流动注射多元校正-络合滴定法同时测定混合金属离子

将流动注射应用于电位络合滴定分析法,建立了一种可同时测定混合金属离子的电位滴定方法。在该方法中,用EDTA与氟化钠的混合溶液作为滴定剂,在流通池中同时插入汞膜电极和氟离子指示电极,在滴定过程中的任一滴定点,流出液的汞电位和反应物的混合比例可由两个电极的电位测定值同时获得,从而可应用多元校正法由相应的滴定曲线求得混合金属离子中每一种组分的含量。应用该方法对混合样品中的Cu2+、Pb2+、Zn2+进行了同时测定,测定结果的相对标准偏差均在0.14%~0.48%(n=5)之间,回收率均在97.3%~103.9%之间。     

多元校正双指示电极电位沉淀滴定法同时测定混合卤素离子

建立一种可同时测定混合卤素离子的电位滴定新方法.在这种方法中,滴定剂是硝酸银和氟化钠的混合溶液,被滴定液中同时插入了氟离子指示电极和银离子指示电极.在滴定过程中的任一滴定点,溶液中Ag 的浓度和滴定剂的加入体积可由两个电极的电位测定值同时获得,从而可应用多元校正法由相应的滴定曲线求得混合卤素离子中每一种离子的含量.用该方法对混合物样品中的Cl-、Br-、I-进行了同时测定,测定结果的相对标准偏差为0.13%～0.45%(n=5),回收率为97.3%～103.4%.     

聚氯乙烯膜碘离子选择电极在溴碘离子共存体系分析中的应用

介绍了聚氯乙烯膜碘离子选择电极(PVC-I-ISE)的制备方法,电极对碘离子的能斯特响应斜率为59 mV/pI,响应的线性范围为4.0×10-5~1.0×10-2mol.L-1,检出限为1.6×10-5mol.L-1,低于用银ISE的检出限,电极的使用寿命为一个月以上。将制备的碘离子选择电极作为指示电极用于对溴、碘混合离子体系进行连续分别电位滴定,并与以银电极为指示电极的电位滴定方法进行了比较。结果表明用PVC-I--ISE作指示电极,可在I--Br-共存的混合溶液中进行两离子的连续电位滴定,而用银-ISE时则不能。     

中性载体双(N-乙基-N-苯基氨基二硫代甲酸)1,4-丁二醇酯PVC膜银离子选择电极的研制

采用双层膜电位法直接测定了溶剂聚合物膜中载体双(N-乙基-N-苯基氨基二硫代甲酸)1,4-丁二醇酯与金属离子生成的络合物生成常数。制备并考察了以双(N-乙基-N-苯基氨基二硫代甲酸)1,4-丁二醇酯为载体的银离子选择性电极的性能。实验结果表明:该选择电极对银离子有良好的灵敏度和高选择性,在1×10-3~1×10-6mol/L的浓度范围内响应斜率为60.2 mV/paAg+,检出限为2.3×10-7mol/L,碱金属、碱土金属及过渡金属离子不干扰银的测定。该电极可作为Ag+准确滴定卤素阴离子的电位滴定指示电极,用于维生素B1药片中维生素B1含量的测定。     

离子选择电极在络合滴定中的应用 (一)用Ca~(2+)、Cd~(2+)及Cu~(2+)选择电极指示微量钙、镉、铜及钆的滴定终点

用离子选择电极指示络合滴定终点来测定溶液中金属离子浓度的方法,具备了络合滴定和离子选择电极直接测定这两者的优点。这种方法既可以消除主观误差,更可以减少测定量,还易于进行自动分析。通常在溶液中存在的外来离子对电极多少会有干扰,因此在用离子选择电极直接测定以前,先要知道溶液中存在的离子及其浓度,然后再作工作曲线。而滴定法是测定溶液中离子的相对浓度变化,这样外来离子在络合滴定中的影响就不太大。此外,各种不同离子的选择电极至今制备得还不多,且大部分是一、二价的。若采用络合反滴定法,则三、四价的离子也可     

硫酸亚铁及氯化铁与硫酸亚铁混合溶液与氢氧化钠溶液反应的沉淀pH曲线的测定及分析

应用手持技术pH传感器,测定了NaOH溶液滴定FeSO4溶液的t-pH曲线,应用origin 9.0分析实验数据,探讨了空气对Fe2+沉淀pH的影响;通过测定并分析FeSO4溶液滴定NaOH溶液的pH曲线,发现了溶液最终pH受金属离子水解程度的影响;通过测定并分析NaOH溶液滴定FeCl3和FeSO4混合溶液的pH曲线,探讨了Fe2+和Fe3+的互相影响,使其沉淀pH范围发生变化;通过测定并分析FeCl3和FeSO4混合溶液滴定NaOH溶液的pH曲线,验证了Fe2+和Fe3+的水解程度不同,Fe （OH）3和Fe （OH）2的存在条件也不一样。     

铜试剂电位滴定法连续测定多种金属离子

Hassan等将光谱纯碳棒经处理制成了对铜试剂-二乙基二硫代氨基甲酸盐(DDC)敏感的电极,以此作为指示电极,NaDDC作滴定剂,在乙醇-水溶液中可分步滴定Cu~(2+)、Ni~(2+)、Zn~(2+)、Cd~(2+)等金属离子。我们发现Ag_2S晶膜电极对DDC有特别敏感的响应。以该电极为指示电极,NaDDC为滴定剂,在50-75％的乙醇溶液中可分步滴定Cu~(2+)、Ni~(2+)、Zn~(2+)、Pb~(2+)、Cd~(2+)、Th~(4+)等金属离子。滴定突跃较Hassan的更为显著。Cu~2+浓度低至2μg/ml亦能测定。用该方     

多元线性回归pH配位滴定法同时测定钙和镁

将多元线性回归分析应用于pH配位滴定,提出△lgK_(MY)较小金属离子混合溶液中各组分同时测定的方法,讨论了方法的原理、回归方程和最佳条件.对钙、镁合成样品及实际水样中钙、镁含量进行测定,结果满意.     

电位滴定法测定铜镁合金中镁

建立电位滴定法测定铜镁合金中的镁含量.以光度电极为指示电极,乙二胺四乙酸二钠溶液为滴定剂.试料用王水溶解,在pH 4.0～4.5时,用硫化钠和铜试剂将大量基体铜和杂质元素沉淀分离.在pH约为10的环境下,以铬黑T为指示剂,用乙二胺四乙酸二钠溶液滴定至电位突跃记为终点,计算镁含量.考察滴定参数的影响,确定了滴定波长为61...     

库仑滴定法间接测定补锌片中锌

以pH 9.2的1.0mol·L~(-1)碘化钾-四硼酸钠溶液为支持电解质溶液,铂电极作为电解电极与指示电极,于室温下电解生成碘10s后加入补锌片样品溶液滴定剩余的半胱氨酸,采用库仑滴定法指示滴定终点,根据法拉第电解定律,间接测定样品溶液中锌含量。锌的质量浓度在0.05～0.50g·L~(-1)内与其消耗的电量呈线性关系,检出限(3s)为0.04mg·L~(-1)。方法用于补锌片样品的分析,测定值的相对标准偏差(n=6)为0.76%～0.92%,测定值与标示量不存在显著性差异。     

Graphite-silver diethyldithiocarbamate as a new potentiometric sensor for titration of some metals,halides, thiols,and sulfonamides

A new simple potentiometric sensor based on the precipitation of AgDDC within a graphite rod is described. The electrode is sensitive for both DDC and silver ions down to 10^?5M and can be used as an indicator electrode for complexometric titration of metallic ions with NaDDC and argentimetric titration of some organic and inorganic compounds. Accurate results are obtained for microdetermination of some metal ions singly or simultaneously (in binary and tertiary mixtures and alloys) and thiols, sulfonamides, and halides in organic compounds.     

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.     

Signal processing with a summing operational amplifier in multicomponent potentiometric titrations

It has been proved that application of two indicator electrodes connected to the ordinary titration apparatus through an auxiliary electronic device (a summing operational amplifier) significantly extends the scope of multicomponent potentiometric titrations in which the analytes are determined simultaneously from a single titration curve. For each analyte there is a corresponding potential jump on the titration curve. By application of the proposed auxiliary device, the sum of the electrode potentials is measured. The device also enables the relative sizes of the potential jumps at the end-points on the titration curve to be varied. The advantages of the proposed signal processing are exemplified by complexometric potentiometric titrations of Fe(III) and Cu(II) in mixtures, with a platinum electrode and a copper ion-selective electrode as the indicator electrodes.     

On potentiometric titration curves in complexometry

An equation is given which describes the potential change during complexometric titration of metals with potentiometric end-point detection. The potential of the indicator electrode (e.g., silver or mercury electrode) depends on the equilibrium of the reaction MY + W right harpoon over left harpoon WY + M, where W represents the indicator metal ion, and M the metal ion determined by titration with the ligand Y, forming 1:1 chelates. Introduction of the conditional stability constants and corresponding side-reaction coefficients facilitates the prediction of the limits of application of this type of titration as well as the optimum conditions for the determination.     

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。     

Titrations using an apparatus for recording the antilogarithm of pH or pM

A titration apparatus plotting either the concentration of sample ion or the concentration of titrant ion has been tested. An antilog apparatus, converting measured e.m.f. values into concentrations is connected to ordinary titration equipment. The instrument has been tested by means of acid—base titrations (titrations of mixtures of weak acids and of a weak and a strong acid), precipitation titrations (determination of the chloride concentration in tap-water, titration of mixtures of halides), titrations with ion-selective electrodes (determination of the fluoride content of toothpaste) and complexometric titrations (determination of copper with EDTA, using mercuric ion as indicator ion and amalgamated silver rod as indicator electrode, or using a copper-selective indicator electrode). The method considerably simplifies the evaluation of the results as compared to conventional potentiometric titrations.     

Sequential potentiometric complexometric redox determination of iron(III) and cobalt(II) with application to alloys

A simple potentiometric method is presented for successive determination of iron(III) and cobalt(II) by complexometric titration of the iron(III) with EDTA at pH 2 and 40 degrees , followed by redox titration of the cobalt(II) complex with 1,10-phenanthroline or 2,2'-bipyridyl at pH 4-5 and 40 degrees , with gold(III). There is no interference in either determination from common metal ions other than copper(II), which severely affects the cobalt determination but can be removed by electrolysis. The method has been successfully applied to determination of iron and cobalt in Kovar and Alnico magnet alloys.     

Ti/TiO2 indicator electrodes formed by plasma electrolytic oxidation for potentiometric analysis

Ti/TiO₂ indicator electrodes were prepared by plasma electrolytic oxidation (PEO) method in the tetraborate electrolyte and were used for potentiometric indication of chemical reactions of different types and for analysis of surface and industrial wastewaters on the example of potentiometric determination of alkalinity and chloride. The electrodes formed at current densities of 0.05, 0.1, 0.15 and 0.2 A/cm² are different in composition, surface morphology and electroanalytical properties. The electrodes formed at a current density of 0.05 A/cm² exhibit the highest pH-sensitivity and generate the highest analytical signal at the equivalence point in the acid–base and precipitation titrations. The maximum analytical signal at the equivalence point, exceeding in magnitude the analytical signal, obtained by classical Pt electrode in oxidation–reduction and complexometric titrations generates PEO layers formed at a current density of 0.05 A/cm² and a platinum-modified nanoparticles. The results of the potentiometric titration of the surface and technogenic waters using as indicator Ti/TiO₂ electrodes are comparable with the conventionally used glass electrode (to determine alkalinity) and Ag electrode (to the determine chloride) and the results of visual titration. The advantage of the obtained metal oxide systems is the ability to determine two hydrochemical parameters due to their multifunctionality and opportunity to work with a single electrode. In addition, these sensors offer some analytical characteristics such as sensitivity, good reproducibility, high mechanical stability and a simple preparation procedure.     

Application of artificial neural network to simultaneous potentiometric determination of silver(I), mercury(II) and copper(II) ions by an unmodified carbon paste electrode

The response characteristics and selectivity coefficients of an unmodified carbon paste electrode (CPEs) towards Ag⁺, Cu²⁺ and Hg²⁺ were evaluated. The electrode was used as an indicator electrode for the simultaneous determination of the three metal ions in their mixtures via potentiometric titration with a standard thiocyanate solution. A three-layered feed-forward artificial neural network (ANN) trained by back-propagation learning algorithm was used to model the complex non-linear relationship between the concentration of silver, copper and mercury in their different mixtures and the potential of solution at different volumes of the added titrant. The network architecture and parameters were optimized to give low prediction errors. The optimized networks were able to precisely predict the concentrations of the three cations in synthetic mixtures.     

Computer Simulation of the Chelatometric Titration of Metal Mixtures

Computer simulation was used to reveal regularities in the form of chelatometric (EDTA) titration curves of metal mixtures depending on the relative stability of the metal chelates, concentration, pH, and other factors. The reliability of calculations was confirmed by potentiometric titration. Criteria determining the possibility of the separate and total determination of components were adjusted. For the analysis of mixtures (e.g., copper-based alloys), it was proposed to record potentiometric titration curves using an electrode sensitive to the metal that yields the most stable metal chelates under the given conditions.