Prediction of precision from signal and noise measurement in liquid chromatography: Mathematical relationship between integration domain and precision

Summary The precision of integration over noisy instrumental output for quantitative analysis is studied. A probability theory is developed to predict the relative standard deviation (RSD) of integration results over an integration domain from one-point integration (peak height measurement) to entire area integration in HPLC. Common integration modes of horizontal zero line and oblique zero line are taken into account, but no peak overlap is assumed. The question of the analytical superiority of peak height measurement or integration for quantitation is answered. In the HPLC apparatus used, the minimum RSD of measurements is found in the integration domain of ca. ±0.5 σ for analytes [peaks are approximated by the Gaussian signal of width, σ (standard deviation)]. The RSD of integration measurements is also shown to depend on the stochastic properties of background noise (uncorrelated noise and correlated 1/f type noise). The theoretical conclusion is verified by Monte Carlo simulation and HPLC experiments for some aromatic compounds. Second Part of series cited as Ref. [1].     

Application of the reference-element technique for fast sequential flame atomic-absorption spectrometry

Fast sequential flame atomic-absorption spectrometry (FS-FAAS) is able to measure a sequence of analyte wavelengths in one monochromator scan and so achieves or exceeds the analysis speed of sequential ICP–OES. The requirements and implementation of an FS-FAAS instrument are presented in detail. FS-FAAS is a sequential multi element technique which retains the advantages of conventional FAAS, for example ease of use. While the FS-FAAS technique is an ideal tool for routine determination of elements in the mg L^–1 concentration range, it is still subject to common sources of error such as transport problems and long-term drift. The reference-element technique can be used to correct for these types of common interference; other advantages include correction of some errors which are induced during sample preparation, and improved analytical accuracy and precision. The reference-element technique when utilizing the FS- FAAS technique is described in detail and benefits of the technique will be demonstrated by comparing performance for selected applications, for example a mineral sample and a scrap wood digest.     

高压下氮气在正庚烷-正辛烷混合溶剂中的溶解度研究

Solubilities of nitrogen in binary mixtures of n-octane and n-heptane have been measured at temperatures from 20 to 70 ℃ and pressures up to 130 atm using a precision gas-liquid solubility apparatus. Experimental results can be expressed by the following equation Inx_(N_2)=A+BP_(N_2)+CP_(N_2)~2+DInP From the results obtained, the partial molar volume of dissolved nitrogen and the Henry's Law constants have also been calculated.     

Estimation of the Cholesky decomposition in a conditional independent normal model with missing data

We investigate the problem of estimating the Cholesky decomposition in a conditional independent normal model with missing data. Explicit expressions for the maximum likelihood estimators and unbiased estimators are derived. By introducing a special group, we obtain the best equivariant estimators.     

飞机结构气动弹性分析与控制研究

随着主动控制技术的发展,飞机结构设计理念已由提高结构刚度的被动设计转变为随控布局的主动设计.主动设计理念不再刻意回避气动弹性问题,而是采用主动控制技术实时调节结构气动弹性,进而减轻结构重量、优化飞机性能. 在飞机随控布局主动设计中,必须深入分析结构与气流之间的耦合,才能更好发挥气动弹性主动控制技术的作用. 从20 世纪80 年代起,航空科技界对该问题进行了长期研究,对飞机结构-空气动力-主动控制相互耦合后的关键力学问题有了深入理解. 然而,已有研究多基于简化模型,导致研究结果难以直接应用于工程. 本文将针对气动弹性动态问题,综述空气动力非线性、控制面间隙非线性、时滞诱发失稳、颤振主动抑制、突风载荷减缓、风洞实验验证等方面的国内外研究进展,重点介绍近年来作者团队所提出的若干方法及相关算例和风洞实验. 最后,指出今后一个时期值得研究的若干气动弹性分析与控制问题.      

高压下氮气在正庚烷-正辛烷混合溶剂中的溶解度研究

高压下气体在混合溶剂中溶解度的测定与研究,无论在理论研究或是实际应用方面均具有重要的意义。但由于进行这类研究,特别是在升温升压下,费时,昂贵和有一定难度,目前这方面的数据十分缺乏。作为本实验室研究系列之一部份,本文将报导文献中尚未见发表的氮气在正庚烷-正辛烷混合溶剂中的溶解度研究结果。实验部份1.试剂氮气纯度99.999%,由北京氧气厂提供;正庚烷,正辛烷由北京化工厂产分析纯试剂,本实验室又进一步精馏纯化。纯化后的试剂用气相色谱分析其纯度高于99.4%.混合溶剂的组成用重量法配制。     

多通道光路在气体分析中的应用

本文在不分光红外分析法的基础上,应用一种多通道的光路,研究在一个气室中分析多种气体成分的方法。即研究在一个气室中周期地透射多种特定的带通很狭的红外波时,其光电响应值与相对应气体成分浓度的关系。结果表明,多通道光路系统的检测精度和稳定性方面均达到了较好水平。     

基于GPS的智能农机载高光谱采集系统的初步研究

为了解决精确农业中高密度的和全面的农田信息采集的需要,本系统利用visual basic和map objects对GPS, GIS和RS进行有机集成, 一方面系统通过集成GPS, 能为采集到的光谱数据提供高精度的空间位置属性,实现光谱数据采集、定位和存储一体化; 另一方面通过集成GIS,实现了具有空间属性的光谱数据可视化管理和分析处理, 实时地显示动点轨迹和各图层对应点属性,计算作物微分光谱和植被指数NDVI等功能, 为专家系统和决策支持系统提供充足的信息。     

Precision and Accuracy Studies of Impaction-Electrothermal Atomization Atomic Spectrometry

Abstract

The precision of aqueous solutions of cadmium, copper, and manganese introduced as an aerosol by an pneumatic nebulizer and electrothermal vaporizer to an impaction-electrothermal atomization atomic absorption spectrometeric system was in the range of 1–3% which was similar to that obtained by manual introduction of similar concentrations of aqueous solutions of cadmium, copper, and manganese to the electrothermal atomizer and atomic absorption spectrometry. The precision of a laboratory air sample was 7.6–9.9%. Accuracy was assessed by comparison to conventional methods of sampling air by collection on a filter followed by digestion of the filter and analysis by flame atomic absorption spectrometry The levels were found to be 59–69% compared to the conventional method.     

The importance of precision in sampling sludges, biowastes and treated soils in a regulatory framework

As part of the European Commission (EC)'s revision of the Sewage Sludge Directive and the development of a Biowaste Directive, there was recognition of the difficulty of comparing data from Member States (MSs) because of differences in sampling and analytical procedures. The ‘HORIZONTAL' initiative, funded by the EC and MSs, seeks to address these differences in approach and to produce standardised procedures in the form of CEN standards. This article is a preliminary investigation into aspects of the sampling of biosolids, composts and soils to which there is a history of biosolid application. The article provides information on the measurement uncertainty associated with sampling from heaps, large bags and pipes and soils in the landscape under a limited set of conditions, using sampling approaches in space and time and sample numbers based on procedures widely used in the relevant industries and when sampling similar materials.These preliminary results suggest that considerably more information is required before the appropriate sample design, optimum number of samples, number of samples comprising a composite, and temporal and spatial frequency of sampling might be recommended to achieve consistent results of a high level of precision and confidence.