Sorption-spectrophotometric determination of zirconium and chromium(VI) from a single sample on a two-layer support using Arsenazo III and 1,5-diphenylcarbazide

The possibility of the sorption-spectrometric determination of zirconium(IV) and chromium(VI) from a single sample using a two-layer support made of polyacrylonitrile fiber filled with a PANF-KU-2 cation exchanger and PANF-AV-17 anion exchanger is studied. After sorption zirconium is determined with Arsenazo III on PANF-KU-2 and chromium is determined with 1,5-dipehnylcarbazide on PANF-AV-17. The sorption of zirconium and chromium is studied in the dynamic mode from solutions of HCl, HNO₃, and H₂SO₄ and the optimal conditions of the simultaneous sorption of zirconium on PANF-KU-2 and chromium on PANF-AV-17 from 0.25 M HCl is chosen. Diffuse reflection spectra of zirconium and chromium complexes have are on the solid phase and the conditions of zirconium determination are optimized. Calibration curves are linear in the range of zirconium and chromium concentration 0.005–0.025 μg/mL; the detection limits are 0.002 μg/mL. The selectivity of zirconium and chromium determination is tested in the presence of interfering ions. A procedure is developed for their determination from a single sample at zirconium to chromium ratios from 3: 1 to 1: 3.     

Reaction of chromium trifluoride with zirconium in NaF + ZrF4 melts

We report on the reaction of chromium trifluoride with zirconium in NaF:ZrF₄ = 50:50 (mol/mol) mixed melts. Chemical analysis, X-ray powder diffraction, differential thermal analysis (DTA), and IR spectroscopy show that at 400–600°C zirconium reduces chromium(III) fluoride to Cr²⁺ or Cr⁰ compounds and reduces zirconium tetrafluoride to ZrF_2–x , where 0 < x < 0.2; the particular products depend on the zirconium concentration in the batch.     

Speciation analysis of chromium in natural water samples by electrothermal atomic absorbance spectrometry after separation/preconcentration with nanometer-sized zirconium oxide immobilized on silica gel

Silica gel was prepared by the sol–gel method, modified with nanometer-sized zirconium oxide, and this material was characterized by X-ray diffraction. A micro-column packed with silica gel modified with nanometer zirconium oxide as sorbent has been developed for the quantitative separation and preconcentration of trace amounts of chromium(III) prior to their determination by electrothermal atomic absorption spectrometry. Total chromium was determined after the reduction of chromium(VI) to chromium(III) by 10% (m/v) of aqueous ascorbic acid as reducing reagent. The adsorption capacity for chromium(III) was found to be 2.36 mg g⁻¹. The detection limit for chromium(III) was 15 ng L⁻¹ with an enrichment factor of 100. The relative standard deviation was 3.2% (n = 7, c = 2.0 ng mL⁻¹).     

Sorption of phosphate ions on iron(III), zirconium(IV), and chromium(III) oxyhydroxides from aqueous electrolyte solutions

The adsorption of phosphate ions from aqueous solutions with an ionic strength of 0.5 on iron(III), zirconium(IV), and chromium(III) oxyhydroxide hydrogels has been studied as influenced by chloride and sulfate ions. Despite the high concentrations of chloride and sulfate ions, they do not inhibit phosphate adsorption on the hydrogels; they only slightly change the isotherm shape. In the range of equilibrium phosphate concentrations equal to 30–50 mmol/l, all isotherms for iron and zirconium oxyhydroxide gels signify the appearance of a second adsorption layer (two-step isotherms). Both steps are satisfactorily fitted by the Langmuir equation. The maximum adsorptions and adsorption constants have been calculated. For chromium oxyhydroxide gels, the intraduction of an electrolyte dramatically decreases the equilibration rate.     

Phase transformations in rapidly quenched Al–Cr–Zr alloys during heat treatment

Results from studying the effect zirconium has on solid-phase processes in aluminum–chromium alloys are presented. Rapidly quenched alloys are prepared via melt spinning. The quenching rate is ~10⁶ K/s. By means of physicochemical analysis, it is shown that doping Al–Cr alloys with zirconium improves the thermal stability of supersaturated solid solutions and stabilizes their microcrystalline structure; this hinders the coagulation of intermetallic phases and thus improves the hardness of the alloys. It is found that supersaturated solid solutions of Cr and Zr in aluminum undergo stepwise decomposition; the temperature and time parameters of each step are shown in TTT diagrams.     

Determination of Chromium by Eta-Aas Using Different Furnace Materials

Abstract

Different kinds of graphite tubes - uncoated, pyrolytically coated, tungsten and zirconium coated - have been tested for optimisation of operating conditions for determination of chromium by GFAAS method. The effect of mineral acids and many metal ions on the absorption signal of chromium has been investigated. The best results were obtained for pyrolytically coated tubep.     

Chemical modification of graphite surfaces for the determination of chromium by electrothermal atomic absorption spectrometry

Different kinds of graphite surfaces (electrographite, pyrolytic graphite, zirconium and tungsten carbide-coated) have been tested for optimization of analytical conditions for the determination of chromium using electrothermal atomic absorption spectrometry. The effect of mineral acids on the peak absorbance signal of chromium has been investigated. Considering pyrolysis temperature and sensitivity, atomization from pyrolytic graphite coated surface showed the best performance.     

Oxidation of chromium carbide

The oxidation of chromium carbide has been studied gravimetrically. Products of reaction have been examined by gas sorption analysis and X-ray diffraction. Changes in phase composition, crystallinity and crystallite size are correlated with the reaction conditions.Chromium carbide, Cr₃C₂, differs from most of the transitional metal carbides in that it forms stable films of metal oxide (Cr₂O₃) around the remaining carbide particles, inhibiting further oxidation. Thus chromium carbide additive inhibits oxidation of interstitial zirconium carbide, ZrC, by forming some chromic oxide which stabilises the zirconia (ZrO₂) layer around the remaining carbide crystallites.     

Volatile beta-ketoiminato- and beta-diketiminato-based zirconium complexes as potential MOCVD precursors

An amine elimination pathway has been used to produce a number of homo- and heteroleptic zirconium complexes, starting from tetrakis(dialkylamido)zirconium complexes and beta-diketimine or, alternatively, Schiff Base compounds. Reaction of 2 equiv of the bidentate beta-diketimine (2Z,4E)-N-methyl-4-(methylimino)pent-2-en-2-amine with Zr(NR(2))(4) (R = Me, Et) affords the six-coordinate heteroleptic compounds bis(N-methyl-4-(methylimino)pent-2-en-2-amido)bis(dialkylamido)zirconium 1 (alkyl = Me) and 2 (alkyl = Et). The dynamic behavior of these two compounds in solution has been investigated. Reaction with the isopropyl-substituted beta-diketimine (2Z)-N-isopropyl-4-(isopropylimino)pent-2-en-2-amine gives the five-coordinate mono(diketiminato)-substituted compound (N-isopropyl-4-(isoropylimino)pent-2-en-2-amido)tris(dimethylamido )zirconium, 3. With employment of the Schiff base (3Z)-4-(methylamino)pent-3-en-2-one, it was also possible to prepare the six-coordinate bis(4-(methylamino)pent-3-en-2-onato)bis(diethylamido)zirconium compound 4. When the bidentate ligand bearing hydrogen as substituent on the imino-nitrogen atom was employed, homoleptic tetrakis(beta-ketoiminato)- and tetrakis(beta-diketiminato)zirconium compounds 5 and 6 can be obtained. Complexes 1 and 5 have been tested for their air stability with reference to Zr(NMe(2))(4). The stability order turned out to be 1 > 5 > Zr(NMe(2))(4). The thermal properties and volatility of all the compounds are discussed in view of their potential application in metal-organic chemical vapor deposition processes (MOCVD) of zirconium nitride.     

On the detection of aluminium by means of aluminon

The well-known reaction of aluminium with aluminon has been modified in such a way as to make it specific for this element. This has been accomplished by adding sulphurous acid beforehand and ethanol and hydrochloric acid afterwards. Thc first reagent prevents the interference of chromium, indium, gallium, and titranium; the second those of beryllium, scandium, zirconium and small amounts of ferric iron.     

Reversed-phase extraction chromatography of iron(III) with tri-n-butyl phosphate on silica gel

Iron(III) is separated by reversed-phase extraction chromatography with TBP as the stationary phase on a column of silica gel, with 2-6M hydrochloric acid as the mobile phase. From knowledge of the distribution coefficients, several separations have been devised, such as separation of Fe(III) from alkali and alkaline earth metals, chromium, manganese, cobalt, nickel, copper, vanadium zirconium, thorium, uranium, yttrium and titanium.     

Extraction and separation studies of uranium/VI/with tris-/2-ethyl hexyl/phosphate

A solvent extraction method is proposed for the extraction and separation of uranium from salicylate media using tris-/2-ethyl hexyl/ phosphate dissolved in xylene as an extractant. The optimum conditions were evaluated from a critical study of pH, salicylate concentration, extractant concentration, period of equilibration and diluent. The method permits the separation of uranium from thorium, cerium, titanium, zirconium, hafnium, copper, vanadium and chromium from binary mixtures and is applicable to the analysis of uranium in synthetic samples. The method is precise, accurate, fast and selective.     

Direct determination of boron in a cobalt-based alloy by graphite furnace-atomic absorption spectrometry

A matrix modifier composed of nickel and zirconium, and a graphite tube treated with zirconium solution were proposed for the determination of boron in cobalt-based alloys by graphite furnace-atomic absorption spectrometry. The effects of this matrix modifier and the treated graphite tube were studied, and the combination of 60 mug of nickel and 20 mug of zirconium as matrix modifier, and a graphite tube soaked with 10 g 1(-1) of zirconium solution were found to give the highest analytical sensitivity. The interference effects of major components (cobalt) and eight minor components (chromium, nickel, tungsten, iron, tantalum, molybdenum, titanium, aluminium and manganese) were studied. Boron in four cobalt-based alloys was determined by graphite furnace-atomic absorption spectrometry employing the proposed matrix modifier and the treated graphite tube, without the preseparation of matrix. The relative standard deviation was 3.3% for 0.048% of boron. A characteristic mass was 500 pg.     

Reaction of Hydride Phases of Zirconium Intermetallic Compounds with Molecular Nitrogen

Reaction of hydride phases of zirconium intermetallic compounds with molecular nitrogen wasstudied at 293, 973 K, nitrogen pressure of 10 MPa. At 293 K, hydride-nitride phases crystallizing inthe structural types of the initial hydride phases are formed in all cases, whereas at 973 K finely dispersedheterophase mixtures of zirconium, molybdenum, and vanadium nitrides with 3d transition metals or mixtures of zirconium nitride with vanadium, molybdenum, chromium, and manganese nitrides are formed.     

Selective separation behavior of silica gel for zirconium in simulated high level radioactive liquid waste

Zirconium in simulated high level radioactive liquid waste (HLLW) was selectively adsorbed and separated by self-made high adsorption activity silica gel. The selective adsorption mechanism was analyzed according to the structure character of self-made silica gel and performance of zirconium in acid simulated HLLW. The results show that the adsorption selectivity of self-made silica gel for zirconium is strong, because zirconium has higher positive charge and zirconium ion hydrolyzes easily. Distribution coefficient of self-made silica gels for zirconium is 53.5 ml/g. There are 6.5 (OH)/nm² on the surface on self-made silica gels which provide more adsorption activity places, thus self-made silica gels have higher adsorption capacity for zirconium (31.4 mg/g). The elution rate of the adsorption of zirconium on self-made silica gel by 0.2 mol/l H₂C₂O₄ is more than 99%. The solubility of the self-made silica gel in nitric acid is low, the chemical stability of self-made silica gel is very strong.     

Determination of fosfomycin by indirect spectrophotometric method

2-(5-Bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) is a sensitive photometric reagent for determination of zirconium, when fosfomycin is added, it can quantitatively replace 5-Br-PADAP by complexing with zirconium, thus, an indirect spectrophotometric method based on ligand exchange has been established. The detection wavelength is at 605 nm, and the apparent molar absorption coefficient was found to be 4.59x10(4) l mol(-1) cm(-1). Beer's law is obeyed in the range of 0-28x10(-6) M. The composition and stability constant of zirconium with 5-Br-PADAP and with fosfomycin has also been estimated. The proposed method is simple and reproducible, it was applicable to the analysis of fosfomycin from pharmaceutical manufacture.     

Analysis of mixtures of hafnium and zirconium by the methylthymol blue-hydrogen peroxide method

The reaction of hydrogen peroxide with the zirconium(IV) and hafnium(IV) Methylthymol Blue complexes (MeMTB) has been investigated. The conditional stability constants of the Zr(IV) and Hf(IV) complexes with hydrogen peroxide [K'(Me(H(2)O(2)))] were determined spectrophotometrically. The K'(Me(H(2)O(2))) values found, which depend on the acidity, are 3.91 x 10(2) 3.24 x 10(2), 2.63 x 10(2) at [HCl] = 0.2, 0.3, 1.0M respectively for Me = Zr(IV) and 0.828, 0.523, 0.319 for Me = Hf(IV). The ratios of the conditional stability constants, K'(Me(H(2)O(2)))/ K'(MeMTB), are: 5.52 x 10(-4), 5.79 x 10(-4), 8.23 x 10(-4) for Me = Zr(IV) and 2.08 x 10(-6), 2.74 x 10(-6), 1.48 x 10 (-5) for Me = Hf(IV) at the three acidities. The maximum of the ratio of the relative conditional stability constants is obtained in 0.2M hydrochloric acid. The conditions which should be complied with for the determination of hafnium in the presence of zirconium are discussed. The results were compared with those obtained by the Xylenol Orange-hydrochloric acid method. They are superior for samples containing less than 20 mole% of hafnium in admixture with zirconium.     

Modification of the(SiO_2/MgO/MgCl_2)·TiCl_x Ziegler-Natta Polyethylene Catalysts Using the Third Metal Elements

Various(SiO_2/MgO/MgCl_2)·Ti Clx Ziegler-Natta catalysts modified by the third metal elements were synthesized by the co-impregnation of water-soluble magnesium and the third metal salts. Several key factors including the electronegativity of the third metal elements, catalyst performances in ethylene homo-polymerization, ethylene/1-hexene copolymerization and hydrogen response were systematically investigated. Both the catalyst performance and the polymer properties are influenced by the introduction of the third metal elements. Compared with the unmodified(SiO_2/MgO/MgCl_2)·Ti Clx Ziegler-Natta catalyst, activity and 1-hexene incorporation are enhanced by the introduction of zirconium, vanadium, aluminum and chromium, while deteriorated by the addition of ferrum, nickel, molybdenum and tungsten. Correlations of the catalyst activities and 1-hexene incorporation ability with the electronegativity of the third metal elements are discovered. It is found that the lower electronegativity of the third metal elements leads to the catalyst with higher activity and higher α-olefin co-polymerization ability. The polyethylene produced by a nickel modified catalyst showed broad molecular weight distribution(MWD) and the lowest average molecular weight(MW), while by using a ferrum modified catalyst, the resulting polyethylene had the highest MW, reaching the ultra-high MW area. Vanadium and chromium modified catalysts demonstrated the best hydrogen response.     

SO42-/ZrO2的制备工艺对催化橡胶籽油裂解油酯化的影响

以SO₄^2-/ZrO₂为催化剂对橡胶籽油裂解油进行甲酯化。研究了锆源、焙烧温度及焙烧时间对催化剂活性的影响,分别采用氨气吸附程序升温脱附(NH₃-TPD)和吡啶红外(Py-IR)对固体酸SO₄^2-/ZrO₂的酸性和酸型进行分析。实验结果表明,以ZrOCl₂为锆源,550℃焙烧4 h所得固体酸SO₄^2-/ZrO₂的催化活性最好,性能较稳定。对酯化产物的组成及性能进行了考察,结果表明,酯化产物的各项性能均优于传统工艺制备的生物燃油,且与0^#柴油相近。     

Analytical applications of a liquid anion-exchanger for the separation of uranium(IV) in malonate solution

Uranium was quantitatively extracted with 4% Amberlite LA-1 in xylene at pH 2.5-4.0 from 0.001 M malonic acid. It was stripped from the organic phase with 0.01 M sodium hydroxide and determined spectrophotometrically at 530 nm as its complex with 4-(2-pyridylazo) resorcinol. Of various liquid anion-exchangers tested, Amberlite LA-1 was found to be best. Uranium was separated from alkali and alkaline earth metal ions, thallium(I), iron(II), silver, arsenic(III) and tin(IV) by selective extraction, and from zinc, cadmium, nickel, copper(II), cobalt(II), chromium(III), aluminium, iron(III), lead, bismuth, antimony(III) and yttrium by selective stripping. The separation from scandium, zirconium, thorium and vanadium(V) was done by exploiting differences in the stability of chloro-complexes.