Determination of Sulphur in Solid and Liquid Samples by Potentiometric Titration with Ion Selective Electrode.

Abstract

This paper describes a potentiometric method for the determination of sulphur in solid and liquid samples, using a sulphide ion selective electrode after the reduction distillation step. The determination of sulphide in solid and liquid samples without prior treatment was carried out by direct and titration potentiometric methods.

The reproducibility of the method and the recovery of sulphate in solid samples was investigated using analytical reagent grade 99% sodium sulphate. Portions of aproximately 100 mg of reagent were subjected to the reduction distillation process. After the ion selective electrode showed a stable value of the potential, indicating that all the sulphate had been reduced to sulphide, the potentiometric titration with lead nitrate solution was performed. A mean recovery of 98% of sulphate was found. The potentiometric titration method described in this work, can be applied to determine S⁼ in solid samples with the advantage that it does not require sample solubilization or extraction prior to the determination. The method yields an almost total reduction of sulphur and also a good precision.     

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。     

多元校正流动注射电位滴定法同时测定苯甲酸和山梨酸

将流动注射应用于酸碱电位滴定分析,建立了一种可同时测定混合有机酸的电位滴定新方法。在该方法中,用氢氧化钠与氯化钾的混合溶液作为滴定剂,在流通池中同时插入pH指示电极和氯离子指示电极,在滴定过程中的任一滴定点,流出液的pH值和酸碱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酸中每一种组分的含量。该方法不仅免去了体积和时间读数,而且减少了试剂和样品的消耗量,分析速度快。应用该方法对混合样品中的苯甲酸和水杨酸进行同时测定,其相对标准偏差分别为0．19％～0．37％,回收率分别为97．3％～102．6％。     

PVC membrane ion selective electrode for the determination of pentachlorophenol in water, wood and soil using tetrazolium pentachlorophenolate

A novel PVC membrane electrode selective for the determination of pentachlorophenolate (PCP) ion based on 2,3,5-triphenyl-2H-tetrazolium (TPT) pentachlorophenolate ion pair as an electroactive material is described. The electrode shows a linear response for PCP ion over the concentration range of 6x10(-5) to 1x10(-2) M with lower detection limit of 4x10(-5) M at 25 degrees C. The electrode posses a Nernstian slope of -55.0+/-1.0 mV/decade and a fast potential response of 45 s, which is almost constant over a pH range of 5.5-10.5. Selectivity coefficient data for some common ions show negligible interference, however, 2,4,6-trichlorophenolate and cetylpyridinium ions interfere. An average recovery of 96.2% with relative standard deviation of 2.3% has been achieved for the determination of 75.0 ppm PCP in wastewater samples. The determination of PCP in soil and wood samples gave results that compare favorably with those obtained by gas chromatography. The electrode has been utilized as an end point indicator electrode for the determination of PCP using potentiometric titration.     

Septonex-tetraphenylborate screen-printed ion selective electrode for the potentiometric determination of Septonex in pharmaceutical preparations

A screen-printed electrode (SPE) was fabricated for the determination of 1-(ethoxycarbonyl)pentadecyltrimethylammonium bromide (Septonex) based on the use of Septonex-tetraphenylborate as the electroactive substance, and o-nitrophenyloctylether (o-NPOE) as the plasticizing agent. The electrode passes a near-Nernstian cationic slope of 59.33 ± 0.85 mV from activity between pH values of 2 to 9 with a lower detection limit of 9×10(-7) M and response time of about 5 s and exhibits an adequate shelf-life of 6 months. The method was applied for the determination of Septonex in pharmaceutical preparations. A percentage recovery of 99.88% was obtained with RSD=1.24%. The electrode was successfully applied in the determination of Septonex in laboratory-prepared samples by direct potentiometric, calibration curve and standard addition methods. Potentiometric titration of Septonex with sodium tetraphenylborate and phosphotungstic acid as a titrant was monitored with the modified screen-printed electrode as an end-point indicator electrode. Selectivity coefficients for Septonex relative to a number of potential interfering substances were determined. The sensor was highly selective for Septonex over a large number of compounds. Selectivity coefficient data for some common ions show negligible interference; however, cetyltrimethylammonium bromide and iodide ions interfere significantly. The analytical usefulness of the proposed electrode was evaluated by its application in the determination of Septonex in laboratory-prepared pharmaceutical samples with satisfactory results. The results obtained with the fabricated sensor are comparable with those obtained by the British Pharmacopeia method.     

Flow injection analysis of fluoride in electroplating baths with potentiometric detection

A high dispersion FIA system with a fluoride selective and a double junction reference electrode in cascade arrangement was developed for the determination of the fluoride content in chromium electroplating baths. The analyses of seven synthetic baths prepared in the laboratory and two samples provided by the industry gave results with a mean recovery value of 100.5%, and a mean variation coefficient of 1.6%. These data were better than those obtained by the EDTA complexometric titration, the reference technique, with a mean recovery of 94.0% and a mean variation coefficient of 7.5%. The sampling rate for the FIA manifold was 20 samples per hour.     

Ion-selective electrodes in organic functional group analysis: microdetermination of nitrates and nitramines with use of the iodide electrode

A simple, selective and accurate method has been described for the rapid micro and submicro determination of organic nitrates and nitramines. It is based on reaction with mercury-sulphuric acid mixture for 5 min at room temperature followed by potentiometric titration of the mercurous ions released, a solid-state iodide-sensitive electrode being used. Three equivalents of potassium iodide as titrant are consumed per mole of nitrate or nitramine group. The results obtained, with sample sizes ranging from 1.0 to 50 mumole, are precise to +/- 0.2% and the average recovery is 99%. None of the other nitrogenous functional groups responds to this reaction.     

Effect of presence of 18-crown-6 on the response of 1-pyrrolidine dicarbodithioate-based lead selective electrode

The lipophilic ammonium salt of 1-pyrrolidine dicarbodithioic acid (PCDT)[I] was introduced as a selective ionophore for a sensitive Pb-ion selective electrode. Also, the effect of immobilization of 18-crown-6 (CW), into the above membrane, on the electrode performance was discussed. The slope of the PCDT-based [I] electrode was (26–30 mV decade⁻¹), while it was (29-30 mV decade⁻¹) for (PCDT+CW)-based [II] electrode according to the doping time. The linear concentration ranges were (1×10⁻⁶–1×10⁻¹ M) and (5×10⁻⁵–1×10⁻¹ M) for electrode types [I] and [II] after one-day doping. The working pH ranges were (5.0–10.0) and (7.0–10.0) for electrode types [I] and [II], respectively. Most of the common cations were tested for the evaluation of the electrode selectivity with correlation to the ionic radii of the tested cations. Among them only Na⁺, Ag⁺ and Fe³⁺ were the real interference. Application of using the electrode for the determination of lead in lubrication oil samples was performed with RSD (0.86–1.03%). The obtained results were compared to those of an atomic absorption spectrophotometric method.     

镉离子选择电极电位滴定测定钙镁

建立了以镉离子选择电极极作指示电极ＥＤＴＡ、ＥＧＴＡ电位滴定测定钙、镁的方法，详细考察了电位滴定的适宜条件，干扰离子的影响及消除办法。在四硼酸钠－氢氧化钠缓冲介质中，ＥＧＴＡ滴定钙，ＥＤＴＡ滴定钙镁含量，测定矿泉水及硅酸盐样品中钙镁含量，结果符合要求。     

Argentomctric coulomelric titration of thioacetamide

The coulometric determination of thioacetamide (TAA) with electrogenerated silver is described. The titration is done in a solution 0.1M in both ammonia and sodium hydroxide, and the end-point is detected potentiometncally with a silver-silver sulphide electrode. On repeat analyses of approx. 2-mg samples of TAA an average error of -04% (relative standard deviation 0.25%) was obtained. Important steps in the procedure include cleaning the silver generating electrode in nitric acid before each titration, purging well with nitrogen to remove oxygen, and not using too large a sample.     

Gran's plot titration and flow injection titration of sulfate in ground and drinking water with a barium ion-selective electrode

The application of a barium ion-selective electrode for the determination of sulfate is reported. Titrations in the batch mode using the Gran's plot method [1] have been carried out. In the presence of a lithium acetate buffer and after the addition of isopropanol it has been possible to determine sulfate with a relative standard deviation (RSD) of 1.5%. The concentration range of the samples was 5–400 mg sulfate/l. Interfering ions were separated by cation-exchange. This indirect titration constituted the basis of a flow injection titration (FIA titration) system for the continuous determination of sulfate. By plotting the peakwidth vs. the logarithm of the sulfate concentration of the injected samples, linear calibration graphs in the range of 50–200 mg sulfate/l were obtained. In this system, the sample stream was pumped through an ion-exchange column, mixed with a buffer stream of lithium acetate and injected in a reagent stream of a BaCl₂ solution. The resulting free Ba(II) concentration was monitored with a barium ion-selective electrode. The content of sulfate in ground and drinking water samples has been determined with a RSD between 1.2% and 1.3%.     

电感耦合等离子体发射光谱(ICP-OES)法分析废钴钼催化剂中关键助剂元素钛含量

通过改变传统的灼烧再酸化处理催化剂的实验方法,采用硝酸-氢氟酸-高氯酸法将石化工业中常用的难溶废钴钼催化剂快速溶解并利用ICP-OES分析法准确测定样品中关键助剂元素钛,为钴钼催化剂后续工艺研究提供了一定的分析依据以及对钛金属元素的回收循环利用具有重要意义。实验优化了ICP-OES仪器最佳工作参数,确定了酸试剂体系及钛元素的分析谱线,对比了不同前处理方法的精密度。结果表明：相比于灼烧再酸化,直接采用硝酸-氢氟酸-高氯酸法溶解样品更为理想,这是由于在灼烧的过程中相当部分金属元素钴与Al2O3反应生成钴青（CoO·n Al2O3）使得回收率降低。在仪器最佳测定条件下校准曲线回归方程的线性相关系数为1,钛的相对标准偏差为0.54%,加标回收率在99%-101%之间。对同一样品与采用分光光度法分析和EDTA滴定法分析做对照实验,结果吻合,但本实验方法简便易操作且适合大批量的检测分析工作。     

Flow injection analysis of fluoride in electroplating baths with potentiometric detection

A high dispersion FIA system with a fluoride selective and a double junction reference electrode in cascade arrangement was developed for the determination of the fluoride content in chromium electroplating baths. The analyses of seven synthetic baths prepared in the laboratory and two samples provided by the industry gave results with a mean recovery value of 100.5%, and a mean variation coefficient of 1.6%. These data were better than those obtained by the EDTA complexometric titration, the reference technique, with a mean recovery of 94.0% and a mean variation coefficient of 7.5%. The sampling rate for the FIA manifold was 20 samples per hour. Received: 27 November 1997 / Revised: 24 February 1998 / Accepted: 1 March 1998     

修饰铂电极上Bi(Ш)的示波双电位滴定法

制备了Bi(Ⅲ)修饰铂电极,用循环伏安法表征了Bi(Ⅲ)在电极上的吸附特性,探讨了电极的响应机理。 通过优化实验条件,建立了一种测定Bi(Ⅲ)的示波双电位滴定法。 在0.1 mol/L的硝酸溶液中(pH=1.0),用制备的修饰铂电极作为双指示电极,以EDTA标准溶液滴定Bi(Ⅲ),利用示波器屏幕上荧光点的显著最大位移指示滴定终点。 Bi(Ⅲ)在1.19×10-4～1.44×10-2 mol/L时,回收率为99.8%～100.1%,检出限(S/N=3)为1.0×10-4 mol/L。 该修饰电极具有良好的稳定性和重现性,在含有1.0×10-2 mol/L Bi(Ⅲ)的溶液中,连续7次测定,所得终点电位值均在100 mV左右,其相对标准偏差(RSD)为0.04%。 应用该方法测定含铋样品,RSD值(n=7)小于0.25%,回收率为99.5%～100.5%,测定结果与指示剂法测定值相符。     

Fe(Ⅱ)-Ce(Ⅳ)双中间体库仑滴定的电极伏安行为及Cr(Ⅵ)测定

采用循环伏安法研究了Fe(Ⅱ)-Ce(Ⅳ)双中间体恒电流库仑滴定体系及工作电极的电化学行为,优化了电解液组成,探讨了S2-和Cl-等的干扰机理。在优化的分析条件下,方法用于测定工业废水中μg级的Cr(Ⅵ),与分光光度法对照,相对误差小于3%,回收率在93.9%～98.9%之间。该法简便、快速、灵敏、准确,且不受试样颜色、浊度及沉淀的影响,无需配制标准溶液,可连续测定。     

1-(5-溴-2吡啶偶氮)-2-萘酚-6-磺酸作指示剂络合滴定连续测定铝和钛

在酸性溶液中加入对铝、钛过量的EDTA标准溶液,在pH4．0煮沸下,铝（Ⅲ）、钛（Ⅳ）与EDTA生成稳定的络合物。以5-Br-PAN-S作指示剂,用硫酸铜标准溶液返滴定过量的EDTA,测定铝钛合量,再用置换法测定钛的量。终点变色敏锐,准确度高,方法用于硅酸盐矿物中铝钛的连续测定,结果满意。     

铝灰及其浸出液中氟的测定

铝灰中的氟化物是铝灰中的环境危害因子.使用X射线荧光光谱(XRF)法、X射线衍射(XRD)法对15份铝灰样品进行了元素及物相组成检测,使用SPSS 25.0对数据进行因子分析和聚类分析,将15份样品分成四类,从每类中选择1～2个样品,共选取5份样品作为代表进行后续实验.使用离子色谱法和氟离子选择电极法对铝灰浸出液中氟离...     

原位水解-硝酸镧电位滴定法测定钛合金化铣腐蚀溶液中总氟化物

基于氟钛配合物的原位水解以及硝酸镧电位滴定法建立了测定钛合金化铣腐蚀溶液中总氟化物浓度的新方法。在六次甲基四胺(HMTA)缓冲溶液中,氟钛配合物发生原位水解并释放出游离氟离子,以氟离子选择电极(F-ISE)为指示电极进行测定。对影响测定的各项参数(如p H值、HMTA溶液用量、钛离子浓度等)做了条件实验并予以优化。实验结果表明Ti(Ⅳ)浓度在0~20 g/L范围内对于氟离子测定无干扰,方法的相对标准偏差(RSDs,n=6)在0.27%~0.62%之间,加标回收率在99.5%~101.1%之间。此外,本文对氟钛配合物原位水解反应的机理也进行了探讨,溶液中氟钛配合物的主要存在形式为TiF_6~(2-),适宜的酸度是水解反应进行的必要条件,HMTA作为缓冲溶液为水解反应持续进行提供恒定的p H环境,La(NO_3)_3作为氟清除剂降低游离氟离子浓度促进水解反应的进行,伴随滴定过程氟钛配合物发生完全水解。     

全自动电位滴定法测定锂电池原料碳酸锂中主成分的含量

采用全自动电位滴定法测定锂电池原料碳酸锂中主成分的含量,用盐酸标准溶液进行滴定,考虑自动电位滴定仪的灵敏性和准确度,通过多次对比实验,确定了仪器的最佳工作参数、滴定剂浓度和样品称样量等滴定条件;对两个不同品位试样分别进行了11次平行测定,相对标准偏差(RSD)均小于1％.在碳酸锂试样中加入基准物质无水碳酸钠进行碳酸根的...     

Determination of calcium in waters, milk and wine by discontinuous-flow analysis

The flow-based analysis method, discontinuous-flow analysis (DFA), was used for the determination of total calcium in drinking water, milk and wine by titration with ethyleneglycoltetraacetic acid. The detector is a coated-wire calcium-selective electrode. The titration can be cycled continuously with a cycle time of about 1 min. This can be carried out with a single sample or with different samples using an autosampler. The method for waters and wine is simple, fast and highly reproducible. For milk, a back-titration method was used because of the complex matrix of the sample.