Direct electrosynthesis of halo and mixed-halo complexes of palladium(II and IV) by the dissolution of a sacrificial palladium anode in aqueous medium

A rapid single-step method for the electrosynthesis of chloro and bromo complexes of palladium(II and IV), viz. M₂[PdX₄] and M₂[PdX₆], by the dissolution of a palladium anode in chloride or bromide containing media is described. Electrolysis of dilute HX solution in the presence of pyridine, 2,2′-bipyridyl or 1,10-phenanthroline gives rise to non-electrolytes, e.g. trans-[PdX₂(py)₂], [PdX₂(bipy)] and [PdX₂(phen)]. Anodic oxidation of palladium in HX medium in the presence of acetonitrile and benzonitrile also gives the non-electrolytes trans-[PdX₂(CH₃CH₂NH₂)₂] and trans-[PdX₂(C₆H₅CH₂NH₂)₂], respectively.     

Reaction of N-(2-hydroxyethyl) ethylenediamine over zeolite and chromite catalysts

N-(2-hydroxyethyl) ethylenediamine reaction was observed over zeolite catalysts giving rise to only dehydrocyclization and over chromite catalysts showing dehydrocyclization together with dehydrogenation. The major product changes from the cyclized compound piperazine to pyrazine when the reactant is switched from zeolite to chromite catalyst. This process stands as a model reaction for characterizing lone acid sites and adjacent acid-base sites over zeolite and chromite catalysts, respectively.IICT Communication No. 3175     

Errors in the determination of silica in lead-bearing samples caused by preliminary separation of lead sulphate

Some procedures for the gravimetric determination of silica in lead-bearing samples involve the extraction of lead sulphate with ammonium acetate. Results for silica are then low because some silica is dissolved in ammonium acetate solution. Correct results can be obtained only by avoiding fuming with sulphuric acid. If samples contain a large proportion of insoluble silica, preliminary fusion with sodium hydroxide is recommended.     

Effect of isomeric butanols on the temperature corresponding to the adiabatic compressibility minimum of water

The effect of isomeric butanols on the temperature corresponding to the adiabatic compressibility minimum of water (T _β) was studied using a variablepath interferometer working at 3 MHz. The structural contribution to the shift inT _β, [ΔT _βstr]_exp, was found to be positive and to increase with concentration to a maximum atX ₂?0.0193, 0.0100, and 0.0090 fort-butanol, sec-butanol, and isobutanol, respectively. The results have been explained on the basis of stabilization of water structure at low concentrations of alcohol. The quantity [ΔT _βstr]_exp forn-butanol is practically zero at low concentrations, while at high concentrations it is negative, indicating rupture of the hydrogen-bonded structure of water by this solute. At any given concentration,t-butanol > sec-butanol > isobutanol >n-butanol is the order of increasing structural contribution to the shift inT _β. Theoretical values of the structural contribution to the shift inT _β are in good agreement with the experimental data.     

Determination of rhodium in water samples using cloud point extraction (CPE) coupled with flame atomic absorption spectrometry (FAAS)

Cloud point extraction was applied as a method for preconcentration of rhodium after formation of a complex with 2-propylpiperidine-1-carbodithioate (2-PPC), and later determined by flame atomic absorption spectrometry using TritonX-114 as surfactant. Rhodium was complexed with 2-PPC in an aqueous phase and kept for 15 min in a thermostatted bath at 40 °C. Separation of the two phases was accomplished by centrifugation for 15 min at 4000 rpm. The chemical variables affecting the cloud point extraction were optimized and successfully applied to rhodium determination in various water samples. Under optimized conditions, the preconcentration system (100 mL sample) permitted an enhancement factor of 50. The detection limits obtained under optimal conditions was 0.052 ng mL⁻¹. The extraction efficiency was investigated at different rhodium concentrations (7.0–42.0 μg mL⁻¹), and good recoveries (96.42–99.14%) were obtained using this method. It has been applied to the determination of rhodium in water and was compared with reported methods in terms of Student’s ‘t’-test and variance ratio ‘f’-test.     

Novel Catalytic Dielectric Barrier Discharge Reactor for Gas-Phase Abatement of Isopropanol

Catalytic gas-phase abatement of air containing 250 ppm of isopropanol (IPA) was carried out with a novel dielectric barrier discharge (DBD) reactor with the inner catalytic electrode made of sintered metal fibers (SMF). The optimization of the reactor performance was carried out by varying the voltage from 12.5 to 22.5 kV and the frequency in the range 200–275 Hz. The performance was significantly improved by modifying SMF with Mn and Co oxide. Under the experimental conditions used, the MnO _x /SMF showed a higher activity towards total oxidation of IPA as compared to CoO _x /SMF and SMF electrodes. The complete destruction of 250 ppm of IPA was attained with a specific input energy of ∼235 J/L using the MnO _x /SMF catalytic electrode, whereas, the total oxidation was achieved at 760 J/L. The better performance of the MnO _x /SMF compared to other catalytic electrodes suggests the formation of short-lived active species on its surface by the in-situ decomposition of ozone.     

New lipids from the soft corals of the Andaman Islands

Sphingolipids and glycolipids including previously unknown (2S,3S,4R)-1,3,4-trihydroxy-2-(2-(R)-hydroxyoctadecanoylamino)octadec-8E-ene, (2S,3R)-1,3-dihydroxy-2-octadecanoylamino-4E,8E-hexadecadiene, and (2-hydroxy-3-hexadecyloxypropyl)--L-fucopyranoside were isolated from soft corals collected on the shelf near the Andaman Islands (Indian Ocean). The structures of all compounds were established by spectroscopic methods and chemical analyses. The lipids possessed antibacterial activity against Bacillus subtilis, Bacillus pumilus, Escherichia coli, and Pseudomonas aeruginosa and antifungal activity against Aspergillus niger, Rhizopus oryzae, and Candida albicans.     

Completeness and fixed-points

In this note the converses of recent fixed-point theorems due toKannan andChatterjea are obtained. An example is constructed to show that a metric space having the fixed-point property for homeomorphisms need not be metrically topologically complete. An example ofConnell is formulated in a more general perspective.     

Anilate Tethered Neutral Tetrahedral Pd(II) Cages Exhibiting Selective Encapsulation of Xylenes and Mesitylene

The design of porous materials for the recognition of multiple hydrocarbons is highly desirable for the energy-efficient separation and recognition of chemical feedstock. Herein, three new iso-structural porous discrete metal–organic cages of formula {[Pd₃(NiPr)₃PO]₄(R-AN)₆} (R-AN=anilate linkers) for the selective recognition of substituted aromatic hydrocarbons are reported. The tetrahedral cages 1 , 2 , and 3 containing anilate, chloranilate, and bromanilate linkers exhibited selective encapsulation of mesitylene, o-xylene, and p-xylene, respectively, over other analogous aromatic hydrocarbons. These selective encapsulations were driven by the variations in the portal diameters present at each of these cages and their interactions with the hydrocarbon guests. These observations are supported by mass spectrometry, NMR studies, and theoretical binding-energy calculations.     

Synthesis of Thermally Stable Energetic 1,2,3‐Triazole Derivatives

Various thermally stable energetic polynitro‐aryl‐1,2,3‐triazoles have been synthesized through Cu‐catalyzed [3+2] cycloaddition reactions between their corresponding azides and alkynes, followed by nitration. These compounds were characterized by analytical and spectroscopic methods and the solid‐state structures of most of these compounds have been determined by using X‐ray diffraction techniques. Most of the polynitro‐bearing triazole derivatives decomposed within the range 142–319 °C and their heats of formation and crystal densities were determined from computational studies. By using the Kamlet–Jacobs empirical relation, their detonation velocities and pressures were calculated from their heats of formation and crystal densities. Most of these newly synthesized compounds exhibited high positive heats of formation, good thermal stabilities, reasonable densities, and acceptable detonation properties that were comparable to those of TNT.