Organometallic chemistry of diphosphazanes. Part 15. Half-sandwich cyclopentadienyl ruthenium complexes of achiral and chiral diphosphazanes

Reaction of [CpRu(PPh3)(2)Cl] (1) {Cp = eta(5)-(C5H5)} with X2PN(CHMe2) PYY' {X = Y = Y' = Ph (L-1); X = Y = Ph, Y' = OC6H4Me-4 (L-4); X = Y = Ph, Y' = OC6H3Me2- 3,5 (L-5); X = Y = Ph, Y' = N2C3HMe2 (L-6)} yields the cationic chelate complexes, [CpRu(eta(2)-(X2PN(CHMe2) PYY')) PPh3] Cl. On the other hand, the reaction of 1 with X2PN(CHMe2)PYY' {X = Ph, YY' = O2C6H4(L-3)} gives the complex, [CpRu(eta(1)-L-2)(2)PPh3] Cl. Both types of complexes are formed with X2PN(CHMe2) PYY' {X = Ph, YY' = O2C6H4 (L-3)}. The reaction of 1 with (R),(S)-(H12C20O2) PN(CHMe2) PPh2 (L-7) yields both cationic and neutral complexes, [CpRu{eta(2)-(L-7)} PPh3] Cl and [CpRu{eta(1)-(L-7)}(2)PPh3] Cl and [CpRu{eta(2)-(L-7)}Cl]. The reactions of optically pure diphosphazane, Ph2PN(*CHMePh) PPhY (Y = Ph (L-8); Y = N2C3HMe2-3,5 (L-9)) with 1 give the neutral and cationic ruthenium complexes, [CpRu{eta(2)-(Ph2PN(R) PPhY)} Cl] and [CpRu{eta(2)-(Ph2PN(R)PPhY)} PPh3] Cl. "Chiral-at-metal" ruthenium complexes of diphosphazanes have been synthesized with high diastereoselectivity. The absolute configuration of a novel ruthenium complex, (SCSPRRu)-[(eta(5)-C5H5) Ru*{eta(2)-(Ph2PN(*CHMePh)P*Ph( N2C3HMe2-3,5))} Cl] possessing three chiral centers, is established by X-ray crystallography. The reactions of [CpRu{eta(2)-(L-8)} Cl] with mono or diphosphanes in the presence of NH4PF6 yield the cationic complexes, [CpRu{eta(2)-(L-8)}{eta(1)-(P)}] PF6 {P = P(OMe)(3), PPh3, Ph2P(CH2)(n)PPh2 (n = 1 or 2)}.

Physical chemistry of mixed conducting zirconia ceramics

Suivant la pression partielle d'oxygène, la zircone peut être conducteur ionique ou électronique. Mise au point de méthodes de mesures de f.é.m. permettant de s'affranchir des sources d'erreur introduites par ces propriétés.

Physical chemistry of the reduction of calcium oxide with aluminium in vacuum

The physical chemistry of "aluminothermic" reduction of calcium oxide in vacuum is analyzed. Basic thermodynamic data required for the analysis have been generated by a variety of experiments. These include activity measurements in liquid AI-Ca alloys and determination of the Gibbs energies of formation of calcium aluminates. These data have been correlated with phase relations in the Ca-AI-0 system at 1373 K. The various stages of reduction, the end products and the corresponding equilibrium partial pressures of calcium have been established from thermodynamic considerations. In principle, the recovery of calcium can be improved by reducing the pressure in the reactor. However,, the cost of a high vacuum system and the enhanced time for reduction needed to achieve higher yields makes such a practice uneconomic. Aluminum contamination of calcium also increases at low pressures. The best compromise is to carry the reduction up to the stage where 3CaO-Al,O, is formed as the product. This corresponds to an equilibrium calcium partial pressure of 31.3 Pa at 1373 K and 91.6 Pa at 1460 K. Calcium can be extracted at this pressure using mechanical pumps in approximately 8 to 15 hr, depending on the size and the fill ratio of the retort and porosity of the charge briquettes.

Tribology of soot suspension in hexadecane as distinguished by the physical structure and chemistry of soot particles

Ethylene gas is burnt to generate soot which is collected thermophoretically from different locations of the flame. Tribological performance of the collected soot in hexadecane suspension is compared with that of carbon black and diesel soot. The soots are analysed to yield a range of mechanical properties, physical structures and chemistry. The paper correlates these property variations with the corresponding variations in friction and wear when the soot suspended in hexadecane is used to lubricate a steel on steel sliding interaction. The particles are dispersed in hexadecane by a non-ionic surfactant, poly-isobutylene succinimide (PIBS), which is mono-functional with no free amine group. The grafting of the surfactant on the soot particles is found to have a profound effect on the dispersion of the soot, in general, while, between the different soot types, the tribology is differentiated by the physical structure and chemistry.

Preparation and characterization chemistry of nano-crystalline Ni-Cu-Zn ferrite

In submitted research; nanocrystalline powders having elements Ni0.5Cu0.25Zn0.25Fe2 xInxO4 with varied amounts of indium ( x = 0.0, 0.1, 0.2, 0.3 and 0.4) were grown-up by modified citrate to nitrate alchemy. The realism of single phase cubic spinel creation of the synthesized ferrite samples was studied by the DTA-TGA, XRD, SEM, EDX, FT-IR, VSM and dielectric measurements. SEM was applied to inspect the morphological variations and EDX was used to determine the compositional mass ratios. The studies on the dielectric constant (epsilon'), dielectric loss (epsilon `'), loss tangent (tan delta), ac conductivity (sigma(ac)), resistive and reactive parts of the impedance analysis (Z' and Z `') at room temperature were also carried out. The saturation magnetizations (Ms) were determined using the vibrating sample magnetometer (VSM). Ms. decreased with the increase In3+ doping content, as Fe3+ of 5(mu B) ions are replaced by In3+ of 5 mu(B) ions. (C) 2012 Elsevier B. V. All rights reserved.

Air oxygenation chemistry of 4-TBC catalyzed by chloro bridged dinuclear copper(II) complexes of pyrazole based tridentate ligands: synthesis, structure, magnetic and computational studies

Four dinuclear bis(mu-Cl) bridged copper(II) complexes, Cu-2(mu-Cl)(2)(L-X)(2)](ClO4)(2) (L-X = N,N-bis(3,5-dimethylpyrazole-1-yl)-methyl]benzylamine with X = H(1), OMe(2), Me(3) and Cl(4)), have been synthesized and characterized by the single crystal X-ray diffraction method. In these complexes, each copper(II) center is penta-coordinated with square-pyramidal geometry. In addition to the tridentate L-X ligand, a chloride ion occupies the last position of the square plane. This chloride ion is also bonded to the neighboring Cu(II) site in its axial position forming an SP-I dinuclear Cu(II) unit that exhibits small intramolecular ferromagnetic interactions and supported by DFT calculations. The complexes 1-3 exhibit methylmonooxygenase (pMMO) behaviour and oxidise 4-tert-butylcatechol (4-TBCH2) with molecular oxygen in MeOH or MeCN to 4-tert-butyl-benzoquinone (4-TBQ), 5-methoxy-4-tert-butyl-benzoquinone (5-MeO-4-TBQ) as the major products along with 6,6'-Bu-t-biphenyl-3,4,3',4'-tetraol and others as minor products. These are further confirmed by ESI- and FAB-mass analyses. A tentative catalytic cycle has been framed based on the mass spectral analysis of the products and DFT calculations on individual intermediates that are energetically feasible.

Chromite-silicate chemistry of the Neoarchean Sittampundi Complex, southern India: Implications for subduction-related arc magmatism

The Neoarchean layered anorthositic complex at Sittampundi in southern India is known for its chromitite layers that are mostly associated with anorthosite (An(90-100)). The chromitites contain FeAl-rich chromites concentrated in layers between amphibole-rich layers with a dominant mineralogy of amphibole-spinel-plagiocase+/-sapphirine. The chromite-rich layers contain only amphibole and plagioclase. Mineral compositions illustrated by X-ray composition maps and profiles show subtle chemical differences. The chrome spinels are of refractory grade with Cr2O3 and Al2O3 contents varying between 34-40 wt.% and 23-28 wt.%. The chromite compositions are noticeably different from those in layered igneous intrusions of the Bushveld-Stillwater type. The existence of original highly calcic plagioclase, FeAl-rich chromite, and magmatic amphibole is consistent with derivation from a parental magma of hydrous tholeiitic composition that was most likely generated in a supra-subduction zone arc setting. In terms of mineralogy and field relations, the Sittampundi chromitites are remarkably similar to anorthosite-hosted chromitites in the Neoarchean Fiskensset anorthositic complex, Greenland. We propose that the Sittampundi chromitites formed by partial melting of unusually aluminous harzburgite in a hydrated mantle wedge above a subduction zone. This melting process produced hydrous, aluminous basalt, which fractionated at depth to give rise to a variety of high-alumina basalt compositions from which the anorthositic complex with its cumulate chromite-rich and amphibole-rich layers formed within the magma chamber of a supra-subduction zone arc. (C) 2011 Elsevier B.V. All rights reserved.

Influence of physical structure and chemistry of diesel soot suspended in hexadecane on lubrication of steel-on-steel contact

Soot generated from the combustion process in diesel engines affect engine tribology. In this paper, two diesel soot samples; from engine exhaust and oil filter are suspended in hexadecane oil and the suspension is used to lubricate a steel ball on steel flat sliding contact at a contact pressure of 1.3 GPa. The friction and wear of the steel flat are recorded. The data are compared with those recorded when the soot is generated by burning ethylene gas. The rationale for the comparatively poor tribology of diesel soot is explored by quantifying the size and shape of primary particles and agglomerates, hardness of single primary soot particles, the crystallinity and surface and near surface chemistry of soot and interparticle adhesion.

Phase chemistry of the system Nb-Rh-O

Phase relations in the system Nb-Rh-O at 1223 K were investigated by isothermal equilibration of eleven compositions and analysis of quenched samples using OM, XRD, SEM and EDS. The oxide phase in equilibrium with the alloy changes progressively from NbO to NbO2, NbO2.422 and Nb2O5-x with increasing Rh. Only one ternary oxide NbRhO4 with tetragonal structure (a=0.4708 nm and c=0.3017 nm) was detected. It coexists with Rh and Nb2O5. The standard Gibbs energy of formation of NbRhO4 from its component binary oxides measured using a solid-state electrochemical cell can be represented by the equation; Delta G(f,ox)(o)(J/mol) = -38,350 + 5.818 x T(+/- 96) Constructed on the basis of thermodynamic information of the various alloy and oxide phases are oxygen potential diagram for the system Nb-Rh-O at 1223 K and temperature-composition diagrams at constant partial pressures of oxygen.

Physics and chemistry of CdTe/CdS thin film heterojunction photovoltaic devices: fundamental and critical aspects

Among the armoury of photovoltaic materials, thin film heterojunction photovoltaics continue to be a promising candidate for solar energy conversion delivering a vast scope in terms of device design and fabrication. Their production does not require expensive semiconductor substrates and high temperature device processing, which allows reduced cost per unit area while maintaining reasonable efficiency. In this regard, superstrate CdTe/CdS solar cells are extensively investigated because of their suitable bandgap alignments, cost effective methods of production at large scales and stability against proton/electron irradiation. The conversion efficiencies in the range of 6-20% are achieved by structuring the device by varying the absorber/window layer thickness, junction activation/annealing steps, with more suitable front/back contacts, preparation techniques, doping with foreign ions, etc. This review focuses on fundamental and critical aspects like: (a) choice of CdS window layer and CdTe absorber layer; (b) drawbacks associated with the device including environmental problems, optical absorption losses and back contact barriers; (c) structural dynamics at CdS-CdTe interface; (d) influence of junction activation process by CdCl2 or HCF2Cl treatment; (e) interface and grain boundary passivation effects; (f) device degradation due to impurity diffusion and stress; (g) fabrication with suitable front and back contacts; (h) chemical processes occurring at various interfaces; (i) strategies and modifications developed to improve their efficiency. The complexity involved in understanding the multiple aspects of tuning the solar cell efficiency is reviewed in detail by considering the individual contribution from each component of the device. It is expected that this review article will enrich the materials aspects of CdTe/CdS devices for solar energy conversion and stimulate further innovative research interest on this intriguing topic.