One Dimensional Face-to-Face Stacking of Anderson–Evans [Cr(OH)6Mo6O18]3− Polyoxometalate Anion: Synthesis, Structure, and Physical Properties of (BEDT-TTF)4[Cr(OH)6Mo6O18]⋅2H2O

The synthesis, structural and magnetic characterizations of a new charge transfer salt (BEDT-TTF)₄[Cr(OH)₆Mo₆O₁₈]2H₂O based on the planar paramagnetic Anderson–Evans polyoxometalate are reported. Structural parameters: T=293 K, triclinic (P ), a=5.9545(2) Å, b=16.3767(6) Å, c=21.8643(6) Å, =110.829(2)°, =91.262(2)°, =98.129(1)°, Z=1, R=0.0540. The crystal structure is characterized by a face-to-face stacking of the anions giving rise to a one-dimensional inorganic chain which develops along the a direction. The organic layers contain two crystallographically independent BEDT-TTF dimers that form alternating stacks along the b direction. This organic chain is perpendicular to the inorganic chains. The charges on BEDT-TTF dimers are deduced to +1.2(1) and +1.7(1) on the basis of the intramolecular bond lengths. The EPR spectrum at 2.5 K is characterized by the superposition of BEDT-TTF⁺ and [Cr^III(OH)₆Mo₆O₁₈]^3– signals. The static susceptibility can be fitted by the Curie–Weiss law down to 1.9 K and the magnetic moment at 300 K is estimated to 4.21 _B , suggesting the uncorrelated spin system with BEDT-TTF⁺ (S=1/2) and Cr^III (S=3/2) ions. This interpretion is consistent with the charge disproportionation on BEDT-TTF dimers along the stack, which is supported by the refined molecular structure and is closely related to the insulating behavior (<10^–9Scm^–1 at RT).     

广东省黄埔港土壤中铬的价态分析研究

采用化学浸提技术对广东省黄埔港土壤中的铬进行了分析,研究了浸提条件及其对测定结果的影响,并运用GF-AAS法定量分析Cr(Ⅵ).检出限为0.03 μg/L,相对标准偏差(RSD,n=12)为1.52%,加标回收率在95.6%-103.6%.     

Corrosive behavior of chromium carbide-based films formed on steel using a filtered cathodic vacuum arc system

The formation of chromium carbide-based hard-coatings on steels using a 90°-bend filtered cathodic vacuum arc (FCVA) has extensive industrial applications; such coatings are free of macroparticles and exhibit excellent characteristics. In this investigation, a working pressure of C₂H₂/Ar was adopted to synthesize amorphous chromium carbide film (a-C:Cr) and crystalline chromium carbide film (cryst-Cr₃C₂) from a Cr target (99.95%) at 500 °C under a substrate voltage of −50 V. The corrosion behavior of a-C:Cr coated on steel (a-C:Cr/steel) and cryst-Cr₃C₂ coated on steel (cryst-Cr₃C₂/steel) were compared in terms of open-circuit potentials (OCP) and polarization resistance (R_p) in an aerated 3.5 wt% NaCl aqueous solution, as determined by electrochemical impedance spectroscopy (EIS). The XRD results indicated that the transformation of a-C:Cr to cryst-Cr₃C₂ is distinct as the working pressure declines from 1.2 × 10⁻² to 2.9 × 10⁻³ Torr. The OCP of a-C:Cr/steel and cryst-Cr₃C₂/steel resemble each other and both assembly are nobler than uncoated steel. The R_p of the coatings exceeds that of the uncoated steel. The SEM observation and the EIS results demonstrate that the cryst-Cr₃C₂/steel more effectively isolates the defects than dose a-C:Cr/steel.     

Crystal Structure and Spectroscopic Properties of Bis[trans‐dichlorobis(2,2‐dimethylpropane‐1,3‐diamine)chromium(III)] Tetrachlorozincate

The structure of trans‐[Cr(Me₂tn)₂Cl₂]₂ZnCl₄ (Me₂tn = 2,2‐dimethylpropane‐1,3‐diamine) was determined by a single‐crystal X‐ray diffraction study at 173 K. The analysis reveals that there are three crystallographically independent chromium(III) complex cations in the title compound. The chromium(III) atoms are coordinated by four nitrogen atoms of Me₂tn and two chlorine atoms in a trans arrangement, displaying a distorted octahedral geometry. The two six‐membered chelate rings in three complex cations are oriented in an anti chair–chair conformation with respect to each other. The Cr–N and Cr–Cl bond lengths average 2.0862(2) and 2.3112(6) Å, respectively. The ZnCl₄^2– have slightly distorted tetrahedral arrangement with Zn–Cl lengths and the Cl–Zn–Cl angles are influenced by hydrogen bonding. The resolved absorption maxima in the electronic d–d spectrum were fitted with a secular determinant for a quartet energy state of the d³ configuration in a tetragonal field. It is confirmed that the nitrogen atoms of the Me₂tn ligand are strong σ donors, but the chloro ligands have weak σ‐ and π donor properties toward the chromium(III) ion.     

Verification of model for adsorption and reduction of chromium(VI) by Escherichia coli 33456 using chitosan bead as a supporting medium

A non-steady-state mathematical model system for the kinetics of adsorption and reduction of Cr(VI) by Escherichia coli (E. coli) biofilm on chitosan bead (EBCB) process was derived. The mechanisms in the model system included Cr(VI) adsorption by chitosan beads, Cr(VI) bioreduction by E. coli cells and Cr(VI) mass transport diffusion. Batch kinetic tests were performed to determine surface diffusivity of Cr(VI), adsorption parameters for Cr(VI) and biokinetic parameters of E. coli 33456. Experiments were conducted using an EBCB reactor system with high recycled rate to approximate a completely-mixed flow reactor for model verification. The experimental results indicated that E. coli biofilm bioregenerated the chitosan beads after E. coli biofilm has grown significantly. Cr(VI) reducing efficiency by E. coli was about 84% when Cr(VI) concentration in the influent was 5 mg/L at a steady-state condition. The concentration of suspended E. coli cells reached up to 10 mg/L while the thickness of attached E. coli cells was estimated to be 150 μm at a steady-state condition by model prediction. The comparisons of experimental data and model simulation show that EBCB model system for Cr(VI) adsorption and reduction can predict the experimental results well.     

Resonance ionization mass spectrometry for precise measurements of isotope ratios

Resonance ionization mass spectrometry offers extremely high sensitivity and elemental selectivity in microanalysis, but the isotopic precision attainable by this technique has been limited. Measured isotope ratios are sensitive to small fluctuations in the pointing, pulse timing, and wavelength of the resonance lasers. We show that, by minimizing these fluctuations using feedback controls and by power-broadening the optical transitions, we are able to measure chromium isotope ratios with statistics-limited precision better than 1%. Small additional improvements in reproducibility come from careful shaping of the electric field in the region where atoms are photoionized and from minimizing pulse-to-pulse variations in the time-of-flight mass spectrometer through which the photoions travel. The increased reproducibility of isotopic measurements on standard materials has enabled us to detect anomalous chromium isotopic abundances in presolar SiC grains extracted from primitive meteorites.     

A kinetic investigation of removal of chromium from aqueous solutions with a strong cation exchange resin

A kinetic investigation was performed with an ion exchange resin for chromium. A strong cation exchange resin (Amberlite IR 120) was used for removal of chromium. The effects of concentration, resin amount, and stirring speed on kinetics were investigated. The metal concentration range studied was between 5 to 160 mg/dm³ (the amount of solution was 4 dm³), the resin amount range was between 5 to 20 mg, and the stirring speed range was between 1000 to 3500 rpm. Equilibrium experiments were performed for calculation of separation factor. Kinetic studies were done using a Kressman-Kitchener stirrer reactor system and the results were compared with existing kinetic models. Two models, Nernst-Plank film diffusion control model (fdc) and solid phase diffusion control model (pdc), respectively were identified, and the dependence of the rate on parameters such as solution concentration, resin amount, stirring speed, etc. was examined for each of them. The interpretation of these data shows that the system is probably controlled by both film and particle diffusion. Correspondence: Sevgi Kocaoba, Department of Chemistry, Faculty of Art and Science, Yildiz Technical University, Davutpasa Cad. No: 127, 34210 Davutpasa-Istanbul, Turkey.     

Synthesis,characterization and ethylene oligomerization and polymerization of 2-(1H-2-benzimidazolyl)-6-(1-(arylimino)ethyl)pyridylchromium chlorides

A series of N^N^N tridentate chromium complexes (C1–C6) bearing 2-(1H-2-benzimidazolyl)-6-(1-(arylimino)ethyl)pyridine derivatives was synthesized and characterized by elemental and spectroscopic analysis along with single-crystal X-ray crystallography. X-ray crystallographic analyses reveal chromium complex C1 as a distorted six-coordinated octahedral geometry. On treatment with modified methylaluminoxane (MMAO), the chromium complexes exhibited high activities for ethylene oligomerization (up to 1.50 × 10⁶ g mol⁻¹ (Cr) h⁻¹) and polymerization (up to 2.06 × 10⁶ g mol⁻¹ (Cr) h⁻¹) at 10 atm ethylene pressure. Various reaction parameters were investigated in detail, and less steric hindrance and electron-withdrawing substituents of ligands enhance the catalytic activities of their chromium complexes.     

激光烧蚀-电感耦合等离子体质谱法测定塑料中的Pb、Cd、Cr和Hg

采用激光烧蚀固体进样技术的电感耦合等离子体质谱法(LA-ICP-MS)测定了塑料中的Pb、Cd、Cr和Hg。选择了线扫描激光烧蚀方式,并从灵敏度和稳定性角度优化了工作参数。根据计算分馏因子考察了分馏效应,结果表明,所测元素分馏效应小。塑料中Hg的记忆效应严重,认为主要来自样品表面吸附,减小样品的表面积可减小Hg的记忆效应。以聚丙烯标准物质及其空白片作校准曲线,应用于ABS、PPS、PA66+30%GF、PVC、PTFE等实际塑料样品的测定,测定结果与ICP-OES(XRF)法测定值基本吻合。Pb、Cd、Cr和Hg的检测下限分别为0.002、0.001、0.08和1.5 mg/kg。     

原子吸收光谱法测定磷酸酯化梨渣吸附的Cr（Ⅵ）离子

通过原子吸收光谱法研究了在不同pH值、吸附剂量、吸附质浓度和吸附时间条件下磷酸酯化改性梨渣吸附Cr（Ⅵ）离子的效果。溶液初始pH 4.5时,Cr（Ⅵ）离子的吸附达到最大值;酯化梨渣≥10g.L-1能除去Cr（Ⅵ）为100μg.L-1溶液中的86.5%的Cr（Ⅵ）离子。酯化梨渣对Cr（Ⅵ）离子的吸附符合Langmuir等温模型,其最大吸附能力为67.56μg.g-1。Cr（Ⅵ）离子达到吸附平衡的时间为90min,准一级反应动力学方程可描述酯化梨渣对Cr（Ⅵ）离子的吸附过程。