原子光谱分析中的流动注射法

流动注射(FIA)法作为分析操作中一种新的溶液处理技术在近十年来得到十分迅速的发展。FIA法的应用使化学分析实验室中的很多传统设备与操作技术发生了重大的变革,从而受到国际分析化学界广泛的重视。近几年来该法越来越多地用于原子光谱分析,其效果十分引人注目。 (一)FIA采样法用于火焰原子吸收(FAAS)及电感耦合等离子体光谱(ICP)的FIA采样装置多数如图1所示,为单线系统。一定体积的试样通过注入口(阀或针筒)被注入流向雾化器的载流中,几秒钟后得一瞬变峰形信号。由于流速,管道长度及注样方式固定,试样于进入雾化器时在载流中的分散程度能很好地加以控制,因此虽然试样溶液在流动的过程中部分被稀释,同时由于注样的体积一般只有数十μl而无足够的时间达到输出     

流动注射分析中试样分散的对流-扩散理论

用两种方法求解适合于单一平直管道且无化学反应的流动注射分析(FIA)体系的对流-扩散方程,得到了描述塞状进样在管道中分散后的浓度分布公式,从而得到F曲线。讨论了反应管和采样管的内径和长度、流速和扩散系数对峰形和分散度的影响;采用数值法解出半峰宽与扩散系数的关系,提出了两种测定扩散系数的方法,为FIA体系的设计和指示物质、操作条件的选择提供了理论依据。     

希土元素的流动注射分析法检出与测定

本文介绍了简便的、以反应光度法为检测器的流动注射分析法装置。讨论了FIA中试样带的分散及其影响因素。论述了注样体积、载流及显色液流量等操作条件对FIA输出信号的影响。研究了若于显色体系的反应速度曲线并讨论了显色速度对FIA测定的影响。系统地研究五种显色体系FIA测定希土元素的条件及灵敏度。首次使用对乙酰基偶氮胂等体系于FIA测定希土元素。本文还介绍了将FIA用于自动检测萃取色层柱淋洗曲线。     

流动注射分析技术的新进展

流动注射分析简称FIA(Flow Injection Analysis),是一种新的分析技术。它是把一定体积的试样溶液注入到无空气分隔的载流中,经过受控制的分散过程,形成高度重复的试样带并送至检测器进行检测的。在有化学反应参与的FIA中试样是与载流中的试剂(或与载流汇合成的试剂流)进行反应的。它以速度快、精     

流动注射-共振瑞利散射法测定盐酸氯丙嗪和盐酸异丙嗪

在HCl介质中,12-钨磷酸(TP)分别与盐酸氯丙嗪(CPZ)和盐酸异丙嗪(PMZ)反应形成离子缔合物,导致溶液的共振瑞利散射(RRS)显著增强,并产生新的RRS光谱.它们的最大RRS峰位于359 nm (TP-CPZ)和346 nm (TP-PMZ),并且在一定范围内,CPZ和PMZ的浓度与散射强度呈线性关系,据此提出流动注射-共振瑞利散射 (FIA-RRS) 联用技术测定CPZ和PMZ的新方法,CPZ和PMZ的检出限分别为1.7和3.0 μg/L.实验优化了流动注射(FIA)参数和反应条件,并以灵敏度较高的CPZ为例,考察了共存物质的影响.本方法具有良好的选择性和重复性;用于药片和猪肝中CPZ的测定,结果满意.     

平头pH电极用于流动注射-电位滴定法测定碱溶液的浓度

以盐酸溶液为滴定剂,采用流动注射-平头pH电极测定强碱(如氢氧化钠溶液)及弱碱(如氨水)溶液的浓度。选择流动注射分析系统的工作参数为:①混合管长度40 cm;②载流盐酸溶液浓度1.027×10-3mol·L-1;③样品进样量310μL;④流速0.82 mL·min-1。结果表明:氢氧化钠和氨水的峰面积、峰高和半峰宽均与其浓度的对数值在一定的范围内呈线性关系。方法用于实际样品分析,滴定灵敏度比手工滴定方法的灵敏度高10倍,测定值的相对标准偏差(n=5)在1.1%~1.8%之间。     

FIA—安培法测定水中的Cr（Ⅲ）和Cr（Ⅵ）

流动注射分析(FIA)测定铬的主要方法有FIA-AAS、FIA-AES和FIA-VIS。Pratt等用铂和金电极流通池、Hwang等用玻璃碳和金电极流通池分别建立了测定Cr(Ⅲ)和Cr(Ⅵ)的FIA安培法,检出限依次是5ng/mL和0.5ng/mL。鉴于Cr(Ⅵ)在负电位下能被还原的性质,我们用廉价的碳作电极材料,用FIA安培法测定了天然水中的痕量铬,结果亦令人满意。 FIA安培法测定系统见图1.TRB-8蠕动泵、注射阀均系东北电力学院仪器仪表厂产品,     

离子选择电极检测流动注射分析测定铜

本文用流动注射分析法测定铜的浓度。检测系统由两个铜离子选择电极组成,一个作为指示电极,另一个作为参考电极。为了获得稳定的基线,采用含10~(-6)mol/L Cu~(2+)的0.1mol/L KNO_3溶液作为载液。文中考察了载液流速和试液pH值对响应的影响。在选定条件下,用本法对含铜废水进行了分析,所得结果与分光光度法测定结果比较接近。本法的检测下限达0.2ppmCu~(2+),进样频率40—60个/时。     

痕量分析中的流动注射法

本文讨论了流动注射分析(FIA)技术在痕量分析中的突出优点,阐述了该技术在痕量分析领域中的应用。文中介绍的流动注射原子光谱分析、流动注射在线分离和浓集技术、流动注射催化动力学方法以及流动注射化学发光、生物发光分析等在痕量分析中具有广阔的发展前景。     

流动注射分析的原理及影响因素

自从Ruzicka和Hansen提出流动注射分析(Flow Injection Analysis,简称FIA)以来,作为湿化学快速自动分析最新成就的FIA法迅速发展起来,这一发展的特点是:分析速度越来越快,自动化程度越来越高。随着微处理机的应用,FIA体系日趋完善与微型化,应用日益广泛,水平不断提高。     

Determination of sulphuric acid in process effluent streams using sequential injection titration

Sulphuric acid in process effluent streams from an electrorefining copper plant was analysed with a sequential injection (SI) titration system using sodium hydroxide as titrant. In the proposed SI titration system a base titrant, acid analyte and base titrant zone were injected sequentially into a distilled water carrier stream in a holding coil and swept by flow reversal through a reaction coil to the detector. The base zones contained bromothymol blue as indicator and the endpoint was monitored spectrophotometrically at 620 nm. The influence of carrier stream flow rate, acid and base zone volumes and titrant concentration on the linear range of the method was studied to obtain an optimum. A linear relationship between peak width and logarithm of the acid concentration was obtained in the range 0.006-0.178 mol l(-1) of H(2)SO(4) for a NaOH concentration of 0.002 mol l(-1). The results obtained for the SI titration of process samples were in good agreement with a standard potentiometric method with an RSD<0.75% and a sample frequency of 23 samples h(-1).     

An on-line potentiometric sequential injection titration process analyser for the determination of acetic acid

An on-line potentiometric sequential injection titration process analyser for the determination of acetic acid is proposed. A solution of 0.1 mol L(-1) sodium chloride is used as carrier. Titration is achieved by aspirating acetic acid samples between two strong base-zone volumes into a holding coil and by channelling the stack of well-defined zones with flow reversal through a reaction coil to a potentiometric sensor where the peak widths were measured. A linear relationship between peak width and logarithm of the acid concentration was obtained in the range 1-9 g/100 mL. Vinegar samples were analysed without any sample pre-treatment. The method has a relative standard deviation of 0.4% with a sample frequency of 28 samples per hour. The results revealed good agreement between the proposed sequential injection and an automated batch titration method.     

FIA acid–base titrations with a new flow-through pH detector

A pH-sensitive detector for flow-through potentiometry based on a graphite/quinhydrone composite electrode was applied for flow-injection analysis (FIA) titrations. Hydrochloric acid and acetic acid were titrated by injection of samples into a sodium hydroxide carrier solution. System conditions were optimised by variation of flow rate, injection volume and titrant concentration. The parameters sampling frequency, residence time and dispersion coefficient were determined. The evaluation of peak width (time between the two inflection points on each side of the peak), peak area and slope of the raising edge of the peak lead were studied with respect to their use for calibration. Hydrochloric acid and acetic acid could be titrated down to a concentration of 2 × 10^–4 mol L^–1 using 150-L injection volumes, which is almost ten times lower than can be achieved using colour indicators and a spectrophotometric detection.Dedicated to the memory of Wilhelm Fresenius     

Novel approaches to analysis by flow injection gradient titration

Two novel procedures for flow injection gradient titration with the use of a single stock standard solution are proposed. In the multi-point single-line (MP-SL) method the calibration graph is constructed on the basis of a set of standard solutions, which are generated in a standard reservoir and subsequently injected into the titrant. According to the single-point multi-line (SP-ML) procedure the standard solution and a sample are injected into the titrant stream from four loops of different capacities, hence four calibration graphs are able to be constructed and the analytical result is calculated on the basis of a generalized slope of these graphs. Both approaches have been tested on the example of spectrophotometric acid–base titration of hydrochloric and acetic acids with using bromothymol blue and phenolphthalein as indicators, respectively, and sodium hydroxide as a titrant. Under optimized experimental conditions the analytical results of precision less than 1.8 and 2.5% (RSD) and of accuracy less than 3.0 and 5.4% (relative error (RE)) were obtained for MP-SL and SP-ML procedures, respectively, in ranges of 0.0031–0.0631 mol L⁻¹ for samples of hydrochloric acid and of 0.1680–1.7600 mol L⁻¹ for samples of acetic acid. The feasibility of both methods was illustrated by applying them to the total acidity determination in vinegar samples with precision lower than 0.5 and 2.9% (RSD) for MP-SL and SP-ML procedures, respectively.     

Spectrophotometric determination of ascorbic acid in pharmaceuticals by background correction and flow injection

Background correction has been shown to be an effective and indispensable modification in the spectrophotometric determination of ascorbic acid. The decomposition of ascorbic acid in pharmaceutical samples was carried out by incubation with sodium hydroxide to give products that were insensitive to ultraviolet light. The rapid oxidation in air of ascorbic acid, especially in dilute solutions, was avoided by the use of the flow injection principle for spectrophotometric determination and by employing a carrier stream of an anti-oxidizing nature consisting of 6 micrograms ml(-1) of 2-mercaptoethanol in 0.25% sulphuric acid. The optimized method with a single channel manifold made use of a carrier stream flow rate of 1.1 ml min(-1), an injection volume of 50 microl, a delay coil of 50 cm (0.5 mm i.d.) and detection at 245 nm. The throughput was at least 180 injections h(-1). The proposed flow injection method yielded results for the analysis of 0-20 micrograms ml(-1) of ascorbic acid that were 99-102% (relative standard deviation 0.6% or better) in agreement with those produced by comparable methods involving titration with iodine, chloranil or 2,6-dichlorophenolindophenol [4-(2,6-dichloro-4-hydroxyphenylimino)cyclohexa-2,5-dieno ne], and high-performance liquid chromatography. When the agreement was not good (as low as 14% with respect to the method being compared), this was traced to the presence of substances which are known to interfere in one or other of the methods of comparison.     

On-line coupling of gas diffusion to capillary electrophoresis

On-line gas diffusion has been coupled to a capillary electrophoresis system (CE) via a specially designed interface. The sample is merged with a modifying solution, e.g., a strong acid, in a flow system to transform the analytes of interest into their respective gaseous forms. These transformed, gaseous analytes permeate through a PTFE membrane into an acceptor stream comprising of a tris-buffer. The continuously flowing acceptor stream is led into an injector forming an integrated part of a flow injection analysis (FIA) system. The sample receiving carrier stream in the FIA system, a chromate buffer, brings the sample, 50 mul, to the FIA-CE interface into which one end of a separation capillary has been inserted. A small portion of the injected sample enters the capillary (electrokinetic injection) and separation takes place. A UV detector is placed at the other capillary end and a run potential of 25 kV is applied to two platinum electrodes positioned in the flow system. Multiple sample injections can be performed in one uninterrupted electrophoretic run. A typical sampling frequency is 15 h(-1); each run may result in quantitation of at least five anions. The overall repeatability is in the range 1.8-3.6% (RSD). The technique has been applied to the analysis of real samples such as soft drinks, vinegar and wine. Selective discrimination of anions which are unable to form volatile species is accomplished. No off-line sample pre-treatment is needed.     

An automatic system for acidity determination based on sequential injection titration and the monosegmented flow approach

An automatic sequential injection system, combining monosegmented flow analysis, sequential injection analysis and sequential injection titration is proposed for acidity determination. The system enables controllable sample dilution and generation of standards of required concentration in a monosegmented sequential injection manner, sequential injection titration of the prepared solutions, data collecting, and handling. It has been tested on spectrophotometric determination of acetic, citric and phosphoric acids with sodium hydroxide used as a titrant and phenolphthalein or thymolphthalein (in the case of phosphoric acid determination) as indicators. Accuracy better than |4.4|% (RE) and repeatability better than 2.9% (RSD) have been obtained. It has been applied to the determination of total acidity in vinegars and various soft drinks. The system provides low sample (less than 0.3 mL) consumption. On average, analysis of a sample takes several minutes.     

Simultaneous determination of nanomole amounts of sulphur dioxide and hydrogen sulphide by flow injection analysis with on-line preconcentration by means of capillary denuder tubes

A simple and rapid method for trace determination of SO2 and H2S in gaseous samples by using a flow injection system with on line preconcentration on capillary denuder is described. The gaseous samples are led through a 0.4 M sulphamic acid solution, retaining nitrogen dioxide, ammonia and hydrogen chloride. The sulphur dioxide is collected from the carrier gas stream (250 cm3 min-1) as sulphuric acid in a capillary denuder tube coated with a thin layer of 0.01-0.03 M hydrogen peroxide solution of 0.05 mM sulphuric acid; hydrogen sulphide passes into a second tube coated with 0.075 mM sodium sulphide solution of 0.1 M aqueous sodium hydroxide. The films containing the sulphuric acid and the sodium sulphide, respectively, are eluted with the corresponding circulating absorbent streams and pass through the detectors. Sulphuric acid is detected by conductimetry and sulphide is determined spectrophotometrically at 230 nm. If nanoequivalent amounts of H2S are present in the sample containing a large concentration of SO2 (SO2/H2S concentration ratio > 20), the sulphur dioxide is filtered out of the sample gas stream by solid sodium hydrogen carbonate. A limit of detection of 3.5 micrograms m-3 is obtained.     

一种自动微量滴定新方法

本文依据传统滴定分析原理，利用流动注射装置提出一种新的自动微量滴定方法，它不仅具有流动注射滴定分析法简便快速，试剂和试样消耗少，仪器装置简单等优点，而且测定信号怀被测组分的浓度直接成线性关系，结果的准确度和精度优于一般流动注射滴定方法。通过用盐酸滴定氢氧化钠进行验证，相关系数为０．９９９９，相对标准偏差（ＲＳＤ）为０．４％。     

Determination of ammonium in Kjeldahl digests by gas-diffusion flow-injection analysis with a bulk acoustic wave-impedance sensor

A novel flow-injection analysis (FIA) system has been developed for the rapid and direct determination of ammonium in Kjeldahl digests. The method is based on diffusion of ammonia across a PTFE gas-permeable membrane from an alkaline (NaOH/EDTA) stream into a stream of diluted boric acid. The trapped ammonium in the acceptor is determined on line by a bulk acoustic wave (BAW)-impedance sensor and the signal is proportional to the ammonium concentration present in the digests. The proposed system exhibits a favorable frequency response to 5.0 x 10(-6)-4.0 x 10(-3) mol l(-1) ammonium with a detection limit of 1.0 x 10(-6) mol l(-1), and the precision was better than 1% (RSD) for 0.025-1.0 mM ammonium at a through-put of 45-50 samples h(-1). Results obtained for nitrogen determination in amino acids and for proteins determination in blood products are in good agreement with those obtained by the conventional distillation/titration method, respectively. The effects of composition of acceptor stream, cell constant of conductivity electrode, sample volume, flow rates and potential interferents on the FIA signals were discussed in detail.