Viscosities and intradiffusion coefficients in the ternary system NaCl−MgCl2−H2O at 25°C

The intradiffusion coefficients of Na⁺, Cl^– ions and water and the tracerdiffusion coefficients of Ca²⁺ ion have been measured in the ternary system NaCl–MgCl₂–H₂O at 25°C. The intradiffusion coefficients of Mg²⁺ in this system have been estimated from the corresponding Ca²⁺ diffusion measurements. Viscosities were measured at the same solution concentrations as were used for the diffusion experiments. Intradiffusion and tracerdiffusion coefficients in a range of temperatures from 5 to 45°C are reported for standard sea-water which is a member of the above ternary set.     

Sol-Gel Poly-Component Nano-Sized Oxide Powders

Nano-sized, amorphous and monodispersed poly-component powders in the Al₂O₃–TiO₂–MgO and Al₂O₃–TiO₂–SiO₂ systems have been obtained by the sol-gel method. These powders have been characterized by XRD, IR spectroscopy, DTA/TGA and EDAX spectrometry. This last method confirmed the composition of the ternary powders, which are formed during the gelation process.The powders were tested as precursors for obtaining advanced ceramics, as tialite, Al₂TiO₅. The samples prepared with powders obtained by sol-gel method have shown a high reactivity, and the formation of tialite was improved.     

Capillary gas chromatography of C1−C4 alkyl tert-butyl ethers

Summary The separation of C₁–C₄ alkyl tert-butyl ethers with the general formula (CH₃)₃C–O–R (R-alkyl substituent) on fused-silica capillary columns coated with dimethylsilicone and cyanopropylmethylsilicone stationary phases was investigated. Retention indices were determined at two temperatures in order to understand their chromatographic behaviour. The respective standard deviations were 0.3 and 0.5 i.u.     

Chromium(III) Hydroxide Solubility in The Aqueous Na+-OH?-H2PO?4-HPO2?4-PO3?4-H2O System: A Thermodynamic Model

Chromium(III)-phosphate reactions are expected to be important in managing high-level radioactive wastes stored in tanks at many DOE sites. Extensive studies on the solubility of amorphous Cr(III) solids in a wide range of pH (2.8–14) and phosphate concentrations (10^–4 to 1.0 m) at room temperature (22±2)°C were carried out to obtain reliable thermodynamic data for important Cr(III)-phosphate reactions. A combination of techniques (XRD, XANES, EXAFS, Raman spectroscopy, total chemical composition, and thermodynamic analyses of solubility data) was used to characterize solid and aqueous species. Contrary to the data recently reported in the literature,⁽¹⁾ only a limited number of aqueous species [Cr(OH)₃H₂PO^–₄, Cr(OH)₃(H₂PO₄)^2–₂), and Cr(OH)₃HPO^2–₄] with up to about four orders of magnitude lower values for the formation constants of these species are required to explain Cr(III)-phosphate reactions in a wide range of pH and phosphate concentrations. The log K^o values of reactions involving these species [Cr(OH)₃(aq)+H₂PO^–₄⇌Cr(OH)₃H₂PO^–₄; Cr(OH)₃(aq)+2H₂PO^–₄⇌Cr(OH)₃(H₂PO₄)^2–₂; Cr(OH)₃(aq)+HPO^2–₄⇌Cr(OH)₃HPO^2–₄] were found to be 2.78±0.3, 3.48±0.3, and 1.97±0.3, respectively.     

Epitaxial Growth of Sr x Ba1 − x Nb2O6 Thin Films Prepared from Sol-Gel Process

In this study, we prepared Sr _x Ba_{1 – x} Nb₂O₆ (x = 0.3, 0.5 and 0.7) thin film on 0.75 wt% La doped SrTiO₃ (100) and (110) single crystal substrates. A homogeneous coating solution was prepared with Sr and Ba acetates and Nb(OEt)₅ as raw materials, and acetic acid and diethlene glycol monomethyl ether as solvents. The substrates were coated with the solution by spin coating method. As-coated thin films were heated from 973 to 1273 K in air. The grains of the thin film on La doped SrTiO₃ (100) were pillar shaped and arranged in right angle to each other. On the other hand, the grains of these thin films on La doped SrTiO₃ were pillar shape and arranged in one direction. The crystallographic relationship of the thin film between Sr _x Ba_{1 – x} Nb₂O₆ and substrate that the 130 and 310 direction of the thin film on the substrate were oriented with c-axis in parallel to the substrate surface. On the other hand, (hk0) phase diffractions of Sr _x Ba_{1 – x} Nb₂O₆ thin film on the substrate (110) were investigated in the XRD theta-2theta measurement. It is expected that the Sr _x Ba_{1 – x} Nb₂O₆ (x = 0.3, 0.5 and 0.7) were highly oriented or epitaxial growing on La doped SrTiO₃ (110) single crystal substrate.     

A study on the liquid–liquid equilibria of 1-alkyl-3-methylimidazolium hexafluorophosphate with ethanol and alkanes

This work demonstrates the ability of the 1-alkyl-3-methylimidazolium hexafluorophosphate to act as an extraction solvent in petrochemical processes for the removal of alkanes from their azeotropic mixture with ethanol. LLE (liquid–liquid equilibrium) of the ternary systems hexane + ethanol + 1-hexyl-3-methylimidazolium hexafluorophosphate (HMIM PF₆) or 1-octyl-3-methylimidazolium hexafluorophosphate (OMIM PF₆) and heptane + ethanol + OMIM PF₆ are carried out at 298.15 K and atmospheric pressure. Experimental liquid–liquid data are correlated by using different equations. The solute distribution ratio and the selectivity, determined from tie-line data, suggest the efficiency of the ILs used as solvents. A comparison with other IL, in terms of solvent capacity, is included. The liquid–liquid extraction process is simulated by using conventional software and the obtained results are shown.     

Thermodynamic Model for the Solubility of Cr(OH)3(am) in Concentrated NaOH and NaOH–NaNO3 Solutions

The main objective of this study was to develop a thermodynamic model for predicting Cr(III) behavior in concentrated NaOH and in mixed NaOH–NaNO₃ solutions for application to developing effective caustic leaching strategies for high-level nuclear waste sludges. To meet this objective, the solubility of Cr(OH)₃(am) was measured in 0.003 to 10.5 m NaOH, 3.0 m NaOH with NaNO₃ varying from 0.1 to 7.5 m, and 4.6 m NaNO₃ with NaOH varying from 0.1 to 3.5 m at room temperature (22 ± 2°C). A combination of techniques, X-ray absorption spectroscopy (XAS) and absorptive stripping voltammetry analyses, were used to determine the oxidation state and nature of aqueous Cr. A thermodynamic model, based on the Pitzer equations, was developed from the solubility measurements to account for dramatic increases in aqueous Cr with increases in NaOH concentration. The model includes only two aqueous Cr species, Cr(OH) ₄ ^– and Cr₂O₂(OH) ₄ ^– (although the possible presence of a small percentage of higher oligomers at >5.0 m NaOH cannot be discounted) and their ion–interaction parameters with Na⁺. The logarithms of the equilibrium constants for the reactions involving Cr(OH) ₄ ^– [Cr(OH)₃(am) + OH^– Cr(OH) ₄ ^– ] and Cr₂O₂(OH) ₄ ^2– [2Cr(OH)₃(am) + 2OH^– Cr₂O₂(OH) ₄ ^2– + 2H₂O] were determined to be –4.36 ± 0.24 and –5.24 ± 0.24, respectively. This model was further tested and provided close agreement between the observed Cr concentrations in equilibrium with Cr(OH)₃(am) in mixed NaOH–NaNO₃ solutions and with high-level tank sludges leached with and primarily containing NaOH as the major electrolyte.     

Migration Effects in Reversible System [Fe(CN)6]3–/4– on a Microelectrode

Migration factors Y are determined for an [Fe(CN)₆]^3–/4– reversible system at a platinum microelectrode 10 m in radius by measuring anodic and cathodic limiting currents at different concentrations of the redox forms in solution, from which Y _a and Y _c are calculated. The obtained results agree with theory. The experimental error for the Y _a/Y _c ratio is smaller than for each factor taken separately.     

Complex compounds of tetracycline with WO 4 2− and MoO 4 2− ions. Investigation by pH-metric and conductometric methods

By using pH-metric and conductometric methods it has been found that tetracycline (H₃TC) forms with WO ₄ ^2– and MoO ₄ ^2– ions the following complex compounds: [WO₃HTC]^2–, [WO₃(H₂TC)₂]^2– and [MoO₃(H₂TC)₂]^2–. Stability constants log/gb ₁ ^k =7.86 and log ₁ ^k =7.80 for [WO₃HTC]^2– and [MoO₃HTC]^2–, respectively, have been calculated from pH-metric measurements.     

Thermal transformation of quaternary compounds in NaF–CaF2–AlF3 system

Details of quaternary compounds formation in the system NaF–CaF₂–AlF₃ are specified. To achieve this aim, the samples of phases NaCaAlF₆ and Na₂Ca₃Al₂F₁₄ have been obtained by high-temperature solid-phase synthesis. Their thermal behavior when heated up to 800 °C has been studied using the methods of high-temperature X-ray diffraction (XRD) and thermal analysis (TA). The system under consideration can be regarded as a quasibinary section CaF₂–NaAlF₄, where at T=745–750 °C invariant equilibrium is implemented with the phases CaF₂–NaCaAlF₆–Na₂Ca₃Al₂F₁₄–(liquid melt)–(NaAlF₄). The peculiarity of the equilibrium is NaAlF₄ metastability at normal pressure. Below the equilibrium temperature the quaternary phase Na₂Ca₃Al₂F₁₄ is stable and NaCaAlF₆ above this temperature. The phase NaCaAlF₆ fixed by rapid quenching from high temperatures and when heated up to 640 °C decomposes, yielding Na₂Ca₃Al₂F₁₄. Further heating in vacuum at temperature up to 740 °C results in decomposition of Na₂Ca₃Al₂F₁₄ into CaF₂ and Na₃AlF₆. The expected reverse transformation of Na₂Ca₃Al₂F₁₄ into NaCaAlF₆ has not been observed under experimental conditions. Transformations in bulk samples reveal direct and reverse transformation of quaternary phases.

Synopsis

Thermal transformation of the quaternary compounds in system (NaF–CaF₂–AlF₃) was investigated using high-temperature X-ray diffraction (XRD) and thermal analysis (TA). In the system the invariant equilibrium is implemented with the phases CaF₂–NaCaAlF₆–Na₂Ca₃Al₂F₁₄–(liquid melt)–(NaAlF₄) at T=745–750 °C.     

Theoretical Evidence of Aromaticity in X3 − (X = B, Al, Ga) Species

We investigated the electronic structure and chemical bonding of the B₃ ^–, Al₃ ^–, and Ga₃ ^– anions, and the gas phase NaB₃, NaAl₃, and NaGa₃ molecules. We found that the ground state of the neutral gas phase salts contains an equilateral triangular anion interacting with a Na⁺ cation. The B₃ ^–, Al₃ ^–, and Ga₃ ^– anions possess two delocalized electrons and are found to be aromatic. The triangular anions have been shown to be related to recently synthesized organometallic compound containing an aromatic -Ga₃ ^2– unit, but they are differ from them by four valence electrons. The reason for earlier appearance of the -orbital in the B₃ ^–, Al₃ ^–, and Ga₃ ^– anions is discussed.     

Peptide β-Bend and 3 10 -Helix: from 3D-Structural Studies to Applications as Templates

The 3 ₁₀-helix is a relatively common secondary structure motif in peptides and proteins. Its building block is one of various types of β-bend conformation which comprises an N ^α-acylated dipeptide alkylamide system. A complete 3D-structural characterization of this ternary helix has been achieved, thus allowing its unambiguous discrimination from the closely related α-helix. Recent applications of rigidified peptide β-bends and 3 ₁₀-helices as templates for investigations in synthetic organic chemistry (macrocyclization, catalysis), host–guest chemistry (molecular recognition), and physical chemistry (donor–acceptor interaction) will be discussed.     

Thermoelectric properties of Cu-doped n-type (Bi2Te3)0.9–(Bi2−xCuxSe3)0.1(x=0–0.2) alloys

n-Type (Bi₂Te₃)_0.9–(Bi_2−xCu_xSe₃)_0.1 (x=0–0.2) alloys with Cu substitution for Bi were prepared by spark plasma-sintering technique and their structural and thermoelectric properties were evaluated. Rietveld analysis reveals that approximate 9.0% of Bi atomic sites are occupied by Cu atoms and less than 4.0 wt% second phase Cu_2.86Te₂ precipitated in the Cu-doped parent alloys. Measurements show that an introduction of a small amount of Cu (x0.1) can reduce the lattice thermal conductivity (κ_L), and improve the electrical conductivity and Seebeck coefficient. An optimal dimensionless figure of merit (ZT) value of 0.98 is obtained for x=0.1 at 417 K, which is obviously higher than those of Cu-free Bi₂Se_0.3Te_2.7 (ZT=0.66) and Ag-doped alloys (ZT=0.86) prepared by the same technologies.     

Silica-Zirconia Sol–Gel Coatings Obtained by Different Synthesis Routes

Homogeneous xSiO₂-(1−x)ZrO₂ coatings have been prepared onto glass-slides, monocrystalline Si and stainless steel (AISI 304) using sols prepared via acid and basic catalysis. Zirconium tetrabutoxide (TBOZr), zirconium n-propoxide (TPZ), tetraethoxysilane (TEOS) and methyltriethoxysilane (MTES) were used as precursors of zirconia and silica, respectively. The different parameters involved in the synthesis procedure, as molar ratios H₂O/alkoxides, NaOH/alkoxides, and sintering temperature have been analysed, correlating the stability and rheological properties of the sols. The evolution and structure of the sols and coatings have been studied by FTIR. Coatings have been prepared by dipping from acid and basic sols. Electrophoretic Deposition (EPD) technique has also been used to prepare coatings onto stainless steel from basic particulate sols in order to increase the critical thickness. A maximum thickness of 0.5 μ m was reached by both dipping and EPD process for 75SiO₂: 25 ZrO₂ composition. The critical thickness decreases with ZrO₂ amount depending strongly of the drying conditions. Si–O–Zr bonds have been identified by FTIR, indicating the existence of mixed network Si–O–Zr in the coatings obtained by the different routes. Crystallisation of ZrO₂(t) was only observed at high sintering temperature (900^∘C) by FTIR and confirmed by DRX.     

Preparation and hydrogen permeation of SrCe0.95Y0.05O3−δ asymmetrical membranes

Asymmetrical thin membranes of SrCe_0.95Y_0.05O_3−δ (SCY) were prepared by a conventional and cost-effective dry pressing method. The substrate consisted of SCY, NiO and soluble starch (SS), and the top layer was the SCY. NiO was used as a pore former and soluble starch was used to control the shrinkage of the substrate to match that of the top layer. Crack-free asymmetrical thin membranes with thicknesses of about 50 μm and grain sizes of 5–10 μm were successfully pressed on to the substrates. Hydrogen permeation fluxes (J_H2) of these thin membranes were measured under different operating conditions. At 950 °C, J_H2 of the 50 μm SCY asymmetrical membrane towards a mixture of 80% H₂/He was as high as 7.6 × 10⁻⁸ mol/cm² s, which was about 7 times higher than that of the symmetrical membranes with a thickness of about 620 μm. The hydrogen permeation properties of SCY asymmetrical membranes were investigated and activation energies for hydrogen permeation fluxes were calculated. The slope of the relationship between the hydrogen permeation fluxes and the thickness of the membranes was −0.72, indicating that permeation in SCY asymmetric membranes was controlled by both bulk diffusion and surface reaction in the range investigated.     

Theoretical calculations of95Mo-NMR chemical shifts for compounds [MoO4−n S n ]2−

Summary Theoretical calculation of⁹⁵Mo-NMR chemical shifts for [MoO_4–n S _n ]^2– (n=0–4) compounds is reported here for the first time on the basis of Fenske-Hall method and Sum-Over-State (SOS) perturbation theory. A systematic decrease in shielding of⁹⁵Mo nuclei with increase of number of sulfur in [MoO_4–n S _n ]^2–, which is observed experimentally, can be reasonably explained by our calculation. A good linear relationship between chemical shifts of calculation and experiment is obtained. The electronic structure and bonding in these compounds are also discussed.Supported by Nature Science Foundation of China     

Electron spin resonance spectra observed in the course of grafting iron carbonyls on sodium-Y zeolites

The adsorption and/or decomposition pathway of Fe₂(CO)₉ or Fe₃(CO)₁₂ on hydrated or dehydrated NaY zeolites has been studied by an ESR technique. The adsorption resulted in the formation of three paramagnetic species withg _iso=2.0450, 2.0378, and 2.0016, which were attributable to Fe₃(CO)₁₁ ^–, Fe₂(CO)₈ ^–, and Fe(CO)₄ ^– anion radicals, respectively. These radicals have been suggested as intermediates in the formation of HFe₃(CO)₁₁ ^– on the hydrated NaY zeolite and Fe₃(CO)₁₂ on the dehydrated NaY zeolite.     

Au-TiO2/Chit modified sensor for electrochemical detection of trace organophosphates insecticides

In this paper, Au–TiO₂/Chit modified electrode was prepared with Au–TiO₂ nanocomposite (Au–TiO₂) and Chitosan (Chit) as a conjunct. The Au–TiO₂ nanocomposite and the films were characterized by electrochemical and spectroscopy methods. A set of experimental conditions was also optimized for the film's fabrication. The electrochemical and electrocatalytic behaviors of Au–TiO₂/Chit modified electrode to trace organophosphates (OPs) insecticides such as parathion were discussed in this work. By differential pulse voltammetry (DPV) measurement, the current responses of Au–TiO₂/Chit modified electrode were linear with parathion concentration ranging from 1.0 ng/ml to 7.0 × 10³ ng/ml with the detection limit of 0.5 ng/ml. In order to evaluate the performance of the detection system, we also examined the real samples successfully in this work. It exhibited a sensitive, rapid and easy-to-use method for the fast determination of trace OPs insecticides.     

Viscosity of aqueous mixtures of silver and thallium nitrates with calcium or cadmium nitrates from pure fused salt to pure water

Fused salt-water systems extending from pure fused salt to pure water have been less studied than dilute aqueous solutions, despite their practical and theoretical importance. Even fewer studies have been made regarding the influence of the temperature upon transport properties. The present publication brings new interesting information on the viscous flow properties of the following two fused nitrate-water systems containing monovalent and divalent cations: AgNO₃–TINO₃–M(NO₃)₂–H₂O where M=Ca or Cd, with the TINO₃ and M(NO₃)₂ mole fractions in the anhydrous salt fixed at 0.436 and 0.100, respectively. The parameters in the Arrhenius, Eyring, Batschinski and the Abraham and Abraham equations are found to be well correlated with the properties of the components of the melts. The temperature effect allows a discussion to be made in terms of structural features such as holes and free volumes.     

New Ion Conductor of (Ba1−xLax)2In2O5+x

The structural characterization, thermogravimetric analysis and electrical properties for solid solution system, (Ba_1–xLa_x)₂In₂O_5+x with perovskite-type structure were investigated. X-ray diffraction showed that the orthorhombic phase was in the range of 0.0<x0.3, the tetragonal phase 0.3<x0.5, and the cubic phase 0.5<x. The sharp transition of electrical conductivity shifted to a lower temperature with increasing x and disappeared at the phase boundary between the orthorhombic and tetragonal phases. This perovskite-related oxide exhibited a pure oxide-ion conduction over the oxygen partial pressure range of 1 atm to 10^–3.5 atm, and the electrical conductivity reached the value of 1.610^–1 (S cm^–1) at 1073 K, which was nearly equal to that of the yttria stabilized zirconia. These properties were successfully explained in terms of disordered oxygen ions.This revised version was published online in November 2005 with corrections to the Cover Date.