Proton transfer rate‐equilibria in apolar aprotic solvents: a historical perspective

Low dielectric constant apolar aprotic solvents, although employed on a limited scale for studying proton transfer reactions as compared with commonly used polar protic or dipolar aprotic ones, offer some particular advantages, namely, specific solute–solvent interactions are virtually eliminated and proton transfer occurs directly in an apolar aprotic solvent. An intriguing feature of these reactions is their general acid‐catalyzed/base‐catalyzed kinetics with a time scale over microseconds to minutes. In fact, the true or intrinsic relative strengths of acids/bases when measured in such solvents come to the fore much more clearly than those obtained in other classes of solvents. Recently, a review documenting the post‐1980 developments relating to proton transfer reactions in apolar aprotic solvents has been published. The present article is a commentary of the pre‐1980 developments in this area since the 1920s Brønsted–Lowry's “proton cult” of acid–base theory. Copyright © 2016 John Wiley & Sons, Ltd.     

Hamilton's Principle and Rankine–Hugoniot Conditions for General Motions of Mixtures

In previous papers [1, 2], we presented hyperbolic governing equations and jump conditions for barotropic fluid mixtures. Now we extend our results to the most general case of twocomponent media. We obtain governing equations for each component. This is not a system of conservation laws. Nevertheless, using Hamilton's principle we are able to obtain a complete set of Rankine–Hugoniot conditions. For the twofluid case, the jump relations do not involve the conservation of the total momentum and the total energy.Sommario. In precedenti lavori [1, 2] sono state dedotte equazioni di governo iperboliche e condizioni di salto per miscele fluide barotropiche. I risultati sono estesi al caso più generale di mezzi a due componenti, ottenendo le equazioni di governo per ciascun componente. Questo sistema non è derivabile dalle leggi di conservazione. Nondimeno, usando il principio di Hamilton è possibile ottenere un insieme completo di condizioni di Rankine–Hugoniot. Nel caso dei due fluidi, le condizioni di salto non coinvolgono la conservazione del momento e dell'energia totali.     

Molar excess free energy of mixing of 1-propanol or 2-propanol with cyclohexane at 298.15 and 308.15 K in terms of association model with a Flory contribution term

Excess molar Gibbs free energies of mixing for 1-propanol or 2-propanol + cyclohexane over the whole composition range at 298.15 and 308.15 K have been calculated from vapour pressure data measured by static method. The data have been analysed in terms of a Mecke-Kempter association model with a Flory contribution term.     

Fluid multiphase equilibria and critical phenomena in binary and ternary mixtures of carbon dioxide, certain n-alkanols and tetradecane

Experimental results of fluid multiphase equilibria occurring in ternary mixtures of near-critical carbon dioxide, certain n-alkanols and tetradecane are presented. The following n-alkanols were used in this investigation: decanol, octanol, heptanol, hexanol and pentanol. In the ternary systems with decanol, octanol or heptanol a closed loop liquid-vapor two-phase region in the three-phase surface liquid-liquid-vapor was found. As far as the ternary system with decanol is concerned, this phenomenon is in agreement with an earlier and unexpected finding of Patton et al. (1993). In addition, it was also found in this study that the phase diagrams of the ternary mixtures with hexanol or pentanol as the n-alkanol show further complications.     

Transport and sedimentation of solid particles in Bénard hexagonal cells

The motion of particles moving under gravity in the velocity field of a liquid in a Bénard hexagonal cell is studied experimentally and numerically for Stokes flow conditions. We then explain the settlement of particles in the centers of cells to form a regular quincunx. It is found that sedimentation also occurs preferentially along the lines connecting the centers of adjacent cells to form a triangle deposition tessellation. Finally, it is explained why particles occupy the central part of each convective cell while the peripheral part of the cell quickly becomes limpid. Numerical results are in agreement with the experimental observations of Bénard and those of the present study.     

Development of an optical trap for microparticle clouds in dilute gases

Long-duration experiments with clouds of microparticles are planned for the ICAPS facility on board the International Space Station ISS. The scientific objectives of such experiments are widespread and are ranging from the simulation of aerosol behaviour in Earths atmosphere to the formation of planets in the early solar system. It is, however, even under microgravity conditions, impossible to sustain a cloud of free-floating, microscopic particles for an extended period of time, due to thermal diffusion and due to unavoidable external accelerations. Therefore, a trap for dust clouds is required which prevents the diffusion of the particles, which provides a source of relative velocities between the dust grains and which can also concentrate the dust to higher number densities that are otherwise not achievable. We are planning to use the photophoretic effect for such a particle trap. First short-duration microgravity experiments on the photophoretic motion of microscopic particles show that such an optical particle-cloud trap is feasible. First tests of a two-dimensional trap were performed in the Bremen drop tower.     

Multiphase equilibria for mixtures containing water, isopropanol, propionic acid, and isopropyl propionate

Vapor pressures of isopropyl propionate and isobaric vapor-liquid equilibrium (VLE) properties of isopropyl propionate + isopropanol and propionic acid + isopropyl propionate were measured. Isothermal vapor-liquid-liquid equilibrium (VLLE) data were also determined experimentally for water + isopropyl propionate and water + isopropyl propionate + isopropanol at temperatures from 323.24 K to 373.15 K. The binary VLE and VLLE data can be correlated well with the NRTL-HOC and the UNIQUAC-HOC models. The ternary VLLE data were used to test the validity of two versions of the UNIFAC model and the NRTL-HOC and the UNIQUAC-HOC models with the parameters determined from the phase equilibrium data of the constituent binaries. The ternary VLLE data were also correlated with the NRTL-HOC and the UNIQUAC-HOC models and the Soave-Redlich-Kwong equation of state with the Wong-Sandler mixing rule.     

Noncooperative stochastic games under a n-stage local contraction assumption

We consider a class of noncooperative stochastic games with general state and action spaces and with a state dependent discount factor. The expected time duration between any two stages of the game is not bounded away from zero, so that the usual N-stage contraction assumption, uniform over all admissible strategies, does not hold. We propose milder sufficient regularity conditions, allowing strategies that give rise with probability one to any number of simultaneous stages. We give sufficient conditions for the existence of equilibrium and ∈-equilibrium stationary strategies in the sense of Nash. In the two-player zero-sum case, when an equilibrium strategy exists, the value of the game is the unique fixed point of a specific functional operator and can be computed by dynamic programming.