A chemical test of the principle of critical point universality: the solubility of nickel (II) oxide in isobutyric acid + water near the consolute point

A mixture of isobutyric acid + water has an upper consolute point at 38.8 mass?% isobutyric acid and temperature near 26?°C. Nickel (II) oxide dissolves in this mixture by reacting with the acid to produce water and nickel isobutyrate. The solubility of nickel (II) oxide in isobutyric acid + water has been measured as a function of temperature at compositions, 25, 38.8, and 60 mass?% isobutyric acid. For values of the temperature, T, which were at least 2 K in excess of the liquid-liquid phase transition temperature, the measured values of the solubility, s, lie on a straight line when plotted in van't Hoff form with ln?s versus 1∕T. The slope, (?ln?s∕?(1∕T)), of the line is negative indicating that the dissolution reaction is endothermic. When the temperature was within 2 K of the phase transition temperature, however, (?ln?s∕?(1∕T)) diverged toward negative infinity. The principle of critical point universality predicts that when excess solid nickel (II) oxide is in dissolution equilibrium with liquid isobutyric acid + water, (?ln?s∕?(1∕T)) should diverge upon approaching the consolute point along the critical isopleth at 38.8 mass?% isobutyric acid. As determined by the sign of the enthalpy of solution, the sign of this divergence is expected to be negative. Not only do our experiments confirm these predictions, but they also show that identical behavior can be observed at both 25 and 60 mass?% isobustyric acid, compositions which lie substantially to either side of the critical composition.     

Reduction of amine N-oxides by diboron reagents

Facile reduction of alkylamino-, anilino-, and pyridyl-N-oxides can be achieved via the use of diboron reagents, predominantly bis(pinacolato)- and in some cases bis(catecholato)diboron [(pinB)(2) and (catB)(2), respectively]. Reductions occur upon simply mixing the amine N-oxide and the diboron reagent in a suitable solvent, at a suitable temperature. Extremely fast reductions of alkylamino- and anilino-N-oxides occur, whereas pyridyl-N-oxides undergo slower reduction. The reaction is tolerant of a variety of functionalities such as hydroxyl, thiol, and cyano groups, as well as halogens. Notably, a sensitive nucleoside N-oxide has also been reduced efficiently. The different rates with which alkylamino- and pyridyl-N-oxides are reduced has been used to perform stepwise reduction of the N,N'-dioxide of (S)-(-)-nicotine. Because it was observed that (pinB)(2) was unaffected by the water of hydration in amine oxides, the feasibility of using water as solvent was evaluated. These reactions also proceeded exceptionally well, giving high product yields. In constrast to the reactions with (pinB)(2), triethylborane reduced alkylamino-N-oxides, but pyridine N-oxide did not undergo efficient reduction even at elevated temperature. Finally, the mechanism of the reductive process by (pinB)(2) has been probed by (1)H and (11)B NMR.     

Mixed alkali effect and optical properties of Ni2+ doped 20ZnO+xLi2O+(30-x)Na2O+50B2O3 glasses

Optical and physical properties of Ni2+ doped 20ZnO+xLi2O+(30-x)Na2O+50B2O3 (5≤x≤25) glasses are carried out at room temperature. Powder XRD pattern of all the glass samples confirms the amorphous nature. Several physical parameters are evaluated for all the glasses with respect to the composition. The optical absorption spectra confirm the site symmetry of the Ni2+ doped glasses are near octahedral. Crystal field and inter-electronic repulsion parameters are also evaluated. It is interesting to observe that the optical band gap and Urbach energies exhibit the mixed alkali effect. The FT-IR spectral investigations of Ni2+ doped glasses exhibit characteristic vibrations of BO3 and BO4 units.     

Nanostructured MnO2: an efficient and robust water oxidation catalyst

Nanostructured MnO(2) exhibits a high turnover frequency for oxygen evolution under visible light and high stability in strong acidic conditions.     

Thermal expansion and heat capacity measurements on Ba10?xCsx(PO4)6Cl2?δ, (x?=?0, 0.5) chloroapatites synthesized by sonochemical process

Ba_10−x Cs _x (PO₄)₆Cl₂, (x = 0, 0.5) chloroapatite ceramics were prepared by sonochemical method of synthesis. The measured room temperature lattice parameters of Ba₁₀ (PO₄)₆Cl₂ and Ba_9.5Cs_0.5 (PO₄)₆Cl_2−δ are practically the same; that is, a = 10.26 (8), c = 7.65 (7) and a = 10.27 (7), c = 7.65 (5), respectively. Heat capacity measurements were carried out on these materials by differential scanning calorimetry (DSC) in the temperature range 298–800 K. The heat capacity values of Ba_9.5Cs_0.5(PO₄)₆Cl_2−δ are found to be slightly higher at all temperatures than those of Ba₁₀(PO₄)₆Cl₂. From the heat capacity data, other thermodynamic functions such as enthalpy and entropy increments were computed. The heat capacity values of Ba₁₀(PO₄)₆Cl₂ and Ba_9.5Cs_0.5(PO₄)₆Cl_2−δ at 298 K are 0.3912 and 0.4310 J K⁻¹ g⁻¹, respectively. Thermal expansion property of the doped and undoped barium chloroapatites was measured by using a home built dilatometer which uses LVDT as displacement sensor. The bulk thermal expansion of Ba₁₀(PO₄)Cl₂ and Ba_9.5Cs_0.5(PO₄)Cl_2−δ is observed to be about 0.9% in the temperature range of 298–973 K.     

Formation of V2O3 nanocrystals by thermal reduction of V2O5 thin films

We report the formation of homogeneous and stable V₂O₃ nanocrystals, directly from V₂O₅ thin films, at 600 °C, as observed by using in situ electron microscopy experiments. Thermally-induced reduction of V₂O₅ thin films in vacuum is remarkably different when compared to reduction of V₂O₅ single crystals and results in the formation of nanophase V₂O₃. Thermally grown V₂O₃ nanocrystals exhibit hexagon or square shape and are stable at higher temperature as well as room temperature. The formation of stable nanocrystals through the reduction process in a non-chemical environment (vacuum) could provide a basis for understanding the complex processes of vanadium oxide phase transitions and for controlling the chemical processes to produce oxide nanocrystals.     

Spatial Stability for Mixed Convection Boundary Layer over a Heated Horizontal Plate

The spatial stability properties of a mixed convection boundary layer developing over a heated horizontal plate is studied here under linear and quasi-parallel flow assumption. The main aim of the present work is to find out if there is a critical buoyancy parameter that would indicate the importance of heat transfer in destabilizing mixed convection boundary layers, when the buoyancy effect is given by Boussinesq approximation. The undisturbed flow used here is that given by the similarity solution of [ 1 ] that implies the wall temperature to vary as the inverse square root of the distance from the leading edge of the plate. The stability of this flow has been investigated by using the compound matrix method (CMM)—that allows finding all the modes in the chosen range in the complex wave number plane for spatial stability analysis. Presented neutral curves for mixed convection boundary layer show the existence of two types of disturbances present simultaneously, for large buoyancy parameter. One notices very unstable high-frequency mode when the buoyancy parameter exceeds the above-mentioned critical value. This unstable thermal mode is in addition to the hydrodynamic mode of isothermal flow given by corresponding similarity profile. The calculated critical buoyancy parameter is shown to qualitatively match with experimental results.     

A four-arm Sagnac interferometric switch

A four-arm Sagnac interferometric switch is demonstrated. The switch works on the nonlinearity of the Pancharatnam's phase in a Young's interference set-up with differently polarized coherent laser beams.     

Synthesis of polysubstituted pyrroles from sulfinimines (N-sulfinyl imines)

Polysubstituted 2-carboxylate and 2-phosphonate pyrroles are prepared by aromatization of the corresponding 3-oxo 2-carboxylate and 2-phosphonate NH-pyrrolidines using air. Reaction of electrophiles with 3-oxo pyrrolidine dianions readily introduces substituents, regioselectively at C-4 in these pyrrolidines.