Memory effects in gas chromatographic detection with a microwave-induced plasma

Capillary gas chromatography coupled to microwave-inducedplasma detection furnishes sensitivity adequate for trace analysis when the signal is monitored at a carbon emission line. Work performed with one of these systems at high electronic gain for the carbon signal has revealed solvent band widths in excess of four minutes; these impeded quantification of peaks eluting after the solvent. This report discusses two phenomena which could be related to the unexpected intensity of this solvent response: photomultiplier tube saturation and carbon deposits in the quartz plasma discharge tube.     

A strategy for multivariate calibration based on modified single-index signal regression: Capturing explicit non-linearity and improving prediction accuracy

In this paper, a modified single-index signal regression (mSISR) method is proposed to construct a nonlinear and practical model with high-accuracy. The mSISR method defines the optimal penalty tuning parameter in P-spline signal regression (PSR) as initial tuning parameter and chooses the number of cycles based on minimizing root mean squared error of cross-validation (RMSECV). mSISR is superior to single-index signal regression (SISR) in terms of accuracy, computation time and convergency. And it can provide the character of the non-linearity between spectra and responses in a more precise manner than SISR. Two spectra data sets from basic research experiments, including plant chlorophyll nondestructive measurement and human blood glucose noninvasive measurement, are employed to illustrate the advantages of mSISR. The results indicate that the mSISR method (i) obtains the smooth and helpful regression coefficient vector, (ii) explicitly exhibits the type and amount of the non-linearity, (iii) can take advantage of nonlinear features of the signals to improve prediction performance and (iv) has distinct adaptability for the complex spectra model by comparing with other calibration methods. It is validated that mSISR is a promising nonlinear modeling strategy for multivariate calibration.     

Analytical applications of organized assemblies for on-line spectrometric determinations: present and future

An amphiphile (surfactant) spread on water can lead to the formation of different aggregates: vesicles, miscelles, emulsions or microemulsions; depending on its concentration; its molecular structure and/or the experimental conditions. Such aggregates, (a) may concentrate products, reactants or analytes and so improve the analytical sensitivity and (b) may solubilize such substances and so favorably change the analytical selectivity. Bilayer membrane vesicles for instance, apart from their wide applications in cosmetic and pharmaceutical industries, have a great analytical potential due to their ability to (i) reversibly sequester metal ions avoiding matrix interference and (ii) improve cold vapor (Hg and Cd) and hydride (As, Se, Pb) chemical generation. Micellar solutions have also found wide applications in different areas of analytical chemistry, showing their capacity to concentrate and separate a significant variety of analytes. Among the numerous micelle-based separation techniques, cloud point extraction offers an excellent enrichment factor for metal ions, allowing their quantification at microgram/litre levels. Also agitating a mixture of water, oil and one or more surfactants under controlled experimental conditions, a cloudy mixture (emulsion) or a transparent solution (microemulsion) can be formed. Adequate formulation is necessary in order to obtain a stable organized media. To fulfill this requirement, a major effort is necessary in order to shorten the gap between the current knowledge on this topic and the promising field of applications that await development. Recent publications show that self-assembly structures from highly viscous samples can be accomplished on-line with the advantages of drastically reducing the time of analysis and assuring the absolute control over the stability of the aggregate. Flow systems allow effective mixing of samples with added surfactant and provide continuous pumping of the resulting mixture to sensitive detectors for the on-line determination of different analytes in complex samples.     

ICP－AES法分析水质的探讨

本文用ＩＣＰ－ＡＥＳ（电感耦合等离子体－原子发射光谱法）测定水中Ａｌ、Ｂ、Ｂａ、Ｂｅ、Ｃａ、Ｃｄ、Ｃｏ、Ｃｒ、Ｃｕ、Ｆｅ、Ｍｇ、Ｍｏ、Ｍｎ、Ｎｉ、Ｐｂ、Ｓｒ、Ｖ、Ｚｎ等１８种微量元素。方法简便、快速，只将样品简单酸化，即可测定。方法检出限为０．０００５－０．５μｇ／ｍＬ。相对标准偏差＜１８％     

利用碘—三辛胺盐酸盐反应分光光度测定TOA,HCl

研究了测定三辛胺盐酸盐的一种新方法－碘光谱法。ＴＯＡ，ＨＣｌ在四氯化碳溶液中与生成电荷转移化合物，该物质的最大吸收波长为３７０ｎｍ，ＴＯＡ，ＨＣｌ在０－４×１０＾－４ｍｏｌ．Ｌ范围内符合比耳定律。该方法准确，简便，快速，其它溶剂的干扰较小，回收率在９４．５％－１０１．９％，能够满足分析的需要。     

基于光谱分析的重载车辆变速箱可靠性评估方法研究

润滑油光谱分析是变速箱磨损状态监测的重要手段。以某重载车辆变速箱台架试验中润滑油原子发射光谱分析得到的元素成分含量检测数据为基础,通过相关性分析和磨损机理分析确定了能够反映整机磨损状态和失效特点的金属元素,并对补油、换油后的光谱检测数据进行了修正,将变速箱试验过程中特征金属元素的含量随试验时间的变化规律表示为线性函数的形式。然后,综合考虑检测数据的时序规律与离散性,利用不同时刻光谱检测数据的正态分布均值和标准差进行变速箱可靠性评估,进一步讨论了失效阈值对可靠性评估结果的影响。研究表明,重载车辆变速箱润滑油中的Cu元素浓度与其他金属元素浓度的相关性较高、绝对值较大,既能够反映变速箱整体磨损状态,又便于检测,利用多个试验样本的润滑油Cu元素浓度光谱检测时序数据,可以对重载车辆变速箱进行可靠性评估;若失效阈值取定值,则失效阈值越大,同一时刻变速箱的可靠度越高;若失效阈值取随机分布,则失效阈值的离散度越大,可靠度随时间延长而降低的趋势越缓慢。当可靠度R大于0.9时,失效阈值的均值对可靠性评估结果的影响十分显著,同一时刻变速箱的可靠度随失效阈值标准差的增大而降低。将光谱分析与概率统计学结合进行变速箱可靠性评估方法研究,扩展了光谱分析技术的应用范围,具有创新性。     

浅析CTS系统在化探中的应用

主要介绍CTS（计算机译谱系统）在化探多元素光谱分析中的应用以及如何建立化探多元素分析方法文件。     

Spectrometric Studies on the Complexation of Pd(II), Fe(III) and Pt(IV) with mandelazo I

Abstract

A spectrometric study of the reaction between Pd(II), Fe(III) and Pt(IV) ions, and Mandelazo I was carried out. The optimum conditions favouring the formation of the complexes are extensively investigated. The stoichiometry of the complexes formed in solution (1:2, 1:1, 1:1), their apparent stability constants (5.45 × 10⁹, 2.39 × 10⁶, 4.12 × 10⁵) and the ranges for obedience to beer's law (0.2 – 6.4, 0.25 – 7.0, 1.5 – 42.0 μg/mL) are reported for Pd(II), Fe(III) and Pt(IV), respectively. The effect of some metal ions including Cu(II), Zn(II), Mn(II), Cd(II), Hg(II), Co(II), Ni(II), Be(II), Al(III), Th(IV) and U(VI), on the maximum absorbance of the formed complexes was also investigated.     

A new type of a spectrometric microtitration set up

A spectrometric microtitrator was developed from a spectrometer with a microreaction chamber and a tri-colour light-emitting diode (LED) as the light source. A novel, vertical, optical geometry of the spectrometric microtitration chamber was introduced and tested. This novel geometry also required a new method for mixing the titrated solution. A laboratory-made 50 μl syringe pump was used for the addition of the titration reagent. The 10-channel module for light effects, which makes possible a low-cost hardware approach to changing the titration protocols, was used for coordinating the operation of the microtitration set up. The system, with 10 channels and a regulated speed of operation, is flexible enough to allow an operator to generate different titration protocols. The performance test showed that the speed of titration-reagent addition can be regulated in the range from 0.87 to 21.8 μl min⁻¹. The smallest achievable volume addition is equal to 35 nl. The mixing rate can be continuously regulated by an electrical pulse that initiates the mixing cycle. The quickest rate is every 1.6 s, and the slowest rate is every 4.8 s. The spectrometric microtitration set up was successfully tested for several different real-life spectrometric titrations, including an iodometric titration, a determination of CO₂ in deionised water, and EDTA titrations of copper(II) ions with no indicator. The volume of the examined solution can be as small as 220 μl. The titration-reagent consumption is usually between 10 and 35 μl. Coefficients of variation of the end point volume determination (n = 5) at different experimental conditions and different average volumes of consumed reagents (7.06, 12.17 and 22.88 μl) were 2.4, 1.3 and 1.2%, respectively. The novel geometry of the spectrometric microtitration chamber proved to be useful for real-life applications.     

Mandelazo I As A Reagent For Zr(IV) Determination

Abstract

A spectromeric study of the reaction of the Zr(IV) ions with Mandelazo I was carried out. Absorption spectra revealed that the maximum absorption of the zirconium compound appears at a wavelength (316 nm) different from the maxima of the reagent (253 and 390 nm). Beer-Lambert law is followed for zirconium concentrations of the order of 8.8x 10^?5 M (i.e. 8 μg Zr (IV)/mL). Possible interferences of ions such as Be(II), Cu(II), Zn(II), Al(III), Th(IV), U(VI), Mn(II), Fe(III), Co(II) and Ni(II) were investigated in connection with some masking agents such as SO₄ ^2- and C₂O₄ ^2-. Also, the solid state Zr(IV)-Mandelazo I compound was prepared and characterized by nitrogen and thermogravimetric analyses.