含铬废物焚烧中CrOH+H→CrO+H2反应机理研究

本文用量子化学密度泛函UB3LYP方法,在6-311 G**基组水平上研究了含铬固体废物焚烧过程中CrOH H→CrO H2的微观反应机理。在相同理论水平上用内禀反应坐标理论(IRC)对最小能量途径进行计算,并进行了详细的讨论。分别计算了正、逆反应的活化能。采用经典过渡态理论计算了正、逆反应的反应速率常数。     

Highly luminescent nanocrystal quantum dots fabricated by lattice-type mismatched epitaxy

Lattice-type mismatched heteroepitaxy is demonstrated as a novel concept for the fabrication of almost ideal, highly luminescent nanocrystal quantum dots that are coherently embedded in a single-crystalline matrix. In this approach, the formation of quantum dots is induced by transformation of a metastable epitaxial 2D quantum well into an array of isolated nanocrystals with-highly symmetric shape. This process is driven by the lattice-type mismatch between the constituent materials and the resulting miscibility gap. The investigated PbTe/CdTe heterosystem has a model character because it combines two compounds with different cubic lattice types but almost identical lattice constants. The obtained epitaxial nanocrystals exhibit outstanding properties such as a well-defined symmetric shape, the absence of strain, intermixing and a wetting layer, which is in contrast to the conventional Stranski–Krastanow quantum dots. The small-rhomboedric-cubo-octahedron PbTe/CdTe nanocrystals on GaAs substrates display intense room temperature mid-infrared luminescence as is crucial for device applications. Ab initio density functional theory is used to clarify the interface structure, indicating that the covalent and ionic bonding character of CdTe and PbTe is maintained across the interface.     

Изотопные мишени для ядерных исследований

A non-contact measuring method on electrostatic potential by using α-ray ionization is proposed. In this method potential of a charged material is estimated from ionic current flowing through an ion collector attached with a small ²⁴¹Am source. As hade electrode surrounding the collector has a function of adjusting sensitivity and potential up to 50 kV was measured with precision of 1 kV.     

Two Types of σ-Allenyl Complexes from Reactions of Silylenes and Germylenes with Chromium Fischer Alkynyl(alkoxy)carbenes

The reactivity of amidinatotetrylenes of the type E(tBu₂bzm)R¹ (E=Si, Ge; tBu₂bzm=N,N′-bis(tertbutyl)benzamidinate; R¹=alkyl or aryl) with the chromium Fischer alkynylcarbene complexes [Cr{C(OEt)C₂R²}(CO)₅] (R²=Ph; ferrocenyl, Fc) has been studied. At room temperature, two different reaction pathways have been identified: (a) attack of the amidinatotetrylene to the alkynyl C² atom (γ-attack), which leads to σ-allenyl complexes in which the original C_carbene atom maintains its attachment to the Cr(CO)₅ and OEt groups (compounds 3 ), and (b) attack of the amidinatotetrylene to the C_carbene atom (α-attack), which ends in σ-allenyl complexes in which the original C_carbene atom is not attached to the metal atom and has been inserted into an E−N bond of the amidinatotetrylene forming an E-C-N-C-N five-membered ring (compounds 4 ). It has been found that compounds 3 are thermodynamically less stable than their corresponding 4 isomers and that some of the former (E=Ge; R¹=CH₂SiMe₃) can be transformed into the latter upon heating. At high temperatures (>70 °C) the reactions involving bulky amidinatotetrylenes (R¹=Mes, tBu) end in the carbene-substitution products [Cr{E(tBu₂bzm)R¹}(CO)₅].     

Spectrophotometric determination of Chromium(VI) using cyclam as a reagent

A simple, rapid, sensitive, and inexpensive method for spectrophotometric determination of chromium(VI), based on the absorbance of its complex with 1,4,8,11-tetraazacyclotetradecane (cyclam) is presented. The complex showed a molar absorbtivity of 1.5?×?10⁴?L?mol^?1?cm^?1 at 379?nm. Under optimum experimental conditions, a pH of 4.5 and 1.960?×?10³?mg?L^?1 cyclam were selected, and all measurements were performed 10?min after mixing. Major cations and anions did not show any interference; Beer's law was applicable in the concentration range 0.2–20?mg?L^?1 with a detection limit of 0.001?mg?L^?1. The standard deviation in the determination is ±0.5?mg?L^?1 for a 15.0?mg?L^?1 solution (n?=?7). The described method provides a simple and reliable means for determination of Cr(VI) in real samples.     

Improved simultaneous adsorption of Cu(II) and Cr(VI) of organic modified metakaolin-based geopolymer

In this paper, a metakaolin-based mesoporous geopolymer (GP-CTAB) was used as adsorbent for Cu(II) and Cr(VI) through a novel and simple synthetic route using cetyltrimethylammonium bromide (CTAB) as an organic modifier. The application of GP-CTAB for the simultaneous removal of metal anions and cations in aqueous solution was studied for the first time. The results of X-ray diffraction (XRD) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, Brunauer, Emmett and Teller (BET), and Barrett, Joyner, and Halenda (BJH) methods indicate that GP-CTAB is still geopolymer even in the presence of quaternary ammonium salt cations. The material was tested to simultaneously adsorb Cu(II) and Cr(VI) from an aqueous solution. The results show that GP-CTAB can adsorb anions simultaneously without sacrificing the adsorption properties of heavy metal cations, which is superior to conventional geopolymers. The maximum theoretical adsorption capacity of GP-CTAB for Cu(II) and Cr(VI) was 108.2 mg/g and 95.3 mg/g in the binary system, respectively. It was also found that the presence of Cu(II) in the solution promoted the adsorption of Cr(VI). Given this characteristic of GP-CTAB, it has shown great application prospects in the prevention and control of heavy metal pollution.     

不锈钢1Cr18Ni9Ti中铬含量测量不确定度的评定

采用国际通用的方法研究了过硫酸铵氧化容量法测定铬含量的不确定度,分析了容量法中摩尔质量、样品质量、溶液的体积、温度等因素对测量不确定度的影响,评估了各参数的标准不确定度、合成标准不确定度和扩展不确定度。找出了影响容量法测定铬含量准确度的主要原因。     

轧辊用高钒高速钢的滚-滑动磨损性能及失效行为研究

在高应力滚-滑动(滑动率约10%)条件下,利用自制的磨损试验机研究了高钒高速钢的磨损性能,并利用电子显微镜分析了失效行为.结果表明:高钒高速钢的相对耐磨性是高铬铸铁(Cr20)的2倍以上.磨损失效形式为显微切削与疲劳剥落的复合,兼有碳化物碎裂.碳化物对磨损失效有重要作用,高铬铸铁中的杆状M7C3型碳化物易于弯曲、碎裂而在其内部形成大量裂纹,促进磨损表面产生大块的疲劳剥落;高钒高速钢中团块状VC硬度高、形态好、具有精细亚结构、不易碎裂,可有效地抵御显微切削和疲劳剥落,是高钒高速钢耐磨性优良的原因.     

ChemInform Abstract: Molecular Structure of Chromium Tetrafluoride in the Gas Phase

is determined by electron diffraction at 195-220 °C. The diffraction patterns are completely consistent with a molecule of tetrahedral (Td) symmetry.