Velocity of sound in two-phase mixtures

Velocity of sound is computed for water, ammonia, Freon-12 and isobutane in two-phase mixtures in thermodynamic equilibrium. A computational method is developed which yields the sound velocity in terms of the thermodynamic coordinates of the substance (T, x) without the use of diagrams. Corresponding velocities of sound for the four substances considered exhibit a certain similarity which is examined statistically. The relationship between the sound velocity and the critical mass flux is also investigated.     

Tautomeric equilibria in phenolic A-ring derivatives of prodigiosin natural products

The prodigiosin natural products contain a common 4-methoxy-pyrromethene chromophore that is attached to a pyrrole A-ring that has its lone-pair nitrogen electrons in conjugation with the pyrromethene entity. This feature is known to play a key role in the biological activities (anticancer, antimicrobial, and immunosuppressive) of the prodigiosins. In an attempt to alter or improve upon the therapeutic potential of the prodigiosins, we have synthesized two new isomeric analogues that contain phenolic A-ring systems (a para (p)-phenol; an ortho (o)-phenol with respect to the pyrromethene) with lone-pair oxygen electrons in conjugation with the pyrromethene chromophore of the natural product. Herein, we report on the optical properties of the phenolic prodigiosin analogues that have been measured using absorbance and steady-state emission spectroscopy. For both analogues absorption measurements in aprotic solvents show that the neutral (L) ligands exist as the enol tautomers with lambda(max) ~ 460 nm, as noted for the parent prodigiosin natural product. However, in polar protic solvents the phenolic derivatives undergo ground-state prototropic tautomerization to generate keto tautomers with lambda(max) ~ 530 nm. This unique feature for a prodigiosin analogue involves proton transfer from the phenolic OH to the pyrromethene N1 proton acceptor atom. Tautomeric equilibrium constants (KT) of 1.4 in 1:4 MeCN/H2O (v/v) have been determined from examination of the absorption spectra. Titration of the o-phenolic derivative with Zn(II) in methanol yielded a 40-fold increase in fluorescence intensity (lambda(max) 542 nm) and generated a new 1:1 complex with Zn(II) with a log K of 5.29, suggesting the potential utility of this analogue to act as a fluorescence probe in a biological matrix to monitor Zn(II) concentrations. Our results demonstrate that phenolic A-ring derivatives of prodigiosins possess some unique properties that may act to enhance the biological properties of the prodigiosin natural products.     

Density functional theory simulations of water–metal interfaces: waltzing waters, a novel 2D ice phase, and more

There are few molecules, if any, more important than water. Yet remarkably little is known about how it interacts with solid surfaces, particularly at the all important atomic level. This is true despite widespread general interest and compelling environmental and economic incentives. Here, I will discuss detailed density-functional theory studies aimed at putting our understanding of water–solid interfaces, specifically water–metal interfaces, on a much firmer footing. In this paper, I will attempt to answer some key questions: Where do isolated water monomers adsorb on flat metal surfaces? How do water monomers diffuse across metal surfaces? How do water dimers adsorb and diffuse across metal surfaces? What factors control the structure and stability of water bilayers on metal surfaces?     

Encapsulation and Polymerization of White Phosphorus Inside Single-Wall Carbon Nanotubes

Elemental phosphorus displays an impressive number of allotropes with highly diverse chemical and physical properties. White phosphorus has now been filled into single-wall carbon nanotubes (SWCNTs) from the liquid and thereby stabilized against the highly exothermic reaction with atmospheric oxygen. The encapsulated tetraphosphorus molecules were visualized with transmission electron microscopy, but found to convert readily into chain structures inside the SWCNT “nanoreactors”. The energies of the possible chain structures were determined computationally, highlighting a delicate balance between the extent of polymerization and the SWCNT diameter. Experimentally, a single-stranded zig-zag chain of phosphorus atoms was observed, which is the lowest energy structure at small confinement diameters. These one-dimensional chains provide a glimpse into the very first steps of the transformation from white to red phosphorus.     

Resonance production and clustering effects in reactions K−p → Λ0 + pions at an incident beam momentum 8.25 GeV/c

We have estimated cross sections for the production of resonances in the reactions K^?p → Λ⁰ + pions. The data have also been analysed by a method which examines event-to-event fluctuations. Within the framework of the simple parametrization of resonance production assumed, the contribution from the resonances is insufficient to explain the observed fluctuations in the longitudinal emission of the final-state particles. These features are well reproduced by an independent cluster emission model.     

Identification of general linear relationships between activation energies and enthalpy changes for dissociation reactions at surfaces

The activation energy to reaction is a key quantity that controls catalytic activity. Having used ab inito calculations to determine an extensive and broad ranging set of activation energies and enthalpy changes for surface-catalyzed reactions, we show that linear relationships exist between dissociation activation energies and enthalpy changes. Known in the literature as empirical Br?nsted-Evans-Polanyi (BEP) relationships, we identify and discuss the physical origin of their presence in heterogeneous catalysis. The key implication is that merely from knowledge of adsorption energies the barriers to catalytic elementary reaction steps can be estimated.     

Numerical modeling of a two-dimensional vertical turbulent two-phase jet

The results of numerically modeling two-dimensional two-phase flow of the “gas-solid particles” type in a vertical turbulent jet are presented for three cases of its configuration, namely, descending, ascending, and without account of gravity. Both flow phases are modeled on the basis of the Navier-Stokes equations averaged within the framework of the Reynolds approximation and closed by an extended k-? turbulence model. The averaged two-phase flow parameters (particle and gas velocities, particle concentration, turbulent kinetic energy, and its dissipation) are described using the model of mutually-penetrating continua. The model developed allows for both the direct effect of turbulence on the motion of disperse-phase particles and the inverse effect of the particles on turbulence leading to either an increase or a decrease in the turbulent kinetic energy of the gas. The model takes account for gravity, viscous drag, and the Saffman lift. The system of equations is solved using a difference method. The calculated results are in good agreement with the corresponding experimental data which confirms the effect of solid particles on the mean and turbulent characteristics of gas jets.     

Comparison of the RANS and PDF methods for air-particle flows

Two simulation methods, namely Reynolds-Averaged Navier–Stokes (RANS) equations, and Probability Distribution Function (PDF) are currently widely used for the modeling of multiphase flows. These two approaches are supplemented with appropriate closure equations that take into account all the pertinent forces and interaction effects on the solid particles, such as: particle–turbulence interactions; turbulence modulation; particle–particle interactions; particle–wall interactions; gravitation, drag and lift forces. The two methods have been used in order to simulate the turbulent particulate flow in upward pipes. The flow domain in all cases was a cylindrical pipe and the computations were carried for upward pipe flow. Monodisperse as well as polydisperse mixtures of particles have been considered. In general, the average velocity results obtained from the two methods are in close agreement, because the methods predict well the average velocity distribution of the carrier fluid as well as the solids. Thus, the differences in the average axial velocities predicted by the methods are not substantial. Differences in the turbulence intensity are more significant. A comparison of the numerical results obtained shows the relative importance of retaining the diffusion terms in both the axial and radial directions in the RANS method. Also the comparisons of the results show the relative effect of the lift forces in the distribution of solid particles.     

Surface energy and surface proton order of ice Ih

Ice Ih is comprised of orientationally disordered water molecules giving rise to positional disorder of the hydrogen atoms in the hydrogen bonded network of the lattice. Here we arrive at a first principles determination of the surface energy of ice Ih and suggest that the surface of ice is significantly more proton ordered than the bulk. We predict that the proton order-disorder transition, which occurs in the bulk at approximately 72 K, will not occur at the surface at any temperature below surface melting. An order parameter which defines the surface energy of ice Ih surfaces is also identified.