Quantum-Chemical Evaluation of the Protolytic Properties of Thiophenols

The enthalpies and free energies of proton affinity (PA) were calculated by the PM3 method for 27 thiophenoxide anions. For thiophenols, linear correlation has been found between the PAs and the values of pK _a measured by different authors in aqueous acetone, aqueous ethanol, and methanol media. The dependences found permit one to predict a priori the protolytic properties of thiophenols. The differential effects of aqueous ethanol media with different ethanol contents on thiophenol acidity were evaluated based on quantum-chemical data.Original Russian Text Copyright © 2004 by A. N. Pankratov and A. V. Shalabai__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 800–806, September–October, 2004.     

Stress and heat flux stabilization for viscous compressible medium equations with a nonmonotone state function

We study a system of quasilinear equations describing one-dimensional flow of a viscous compressible heat-conducting medium with a nonmonotone state function and mass force. The large-time behavior of solutions is considered for arbitrarily large initial data. In spite of possible nonuniqueness and discontinuity of the stationary solution, we prove L²-stabilization for the stress and heat flux as t → ∞ along with corresponding global energy estimates for them. The new method of proof utilizes a combination of energy type equalities for the stress and heat flux. Consequently, H¹-stabilization of the velocity and temperature along with global estimates for their derivatives are valid as well.     

Pattern forming precipitation in gels due to coupling of chemical reactions with diffusion

Precipitate-forming chemical reactions have been studied in chemically cross-linked poly(vinyl alcohol) gel medium. One of the reactive components was incorporated into the gel, the other was allowed to diffuse into it. Depending on the experimental conditions the reaction-diffusion process often results in patterns of different type. Experiments performed in tubes and in thin layers were carried out in order to investigate the effects of various factors (cross-linking density, swelling degree as well as the concentrations of the outer and inner electrolytes) on the morphologies of the precipitate patterns. It was found that precipitation occurs not only in the Liesegang bands, but also between bands. Beside Liesegang-type structures, tree-like patterns have been observed, showing a characteristic periodicity in the density profile obtained by digitalized image analyses.     

Planar nematic anchoring on SiO-coated substrates

Summary The nematic planar anchoring is usually explained by using simple elastic models: the surface easy axis corresponds to the surface direction that minimizes the excess of nematic elastic energy. When anisotropic rough substrates are used to align nematic liquid crystals, due to the complex surface morphology, usual elastic models are not directly applicable. This paper presents quantitative topographical data of rough substrates, obtained with oblique SiO evaporation under vacuum for nematic planar anchoring. Experimental data are obtained by means of Atomic Force Microscopy and they are used to demonstrate the self-affine nature of these substrates and to relate the nematic anchoring with the anisotropy of the local fractal properties of the substrate itself. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Interactions between kinetic and radiative processes inside moving absorbing fluids

The aim of this paper is to present several features of the couplings occurring between radiative transfer and the kinetics of a moving dielectric. After determining how the velocity field affects the apparent thermo-optical properties of matter, the energy transport problem is investigated in instationary regime and the general form of transient radiative transfer equation inside a moving medium is built. Then, the model is applied to the particular case of turbulent flows: a system of two equations for mean and fluctuating radiative energies is presented, and the resolution of this system is finally carried out.     

Electro-optical performance of polymer stabilized cholesteric texture cell: The influence of chiral dopant and monomer concentration

Reverse-mode polymer stabilized cholesteric texture (PSCT) cells with various chiral dopant and monomer concentrations were fabricated. Experimental results indicate that the chiral dopant concentration and the monomer concentration significantly influence the threshold voltage and hysteresis of the cells. The chiral dopant and monomer deform the hysteresis loop. Increasing the monomer concentration reduces the width of the hysteresis loop of the reverse-mode PSCT cell.     

Thermodynamic and surface properties of Sb-Sn and In-Sn liquid alloys

The thermodynamic properties of Sb-Sn and In-Sn liquid alloys have been studied using the quasi-chemical model for compound forming binary alloys and that for simple regular alloys. The concentration fluctuation S _cc(0) and the Warren-Cowley short-range order parameter (α ₁) were determined for the whole concentration range at a temperature of 770 K. The surface tensions of these liquid alloys were determined for the whole concentration range by using energetics determined from thermodynamic calculations. In all calculations, In-Sn manifested properties very close to alloys of ideal mixing, while Sb-Sn showed properties that are asymmetric about equiatomic composition. Our results suggest that a weak complex of the form SbSn₂ could be present in the Sb-Sn alloy at a temperature of about 770 K.     

Electroanalytical and chromatographic determination of pentachlorophenol and related molecules in a contaminated soil: a real case example

Electroanalytical and chromatographic methodologies have been applied for the determination of pentachlorophenol (PCP) and some of its derivatives in real soil samples contaminated by industrial discharge. The analytes were extracted with hexane from soil samples collected at different points of the site and mixed to produce a representative sample. Square wave voltammetry (SWV) experiments were carried out on either a boron-doped diamond (BDD) electrode or a gold ultramicroelectrode (Au-UME) in an analyte composed by the Britton-Robinson (B-R) buffer at pH 5.5 with the direct addition of proper amounts of the extract. The voltammetric responses revealed an irreversible anodic peak at approximately 0.80 V vs. Ag/AgCl with a peak current showing a linear dependence on PCP concentration. This linear relationship yielded a detection limit (DL) of 2×10⁻⁸ mol l⁻¹ (or 5.5 μg l⁻¹) for the BDD electrode and 6.9×10⁻⁸ mol l⁻¹ (18.4 μg l⁻¹) for the Au-UME, while the independently measured HPLC detection limit was 1.1×10⁻⁸ mol l⁻¹ (3.0 μg l⁻¹). The application of electroanalytical and chromatographic methodologies in the analysis of soil extracts revealed, besides the PCP responses, signals for some related molecules such as o-tetrachlorobenzoquinone (o-chloranil), hexachlorobenzene and tetrachlorophenol. Recovering experiments for PCP showed a concentration of 27.5 mg kg⁻¹ for the electroanalytical determinations and 26.8 mg kg⁻¹ for the HPLC analysis, values exceedingly high if considering that the maximum residue limit established for natural waters by the Brazilian Environmental Agency is 10 μg l⁻¹.