Thermodynamic investigation of liquid properties of the Ni–Sn–Ti ternary system using CALPHAD method and geometric models

Predictions for the liquid Ni–Sn–Ti alloys thermodynamic properties (molar excess Gibbs energy) are presented. The calculations were performed in the temperature range 1000–2000 K. Geometric models (using data from the binary end-systems) were used and the respective calculated molar excess Gibbs energy values were compared to CALPHAD method assessments. The concentration dependences of the liquid phase thermodynamic properties along different vertical sections Sn:Ti, Ni:Ti and Ni:Sn were estimated.Ternary interaction parameters (L0, L1 and L2) of the liquid phase were determined using General solution (geometric) model from thermodynamic data of the binary end–systems (Ni–Sn, Ni–Ti, Sn–Ti). Ternary parameters exhibit values: L0 = - 70360.5 - 0.263*T; L1 = -113023 - 11.574*T; L2 = - 131755 - 17.101*T. Negative molar excess Gibbs energies were obtained by all models.

Facing interfaces A clustering approach to grammaticalization and related changes

It has long been recognized that many instances of change that have been discussed within the framework of grammaticalization studies notoriously defy categorization, for instance because they share properties of grammaticalization and lexicalization (Brinton & Traugott 2005), or because they share some properties of grammaticalization, but not all of them, as in the case of discourse markers (e.g. Ocampo 2006). In order to avoid these classification issues, we will argue that it is more useful to reduce grammaticalization and related changes to their “main mechanisms” (formal reanalysis and semantic reinterpretation), “primitive changes” (micro-changes on the levels of phonology, morphology, syntax, semantics and/or discourse), and “side effects” (e.g. obligatorification or layering). In grammaticalization and related changes, formal reanalysis and semantic reinterpretation tend to coincide with different sets of primitive changes. Primitive changes will be defined as ternary parameters with the values reduction, expansion, or zero, and it will be seen that they tend to cluster in different ways. Some of these clusters may coincide with changes traditionally labeled “grammaticalization”, “degrammaticalization”, or “lexicalization”, but changes may also cluster in alternative ways. This novel approach to composite changes we term the “clustering approach”, and we aim to show that this model of analysis allows for a more fine-grained account of composite changes than definition-based taxonomies.

Pitzer Model Based Study of CsX-NiX2-H2O (X = Cl, Br) Systems at 298.15 K

The Pitzer ion-interaction model was used for simulating the CsX-NiX2-H2O (X = Cl, Br) systems at 298.15 K. The necessary thermodynamic functions (binary and ternary parameters, thermodynamic solubility products) were calculated and the theoretical solubility diagrams plotted. A very good agreement was found between the calculated and observed data.

Liquid-Liquid Equilibrium in the Water-Methyl tert-Butyl Ether-Nitromethane-Ethylene Glycol System

The liquid-liquid equilibrium was measured at 20 °C in the title quaternary system and in the three nitromethane-containing ternary subsystems. The data were compared with those predicted by a superposition of the Wilson and Redlich-Kister equations including the ternary parameters. The agreement between the observed and calculated data is very good both for the quaternary system and for the three ternary systems.

Liquid-liquid equilibrium in the water-ethanol-toluene system. Correlation of equilibrium data

Liquid-liquid equilibrium data in the water-ethanol-toluene system were correlated by the superposition of the Wilson and Redlich-Kister equations with a ternary term. The correlation of both homogeneous binary systems was taken from the literature. The ternary liquid-liquid equilibrium data were at all temperatures satisfactorily described on using only three ternary parameters determined from the equilibrium data at 50 °C. The parameters obtained by the correlation yield also a good estimate of boiling point and composition of homogeneous azeotropic mixture.