Dosage du silicium par précipitation du complexe silicomolybdique jaune par la quinoléine

The authors have studied the conditions of precipitation of complex silicomolybdic yellow by quinoline from the point of view of the determination of silicon.Under the conditions that produce complete development of the complex, the precipitation is itself quantitative in the presence of an excess of quinoline, the role of which is to make the precipitate insoluble in its formation surroundings. The precipitation of free molybdate is prevented by adding the quantity of acid necessary for complexing it.The precipitate thus obtained filters without difficulty, and only needs to be dried for 1 hour at 150° in order to attain constant weight. It corresponds then exactly to the formula: SiO₂.12MoO₃.4(C₉H₇N).2H₂O.     

Spectrophotometric determination of vanadium (V) with 2-naphthohydroxamic acid

2-Naphthohydroxamic acid in methanol gives an intense and stable red-orange color with vanadium (V), sensitive to 0.009 μg V/cm², for log I₀/I = 0.001 abs. unit at wavelength 450 mμ. The value for σ is ±0.006 a.u., equivalent to ±0.08 p.p.m. V. The colored complex obeys Beer's law over the range 1–10 p.p.m. vanadium. The absorbance (in 1-cm cell) at 10 p.p.m. was so great that no data were obtained at higher concentrations. Under the conditions of the reaction, the combining ratio of vanadium and 2-naphthohydroxamic acid appears to be 1 to 2. Optimum conditions for the use of 2-naphthohydroxamic acid as a spectrophotometric reagent for vanadium-(V) were established; the procedure was applied to the determination of vanadium in steels and non-ferrous alloys with good precision and accuracy.     

Adsorption of thorium (IV) by amorphous silica; response surface modelling and optimization

The amorphous SiO₂ (200–300 nm) was synthesized as an absorbent and thorium adsorption of SiO₂ was investigated using experimental and RSM method. The SiO₂ particles were made for the adsorption of thorium from aqueous solutions, and characterized by particle size measurement, XRD and SEM. The adsorption of thorium process was optimized with RSM method. The correlation between four variables was modeled and studied. Under optimum conditions, the adsorption capacity of SiO₂ particles was found to be 134.4 mg/g, the correlation coefficient (R²) and the F value was obtained 0.96 and 1.98?×?10^?6, respectively. In addition, the adsorption isotherms were examined.     

Preparation of high-purity thorium by solvent extraction with di-(2-ethylhexyl) 2-ethylhexyl phosphonate

The extraction behavior of thorium(IV) by di-(2-ethylhexyl) 2-ethylhexyl phosphonate (DEHEHP, B) from nitric acid media has been investigated. The influence factors including the concentration of HNO₃, salting-out reagents, temperature, the concentration of metal ions and DEHEHP have been examined systematically. A possible extraction mechanism is proposed and the extracted species as Th(NO₃)₄·2B _(o) is confirmed by the slope analysis method. The extraction equilibrium constants (K _ex) and thermodynamic parameters (ΔG, ΔH and ΔS) were calculated under the present experimental conditions. DEHEHP shows a high selectivity of thorium(IV) over rare earths(III). Stripping study indicates that thorium can be completely stripped by distilled water from the Th-loaded DEHEHP. Furthermore, a solvent extraction process including six extraction stages, six scrubbing stages, and six stripping stages was designed for the preparation of highly pure thorium from thorium concentrate with DEHEHP as extractant in laboratory scale, and finally thorium product can be obtained with a purity of 99.999 % and a yield of 98 %.     

The formation of submonolayer thorium coatings on a silicon oxide surface by electrochemical deposition

Data are reported on the mechanisms of the formation of submonolayer coatings based on thorium oxide on the surface of Si(111) single crystal with natural oxide as a result of electrochemical deposition. It is experimentally shown that the deposition of thorium atoms from an acetone solution of Th(NO₃)₄ onto the surface of natural silicon oxide leads to the formation of defects in the thin silicon oxide layer, which is accompanied by the deposition of thorium nanoclusters onto a pure silicon surface. The observed effects have been qualitatively explained assuming the breakdown of natural silicon oxide due to the presence of an electrical double layer in the near-surface region of the cathode.     

Physicochemical studies on cross-linked thorium(IV)–alginate complex especially the electrical conductivity and chemical equilibrium related to the coordination geometry

The electrical conductivity of cross-linked thorium(IV)–alginate complex in the form of circular disc has been investigated as a function of temperature. The Arrhenius plot of log σ vs. 1/T showed a simple parabolic shape at the early stages, followed by a sharply increase in o values with raising the temperature at the final stages. This behaviour was interpreted by the formation of free-radicals at the initial stages, followed by the degradation of the complex at elevated temperatures to give rise to thorium oxide product. The heterogeneous chemical equilibrium for exchange of Th⁴⁺ counter ions in the complex by H⁺ ions has been investigated by titrimetric and complexometric techniques. The thermodynamic equilibrium constant was found to be 26 ± 0.25 dm⁹ mol^?3 at 25 °C. The X-ray diffraction pattern indicated that thorium(IV)–alginate complex is amorphous in nature. Infrared absorption spectra indicated that Th⁴⁺ is chelated to alginate macromolecular chains and displayed υ_s OCO^? and υ_as OCO^? in the ranges of 1419 and 1635 cm^?1, respectively. A geometrical structure for chelation of thorium(IV) to the functional groups of alginate macromolecule is suggested and discussed in terms of complex stability.     

Quantitative and qualitative studies of silica in different rice samples grown in north of Iran using UV-vis, XRD and IR spectroscopy techniques

Silicon is an essential trace element and is found in vegetables, fruits, cereals, water, pasta and rice (Oryza sativa). In this work, the silica content of different types of rice grains were measured. Here, we used the heteropoly blue photometric method with a double beam UV-vis spectrophotometer to determine the amount of silicon in rice samples (n = 7) that were collected in the north of Iran. The samples were digested with wet-ashing method by microwave-assisted heating and then treated with ammonium molybdate to produce a yellow color compound in acidic solution (ca. pH 1.2) and then reduced to give a heteropoly compound with a blue color. Analyses were performed using standard addition method and absorbance values were measured with double beam UV-vis spectrophotometer at λ_max = 815 nm. Results indicated that the silica content was 307-451 mg/kg for the samples. X-ray diffraction patterns and infra-red spectra were obtained from rice samples without any sample treatment.     

Chromatographic detection of scandium

Scandium was readily detected by paper chromatography using methyl acetate as the solvent and quinalizarin for the developer. The reddish-violet color formed with scandium resembled the colers obtained with thorium, titanium, zirconium and the rare earths, but the difference in R_F values gave definite separation of these elements. Positive chromatographs were obtained by using 0.01 ml of solution 0.005M respect to scandium.     

Chemistry of thorium : Volumetric determination of thorium

Thorium has been determined volumetrically. It has been precipitated with m-nitrobenzoic acid according to the method of Neish. Thorium m-nitrobenzoate has been then dissolved in sulphuric acid and titrated with titanous chloride to determine the NO₂-group which gives the amount of thorium directly.     

Direktthermometrische bestimmung von thorium und lanthan in gläsern

A rapid method is described for the determination of thorium and lanthanum in non-silicate glasses. It is suitable for routine use in a works laboratory. The samples are dissolved in nitric acid. The thorium content is calculated from the measured heat of precipitation of thorium iodate, and the lanthanum content by difference from the heat of precipitation of both thorium and lanthanum oxalates together. The apparatus is calibrated by using standard solutions of the two metal ions. The standard deviations for the middle of the range (around 250 mg of the oxides) were 3·1 mg for ThO₂ and 1·7 mg for La₂O₃. An analysis takes about 1·5 hr.     

钍含量对Co/HMS催化剂结构和费托合成的影响

详细研究了钍含量对15% Co/HMS催化剂结构、费托合成CO转化率和烃分布的影响, 结果表明: 钍助剂的添加降低了催化剂的钴还原度, 并可使催化剂钴晶粒减小, 且存在钍物种对钴物种的覆盖; 钴晶粒的减小、较高钍含量时催化剂里钍物种对钴物种的覆盖和钴物种还原性能的降低, 使催化剂存在最优的钍含量, 此时催化剂表面暴露的金属钴原子最多, 较好地解释了钍含量达到1.5 wt%时, 催化剂CO转化率最高的实验现象. 烃分布研究表明: 反应温度较低时钍助剂将促进产物链的增长和高碳烃选择性的增加, 但反应温度较高时难以促进产物链的增长.     

Insights into the Antimicrobial Activity of Hydrated Cobaltmolybdate Doped with Copper

Molybdates are biocidal materials that can be useful in coating surfaces that are susceptible to contamination and the spread of microorganisms. The aim of this work was to investigate the effects of copper doping of hydrated cobalt molybdate, synthesized by the co-precipitation method, on its antibacterial activity and to elucidate the structural and morphological changes caused by the dopant in the material. The synthesized materials were characterized by PXRD, Fourier Transformed Infrared (FTIR), thermogravimetric analysis/differential scanning calorimetry (TG/DSC), and SEM-Energy Dispersive Spectroscopy (SEM-EDS). The antibacterial response of the materials was verified using the Minimum Inhibitory Concentration (MIC) employing the broth microdilution method. The size of the CoMoO₄·1.03H₂O microparticles gradually increased as the percentage of copper increased, decreasing the energy that is needed to promote the transition from the hydrated to the beta phase and changing the color of material. CoMoO₄·1.03H₂O obtained better bactericidal performance against the tested strains of Staphylococcus aureus (gram-positive) than Escherichia coli (gram-negative). However, an interesting point was that the use of copper as a doping agent for hydrated cobalt molybdate caused an increase of MIC value in the presence of E. coli and S. aureus strains. The study demonstrates the need for caution in the use of copper as a doping material in biocidal matrices, such as cobalt molybdate.     

Thermal decomposition of thorium(IV) complexes with benzenecarboxylic acids in air atmosphere

The conditions and products of thermal decomposition of thorium(IV) complexes with general formula Th(R-C₆H₄COO)₄ (whereR=2-CH₃, 3-CH₃, 4-CH₃), Th(OH)₂(4-CH₃C₆H₄COO)₂. H₂O and Th(OH)₂(R-C₆H₄COO)₂·nH₂O (whereR=2-COO, 3-COO,n=2;R=4-COO,n=1) were studied. Anhydrous thorium(IV) complexes decompose in two steps. On heating, tetra(2-methylbenzoato)-thorium(IV) decomposes to yield ThO₂ through the intermediate ThOCO₃ whereas tetra(3-methylbenzoato)thorium(IV) and tetra(4-methylbenzoato)thorium(IV) decompose to ThO₂ through oxocomplexes. Hydrated thorium(IV) complexes are dehydrated in one step and then anhydrous complexes decompose to ThO₂. Di [1,2-(benzene)dicarboxylato]dihydroxythorium(IV) decomposes directly to ThO₂, whereas the 1,3- and 1,4-isomers through the intermediate thorium(IV) oxocarbonates.     

Regioselective sulfation of trimethylsilyl cellulose using different SO3-complexes

Trimethylsilyl cellulose (DS_Si = 2.9) dissolved in dry tetrahydrofurane was reacted with SO₃-complexes of N,N-dimethylformamide, triethylamine, pyridine and ethyldiisopropylamine. Under the given reaction conditions, i.e. 25 °C, 24 h, 2.2 mol equivalent SO₃-complex, the SO₃ attacks the trimethylsilyl ether groups followed by the formation of sodium sulfate cellulose under sodium hydroxide work-up conditions. The regioselectivity of the sulfation is controlled by the complex partner of SO₃. Cellulose sulfates with preferred O-6 sulfation were obtained using SO₃-N,N-dimethylformamide. In case of SO₃-triethylamine, cellulose-2-sulfates could be prepared with good regioselectivity. Small residual amounts of silicon in the cellulose sulfates (0.1–0.2% w/w) can be quantified using inductively coupled plasma-optical emission spectroscopy (ICP-OES), and can be decreased up to 80% by heating (70 °C, 24 h) the polymers in vacuum.     

Changes in the phase composition of a multicomponent Co-Mo-Bi-Fe-Sb-K-O catalyst under conditions of the partial oxidation of isobutylene to methacrolein: A comparison with the oxidation of propylene to acrolein

The partial oxidation of isobutylene to methacrolein on a multicomponent multiphase Co-Mo-Bi-Fe-Sb-K-O catalyst and on catalysts from which some components were absent was studied. Activity and selectivity changes in the case of isobutylene oxidation were the same as in the oxidation of propylene; however, the rate of propylene oxidation was higher than that of isobutylene oxidation. The X-ray diffraction analysis of the catalysts before and after the reaction indicated the occurrence of a number of phases in the samples: α-CoMoO₄, β-CoMoO₄, Fe₂(MoO₄)₃, reduced bismuth molybdate species, MoO₃, and reduced MoO _x species. Under catalytic reaction conditions, redox phase transformations occurred. Iron molybdate and molybdenum oxide phases underwent the largest transformations. Of two molybdenum oxide phases, a β-Mo₄O₁₁ phase with a structure of a crystallographic shift is formed in the course of catalysis, whereas the second phase (MoO₃) almost does not participate in catalysis and occurs in an excess.     

Optical and Chromaticity Characteristics of Adsorbates of the Thorium Complex of Arsenazo I

The immobilized reagent Arsenazo I was used for the direct determination of trace thorium by diffuse reflectance spectrometry and chromaticity measurements. Silica gels Silochrom C-120 and C₁₈ were studied as supports. The optimal conditions of sorption were found. The dependence of chromaticity functions (chromaticity coordinates, color lightness, saturation, yellowness, and whiteness) on different chemical factors was studied. The advantages of the use of yellowness, color hue, and total color difference in comparison with other chromaticity functions was demonstrated. A method was developed for the determination of thorium with a detection limit of 0.02 g/mL.     

Estimation of palladium

Summary In presence of tartaric acid and ammonium chloride, quinaldinic acid quantitively precipitates palladium from a hot solution at a p_H range 3 to 7 whereas other ions such as arsenic (As³⁺ and As⁵⁺), mercury (Hg²⁺), cadmium, bismuth, antimony, iron, chromium, aluminium, beryllium, thorium, cerium (Ce³⁺), titanium, zirconium, uranium (UO₂ ²⁺), vanadate, molybdate, tungstate, cobalt, nickel, manganese, magnesium, calcium, barium and strontium remain in solution. The palladium complex is quite insoluble in hot water and can be dried at any temperature up to a maximum of 353° C when it decomposes.     

Spectrophotometric determination of molybdenum with phenylfluorone

Spectrophotometric studies on the reaction between molybdenum as molybdate (MoO₄^2?) and phenylfluorone are presented. The reaction conditions are optimized to develop an intense color (molar absorptivity is 3.8 × 10³) selective and sensitive for the Spectrophotometric determination of molybdenum. The absorbance is measured at 560 nm, at a pH of 1.5–3. The colored complex is stable for up to 24 hr, Beer's law is obeyed, over the concentration range of 1 to 4 μg/25 ml. The relative standard deviation is 2% and the sensitivity of the method is 1.60 × 10^?4 mg/ml.     

Separation of trace concentrations of tantalum from niobium and some other heavy metal ions by extraction with N-oxide of trioctylamine

The distribution of tantalum(V) between 0.1M trioctylamine oxide dissolved in xylene and sulphuric acid solutions has been studied. On the basis of results on the distribution, it is concluded that at sulphuric acid concentration 0.5M, tantalum is probably extracted by a solvate mechanism as the complex Ta(OH) (SO₄)₂·3TOAO. It has also been shown that tantalum can be quantitatively separated from niobium, uranium, thorium and rare earth elements by extraction with N-oxide of trioctylamine from 0.5M sulphuric acid solution.     

Gas phase nucleophilic substitution reactions; Transaminations of silanamines

Ion cyclotron resonance spectroscopy has been employed in the study of gas phase transaminations of silanamines. The dominant reaction pathway is found to involve a bimolecular nucleophilic substitution at silicon. Under suitable conditions the ICR method permits direct observation of intermediate reaction complexes. The possible relationship of these complexes to S_N2 intermediates is discussed.