∼ 315 K), whereas it increases at lower temperatures. In agreement with previous experiments, we find evidence for sign inversion in the Soret coefficient of NaCl and KCl solutions. We use an atomistic non-equilibrium molecular dynamics approach to compute the Soret coefficients in a wide range of conditions and to attain further microscopic insight on the heat transport mechanism and the behavior of the Soret coefficient in aqueous solutions. The models employed in this work reproduce the magnitude of the Soret coefficient, and the general dependence of this coefficient with temperature and salt concentration. We use the computer simulations as a microscopic approach to establish a correlation between the sign and magnitude of the Soret coefficients and ionic solvation and hydrogen bond structure of the solutions. Finally, we report an analysis of heat transport in ionic solution by quantifying the solution thermal conductivity as a function of concentration. The simulations accurately reproduce the decrease of the thermal conductivity with increasing salt concentration that is observed in experiments. An explanation of this behavior is provided.