The classification of phase transitions in first-order and second-order (or continuous) ones is widely used. The nematic-to-isotropic (NI) transition in liquid crystals is a weakly first-order transition, with only small discontinuities in enthalpy and specific volume at the transition which are not always easy to measure. On the other hand, fluctuation effects near the transition, typical for a continuous transition, are present because of the only weakly first-order character. In a recent paper [Phys. Rev. E 69, 022701 (2004)], it was concluded from the static dielectric permittivity in the isotropic phase near the NI transition that less polar mesogens (with little or no pretransitional effects) are characteristic for a first-order NI phase transition, whereas in the case of strongly polar ones (with large pretransitional effects) the NI transition is close to second order. In this paper, we address the question whether it is, indeed, possible to use these fluctuation effects in the isotropic phase to quantify the "strength" of a weakly first-order transition, i.e., how far it is from second order. Therefore, we measured the temperature dependence of the enthalpy near the NI transition of seven liquid crystals with adiabatic scanning calorimetry and compared the measured values of the latent heat with pretransitional effects in the dielectric constant and the specific heat capacity. The compounds used in the comparison are MBBA, 5CB, 8CB, 5NCS, 5CN, 8CHBT, and D7AB. From our analysis we find, contrary to the assertion in the above reference, no correlation between the strength of the NI transition of a given compound and the pretransitional effects observed, neither dielectrically, nor thermally.

We investigated the smectic-A-hexatic-B (SmA-HexB) transition in the liquid-crystal n-hexyl-4'-n-pentyloxybiphenyl-4-carboxilate (650BC) with adiabatic scanning calorimetry. We were able to prove in a direct way that this transition is indeed very weakly first order, as was already suggested in the literature. The latent heat at the transition was determined to be deltaHL = 0.04 +/- 0.02 J/g. Our experiments confirm the high value for the heat capacity critical exponent earlier reported, yielding alpha = 0.64 +/- 0.05.

We studied the thermal conductivity, thermal effusivity, and specific heat capacity at constant pressure of the critical binary liquid mixture aniline-cyclohexane near the consolute point, using a photopyroelectric (PPE) technique and adiabatic scanning calorimetry (ASC). According to recent theoretical predictions based on renormalization group theory calculations, a substantial (but not diverging) enhancement in the thermal conductivity in the homogeneous phase near the critical temperature was expected for this binary system near the consolute point. However, within an experimental precision of 0.05%, we found no deviation from linear behavior in the range of 5 K above Tc down to Tc. The specific heat capacity calculated from the results for the thermal conductivity and effusivity is in good agreement with that measured by ASC. For the ASC results, the theoretical power law expression with the Ising critical exponent was fitted to the specific heat capacity both above and below the transition temperature. Good agreement with theory was found both for the amplitude ratio and the two-scale universality.

Experimental investigations on binary liquid mixtures near the critical mixing point are presently leading to a controversy about the anomaly in the thermal conductivity. A photopyroelectric technique is used to determine the thermal conductivity and the effusivity of the binary liquid mixture n-butoxyethanol-water at its critical concentration near the critical mixing point. It is proven that, contrary to previous reports, there is no critical enhancement in the thermal conductivity. The specific heat capacity is calculated from these results and compared with the results from measurements performed by adiabatic scanning calorimetry.

Articles you may be interested inLarge heat capacity anomaly near the consolute point of the binary mixture nitromethane and 3-pentanol J. Chem. Phys. 134, 044505 (2011); 10.1063/1.3535567Static and dynamic thermal quantities near the consolute point of the binary liquid mixture aniline-cyclohexane studied with a photopyroelectric technique and adiabatic scanning calorimetry Thermal conductivity, thermal effusivity, and specific heat capacity near the lower critical point of the binary liquid mixture n-butoxyethanol-water Heat capacity of the liquid-liquid mixture perfluoroheptane and 2,2,4-trimethylpentane near the critical point Heat capacity and turbidity near the critical point of succinonitrile-waterWe investigated the specific heat capacity near the demixing transition of ternary mixtures of water, 3-methylpyridine and sodium bromide as a function of salt concentration. In this system, a crossover from Ising to tricritical behavior caused by the appearance of a new ''microheterogeneous'' phase was reported from light-scattering measurements ͓Jacob et al., Phys. Rev. E 58, 2811 ͑1998͔͒. We used adiabatic scanning calorimetry, a very sensitive technique for detecting and characterizing phase transitions, to investigate this system and found no specific heat anomaly to be associated with the formation of a new phase. In the one phase region, the critical exponent ␣ is consistent with the Ising value and is incompatible with the tricritical value for all the investigated samples. In the phase-separated region, the values of the exponent are substantially lower and even negative. This is probably caused by the change in salt concentration of the two phases close to the critical point.