The entropy effects in binary mixtures of polar mesogenic solvent/nonpolar solute

The paper concerns two aspects of the entropy in mesogenic systems: (i) the entropy jump (Delta S (0) NI) at the phase transition from the isotropic liquid (I) to the nematic liquid crystalline state (N), and (ii) the entropy increment (Delta S) caused by the ordering action of the probing electric field applied to the dipolar system. The system studied are the mixtures of strongly polar mesogenic solvent n-hexylcyanobiphenyl (C 6H 13PhPhCN, 6CB) and the nonpolar nonmesogenic admixture 4-ethylcyclohexyl-4'- n-nonylphenyl (C 2H 5CyHxPhC 9H 19, 2CyPh9). The entropy jump at the I-N phase transition in pure 6CB [Delta S (0) NI= 1.52 J/(mol K)] was evaluated from the analysis of the phase diagram of the mixture 6CB + 2CyPh9 with use of the Landau-Lifshitz theory; the resulting value of the transition enthalpy (Delta H (0) NI = T NIDelta S (0) NI = 0.50 kJ/mol) agrees well to that obtained with the calorimetric methods. The field-induced entropy increment (Delta S) was calculated, at the given temperature, from the static dielectric permittivity derivative value (depsilon s/d T), with use of the Fr?hlich theory. The singularities in dependence of the entropy increment on the temperature and on the mixtures composition are discussed in terms of the prenematic molecular self-organization extent in mesogenic liquids of different density of dipoles.