X射线衍射多谱峰匹配强度比定量相分析方法

提出了1种采用x射线衍射多谱峰匹配强度比进行定量相分析的新方法;该法是利用混合物样品x射线衍射谱图中的多谱峰数据,结合ICDD卡中的各相标准谱峰的相对强度分布数据进行最小二乘法回归分析,求得混合物样品中各相间的多谱峰匹配强度比;以多谱峰匹配强度比取代通常采用的特定单一谱线强度比,用于混合物样品的x射线衍射定量相分析,有利于提高定量相分析的精度;采用多谱峰匹配强度比结合绝热法和基体清洗法X射线衍射定量相分析原理,通过对4组分混合物样品的分析,证实实验结果和理论完全一致。     

X射线衍射定量相分析的检测限

X射线衍射定量相分析可以获得混合物中各物相的含量。混合物中各相的含量,由於吸收效应,一般不与其衍射线强度成正比关系,但含量与强度仍成一定的比例关系。在物相定性和定量分析中,人们对检测限是很感兴趣的。例如在常见的产物鉴定和相变研究中,通常需要知道物相的纯度。解决这个问题惯用的办法是将微量相含量一次一次减少地加入到基体中去,配制一系列不同标样,观察其衍射线强度;衍射线刚好消失时对应的含量,即为检测     

电子计算机自动X射线物相分析进展

利用X射线粉末衍射谱进行物相分析,由于不破坏样品,过程简单,结果准确可靠而成为化学化工、金属、地质及其它材料学科中最广泛使用的方法。 X射线物相分析是把待鉴定样品的衍射谱与一套物相已知的标准衍射谱进行对比,以确     

样品质量控制对X射线衍射测量结果的影响

以生物材料羟基磷灰石（HA）为样品模型,系统研究了HA样品在不同质量状态下对X射线衍射测试结果的作用。通过考察样品状态确认（块体、层状和粉末等）、实验方法选择（粉末多晶衍射和薄膜掠入射衍射等）以及环境条件控制（温度、湿度及X射线下辐照时间等）等因素,评价样品的质量控制对X射线衍射（XRD）检测数据准确性与真实性的影响。结果表明,与HA块状样品相比,经过研磨过筛处理后的粉末试样XRD特征峰强度显著增强,差异可增加至1倍以上。针对HA多层状生长样品,结合掠入射和常规粉末衍射可精准实现各层物相解析。HA粉末样品的粒径、样品量及对应的装填方式会影响XRD检测结果,粒径37μm的HA粉末样品的特征峰强是粒径137μm样品1倍左右;而少量样品的中部空置制样,可导致特征峰峰位由31.8（°）偏移至31.4（°）,峰强从11213.68降到601.65。另外,对于稳定性不佳或对环境温湿度敏感的试样,采取合适的保存和检测方式,可有效预防和避免错误的检测与结果分析。因此,全面的质量控制对高质量的XRD检测数据获取和确保实验数据质量至关重要。     

X射线微量物相分析

前言固体微粒的X射线物相分析,可用以研究合金、矿物、颜料、空气或水里的污染粒子以及其它晶体微粒。在通常的实验条件下,使用X射线照相法能测定直径约在十微米(相当于微微克数量级)的单个固体微粒。但是在研究混合物样品的微粒时,困难就较大一些。由于样品中待测物质的量较少,信息微弱,所摄取的底片中往往只能显示一小部分衍射线条,而且,各组分的衍射线还可能重迭干扰。这些不利因素都会影响分析的结果。     

应用X射线无标样相定量法研究V_2O_5-TiO_2体系的表面分散

载在TiO_2上的V_2O_5是烃类氧化有活性和选择性的催化剂,许多作者对其物理化学性质和催化性能进行了研究,认为V_2O_5能在TiO_2表面上分散。北京大学物理化学研究所用X射线相定量等方法研究了某些催化剂活性组份在载体表面分散的自发倾向,对于比表面大的载体,活性组份晶相的消失或减少非常明显。X射线相定量通常需要有纯相标样,混合加入内标或参比物以测量X射线参比强度。无标样联立方程法不需用纯相标样和参比物,通过对不同含量的分析试样所建立的各相     

X射线衍射分析氧化铁脱硫剂中γ-FeOOH的含量

采用X射线衍射分析技术, 建立了氧化铁脱硫剂中γ-FeOOH的检测方法.在质量分数为30%~100%的测定范围内, γ-FeOOH定量衍射峰积分强度和其质量分数呈现良好的线性关系, 线性相关系数为0.997 7, 为不同晶型FeOOH的含量测定提供了研究思路.对已知含量的γ-FeOOH脱硫剂样品进行测定, 相对误差3.7%.方法可以定性定量分析脱硫剂中FeOOH的多态混合物, 对于进一步研究脱硫剂中FeOOH多态混合物具有重要意义.方法准确可靠, 操作简单, 具有一定的可行性, 为生产企业进行氧化铁脱硫剂中γ-FeOOH定性定量分析提供了参考.     

X射线吸收分析法简介

近十余年来,X射线化学分析法已被广泛采用。利用X射线进行化学分析,有三类不同方法:衍射分析法,发射光谱分析法和吸收分析法。衍射分析法常称物相分析,它是根据晶态物质的X射线衍射花样的特征和衍射线的强度来进行定性与定量分析的。分析结果直接给出样品中所含晶体的种类、数目及其相对含量。非晶态物质沒有一定的衍射花样,故不能用此法分析。发射光谱分析法(包括初级发射光谱法及熒光X光谱分析法)的原理与通常的光学光谱分析法相同,是根据各种元素所固有的特征X射线的波长及强度来进行定性定量分析的,分析结果给出样品中所含元素的种类及含量。上述二法本刊已先后作过介绍,本文之目的是要对吸收分析法的原理、设备及应用作一简要介绍。     

热处理对Nylon—11结构的影响

对不同温度热处理过的Nylon－11样品，采用广角X射线衍射（WAXD），根据X射线衍射强度理论，用多重峰图解分峰方法研究了Nylon－11结构的变化，并导出了计算Nylon－11结晶度的公式．所得结果与密度法、DSC法进行了比较．同时也给出了Nylon－11的有关热力学参数，     

X射线衍射法钾混盐无标样定量相分析

采用EVD、TOPAS应用软件和TOPAS结构数据库以及无机晶体结构数据库,对一些混合盐样品(如钾混盐、尾矿等)进行了X射线粉末衍射无标样定量相分析全谱拟合模拟研究。在用Rietveld分析法对上述样品中无机盐成分的X射线衍射谱进行模拟过程中,选择基本参数函数为峰形函数,并通过March-Dolase择优取向校正拟合,提高了拟合精度。测得钾混盐样品中钾盐镁矾相含量为72.44%,岩盐相含量为27.56%,误差值Rwp(17.45),Rp(12.21)和拟合度S(4.91)均有所降低。     

Standard-addition procedure for the determination of traces of lead in solid samples by x-ray fluorescence spectrometry

A standard-addition procedure for analysis of powdered solid samples by energy-dispersive X-ray fluorescence is described. Different amounts of the element to be determined are added to 4–6 specimens of the unknown sample. The spiked samples are prepared by mixing the powdered sample with an aqueous standard solution and drying the mixture. Homogeneously spiked samples are thus obtained with analyte and spike concentrations at the ppm level. The procedure has been investigated theoretically, and it is found suitable for the quantitative determination of lead at the ppm level. The accuracy of the technique for traces of lead has been tested on solid reference materials for the determination of lead. The quantitative results obtained compare well with those found by potentiometric stripping analysis.     

A laser-induced fluorescence dual-fiber optic array detector applied to the rapid HPLC separation of polycyclic aromatic hydrocarbons

A multi-channel detection system utilizing fiber optics has been developed for the laser-induced fluorescence (LIF) analysis of chromatographic eluents. It has been applied to the detection of polycyclic aromatic hydrocarbons (PAH) in a chromatographically overlapped standard mixture and to a complex soil sample extract obtained during fieldwork. The instrument utilizes dual-fiber optic arrays, one to deliver multiple excitation wavelengths (258-342 nm) generated by a Raman shifter, and the other to collect fluorescence generated by the sample at each excitation wavelength; the collected fluorescence is dispersed and detected with a spectrograph/CCD combination. The resulting data were arranged into excitation emission matrices (EEM) for visualization and data analysis. Rapid characterization of PAH mixtures was achieved under isocratic chromatographic conditions (1.5 mL min(-1) and 80% acetonitrile in water), with mid microg L(-1) detection limits, in less than 4 minutes. The ability of the instrument to identify co-eluting compounds was demonstrated by identifying and quantifying analytes in the rapid analysis of a 17 component laboratory-prepared PAH mixture and a soil extracted sample. Identification and quantification were accomplished using rank annihilation factor analysis (RAFA) using pure component standards and the EEMs of mixtures measured during the rapid high-performance liquid chromatography (HPLC) method as the unknowns. The percentage errors of the retention times (RTs) determined using RAFA compared to the known RTs measured with a standard absorbance detector were between 0 and 11%. For the standard PAH mixture, all 17 components were identified correctly and for the soil extracted sample, all 8 analytes present were correctly identified with only one false positive. Overall, the system achieved excellent qualitative performance with semi-quantitative results in the concentration predictions of both the standard mixture and the real-world sample. Electronic supplementary material to this paper can be obtained by using the Springer LINK server located at http://dx.doi.org/10.1007/s00216-001-1125-6.     

Repetitive spectral subtraction method for the spectrophotometric determination of rare earth elements

Summary A new multiwavelength data-analysis method for the determination of multicomponent mixtures, the repetitive spectral subtraction method (RSSM), is proposed. In RSSM, spectral data are obtained at evenly spaced wavelengths in the range of interest, and the analysis of the spectrum is performed as repetitive determination-subtraction cycle. In the determination step, the series of data in the narrow wavelength range is used, which is specified as to include the most characteristic or the largest peak for each component. Assuming a linear background, the target component, which can be a small group of components, is simultaneously determined together with co-existing components. In the next subtraction step, the calculated contribution of the component is subtracted from the spectral data in the whole measured wavelength range, and the component is assigned as determined and is excluded from the following analysis. This determination-subtraction cycle is repeated until all the components are determined.With RSSM, a mixture of many components can be precisely determined by the use of most information contained in the spectrum. The accuracy of determination can be improved by automatic estimation of the background and the gradual decrease of interferences. In order to demonstrate the usefulness of RSSM, the 8 rare earth elements (Pr, Nd, Sm, Eu, Dy, Ho, Er, Tm) in the model mixtures were determined by spectrophotometry, and the results were compared with those of the usual correction factor method and the derivative method. Furthermore, the 8 rare earth elements were determined in ores, monazite and xenotime.

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Spektralphotometrische Bestimmung von Seltenen Erden mit Hilfe eines Verfahrens der wiederholten Subtraktion

     

High-performance liquid chromatography determination of phenolic components in wine using off-line isotachophoretic pretreatment

The off-line combination of isotachophoresis (ITP) and high-performance liquid chromatography (HPLC) to improve sample pretreatment and determination of phenolic compounds in wine was investigated. The ITP system provided an enhanced sample load capacity and served as a sample clean-up technique, HPLC performed a final separation of the analytes presented in samples. The phenolic components were separated by Discovery RP Amid C16 chromatography column using water-methanol-acetonitrile-orthophosphoric acid gradient. The identification of phenolic compounds was made by comparison of the retention data obtained for the standard mixture, pretreated sample and the sample spiked standard additions. Satisfactory recoveries for all components analysed were observed between 86.1 and 109.2%.     

Linear titration plots for the analysis of mixtures of three weak acids or bases

Linearly related functions have been derived which enable mixtures of three weak acids or bases in solution to be analysed by means of pH-titration data. This theory has been tested with data from the titration of a variety of mixtures of acids. The data required for the functions are pH, volume of titrant, the equilibrium constants relevant to the mixture, and an independently determined equivalence volume. This may be the equivalence volume for one of the components of the mixture or the sum of the equivalence volumes for any two or all three of the components. It is immaterial how this equivalence volume is obtained, but it is usually possible to obtain the total equivalence volume from data in another part of the same titration curve (when a large excess of titrant has been added).     

免疫算法用于复杂样品的GC-MS快速分析

建立了一种基于免疫算法的复杂样品气相色谱-质谱联用(GC-MS)快速分析方法,该方法采用快速温度程序测定复杂样品的GC-MS信号,再通过快速解析得到各组分的信息.计算过程中,采用各种可能存在于混合物中的组分质谱作为算法的输入,按照保留时间的顺序逐一对重叠的质谱信号进行解析,得到各组分的色谱信息.对于混合物中实际存在的组分可得到该组分的色谱流出曲线,而对于混合物中不存在的组分所得色谱流出曲线几乎为零.采用所建立的方法对含有16个组分的有机磷农药混合物进行了分析,在保留时间10 min内得到了所有组分的色谱信息.     

分枝定界算法用于有机混合物的同时定性定量分析

分枝定界法用于多组分同时定性定量分析，只需解析一份试样测得的数据，即可同时得到待测样品中所含组分的种类、数目及含量，具有简单、快速、准确等优点。此文对分枝定界法在判据应用方面进行了改进，应用四个判据，解决了最佳子集难判断的问题。建立了精蒽中不经分离同时测定蒽、菲和咔唑的方法。     

Simultaneous determination of N-unsubstituted and N-substituted nitroazoles and criteria for their identification-III Chromatographic separation and polarographic determination of halo-nitroimidazoles

Methods for identifying and determining halo-nitroimidazoles appearing together during synthetic processes, regardless of the preparation methods, are proposed. Polarographic determination can be used in all synthetic processes when halo-nitroimidazoles have been obtained by nitration of the halo-imidazoles. When the halo-nitroimidazoles have been obtained from 5(4)-halo-4(5)-nitroimidazoles by substitution of the imino hydrogen atom, and when only one N-substituted derivative has been obtained in a reaction mixture, simultaneous polarographic determination of both compounds is possible, but only when an alkaline medium is used as supporting electrolyte. In some cases, simultaneous polarographic determination of all three compounds present in a reaction mixture during N-substitution processes [one 5(4)-halo-4(5)-nitroimidazole and two N-substituted isomers] is also possible with alkaline supporting electrolyte. Explanations are given of the phenomena on which the simultaneous polarographic determination is based. When simultaneous polarographic determination cannot be used to determine the amount of each polarographically-active compound present in a reaction mixture, the compounds can be separated chromatographically and then determined individually by polarography.     

Optimisation of high-performance liquid chromatography with diode array detection using an automatic peak tracking procedure based on augmented iterative target transformation factor analysis

An automated method for the optimisation of high-performance liquid chromatography is developed. First of all, the sample of interest is analysed with various eluent compositions. All obtained data are combined into one augmented data matrix. Subsequently, augmented iterative target transformation factor analysis performs the integrated tasks of curve resolution and peak tracking. Since this type of curve resolution processes all data at once, it can deal with strong peak overlap and reveal the correspondence of compounds between runs, i.e. peak tracking. The retention time and peak width at half height for each component of the sample are determined for every eluent composition. Next, models are built for the retention time and the peak width at half height. These models are used to predict the resolution and the analysis time for each point in factor space. Finally, a multi-criterion decision-making method, Pareto optimality, is used to find the optimum. The method completes all calculations within a few minutes and without user intervention. By means of this procedure, a mixture of three benzodiazepines is successfully separated using a ternary mobile phase. There are two requirements for the automated optimisation method to work correctly. Firstly, all components of the sample must have sufficiently different spectra. Secondly, each compound should have the same spectrum under all experimental conditions.