Dipole moments and structure of organophosphine and organoarsine compounds

The formal charge distributions in and the dipole moments of some organophosphines and arsines have been calculated, and the dipole moments of (p-chlorophenyl)dichlorophosphine (2.28 D) and (p-bromophenyl)dichlorophosphine (2.04 D) have been determined in benzene at 35° C. The differences between the observed and the calculated moments are explained in terms of dπ---pπ back-bonding and hyperconjugative effects in alkylhaloarsines. The mesomeric effects operating in the aromatic systems are evaluated by comparing the moments with those for the corresponding aliphatic systems. In unsaturated compounds the differences are attributed to mesomeric effects involving the expansion of arsenic valence shell.

Dipole moments and structure of organophosphine and organoarsine compounds

The formal charge distributions in and the dipole moments of some organophosphines and arsines have been calculated, and the dipole moments of (p-chlorophenyl)dichlorophosphine (2.28 D) and (p-bromophenyl)dichlorophosphine (2.04 D) have been determined in benzene at 35° C. The differences between the observed and the calculated moments are explained in terms of dπ---pπ back-bonding and hyperconjugative effects in alkylhaloarsines. The mesomeric effects operating in the aromatic systems are evaluated by comparing the moments with those for the corresponding aliphatic systems. In unsaturated compounds the differences are attributed to mesomeric effects involving the expansion of arsenic valence shell.

Geochemistry of fluoride rich groundwater in Kolar and Tumkur Districts of Karnataka

Groundwater is a significant water resource in India for domestic, irrigation, and industrial needs. By far the most serious natural groundwater-quality problem in India, in terms of public health, derives from high fluoride, arsenic, and iron concentrations. Hydrogeochemical investigation of fluoride contaminated groundwater samples from Kolar and Tumkur Districts in Karnataka are undertaken to understand the quality and potability of groundwater from the study area, the level of fluoride contamination, the origin and geochemical mechanisms driving the fluoride enrichment. Majority of the groundwater samples did not meet the potable water criteria as they contained excess (>1.5 mg/L) fluoride, dissolved salts (>500 mg/L) and total hardness (75-924 mg/L). Hydrogeochemical facies of the groundwater samples suggest that rock weathering and evaporation-crystallization control the groundwater composition in the study area with 50-67% of samples belonging to the Ca-HCO3 type and the remaining falling into the mixed Ca-Na-HCO3 or Ca-Mg-Cl type. The saturation index values indicated that the groundwater in the study area is oversaturated with respect to calcite and under-saturated with respect to fluorite. The deficiency of calcium ion concentration in the groundwater from calcite precipitation favors fluorite dissolution leading to excess fluoride concentration.

Compositional dependence of crystallization of As-Te glasses

Thermal crystallization studies have been carried out on bulk, semiconducting AsxTe100−x glasses of different compositions using Differential Scanning Caloritmery. AsxTe100−x glasses with x < 40, are found to exhibit one glass transition and one crystallization. On the other hand, glasses with composition 40 less-than-or-equals, slantxless-than-or-equals, slant 50 show one glass transition and two crystallization reactions. It has been found that in glasses with x greater-or-equal, slanted 40, the two crystallization reactions progressively merge with an increase in arsenic concentration. Consequently AsxTe100−x glasses with x greater-or-equal, slanted 50 show only one crystallization. The composition dependence of crystallization temperatures and activation energies for crystallization estimated by Kissinger's method, show marked deviations at a composition x = 40. These observations can be explained in terms of the changes in the local structure of the material with composition.

Coupled substitution of niobium and silicon in potassium titanyl phosphate and arsenate (KTiOPO4 and KTiOAsO4. Synthesis and nonlinear optical properties of KTi1-xNbxOX1-xSixO4 (X = P, As)

Coupled substitution of Nb(V) and Si(IV) for Ti(IV) and P(V)/As(V) in KTiOP04 (KTP) and KTiOAsO4 (KTA) giving new series of nonlinear optical materials, KTi1-xNbxOX1-xSixO4 (X=P,As), has been investigated. Substitution up to x = 0.40 readily occurs, the members retaining the orthorhombic (Pna2(1)) structure of KTP. The second harmonic generation (SHG) property of the parent KTP and KTA is not adversely affected by the coupled substitution. SHG intensity of the powder samples of the X = P series shows a slight increase with x up to x = 0.15; for 0.15 < x less-than-or-equal-to 0.40, there is a decrease in SHG intensity as compared to that for KTP. A similar trend in SHG intensity is seen for the arsenic analogs.

Electrical switching and short-range order in As-Te glasses

The local structural order in chalcogenide network glasses is known to change markedly at two critical compositions, namely, the percolation and chemical thresholds. In the AsxTe100-x glassy system, both the thresholds coincide at the composition x = 40 (40 at. % of arsenic). It is demonstrated that the electrical switching fields of As-Te glasses exhibit a distinct change at this composition.

Mo3O5(OH)(2)(AsO4)2: A new solid with a structure related to beta VOPO4

Mo3O5(OH)(2)(AsO4)(2) was prepared at 100 degrees C from an aqueous solution of MoO3 containing arsenic and nitric acids. It crystallises in the monoclinic system, a = 13.024(1)Angstrom, b = 7.2974 (2) Angstrom, c = 13.281(1) Angstrom, beta = 121.124(8)degrees, Z = 4, space group C2/c. The structure was determined by Rietveld refinement from X-ray powder diffraction data. The three-dimensional structure is built up from MoO6 and MoO5OH octahedra and AsO4 tetrahedra sharing corners. The octahedra share two opposite vertices forming zigzag chains that run parallel to [10(1) over bar]. Each AsO4 tetrahedron is connected to four octahedra, two of which belong to the same chain, thus linking three chains. The resulting covalent framework is similar to that of beta VOPO4 in which one tetrahedral P site for every three is empty. The two protons are likely to be bonded to two (out of four) unshared oxygen atoms surrounding this empty site. All the Mo atoms are strongly off-centred in the octahedra; and the off-centring is disordered. The disorder is discussed in terms of Mo shifts perturbed by a disordered hydrogen bonding scheme.

Removal of As(V) by adsorption onto mixed rare earth oxides

Arsenic pollution of water is a major problem faced worldwide. Arsenic is a suspected carcinogen in human beings and is harmful to other living beings. In the present study, a novel adsorbent was used to remove arsenate [As(V)] from synthetic solutions. The adsorbent, which is a mixture of rare earth oxides, was found to adsorb As(V) rapidly and effectively. The effect of various parameters such as contact time, initial concentration, pH, and adsorbent dose on adsorption efficiency was investigated. More than 90% of the adsorption occurred within the first 10 min and the kinetic rate constant was found to be about 3.5 mg min(-1). Adsorption efficiency was found to be dependent on the initial As(V) concentration, and the adsorption behavior followed the Langmuir adsorption model. The optimum pH was found to be 6.5. The presence of other ions such as nitrate, phosphate, sulphate, and silicate decreased the adsorption of As(V) by about 20-30%. The adsorbed As(V) could be desorbed easily by washing the adsorbent with pH 12 solution. This study demonstrates the applicability of naturally occurring rare earth oxides as selective adsorbents for As(V) from solutions.

Structural, optical, and electrical properties of bulk single crystals of InAsxSb(1-x) grown by rotatory Bridgman method

Radially-homogeneous and single-phase InAsxSb(1−x) crystals, up to 5.0 at. % As concentration, have been grown using the rotatory Bridgman method. Single crystallinity has been confirmed by x-ray and electron diffraction studies. Infrared transmission spectra show a continuous decrease in optical energy gap with the increase of arsenic content in InSb. The measured values of mobility and carrier density at room temperature (for x = .05) are 5.6×104 cm2/V s and 2.04×1016 cm−3, respectively.

Non-linear electrical response of chalcogenide glasses: Memory state phenomena

Investigations on the switching behaviour of arsenic-tellurium glasses with Ge or Al additives, yield interesting information about the dependence of switching on network rigidity, co-ordination of the constituents, glass transition & ambient temperature and glass forming ability.

Photocatalytic degradation with combustion synthesized WO3 and WO3-TiO2 mixed oxides under UV and visible light

The photocatalytic activity of commercial titanium dioxide under UV and visible radiation was improved by composites of tungsten trioxide (WO3) with TiO2. WO3 was prepared by solution combustion synthesis and the mixed oxides/composites of WO3-TiO2 were prepared in different weight ratios (0, 0.10, 0.15, 0.20, 0.25, 0.50, 0.75, and 1) by physical mixing. These catalysts were characterized by XRD, DRS, BET, SEM, TEM, pH drift method, TGA and photoluminescence. The photocatalytic activity varies with the WO3 loading in the composites. The optimum loading of WO3 in the composites was found to be 15 wt% for both UV and visible radiation. This loading showed faster dye degradation rate than commercial TiO2 (TiO2-C) and WO3 (WO3-C). The effect of initial concentrations of methylene blue (MB) and orange G (OG) and the effect of the functional group on dye degradation was studied with both anionic and cationic dyes with 15 wt% WO3-TiO2. (C) 2012 Elsevier B.V. All rights reserved.

Influence of anthropogenic contamination on fluoride concentration in groundwater: A study of Mulbagal town, Kolar district, Karnataka

Groundwater contamination is a serious concern in India. Major geogenic contaminants include fluoride, arsenic and iron, while common anthropogenic contaminants include nitrate, metals, organics and microbial contamination. Besides, known point and diffuse sources, groundwater c ontamination from inf iltration of pit to ilet leachate is an emerging concern. The study area of this paper is Kolar district in Karnataka that is hot spot of fluoride contamination. The absence of fluoride contamination in Mulbagal town and the alterations in groundwater chemistry from infiltration of pit toilet leachate motivated the author to examine the possible linkages between anthropogenic contamination and fluoride concentration in groundwater of Mulbagal town. Analysis of the groundwater chemistry revealed that the groundwater in Mulbagal town is under saturated with respect to calcite that suppresses the dissolution of fluorite and the fluoride concentration in the groundwater. The slightly acidic pH of the groundwater is considered responsible to facilitate calcite dissolution under saturation.