Raman and infrared spectroscopic studies of phurcalite from Red Canyon, Utah, USA – Implications for the molecular structure

Raman and infrared spectra of the uranyl mineral phurcalite, Ca2(UO2)3O2(PO4)2⋅7H2O, from Red Canyon, Utah, USA, were studied and tentatively interpreted. Observed bands were assigned to the stretching and bending vibrations of (UO2)2+ and (PO4)3− units and to the stretching and bending vibrations and libration modes of water molecules. Approximate lengths of U–O in (UO2)2+ and O–H⋯O hydrogen bond lengths were inferred from observed stretching vibrations. The presence of structurally nonequivalent U6+ and P5+ was inferred from the number of corresponding stretching bands of (UO2)2+ and (PO4)3− units observed in the Raman and infrared spectra..

Synthesis, characterization and X-ray structure of hexahydrazinium diuranyl pentaoxalate dihydrate, (N2H5)6(UO2)2(C2O4)5·2H2O

A new hydrazinium uranyl oxalate complex (N2H5)6[(UO2)2(C2O4)5]·2H2O has been prepared and characterized by chemical analysis, infrared, visible spectra and TG-DTA. The single crystal X-ray structure of the complex shows the presence of discrete N2H5+ cations, water molecules and [(UO2)2(C2O4)5]6− anions. In the anion, the linear uranyl groups are coordinated by two chelating bidentate oxalates and one bridging oxalate which lies on the center of symmetry between the two uranyl groups. The coordination polyhedron around each uranium atom is approximately a pentagonal bipyramid.

Komplexe von Lanthanidnitraten mit 2-Methylpyridin-1-oxid

Complexes of lanthanide nitrates with 2-methylpyridine-1-oxide of the formuleLn(2-MePyO)3(NO3)3 whereLn=Nd, Sm, Tb, Dy and Yb and La(2-MePyO)3(NO3)3·2H2O have been prepared and characterized by chemical analyses, IR spectral, conductance andDTA data. IR spectral data have been interpreted in terms of the coordination of the ligand to the metal through the oxygen of the N–O group. Conductance and IR spectral data show that all the nitrate groups are bidentate and that two of the nitrate groups are bound to the metal in a different manner than the other.

Dynamic simulation of activated sludge based wastewater treatment processes: Case studies with Titagarh Sewage Treatment Plant, India

STOAT has been extensively used for the dynamic simulation of an activated sludge based wastewater treatment plant in the Titagarh Sewage Treatment Plant, near Kolkata, India. Some alternative schemes were suggested. Different schemes were compared for the removal of Total Suspended Solids (TSS), b-COD, ammonia, nitrates etc. A combination of IAWQ#1 module with the Takacs module gave best results for the existing scenarios of the Titagarh Sewage Treatment Plant. The modified Bardenpho process was found most effective for reducing the mean b-COD level to as low as 31.4 mg/l, while the mean TSS level was as high as 100.98 mg/l as compared to the mean levels of TSS (92 62 mg/l) and b-COD (92.0 mg/l) in the existing plant. Scheme 2 gave a better scenario for the mean TSS level bringing it down to a mean value of 0.4 mg/l, but a higher mean value for the b-COD level at 54.89 mg/l. The Scheme Final could reduce the mean TSS level to 2.9 mg/l and the mean b-COD level to as low as 38.8 mg/l. The Final Scheme looks to be a technically viable scheme with respect to the overall effluent quality for the plant. (C) 2009 Elsevier B.V. All rights reserved.

The ambient aerosol characterization during the prescribed bushfire season in Brisbane 2013

Prescribed burnings are conducted in Queensland each year from August until November aiming to decrease the impact of bushfire hazards and maintain the health of vegetation. This study reports chemical characteristics of the ambient aerosol, with a focus on source apportionment of the organic aerosol (OA)fraction, during the prescribed biomass burning (BB) season in Brisbane 2013. All measurements were conducted within the International Laboratory for Air Quality and Health (ILAQH) located in Brisbane’s Central Business District. Chemical composition, degree of ageing and the influence of BB emission on the air quality of central Brisbane were characterized using a compact Time of Flight Aerosol Mass Spectrometer (cToF-AMS). AMS loadings were dominated by OA (64 %), followed by, sulfate (17 %), ammonium (14 %) and nitrates (5 %). Source apportionment was applied on the AMS OA mass spectra via the multilinear engine solver (ME-2) implementation within the recently developed Source Finder (SoFi) interface. Six factors were extracted including hydrocarbon-like OA (HOA), cooking-related OA (COA), biomass burning OA (BBOA), low-volatility oxygenated OA (LV-OOA), semivolatile oxygenated OA (SV-OOA), and nitrogen-enriched OA (NOA). The aerosol fraction that was attributed to BB factor was 9 %, on average over the sampling period. The high proportion of oxygenated OA (72 %), typically representing aged emissions, could possess a fraction of oxygenated species transformed from BB components on their way to the sampling site.

Synthesis, characterization and photoluminescence properties of Gd2O3:Eu3+ nanophosphors prepared by solution combustion method

Gd2O3:Eu3+ (0.5-8.0 mol%) nanophosphors have been prepared by low temperature solution combustion method using metal nitrates as oxidizers and oxalyl dihydrazide (ODH) as a fuel. The phosphors are well characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and photoluminescence (PL) techniques. PXRD patterns of as-formed and calcined (800 degrees C, 3 h) Gd2O3 powders exhibit monoclinic phase with mean crystallite sizes ranging from 20 to 50 nm. Eu3+ doping changes the structure from monoclinic to mixed phase of monoclinic and cubic. SEM micrographs shows the products are foamy, agglomerated and fluffy in nature due to the large amount of gases liberated during combustion reaction. Upon 254 nm excitation the photoluminescence of the Gd2O3:Eu3+ particles show red emission at 611 nm corresponding to D-5(0)-> F-7(2) transition. It is observed that PL intensity increases with calcination temperature. This might be attributed to better crystallization and eliminates the defects, which serve as centers of non-radiative relaxation for nanomaterials. It is observed that the optical energy gap (E-g) is widened with increase Eu3+ content. (C) 2010 Elsevier B.V. All rights reserved.

Synthetic and physicochemical studies of uranium complexes with semicarbazone and hydrazone

Uranyl complexes of two Schiff bases, semicarbazone and hydrazone containing OON donor atoms have been synthesized and characterized on the basis of NMR, IR and electronic spectral studies, conductance, magnetic susceptibility and thermogravimetric data. The 1H NMR spectrum of the semicarbazone complex shows low field signals due to OH, NH and ---CH=N groups at 10.23, 9.31 and 8.17 ppm, respectively. The aromatic protons appear in the range 7.74–7.40 ppm. On complexation with U(VI) the signals due to OH and NH disappear evidently due to their participation in coordination. The coordination number of the o-vanillin semicarbazone (oVSC) complex is 6 whereas, that of the o-vanillin isonicotinic acid hydrazone (oVINAH) complex is 8, in addition to the two oxygen atoms already bonded to U(VI) in each species. The thermograms show the presence of 3 and 2 water molecules in these complexes, respectively and the IR spectral data also support the above conclusion. Suitable structures have been assigned.

Combustion synthesis of rare earth cuprates

Rare earth cuprates, La2CuO4 Nd2CuO4, La1.8M0.2CuO4 (M=Ca.Sr) and Nd1.85Ce0.15CuO4 have been prepared by the combustion of redox mixtures containing corresponding metal nitrates and maleic hydrazide, C4H4N2O2, at 350°C. The solid combustion products are submicron size amorphous powders which on heat treatment (700°C, 30 minutes) yield crystalline single phase cuprates. Strontium doped lanthanum cuprate, La1.8Sr0.2CuO4, shows an onset of superconductivity at 36K.

Spectroscopic investigations of phase transitions in complex solids

Spectroscopic methods have provided information of seminal importance in understanding phase transitions in solids. After briefly examining some fundamental concept related to phase transitions, we shall discuss several case studies particularly involving the use of vibrational (IR and Raman) spectroscopy. Examples will include both order-disorder and displacive transitions. Under the former are included transitions in nitrates, ammonium halides, alkylammonium salts, plastic state of C60 and superionic conductors (specially CsHSO4). In addition, we shall discuss some aspects of incommensurate phase transitions, the glass transition and electronic phase transitions. Transitions of phosphonitrilic halide tetramers and alkane dicarboxylic acids are also examined

Combustion synthesis and properties of Ln3Fe5O12 and yttrium aluminium garnets

The rare earth iron garnets Ln3Fe5O12 and Y3AlxFe5-xO12, where x=1.0-5.0, and Y1.5Gd1.5Al0.2Fe4.8O12 have been prepared by the combustion of redox mixtures containing corresponding metal nitrates and oxalyl dihydrazide, i.e. C2H6N4O2 at 350-degrees-C. The solid combustion products are amorphous, submicrometre-sized powders which, on heating at 750-degrees-C for 3 h, yield crystalline single-phase garnets. The particle size of the garnets is below 1 mum and the surface area ranges from 16 to 90 m2 g-1. Yttrium iron garnet could be sintered to a density of more than 95% at 1200-degrees-C for 3 h, giving an average grain size of 3-5 mum.

Combustion synthesis of oxide materials for nuclear waste immobilization

Oxide materials like perovskite, zirconolite, hollandite, pyrochlore, NASICON and sphene which are used for nuclear waste immobilization have been prepared by a solution combustion process. The process involves the combustion of stoichiometric amount of corresponding metal nitrates and carbohydrazide/tetraformyl trisazine/diformyl hydrazide at 450 degrees C. The combustion products have been characterized using powder X-ray diffraction, infrared spectroscopy, and Si-29 MAS-NMR. The fine particle nature of the combustion derived powders has been studied using density, particle size, BET surface area measurements and scanning electron microscopy. Sintering of combustion derived powder yields 85-95% dense ceramics in the temperature range 1000 degrees-1300 degrees C.

Synthesis and properties of tialite, beta-AL2TIO5

Tialite, beta-Al2TiO5, a low expansion material, has been synthesised by the combustion of corresponding metal nitrates and carbohydrazide (CH) or urea redox mixtures at 500-degrees-C. As prepared powders contained tialite, rutile, and corundum in the mole ratios of 50:25:25 (CH) and 20:40:40 (urea). The combustion derived powders, when calcined 30 min at 1300-degrees-C, gave single phase beta-tialite having a surface area of 20-25 m2 g-1 and a particle size of 0.79-1.03 mum.

Synthesis and properties of rare earth doped lamp phosphors

Red, blue and green emitting lamp phosphors such as EU(3+) doped Y2O3 (red phosphor), EU(2+) doped Ba0.64Al12O18.64, BaMgAl10O17 and BaMg2Al16O27 (blue phosphors) and Ce0.67Tb0.33MgAl11O19 and Eu2+, Mn2+ doped BaMgAl10O17 (green phosphors) have been prepared by the combustion of the corresponding metal nitrates (oxidizer) and oxalyl dihydrazide/urea/carbohydrazide (fuel) mixtures at 400 degrees-500 degrees C within 5 min. The formation of these phosphors has been confirmed by their characteristic powder X-ray diffraction patterns and fluorescence spectra. The phosphors showed characteristic emission bands at 611 nm (red emission), 430-450 nm (blue emission) and 515-540 nm (green emission). The fine-particle nature of the combustion derived phosphors has been investigated using powder density, particle size and BET surface area measurements.

Synthetic, spectroscopic and structural studies on uranium and thorium complexes of diphosphazane dioxides

Co-ordination complexes of the diphosphazane dioxides Ph(2)P(O)N(Pr-i)P(O)Ph(2) L(1). Ph(2)P(O)N(Pr-i)P(O)Ph(OC(6)H(4)Me-4) L(2) and Ph(2)P(O)N(Pr-i)P(O)(O2C12H8) L(3) with UO22+ or Th4+ ions have been synthesised and characterised by IR and NMR spectroscopy. The structures of [UO2(NO3)(2)L(1)] and [Th(NO3)(2)L(3)(1)][Th(NO3)(6)] are established by X-ray crystallography. In the former, the uranyl ion is bonded to two bidentate nitrate groups and the two phosphoryl groups of the ligand L(1); the co-ordination polyhedron around the metal is a hexagonal bipyramid. The cationic moiety in the thorium complex contains three bidentate diphosphazane dioxide ligands and two bidentate nitrate groups around the ten-co-ordinated metal.

Synthesis and properties of La1-xSrxFeO3

Fine particle strontium substituted lanthanum ferrites La1-xSrxFeO3, where x = 0.0-1.0, have been synthesized by the solution combustion method using corresponding metal nitrates, oxalyl dihydrazide (ODH) or tetra formal tris azine (TFTA). Formation of La1-xSrxFeO3 was confirmed by the XRD and the fine particle nature of the ferrites investigated using SEM, particle size analysis and BET surface area measurements. La1-xSrxFeO3 (up to x = 0-0.4) exhibited low resistivity near the Neel temperatures. La1-xSrxFeO3 with x greater than or equal to 0.8 when used as bifunctional electrodes, showed oxygen evolution and reduction activity comparable with the orthoferrites prepared by the conventional solid state method. (C) 1999 Elsevier Science B.V. All rights reserved.