亚乙烯基卡宾H2CCC：的氢氢键插入和加成反应机理的研究

用HF/3-21G解析梯度方法研究H_2CCC:的氢氢键插入和加成反应机理,结果表明,H2CCC:的H—H插入为直接插入,取端端(end-on)接近方式;H_2加成经两步完成.第一步是2+2加成,因对称性禁阻取三中心过渡态,四中心作用发生在反应的后期,第二步是CH_3CHC:的1,2氢重排.预言气相中H—H插入容易发生,势垒值约为45 kJ/mol.     

电荷注入检测器—端视等离子体原子发射光谱中分析动态范围

实验研究了电荷注入检测器－端视电感耦合等离子体光谱中分析动态范围，测量了ＡＬ，Ｂ、Ｂｅ，Ｃｄ，Ｃｕ，Ｃｏ，Ｆｅ，Ｌｉ，Ｓｒ，Ｖ，Ｋ，Ｓｒ等１２个元素的不同光谱级次的４４条分析工作曲线。结果表明，分析范围为４－５个数量级，无明显自吸收，Ｌｏｍａｋｉｎ公式的自吸收系数ｂ＝１，说明在ＣＩＤ－ＡＶＩＣＰ光谱中有较宽的分析动态范围 。     

微波等离子体炬耦合方式的研究

采用气动雾化连续进样、端视观测法,考察了微波等离子体炬原子发射光谱法中等离子体Ar线的背景发射以及Al,Mg,V等元素的信号发射强度随天线耦合连接点位置的不同而发生的变化.结果表明,当天线位于炬管顶端,即天线距离活塞3λ/4和λ/4时均能获得较好的等离子体,λ/4略好,信号发射强度和信背也较大,只是精密度略差一些.初步探讨了MPT炬管的电磁场结构.     

Summary of ISO/TC 201 Technical Report: ISO/TR 19319: 2003—Surface chemical analysis—Auger electron spectroscopy and x‐ray photoelectron spectroscopy—Determination of lateral resolution,analysis area and sample area viewed by the analyser

ISO Technical Report 19319:2003 contains information on the determination of lateral resolution, analysis area and sample area viewed by the analyser in surface analyses by Auger electron spectroscopy and x‐ray photoelectron spectroscopy. This article provides a brief summary of this information. Copyright © 2004 John Wiley & Sons, Ltd.     

端视ICP-AES法测定钕铁硼永磁材料中常量及微量元素

报道了用高灵敏度的电感耦合等离子体原子发射光谱法（ＩＣＰ－ＡＥＳ）直接测定钕铁硼永磁材料中常量、少量及微量元素：Ｎｄ、Ｆｅ、Ｃｏ、Ｂ、Ｌａ、Ｃｅ、Ｐｒ、Ｄｙ、Ｇｄ、Ｓｍ、Ａｌ、Ｍｎ、Ｃａ、Ｍｇ、Ｇａ和Ｓｉ的分析方法。选择了合适的分析线，研究了基体元素Ｎｄ、Ｆｅ、Ｃｏ对被测杂质元素分析线的光谱干扰，采用基体匹配与背景扣除法进行校正。各被测元素的检出限为０．５～３０μｇ／Ｌ，回收率为９２～１１０％，相对标准偏差小于７％。本法已用于钕铁硼产品的快速检验，并获得了满意的结果。     

带形上随机环境中随机游动的内蕴分枝结构

揭示了带形上随机环境中随机游动的内蕴分枝结构一带移民的多物种分枝过程.利用内蕴分枝结构,可精确表达游动的首次击中时.给出了内蕴分枝结构的如下两个应用:(1)计算出首次击中时的均值,给出游动大数定律速度的显示表达,(2)得到从粒子角度看环境的马氏链不变测度的密度函数的显示表达,进而可用另一种"站在粒子看环境"的方法直接证明游动的大数定律.     

Advantages and effects of nitrogen doping into the central channel of plasma in axially viewed-inductively coupled plasma optical emission spectrometry

The effects and benefits of N₂ addition to the central channel of the ICP through the nebulizer gas used in ICP OES with axial view configuration were investigated in the present study. The N₂ flow rate, nebulizer gas flow rate, RF power and sample uptake rate were evaluated and compared for two sample introduction systems (pneumatic nebulization/aerosol desolvation and conventional pneumatic nebulization). It was observed that N₂ did not affect solution nebulization and aerosol transport but affects the ICP characteristics. The higher thermal conductivity of N₂ (in comparison with Ar) changes energy distribution in the ICP, observed by monitoring the signals of Ar emission lines and sodium emission. The ratio Mg(II)-280.270 nm/Mg(I)-285.213 nm was utilized as a diagnostic tool for plasma robustness. The addition of N₂ (20 mL min⁻¹) increased plasma robustness significantly and mitigated effects caused by Na, K and Ca. For 40 spectral lines evaluated, it was observed that the emission signals of ionic spectral lines were in general more affected by N₂ than those of atomic spectral lines. Detection limits, precision, sensitivity and linearity of calibration curves obtained using N₂-Ar-ICP were almost similar to those obtained using Ar-ICP. The analysis of 5 different reference materials revealed that accuracy was not degraded by adding N₂ to the Ar-ICP.     

新型固态检测器端视ICP-AES中Ca、Mg基体效应的研究

本文详细研究了0．1％Ca和0．1％Mg基体在端视ICP中对激发电位不同的谱线的干扰效应;对端视与侧视ICP中的基体干扰进行了比较;探讨了主要工作参数对基体干扰的影响。结果表明,在Ca、Mg基体存在时,大部分待测元素的谱线受到抑制,并且激发电位较高的谱线受抑制程度较大;侧视ICP中基体干扰比端视ICP中略好;适当增大功率和选择合适的载气流量可减少Ca或Mg基体的干扰。     

Evaluation of inductively coupled plasma optical emission spectrometers with axial configuration: interfaces with end-on gas and shear gas

In this investigation, samples of whole bovine milk were diluted with water-soluble tertiary amines solution and introduced in two axially viewed inductively coupled plasma optical emission spectrometer (ICP OES) instruments equipped with different interfaces (shear gas and end-on gas interface). The accuracy and the Mg II (280.2 nm)/Mg I (285.2 nm) ratio were evaluated. Higher values for Mg II/Mg I were observed with the shear gas interface. However, these values were less affected by changes of instrumental parameters when using the end-on gas interface. Results with suitable accuracy were obtained for a certified reference material of powdered whole milk (NIST SRM 8435) using instruments equipped with each interface.