Thermophobicity of liquids: heats of transport in mixtures as pure component properties--the case of arbitrary concentration.

We have measured Soret coefficients of a large number of binary mixtures of 23 different organic solvents. The present analysis is based on 77 equimolar mixtures and strongly supports the thermophobicity concept previously developed for the heats of transport of originally 10 different substances [S. Hartmann, G. Wittko, W. Köhler, K. I. Morozov, K. Albers, and G. Sadowski, Phys. Rev. Lett. 109, 065901 (2012)]. Among the investigated compounds, cis-decalin is the most thermophobic, hexane the most thermophilic one. In addition to the equimolar mixtures, we have also analyzed the composition dependence of the Soret coefficients and the heats of transport for 22 selected binary mixtures. Both the interpretation of the heats of transport in equimolar mixtures as pure component thermophobicities and the composition dependence of the Soret coefficient can be understood on the basis of the thermodiffusion theory developed by Morozov [Phys. Rev. E 79, 031204 (2009)], according to which the composition dependence is determined by the excess volume of mixing.

Thermophobicity of liquids: heats of transport in mixtures as pure component properties.

We have measured the Soret coefficients of 41 out of 45 possible equimolar binary mixtures of 10 different organic solvents and found an additive rule for the heats of transport. These can, except for an undetermined offset, uniquely be assigned to the pure components. Based on their heats of transport, the fluids can be arranged according to their thermophobicity, similar to the standard electrode potential. A qualitative explanation of this unexpected additivity is based on the work of Morozov [Phys. Rev. E 79, 031204 (2009)].

Influence of isotopic substitution on the diffusion and thermal diffusion coefficient of binary liquids.

The mutual mass diffusion coefficient (D) and the thermal diffusion coefficient ( D (T)) of the liquids acetone, benzene, benzene-d1, benzene-d3, benzene-d5, benzene-d6, benzene- 13C6, n-hexane, toluene, 1, 2, 3, 4-tetrahydronaphtalene, isobutylbenzene, and 1, 6-dibromohexane in protonated and perdeuterated cyclohexane have been measured with a transient holographic grating technique at a temperature of 25 degrees C. The mass diffusion coefficient shows a pronounced concentration dependence. Perdeuteration of cyclohexane only leads to marginal changes of the mass diffusion coefficient. The Stokes-Einstein equation describes the limiting tracer diffusion coefficients well if the solute molecule is smaller than the solvent. It is not capable to describe the small isotope effect of a few percent. On the other hand, the isotope effect, which is independent of concentration, is in agreement with the Enskog theory, that does not provide the absolute value of the mass diffusion coefficient of the liquid mixtures. The thermal diffusion coefficient of all the binary mixtures shows a moderate and almost linear concentration dependence. Its isotope effect, which is the change of D(T) upon deuteration of cyclohexane, varies with mole fraction. The thermophoretic force acting on any tracer molecule in cyclohexane changes by the same amount when cyclohexane is perdeuterated, irrespective of the magnitude of the thermophoretic force before deuteration. This change of the thermophoretic force is equal but of opposite sign to the difference between the thermophoretic forces acting on cyclohexane and perdeuterated cyclohexane as tracers in any of the above liquids.

Universal isotope effect in thermal diffusion of mixtures containing cyclohexane and cyclohexane-d12.

The Soret coefficients S(T) of the liquids acetone, benzene, benzene-d1, 1,3,5-benzene-d3, benzene-d5, benzene-13C6, benzene-d6, n-hexane, toluene, 1,2,3,4-tetrahydronaphthalene, isobutylbenzene, and 1,6-dibromohexane have been measured in protonated and perdeuterated cyclohexane by a transient holographic grating technique. It has been found that S(T) can be either positive or negative and even change its sign as a function of concentration. The isotope effect DeltaS(T)=-0.99 x 10(-3) K(-1), which is the change of S(T) after isotopic substitution of cyclohexane, neither depends on concentration nor on the nature of the mixing partner. Only in the case of the polar acetone is DeltaS(T) approximately 30% larger but still concentration independent. Based on the experimental findings, some general conclusions about the dependence of the Soret coefficient on molecular properties are drawn.