非配对型电极上的示波沉淀滴定

本文研究了非配对型铂电极上的示波沉淀滴定,提出了一种处理电极的新方法即硝酸-王水法,讨论了非配对型电极上示波滴定的机理。     

示波极谱滴定的研究 ⅩⅩⅩⅡ.金电极上的示波极谱滴定法

本文研究了用微金电极为工作电极的示波极谱滴定法。在同样的条件下,用金电极时某些离子如Co~(2+)和Ni~(2+)能产生敏锐的切口,而用铂电极时无切口。用两个相同的微铂电极时,EDTA和某些有机物质可以有灵敏的切口,但用金电极时无切口。微金电极能用于络合、沉淀和氧化还原滴定。这时Mn~(2+),Fe~(2+),Co~(2+),Ni~(2+),Hg~(2+),和Cu~(2+)有灵敏的切口,能用于示波极谱滴定。滴定结果较好,标准偏差不大于0.12％。     

再论极弱酸(碱)水溶液的直接测定

用通常的指示剂滴定法不能直接在水溶液中用强酸(碱)滴定极弱碱(酸)。陈淑萍等曾使用汞电极为工作电极,用指示剂切口的变化来指示交流示波极谱中和滴定的终点,在水溶液中直接进行极弱酸碱的滴定。但此方法存在以下缺点:(1)汞电极不适用于强酸性及氧化性溶液;(2)实验条件苛刻,要严格控制指示剂的滴数以确定滴定体积。庄建元等为了弥补汞电极的不足,进行了钻电极上的示波极谱中和滴定,但仅用HCl滴定了氨基比     

两Ag-TPB电极上的零电流示波双电位滴定法

将银片(或碳棒、铂片等)依次浸入Na-TPB及AgNO_3溶液中,得到用于示波电位滴定的Ag-TPB电极。在这种电极上进行双电位滴定。并用示波器直接指示⊿E的变化,确定滴定终点。方法简便灵敏,且可用于药物分析。     

零电流示波电位滴定的研究 Ⅰ.非配偶型铂电极上的螯合滴定:EDTA滴定金属离子

(一)前言螯合电位滴定是电位滴定的一个主要组成部分,文献极为丰富。这些滴定主要是在金属电极和离子选择电极上进行的。金属电极分为两类:配偶型和非配偶型。配偶型电极如Pt/Fe~(3+);Fe~(2+)、Hg/Hg~(2+);HgY~(2-);MY~(n-4)M~(n+),其“电极/溶液”界面上总有一对决定电位的电对。非配偶型电极的界面上则不存在明显的电对,如铂电极上EDTA滴定Ca~(2+),溶液中不外加高价的铂离子;滴定Fe~(3+),也不外加Fe~(2+)。关于非配偶型电极上的螯合滴定,虽有     

非配偶型铂电极上的电位滴定

配偶型铂电极上的电位滴定是Nernst型滴定,其“电极/溶液”界面上总有一对决定电位的电对。非配偶型电极的界面上不存在明显的电对,通常终点很难判断。本文采用示波器代替电位测量仪指示电位变化。由于荧光点的移动十分迅速又无惯性,所以在滴定终点时能敏锐地反映瞬时电位峰,指示终点,使一大类原来不能进行的滴定得以进行。     

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。     

氟离子电极作指示电极自动电位滴定法测定氟

氟离子电极在各方面的应用日渐增多。利用氟离子电极作指示电极以硝酸镧溶液滴定氟。Lingane和Berns进行了研究,但均未见实际应用的详细报道。本文研究了试样经高温水解分离氟后,用氟离子电极作指示电极,自动电位滴定仪控制滴定终点,在酒精溶液中以La(NO_3)_3溶液滴定氟并计算氟化钙的方     

四苯硼酸钠电位滴定法测有机硫

Selig用氧瓶分解有机硫化合物,生成的硫酸根用高氯酸铅作电位滴定,惜硫酸铅的溶解度较大,且F~-、Cl~-共存时干扰测定。Levins使聚乙二醇(PEG)及其衍生物与钡生成(钅羊)离子,以金属银电极作指示电极,用四苯硼酸钠(TPB钠盐)滴定,测定PEG及其衍生物含量。殷学锋等利用此反应在PEG存在下,以TPB电极作指示电极,用TPB钠盐返滴定钡测定镀铬液中的硫酸根。本文试验将此反应用于有机硫的测定,证明TPB液膜电极及硫化银电极均可用作电位滴定指示电极。本文并对不同分子量PEG的选择及其对电位滴定曲线的影响机理等问题作了初步探讨。     

橙黄Ⅳ-碱性染料或季铵盐体系电势滴定曲线研究

研究了以10^-3M或10^-4M橙黄Ⅳ滴定25种碱性染料和19种季铵盐的电势滴定曲线。提出了一种估价电势滴定曲线的方法并确定了这些曲线体系的优劣次序。讨论了碱性染料和季铵盐结构对电势滴定曲线的影响。结果表明,有些曲线可用于较高灵敏度的分析,电势滴定曲线的优劣次序可为寻找阴离子选择电极的电活性物质提供途径。     

钯膜电极在电位滴定中的应用研究

报道钯膜电极在电位滴定中的应用。研究证明,它适用于化学分析法的五种类型的滴定,如沉淀滴定、氧化－还原滴定、酸碱滴定、非水溶剂滴定和某些形成络合物反应的滴定中作为指示电极,所获结果与化学标准方法吻合。     

The titration error in potentiometric precipitation titration

The titration error can be calculated with the aid of the value of the buffer index determined at the inflection point of the titration curve when a precipitation titration is followed with an ion-selective electrode. When the precipitate is not formed ideally in the titration (i.e., is not formed under equilibrium conditions) the titration error cannot be predicted from the values of the solubility product, nor can the values of the solubility product be calculated from titration data at the inflection point.     

Mercurous nitrate as a reductimetric reagent: The potentiometric titration of ferric iron in the presence of ions forming highly coloured thiocyanates

The reduction of ferric iron by means of mercurous salts in the presence of an excebs of ammonium, thiocyanate can be predicted on theoretical grounds. By consideration of the oxidation potentials involved it has been shown by calculation that quantitative reduction of the ferric iron is to be expected.—The titration may be effected potentiometrically using a bright platinum indicator electrode in conjunction with a silver/silver chloride electrode or a saturated calomel reference electrode. Ferric iron can be titrated in the presence of ions such as cobalt which form intensely coloured thiocyanate complexes.A possible method for the titration of molybdate by means of mercurous nitrate has been examined. The sensitivity of the method suffers from the instability of potential of the system under titration, but particularly since tungstate does not interfere, the method is worthy of further study.     

Amperometric complex-formation titration of traces of thorium

Thorium has been determined in the microgram range by complexometric titration with EDTA. The end-point was detected by following the anodic wave of EDTA at a rotating mercury electrode. It has been shown that thorium can be titrated in the presence of large amounts of other metals. Following electrolysis at a mercury pool electrode the titration is selective for thorium.     

Application of Polyaniline Incorporated Carbon Particles Coated Platinum Electrode in Coulometric Titration to Determination of Polyisoprene Alcohol

The feasibility of using electrodes modified with polyaniline incorporated carbon particles films for im-proving the precision of coulometric titration is demonstrated. The problem of large deviation produced dur-ing determining polyisoprene by coulometric titration with direct titration technique (double Pt electrodes indi-cating electrode) has been solved. In the titration process, polyisoprene alcohol, an electro-inactive species, is adsorbed on the surface of the bare Pt electrode, which inhibits the electrode reaction of Br- and Br2. Therefore, when the titration reaches the end-point, the detected current will slowly change with time, which can make the repeatability of end-point poor, The atomic force microscopic images show the morpholo-gy of the electrode surface of adsorbing polyisoprene alcohol. The application of the chemically modified elec-trode instead of the bare Pt electrode to indicating the end-point has been investigated. The results show that the Pt electrode coated with polyaniline incorporated carbon particles films is an excellent indicator electrode. This electrode has advantages that the indicating signals are sharp and repeatable at end-point. The precisionand the accuracy of the determination of polvisoprene alcohol are satisfactory.     

Comments on the potentiometric titration of halides including fluoride with a mixed titrant

An attempt was made to verify work reported by others on the potentiometric titration of halides including fluoride with a mixed titrant of silver nitrate and thorium nitrate. The platinum indicator electrode can indeed be used to monitor the titration of bromide and chloride. However, we could not verify the results reported for fluoride. There seems to be no theoretical basis on which to expect the platinum electrode to respond to changes in fluoride ion concentration.     

Potentiometric titrations in nonaqueous cerimetry

Summary Potassium iodide and hydroquinone can be estimated potentiometrically in nonaqueous medium using ammonium nitrato cerate as oxidant. A platinum indicator electrode coupled with either a glass electrode or an antimony electrode as reference electrode, can be used in nonaqueous medium satisfactorily, for following the potentiometric titration. Direct potentiometric titration of xanthate with ammonium nitrato cerate in nonaqueous medium yields slightly lower values than the actual values in presence of platinum indicator electrode.

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Zusammenfassung Kaliumjodid und Hydrochinon können in nichtwÄ\rigem Medium mit Ammoniumnitratocerat als Oxydationsmittel potentiometrisch bestimmt werden. Dabei wird eine Platin-Indicatorelektrode und eine Glasoder Antimon-Bezugselektrode mit gutem Erfolg benutzt. Die direkte potentiometrische Titration von Xanthat mit Ammoniumnitratocerat in nichtwÄ\rigem Medium gibt mit der Platin-Indicatorelektrode etwas zu niedrige Werte.

     

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。     

Simultaneous determination of halide and thiocyanate ions by potentiometric precipitation titration and multivariate calibration

Halide and thiocyanate ions can be determined by a precipitation titration with silver nitrate as the titrant, and the end-point can be evaluated by a potentiometric method, in which generally a silver indicator electrode is used as the indicator electrode and a double-junction Ag–AgCl electrode as the reference electrode. However, when mixtures of halide and thiocyanate are titrated, it is difficult to determine these components individually for there are overlapping steps in the potentiometric titration curves, especially in the case that there are obvious differences between concentrations of the components. In this paper, the linear equation for the potentiometric precipitation titration of a mixture of halide and thiocyanate ions was developed and it was then used for determining the components in the mixtures simultaneously with the aid of multivariate calibration methods. By application of this model, 27 synthetic mixtures with three- and four-component combinations of chloride, bromide, iodide and thiocyanate with low concentration levels from 1.8×10⁻⁴ to 6.2×10⁻⁴ mol l⁻¹ were analyzed and acceptable results were obtained.