近年物理化学滴定进展

评述了近五年国内外物理化学滴定（用作图确定终点）的新进展，内容包括：（１）光学滴定（含光度、荧光、磷光、化学发光滴定）；（２）电滴定（含电位、电导、电流、库仑滴定）；（３）量热滴定。每类滴定均再按滴定用介质分为水介质和非水介质滴定，按滴定反应分为酸－碱、氧化－还原、络合、沉淀滴定，按滴定方式分为直接滴定、代滴、回滴。引用文献１０６篇。     

氧化还原滴定理论处理的一种通用方法

氧化还原滴定理论处理的一种通用方法魏永巨，李克安，童沈阳（北京大学化学系，１００８７１）氧化还原滴定的计量关系远比酸碱与络合摘定复杂，因而，严格的理论处理比较困难￣［１］。特别是涉及到不对称电对的氧化还原滴定，通常难以对滴定过程中各组分的平衡浓度及相...     

同时求出滴定剂与被滴定物质浓度的氧化还原滴定计算分析法

对氧化还原滴定计算分析法同时测定Ce^4 与Fe^2 进行了研究。以铂电极为指示电极，在Fe^3 存在的条件下，用Ce^4 溶液滴定Fe^2＋溶液，可同时求出Ce^4 与Fe^2 的浓度。讨论了Fe^3 浓度对测定结果的影响。     

MgO－B2O3－MgCl2－H2O体系与盐酸滴定反应的研究

ＭｇＯ－Ｂ２Ｏ３－ＭｇＣｌ２－Ｈ２Ｏ是含硼盐湖日晒浓缩盐卤的典型体系，它与盐酸反应生成硼酸，是从天然浓缩盐卤中制取硼酸的工艺基础，以量热滴定法和ＰＨ滴定法研究该反应，结果表明，析出硼酸的反应分两步进行；合成盐卤中硼酸盐可用ＭｇＢ２ｎＯ３Ｎ＋１（ｎ＝１，２，３）综合统计形式来表示；天然浓缩盐卤中硼酸盐可以用四硼酸镁的统计形式进行表示。     

恒速滴定—固定△pH法直接测定α—萘乙酸钾的研究

用微量滴定管控制恒速滴定，用记录仪描绘滴定曲线，在固定的ｐＨ值区间测量有关信号，用盐酸溶液直接测定α－萘乙酸钾，本法不需要准确知道滴定剂所消耗的物质的量，数分钟即可缓出一条滴定曲线，加标回收率为９８．８％－１０１．４％，相对标准偏差为１．６％（ｎ＝１１），适用于工业品及试剂α－萘乙酸钾的常规分析。     

一种新的库仑微水滴定仪的设计方法

在传统微库仑滴定仪原理的基础上，利用８７５１单片机和微机，采用对电解电流时间调制的方法以及测量精度为准则判断滴定终点，从而大大地提高了仪器的测量精度和重复性。     

滴定分析

本文是《分析试验室》定期评述中“滴定分析”的第二篇论文，它涉及约１９９０年７月至１９９４年８月，主要是国内的文献（２６０篇）。     

两点电位滴定法及其应用

提出了只需两组数据即可计算电位滴定计量点的电位滴定数据处理新方法－两点法，并在此理论基础上，提出了两点电位测定法。该法只需记录两次电极电位值和相应滴定剂体积，利用公式即可计算滴定化学计量点。详细讨论了各因素对方法准确度的影响，给出了衡量滴定进行程度的客观指标，为两点位置的选择提供了充分的理论依据。实验结果表明：该法操作方便，数据处理简单，精密度与准确度均较高，分析速度较经典电位滴定法有较大提高。     

二点滴定法研究

就二点滴定法的原理，方法和应用进行了讨论，导出了二点滴定法计算公式。讨论了滴定剂加入量与测定结果准确度的关系。已用本法对标样样液及试样进行了多次测定，测定结果相对误差及相对标准偏差约０．２％。本法简便，快速，准确，且昨达于任何滴定类型的通用方法。     

同时求出酸浓度和质子化常数的一元酸线性滴定法

利用一元酸的滴定计算式，线性回归同时求出酸浓度与质子比常数，实验只需等步长电位滴定化学计量点前约５个点。测定包括Ｋ＝１０＾１２的Ｈ２Ｏ２等１１种酸，得到了满意结果。本法有较大的应用价值。     

基于反射式光度传感器的自动光度滴定仪的研制及应用

研制了一种以颜色变化为滴定终点的自动光度滴定仪,仪器以光度传感器为核心,包括光度探头、滴定装置、AT89S52单片机、电磁阀、二极管和磁力搅拌器等部件。传感器采用开放设计,对溶液吸光度变化反应迅速。仪器用于红醋酸度的测定,所得结果与电位滴定分析法结果相符。     

络合体系中的相对滴定法及其应用于铝的测定

本文提出了络合体系中的相对滴定分析法，它以滴定到一定的状态时，滴定剂体积与被测物的基之间的线性关系为定量基础，用仪器分析的定量方法进行定量，适应于所有类型的络合体系，即使对滴定突跃很小或根本无突跃的体系也同样适用。用氟离子滴定铝离子的实验结果表明本方法的精密度很高。一般相对误差小于0．1％。即使对于铝离子的量小到10-7mol／L时，在最佳实验条件下的相对误差也不大于0．2％。该方法既具有滴定分析法的高精密度，又具有仪器分析法可以测量微量物质的优点，并且设备和方法简单。     

Theory of the surface acoustic wave/impedance sensor system and its application to the end-point determination in titrimetry

Theory and characteristics of the surface acoustic wave (SAW)/impedance sensor system in electrolyte solution are reported. This kind of sensor was constructed by a 62-MHz SAW resonator and a pair of conductive electrodes in series. By using the circuit network analysis theory, two oscillation equations were derived and used to explain the frequency-shift response to solution conductance. Results showed that the sensor possesses high sensitivity to the solution conductivity and can be applied to conductivity measurements in solution. Its sensitivity and accuracy could be improved in the presence of a large amount of unreacting foreign electrolytes. The sensor was successfully applied to four types of titration (acid-base, precipitation, oxidation-reduction and compleximetric titration) by monitoring the frequency-shift response. Factors influencing the frequencimetric titration curve were also investigated. Analytes at levels down to 1 × 10⁻⁵ M could be determined by the proposed titration technique. The total acidity in several food samples was determined and the results were consistent with those obtained by conventional methods.     

模拟合成盐卤与盐酸反应的热化学研究

青藏高原新类型盐湖卤水日晒蒸发过程中硼酸盐在浓缩卤水中富集L‘。，我们在前又问中曾报道天然浓缩盐卤中硼酸盐是以“四硼酸盐”的综合统计形式存在，当盐卤浓缩到氯化镁共饱和时，可视为MgO－BZO3－MgC12－HZO四元体系中的一个特定的膺三元体系MgO·2B2O3－MgC12－H。O．该四元体系20oC热力学非平衡态液固相图问与25oC热力学平衡态相图＊存在较大差别．由于聚合翻氧配阴离子的存在，使得对含棚浓缩盐卤的研究变得复杂而困难＊．李积才等“～SJ对合成盐卤的稀释热和表观摩尔热径进行过测定，李军间在对多种水合硼酸盐在盐酸中…     

Determination of Nitrates in Water Samples by In‐Electrode Coulometric Titration in Copper Coated Porous Vitreous Carbon Electrode

Nitrate in water samples was determined by in‐electrode coulometric titration in porous electrode made of vitreous carbon particles coated with copper. The sample was mixed with diluted sulfuric acid containing 1 mmol/L hydrochloric acid, the solution was filled into the cell and electrode and the nitrate ions were directly reduced by constant current to ammonium ions. The stoichiometry of the electrode reaction was found by coulometric and photometric measurements. The detection limit and precision were found to be 0.2 mg/L and 1.7 %, respectively. The interfering effect of high chloride contents was eliminated by precipitating chlorides with silver sulfate. The method was applied for the analysis of various water samples and beverages. The results were in good agreement with data from isotachophoretic and photometric measurements.     

非水光度滴定法测定钢中低碳

研究了非水滴定定碳法中非水吸收液的组成、指示剂的配比及滴定终点时溶液色泽的吸光度变化。结果表明,由乙醇、乙醇胺及不饱和多胺组成的非水体系对钢样燃烧时所释出的二氧化碳能最有效的吸收。试验选择了百里酚酞和茜素黄R的混合液为滴定指示剂,能给出敏锐的终点指示。在此基础上设计了一套非水定碳的自动分析装置。无论自动仪器或手工操作所得的分析结果都与标准值符合。方法应用于低含量碳的测定。     

Polyelectrolyte titration using fluorescent indicator. I. Direct titration of anionic and cationic polyelectrolytes with 10−4N standard solutions

The polyelectrolyte titration, which was originally called colloid titration, is based on the stoichiometric reaction between positively charged colloidal particles and negatively charged ones. In the conventional method, the metachromatic color change of the indicator, toluidine blue, from blue to red-purple has been applied for the determination of the end point in the titration. 2.5 × 10^?3N potassium polyvinylsulfonate (KPVS) is usually used as the standard titrant. In this work, fluorescent indicators such as 6-(p-toluidino)-2-naphthalene sulfonate (TNS), acridine orange, etc., have been introduced. The fluorescence intensity was measured using the spectrophotometer equipped with magnetic stirrer and connected with a vinyl tube attached to the hand piston burette. For example, TNS is practically nonfluorescent, but it exhibits strong fluorescence when it is bound to a cationic polyelectrolyte (CP). The fluorescence of the TNS–CP complex is diminished by titration with KPVS standard solution since TNS is liberated from the complex by substitution with KPVS. After the equivalent point, the fluorescence intensity becomes constant and the end point can thus be detected by that point. It has been elucidated that the very dilute standard solution like 1 × 10^?4N can be used because the sensitivity of fluorescence detection is extremely high. © 1993 John Wiley & Sons, Inc.     

金属电极上中和滴定的研究(Ⅰ)——零电流示波双电位滴定法

研究了在Hg(Ag)、Pt、Sb、W₄种金属电极上的零电流示波双电位中和滴定法。从阳极极化的Hg(Ag)、Pt电极和经蒸馏水浸泡的Sb、W电极中,任取两支相同或相异金属作成的一对电极皆可用于酸碱滴定;对更稀的酸碱,可用一支经阳极极化和一支未极化的电极。该法简单、准确、直观、快速。初步探讨了Cl-影响Hg(Ag)、Pt电极电位滴定曲线的机理。     

Determination of cationic polyelectrolytes using a photometric titration with crystal violet as a color indicator

The reaction of the cationic dye, crystal violet (CV) with the anionic polyelectrolytes such as potassium poly (vinyl sulfate) (PVSK) results in a decrease of the absorbance of CV at the maximum absorption wavelength (590 nm). This change of the absorption spectra of the CV has been already applied to the determination of anionic polyelectrolytes using flow injection analysis method. In this paper, CV was applied to the indicator for the determination of cationic polyelectrolytes such as poly (diallyldimethylammonium chloride) (Cat-floc) by photometric titration, using a PVSK solution as a titrant. The end-point of the titration is detected as the break point of the titration curve. A linear relationship between the concentration of cationic polyelectrolyte and the end-point volume of the titrant exists in the concentration range from 0 to 5×10⁻⁵ eq. mol dm⁻³ for Cat-floc, glycol chitosan and methylglycol chitosan. The effects of the concentration of CV and coexisting electrolytes in the sample solution and the effect of pH of the sample solution on the degree of the change of absorbance at the end-point were also examined.