PVTx relationships and solid-liquid equilibria for the m-xylene-p-xylene system under high pressures

PVTx relationships of the m-xylene-p-xylene system have been measured with a glass piezometer at 283.15 and 298.15 K and pressures up to 200 MPa, or up to the point of solidification of m-xylene where this occurred at a lower pressure. Freezing pressures of m-xylene were observed as a discontinuity in the volume at increasing pressure. Approximate solid-liquid equilibria under high pressures were obtained from the freezing pressure measurement. The Carnahan-Starling-van der Waals (CS-vdW) equation of state was used to correlate the PVTx data. The solid-liquid equilibria under high pressures were calculated with the CS-vdW equation of state for the liquid phase and a simple equation of state for the solid phase. In order to test the validity of the calculation method, the solid-liquid equilibrium relationships of the benzene-cyclohexane system were also calculated. It was found that the solid molar volume should be treated as a function of temperature and/or pressure to fit the experimental data.     

An attempt directed toward enhanced shape selectivity in reversed-phase liquid chromatography: preparation of the dodecylaminated beta-cyclodextrin-bonded phase.

With the aim of preparing a stationary phase with a high shape-recognition ability for liquid chromatography, a new bonded phase was synthesized by coupling multiply dodecylamino-substituted beta-cyclodextrin (beta-CD) to 3-glycidoxypropyl-derivatized silica gel. The stationary phase prepared in this way was expected to have increased shape selectivity compared with that of conventional reversed-phase materials, due to solute interactions with the alkyl chain piles built up on the beta-CDs bonded to silica. The separation characteristics of the bonded phase were investigated using polycyclic aromatic hydrocarbons (PAHs) with different molecular shapes and compared with those of monomeric ODS and native beta-cyclodextrin-bonded phases. The newly developed stationary phase was found to be highly selective for PAHs.     

The role of a radial ion-track distribution in semiconductors studied by numerical simulations

The effect of radial ion-track distribution on the transient current in semiconductors caused by a high-energy heavy ion strike was studied. Reasonable agreement was observed in experimental and calculated transient currents for ion energies ranging from several to several hundred MeV when the radius of the ion track used in the numerical simulations was shorter or equivalent to that of the penumbra radius.     

Discontinuous boundary implementation for the shallow water equations

Quasi‐bubble finite element approximations to the shallow water equations are investigated focusing on implementations of the surface elevation boundary condition. We first demonstrate by numerical results that the conventional implementation of the boundary condition degrades the accuracy of the velocity solution. It is also shown that the degraded velocity leads to a critical instability if the advection term is present in the momentum equation. Then we propose an alternative implementation for the boundary condition. We refer to this alternative implementation as a discontinuous boundary (DB) implementation because it introduces at each boundary node two independent mass–flux values that result in a discontinuity at the boundary. Numerical results show that the proposed DB implementation is consistent, stabilizes the quasi‐bubble scheme, and leads to second‐order accuracy at the surface elevation specified boundary. Copyright © 2004 John Wiley & Sons, Ltd.     

Molecular distortion effect on ff-emission in a Pr(III) complex with 4,7-diphenyl-1,10-phenanthroline.

The electronic and structural behaviour of a Pr(III) complex with 4,7-diphenyl-1,10-phenanthroline, [Pr(bathophen)(2)(NO(3))(3)], is investigated with respect to the effect of configuration changes on the Pr(III) centre. [Pr(bathophen)(2)(NO(3))(3)] luminesces from the excited states of the ligand and the metal ion. The fluorescence, ff-emission ((1)D(2)-->(3)H(4)), and phosphorescence bands appear at 394, 608.2 and 482 nm, respectively, in the solid state. In acetonitrile, the complex also shows multiple emissions. From the time-resolved emission and the lifetime measurements, the excitation energy-transfer in [Pr(bathophen)(2)(NO(3))(3)] is clarified, that is, the upper excited triplet level of the ligand acts as an energy donor, while the (1)D(2) levels of Pr(III) is the acceptor. Additionally, the emission phenomena of the complex can be modified by molecular distortion, particularly by rotation of the phenyl groups in the ligand.     

Electro-electrodialysis of HI–I2–H2O mixture using radiation-grafted polymer electrolyte membranes

In the thermochemical water-splitting iodine–sulfur process for hydrogen production, new polymer electrolyte membranes were applied in an electro-membrane process (electro-electrodialysis, EED) to increase the HI molality of HIx solution (HI + I₂ + H₂O mixture) to be over quasi-azeotropic. Radiation grafting of a styrene monomer into a poly(ethylene-co-tetrafluoroethylene) base film and subsequent sulfonation provided electrolyte membranes that had ion exchange capacities (IECs) of 1.1–1.6 mmol/g. With the EED of the HIx solutions using [HI] = [I₂] = 10 mol/kg at 40 °C the transport number of protons, ratio of permeated quantities of water to the protons, and current efficiency all appeared to depend on the IEC of the resulting membranes. When compared to Nafion, the self-made membranes exhibited lower electric cell resistance, and thereby decreasing up to 32% of the overall energy required in the concentration operation.     

Binary nucleation rates for ethanol/water mixtures in supersonic Laval nozzles

Although the conditions corresponding to the onset of condensation of aqueous-alcohol mixtures have been measured in supersonic nozzles [B. E. Wyslouzil et al., J. Chem. Phys. 113, 7317 (2000)], the true nucleation rates have not. Here, we propose a new analytical method to estimate the temperature, the concentrations of condensable species in both the vapor and the liquid phases, and the amount of the condensate using only the measured static pressure profiles in the nozzle. We applied the method to ethanol/water (CH(3)CH(2)OH/D(2)O or CH(3)CH(2)OD/D(2)O) mixtures and confirmed that the aerosol volume fractions derived from pressure measurements and small angle neutron scattering measurements are in very good agreement when this method is used. Combining the results from the pressure measurements with the number densities of the condensed droplets, measured either by small angle neutron or small angle x-ray scattering, we determined the first quantitative ethanol/water binary nucleation rates in the supersonic nozzle at a temperature of 229±1?K.     

Quantum dynamics of a driven correlated system coupled to phonons

Nonequilibrium interplay between charge, spin, and lattice degrees of freedom on a square lattice is studied for a single charge carrier doped in the t-J-Holstein model. In the presence of a static electric field we calculate the quasistationary state. With increasing electron-phonon (e-ph) coupling the carrier mobility decreases; however, we find increased steady state current due to e-ph coupling in the regime of negative differential resistance. We explore the distribution of absorbed energy between the spin and the phonon subsystem. For model parameters as relevant for cuprates, the majority of the gained energy flows into the spin subsystem.     

Lithium ion conduction in lithium borohydrides under high pressure

The high-pressure effects on lithium ion conduction in LiBH₄ have been investigated. The high-pressure ac-impedance measurement was performed by using a cubic anvil-type apparatus under 2 to 6 GPa at various temperatures. For the hexagonal structure (Phase I), the activation volume for lithium ion conduction was found to be around 3 cm³/mol (≈ 0.09V_m, where V_m means its molar volume). This activation volume is almost comparable to that for other fast-ion conductors such as NASICONs. The lithium ion conductivities of orthorhombic (Phase III) and cubic (Phase V) structures were also measured. Regardless of crystal structures, the activation energies of Phases I, III, and V were almost identical at around 50 to 60 kJ/mol; on the other hand, the pre-exponential terms of Phases III and V were smaller than those of Phase I by one to two orders of magnitude.     

Remark on the Helmholtz decomposition in domains with noncompact boundary

Let \(\varOmega \) be a domain in \(\mathbb {R}^{d+1}\) whose boundary is given as a uniform Lipschitz graph \(x_{d+1}=\eta (x)\) for \(x \in \mathbb {R}^d\) . For such a domain, it is known that the Helmholtz decomposition is not always valid in \(L^p(\varOmega )\) except for the energy space \(L^2 (\varOmega )\) . In this paper we show that the Helmholtz decomposition still holds in certain anisotropic spaces which include vector fields decaying slowly in the \(x_{d+1}\) variable. In particular, these classes include some infinite energy vector fields. For the purpose, we develop a new approach based on a factorization of divergence form elliptic operators whose coefficients are independent of one variable.