时间分辨红外发射光谱法对自由基反应的研究

在过去的 15年中 ,傅立叶变换红外发射光谱法广泛应用于研究气相自由基反应 .Sloan首先研究了O(1D)的反应 ,随后Leone和Hancock研究了O(3 P)的反应 .此后 ,孔繁敖和朱起鹤等研究了小自由基 ,包括CH、CH2 、CH3 、C2 H3 、C2 H5、C2 H、C3 H3 和C3 H5与O2 、NO、N2 O、NO2 等分子的反应。在红外光谱中观察到各个反应的初生产物和初步反应通道 ,和从头算的理论研究结合起来 ,这些反应的机理已基本弄清 .     

甲醛与乙腈相互作用的理论研究

在HF/ 6 311G(d ,p)、MP2 / 6 311G(d ,p)和B3LYP/ 6 311G(d ,p)水平上 ,对H2 CO和CH3 CN以及设计的 4种结构H2 CO…CH3 CN复合物等进行几何全优化和振动频率计算 ,排除振动频率为负值的非局域极小点结构 ,并对稳定的环状构型复合物结合能进行基组重叠误差校正和零点振动能校正 .分子间相互作用的能量分解分析显示 ,静电能在H2 CO…CH3 CN相互作用能量中占主导地位 ,电荷转移能居第二位 .     

回填材料膨润土对放射性气体滞留能力模拟研究

利用各种分析手段对膨润土的物理特性进行了表征 .X射线衍射分析表明钠基膨润土呈典型的六方晶胞 ,晶胞参数是 :a轴 4 .913,c轴 5 .4 0 5 ;差热分析曲线在低温区和高温区有明显的吸热峰出现 ;元素分析钠、钾离子的含量大于钙、镁离子的含量 ,在性能上表现为钠质膨润土具有较强的离子交换能力 ;显微分析表明其表面呈皱隙状 ,测定比表面积高达 2 4 .5 2m2 /g;吸水率测定表明膨胀率大 ,说明它具有密封功能 ,可有效阻滞地下水的渗入 .利用SF6示踪技术 ,通过采集不同时间段取样池样品 ,分析样品中示踪气体浓度 ,绘制取样池示踪气体浓度随时间的变化关系曲线 ,根据费克扩散定律计算扩散系数 .实验结果表明 ,随着压实膨润土密度的增大 ,示踪气体扩散系数迅速减小 ,当密度大于 1.8g/cm3 时 ,扩散系数降至 10 -9m2 /s.研究结果表明 ,膨润土性能优化是通过在膨润土中添加适量的活性炭 ,可明显改善其对气体的阻滞能力 ;增加其对放射性气体滞留能力 ;添加少量的石英砂增加其机械性能、导热性和减少蠕变性 ,将引起对气体阻滞能力的下降 .综合考虑 ,在膨润土中各添加 5 %活性炭和石英砂 ,既对气体具有较好的滞留能力 ,又具有较好的工程特性 .     

Ziegler-Natta催化剂催化乙烯气相聚合

本文综述了乙烯气相聚合催化剂研究状况,列举了一些制备气相聚合催化剂有代表性的方法。同时对预聚合的作用及气相聚合与淤浆聚合表观动力学行为的不同性也作了简要介绍。     

Applicability of glass fiber as a support material for generation of gaseous standard mixtures using thermal decomposition of the surface compound. Calibration of analytical equipment

The use of glass fiber as a support material for a surface compound serving to generate gaseous standard mixtures of ethene is described. The technique is based on the process of thermal decomposition of the surface compound in a desorber connected on‐line via a multi‐port valve to the calibrated device. The surface compound undergoes thermal decomposition at 245°C, yielding known amounts of ethene. The method enables on‐line preparation of a standard mixture immediately before the calibration step. Consequently, it can be also applied for the generation of standard mixtures containing volatile, malodorous, unstable, and toxic compounds.     

Determination of long-lived radionuclides in concrete matrix by laser ablation inductively coupled plasma mass spectrometry

A laser ablation system using a Nd:YAG laser was coupled both to a quadrupole inductively coupled plasma (ICP) mass spectrometer and to a double-focusing sector field ICP mass spectrometer. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was applied for the determination of long-lived radionuclides in a concrete matrix. The investigated samples were two laboratory standards with a concrete matrix, which we doped with different long-lived radionuclides (e.g. ⁹⁹Tc, ²³²Th, ²³³U, ²³⁷Np) from the ng g⁻¹ to μ g⁻¹ concentration range and an undoped concrete material (blank). Detection limits for long-lived radionuclides in the 10 ng g⁻¹ range are reached for LA-ICP-MS using the quadrupole mass spectrometer. With double-focusing sector field ICP-MS, the limits of detection are in general one order of magnitude lower and reach the sub ng g⁻¹ range for ²³³U and ²³⁷Np. A comparison of mass spectrometric results with those of neutron activation analysis on undoped concrete sample indicates that a semiquantitative determination of the concentrations of the minor and trace elements in the concrete matrix is possible with LA-ICP-MS without using a standard reference material.     

Thermodynamic properties of the gaseous barium silicates BaSiO2 and BaSiO3

In the present study, the stability of gaseous barium silicates was confirmed by the high temperature mass spectrometry. On the basis of equilibrium constants measured for gas-phase reactions, the standard formation enthalpies were determined for gaseous barium silicates as (−510 ± 15) kJ · mol⁻¹ and (−884 ± 18) kJ · mol⁻¹ at 298 K; standard atomization enthalpies as (1637 ± 17) kJ · mol⁻¹ and (2318 ± 20) kJ · mol⁻¹ at 298 K for BaSiO₂ and BaSiO₃, respectively. Based on the results obtained the critical analysis of the literature data was carried out.     

气相反应C_(60)+O_3=C_(6O)(C_(2v))+O_2热力学函数的计算

计算了气相反应C60＋O3＝C6O（C2v）＋O2的热力学函数．得到了该反应Gibbs自由能的具体数值，结果表明在所研究的温度范围内Gibbs自由能为负值，从热力学角度来说，该反应可以自发进行,在计算该气相反应热力学函数的基础上，给出了气相C6O（C2v）的标准热力学函数     

Thermal decomposition of surface compounds for the generation of small quantities of acetaldehyde: Calibration of a thermal desorption-gas chromatography-flame ionization detection

The paper presents a new method for the generation of acetaldehyde in the amounts that allow to calibrate the measuring system. The method is based on thermal decomposition of surface compounds at the range 130-190 °C, in which an acetaldehyde as the decomposition product is released. The synthetic pathway leading to the desired surface compounds is described. Investigations demonstrated that the synthesis of the compounds on the surface of the support material (silica gel) was carried out homogeneously. The technique proposed was used for the generation of gaseous standard mixtures containing acetaldehyde for the calibration of a thermal desorber-gas chromatograph-flame ionization detector system.