Connection between dynamics and thermodynamics of liquids on the melting line

The dynamics of a large number of liquids and polymers exhibit scaling properties characteristic of a simple repulsive inverse power law (IPL) potential, most notably the superpositioning of relaxation data as a function of the variable TV{\gamma}, where T is temperature, V the specific volume, and {\gamma} a material constant. A related scaling law, TmVm{\Gamma}, with the same exponent {\Gamma}={\gamma}, links the melting temperature Tm and volume Vm of the model IPL liquid; liquid dynamics is then invariant at the melting point. Motivated by a similar invariance of dynamics experimentally observed at transitions of liquid crystals, we determine dynamic and melting point scaling exponents {\gamma} and {\Gamma} for a large number of non-associating liquids. Rigid, spherical molecules containing no polar bonds have {\Gamma}={\gamma}; consequently, the reduced relaxation time, viscosity and diffusion coefficient are each constant along the melting line. For other liquids {\gamma}>{\Gamma} always; i.e., the dynamics is more sensitive to volume than is the melting point, and for these liquids the dynamics at the melting point slows down with increasing Tm (that is, increasing pressure).Comment: 20 pages, 8 figures, 1 tabl

Quantum correlations in Newtonian space and time: arbitrarily fast communication or nonlocality

We investigate possible explanations of quantum correlations that satisfy the principle of continuity, which states that everything propagates gradually and continuously through space and time. In particular, following [J.D. Bancal et al, Nature Physics 2012], we show that any combination of local common causes and direct causes satisfying this principle, i.e. propagating at any finite speed, leads to signalling. This is true even if the common and direct causes are allowed to propagate at a supraluminal-but-finite speed defined in a Newtonian-like privileged universal reference frame. Consequently, either there is supraluminal communication or the conclusion that Nature is nonlocal (i.e. discontinuous) is unavoidable.Comment: It is an honor to dedicate this article to Yakir Aharonov, the master of quantum paradoxes. Version 2 contains some more references and a clarified conclusio

On the correlation between fragility and stretching in glassforming liquids

We study the pressure and temperature dependences of the dielectric relaxation of two molecular glassforming liquids, dibutyl phtalate and m-toluidine. We focus on two characteristics of the slowing down of relaxation, the fragility associated with the temperature dependence and the stretching characterizing the relaxation function. We combine our data with data from the literature to revisit the proposed correlation between these two quantities. We do this in light of constraints that we suggest to put on the search for empirical correlations among properties of glassformers. In particular, argue that a meaningful correlation is to be looked for between stretching and isochoric fragility, as both seem to be constant under isochronic conditions and thereby reflect the intrinsic effect of temperature

An integrated view of theiInfluence of temperature, pressure, and humidity on the stability of trimorphic cysteamine hydrochloride

Understanding the phase behavior of pharmaceuticals is important for dosage form development and regulatory requirements, in particular after the incident with ritonavir. In the present paper, a comprehensive study of the solid-state phase behavior of cysteamine hydrochloride used in the treatment of nephropathic cystinosis and recently granted orphan designation by the European Commission is presented employing (high-pressure) calorimetry, water vapor sorption, and X-ray diffraction as a function of temperature. A new crystal form (I2/a, form III) has been discovered, and its structure has been solved by X-ray powder diffraction, while two other crystalline forms are already known. The relative thermodynamic stabilities of the commercial form I and of the newly discovered form III have been established; they possess an overall enantiotropic phase relationship, with form I stable at room temperature and form III stable above 37 degrees C. Its melting temperature was found at 67.3 +/- 0.5 degrees C. Cysteamine hydrochloride is hygroscopic and immediately forms a concentrated saturated solution in water with a surprisingly high concentration of 47.5 mol % above a relative humidity of 35%. No hydrate has been observed. A temperature composition phase diagram is presented that has been obtained with the unary pressure temperature phase diagram, measurements, and calculations. For development, form I would be the best form to use in any solid dosage form, which should be thoroughly protected against humidity.Postprint (author's final draft

Thermal and X-ray measurements on nn-hexatriacontane (C36_{36}H74_{74})

The polymorphism of n-hexatriacontane (C$_{36}$H$_{74}$) was investigated by X-ray diffraction and DSC thermal analysis. C$_{36}$H$_{74}$ displays at least two stable monoclinic phases and a rotator phase. Starting from a solution-grown sample of very high purity the following phases are observed with increasing temperature: M011 $<$ 345K $<$ M101 $<$ 346K $<$ RIII $<$ 348K $<$ liquid. Depending on the thermal treatment also other forms may be obsaved. During these transitions, both the crystalline volume and the lamellar thickness increase. The higher order reflections of the layer structure was precisely measured by X-ray diffraction. Using a Fourier synthesis, electron density profiles of the three phases were analysed. The results show that the interlamellar structure is disturbed by inaeasing molecular motions with elevating temperatures. For some homologous alkanes also p(T) phase diagrams and binary systems have been studied