微波消解-ICP-OES法测定哈氏C-276合金中Cr、Fe、Mo、W元素

建立了微波消解-电感耦合等离子体发射光谱法同时测定哈氏C-276合金中Cr、Fe、Mo、W元素含量的分析方法.采用10 m L HCl-HNO3-HF(体积比为10:1:1)混合酸溶解试样.研究了合金不同溶解方式、元素谱线的选择、背景校正等试验条件,并对仪器分析参数进行了优化,确定了最佳的试验条件,各元素分析谱线依次为Cr2 67.716 nm、Fe 238.204 nm、Mo 202.031 nm、W 209.712 nm,建立的校准曲线各元素相关系数均在0.999 5以上.实际样品分析中,加标回收率为97.8%~102.7%,重复测定结果的相对标准偏差小于1.64%(n=6),试验测定结果与镍基标准样品标准值做对照,结果表明方法准确、快速,能够满足日常生产的检测要求.     

悬浮液直接进样ICP–OES法测定高纯氧化铝中的铁、钛、硅、铬

采用悬浮液直接进样电感耦合等离子体发射光谱法(ICP–OES)测定高纯氢氧化铝中铁、钛、硅、铬的含量。悬浮液用电磁搅拌器搅拌,均匀地分散在溶液中,通过仪器蠕动泵进入雾化室,均匀无阻地导入ICP光源。Fe,Ti,Si,Cr的分析谱线分别为259.940,336.112,251.611,205.552 nm;RF功率为1 300W,等离子体气流量为13.0 L/min,雾化器气体流量为0.60 L/min,辅助气流量为1.00 L/min。Fe,Ti,Si,Cr的质量浓度分别在0.0~30.0,0.0~15.0,0.0~90.0,0.0~15.0μg/m L范围内与信号强度呈良好的线性,线性相关系数均大于0.999,方法的检出限为0.027 6~0.993 9μg/m L,测量结果的相对标准偏差为0.65%~6.84%(n=11),回收率为95.0%~104.8%。该法抗干扰能力强、线性范围宽,适用于高纯氢氧化铝中铁、钛、硅、铬含量的分析。     

超声辅助提取/离子色谱法测定铬污染土壤中的六价铬

建立了超声辅助提取/离子色谱法测定铬污染场地中铬（Ⅵ）的方法。选用0.3 mol/L的KCl溶液作提取剂,对12组土壤样品中的铬（Ⅵ）进行超声辅助提取20 min。采用Metrosep A Supp 4-250（250 mm×4.0mm）型阴离子分离柱,以4 mmol/L Na₂CO₃-1 mmol/L NaHCO₃混合溶液为淋洗液对样品进行分离分析。铬（Ⅵ）在0.01²0 mg/L浓度范围有较好的线性关系,相关系数（r²）为0.999 8;该方法的检出限为0.003 mg/L,加标回收率为96.4%¹06.8%,相对标准偏差（RSD,n=3）为0.56%。该方法具有简便、快速、准确等优点,适用于铬污染场地的监测与调查。     

Vibrational spectra and factor group analysis of rare-earth chromium borates,RCr3(BO3)4, with R = La–Ho

Anhydrous orthoborates RM₃(BO₃)₄, where R = Y, La–Lu, M = Al, Ga, Cr, Fe, with huntite structure type are considered as multifunctional laser materials. The crystal structure of these borates is either rhombohedral with space group R32 (D₃⁷) (Z = 3) or monoclinic with space group C2/c (C_2h⁶) (Z = 4) depending on the growth conditions. Both modifications have very close polytypic structures, and it is difficult to identify them by powder diffraction data. In this context, double borates of rare-earth cations and Cr³⁺ have been grown from high-temperature solutions and are characterized by Raman and infrared spectroscopy in a crystalline state in combination with factor group analysis of vibrational modes. The assignment for the stretching and bending vibrations of BO₃³⁻ groups and external modes has been made. Some external modes have been identified by study of mass effect (Al–Cr, La–Ho). Comparison of the Raman spectra of these borates shows redistribution of band intensities of two spectral modifications, related to different symmetry groups. As predicted by factor group analysis, the number of IR-active vibrational modes of stretching and bending vibrations of BO₃³⁻ units significantly increases in infrared spectra of monoclinic borates in comparison with rhombohedral ones. The dependence of the realized borate space group on the crystal growth conditions and the sort of rare-earth atom was revealed. Both GdCr₃(BO₃)₄ and EuCr₃(BO₃)₄ borates crystallize in space group R32 irrespective of growth conditions. The borates with the large rare-earth elements La–Nd always form the monoclinic structures, irrespective of crystallization temperature. The borates SmCr₃(BO₃)₄, TbCr₃(BO₃)₄ and DyCr₃(BO₃)₄ have been obtained in two modifications in dependence of crystalline borate substance/solvent ratio and related temperature of crystallization.     

The Ligand‐Based Quintuple Bond‐Shortening Concept and Some of Its Limitations

Herein, the ligand‐based concept of shortening quintuple bonds and some of its limitations are reported. In dichromium–diguanidinato complexes, the length of the quintuple bond can be influenced by the substituent at the central carbon atom of the used ligand. The guanidinato ligand with a 2,6‐dimethylpiperidine backbone was found to be the optimal ligand. The reduction of its chromium(II) chloride–ate complex gave a quintuply bonded bimetallic complex with a Cr? Cr distance of 1.7056 (12) Å. Its metal–metal distance, the shortest observed in any stable compound yet, is of essentially the same length as that of the longest alkane C? C bond (1.704 (4) Å). Both molecules, the alkane and the Cr complex, are of remarkable stability. Furthermore, an unsupported Cr^I dimer with an effective bond order (EBO) of 1.25 between the two metal atoms, indicated by CASSCF/CASPT2 calculations, was isolated as a by‐product. The formation of this by‐product indicates that with a certain bulk of the guanidinato ligand, other coordination isomers become relevant. Over‐reduction takes place, and a chromium–arene sandwich complex structurally related to the classic dibenzene chromium complex was observed, even when bulkier substituents are introduced at the central carbon atom of the used guanidinato ligand.     

Non-chromatographic speciation analysis of chromium in natural waters

The difference in toxicity between Cr(III) and Cr(VI) species is one of the main reasons for the recent developments in analytical procedures for their differentiate. Non-chromatographic methods offer highly convenient tools for this purpose and can be used as a fast and cheap alternative to the chromatographic processes. The present work overviews and discuss different non-chromatographic procedures for speciation of chromium in natural water samples such as coprecipitation, dialysis, solvent and solid phase extraction. This survey will attempt to cover the state of-the art from 2005 to 2010.     

Adsorptive transfer voltammetry applied to the study of chromium-induced DNA damage in the presence of curcumin

The interaction between double-stranded (ds) calf-thymus DNA and chromium in the presence of curcumin (CC) was studied by differential pulse adsorptive transfer voltammetry using carbon paste electrode (CPE). Curcumin–Cr complex generated changes in calf thymus DNA. The mechanism for DNA cleavage by curcumin–Cr complex appears to involve both the hydroxyl radical as well as singlet oxygen. The characteristic peak of dsDNA, due to the oxidation of guanine residues, drastically decreased. The increased DNA damage by curcumin–Cr complex was observed in the presence of various concentrations of chromium(VI).     

钾对铬催化剂脱氢环化反应的影响

采用等体积分步浸渍法制备了不同K2O含量的K-Cr2O3/Al2O3催化剂,并用BET、XPS、UV-Vis、H2-TPR、NH3-TPD和TG等技术对催化剂进行了表征,考察了催化剂对二异丁烯(2,4,4-三甲基戊烯)脱氢环化为对二甲苯的催化性能.结果表明,K不仅可以降低氧化铝载体的酸性,而且促进了活性组分Cr在载体表面的分散.K2O含量为1.5%时,催化剂的脱氢环化性能达到最佳.     

聚乙烯亚胺改性氧化石墨对水中Cr(Ⅵ)的吸附

通过对石墨氧化、酯化,将聚乙烯亚胺耦合接枝到氧化石墨表面,制备聚乙烯亚胺改性氧化石墨(PEI-GO).通过FTIR、XRD、TEM、RS和XPS等对合成材料进行表征,并研究了其对水中的Cr(Ⅵ)吸附和脱附性能.表征结果表明,聚乙烯亚胺成功嫁接到氧化石墨上,其氨基含量为4.36 mmol·g^-1.PEI-GO对水中Cr(Ⅵ)具有很好的吸附性能,吸附等温线符合Freundlich方程,吸附动力学可用拟二级动力学方程来描述.PEI-GO对水中Cr(Ⅵ)的吸附随pH的升高而降低.阴离子的存在降低吸附剂对Cr(Ⅵ)的吸附,不同阴离子的影响大小顺序为PO₄^3- >SO₄^2- >NO^3- >Cl^-.XPS结果表明,PEI-GO对Cr(Ⅵ)的去除是吸附-化学还原耦合作用的结果.经4次脱附再生循环,PEI-GO对Cr(VI)仍具有较高吸附量,表明该吸附剂再生性好,可循环使用.     

Oxidation of Benzoins to Benzils with Chromium Trioxide Under Viscous Conditions

Reaction of chiral allylic cyclic carbonates with Grignards reagent in the presence of NiCl₂(dppe) as a catalyst afforded the alkylated (E)-allylic alcohols with high regio- and diastereoselectivity.