Pneumatoamperometric determination of chlorine in water

Free chlorine in water can be determined by acidifying the water sample, purging it with nitrogen and determining the chlorine present in the nitrogen stream with a gold porous electrode. The current response of gold porous electrode is related to the concentration of free chlorine by using a calibration curve. This pneumatoamperometric method gives results fully comparable to the standard o-toluidine photometric method used for water supplies. It is uninfluenced by the presence of other dissolved oxidants and requires only one milliliter of sample.     

γ干扰素免疫电极及其响应机理的研究

在醋纤维孔膜上利用溴化氰固定了马抗人γ干扰素抗体。抗体膜经竞争性温育反应后置于碘离子选择电极上而构成免疫电极; 另一碘电极与参比膜作为参比电极。测定了电极在0.1mmol.dm^-3KI+4.4mmol.dm^-3H2O2+0.1mol.dm^-3柠檬酸盐,PH5.0缓冲液中响应电位, 研究了温度反应时间、电解液组成等因对电极响应影响,提出了电极向应线性化方法, 并得到了实验验证。     

A dual ion-selective electrode detector for the simultaneous detection of bromine- and chlorine- containing compounds in gas chromatography

A dual ion-selective electrode gas chromatographic detector which allows the simultaneous detection of chlorine- and bromine-containing compounds through two-channel operation is described. Components eluted from the g.c. column are hydrogenated, the hydrogen chloride and hydrogen bromide produced being absorbed in a standard solution of halide; the ion concentrations in the resulting solution are monitored by chloride- and bromide-selective electrodes. The dual electrode detector gives two chromatograms simultaneously, one selective for chlorine- and bromine-containing compounds and the other for bromine-containing compounds. The response ratio, i.e., the peak area of the readout from the chloride channel divided by that from the bromide channel for the same compound, gives valuable information. The Cl/Br ratio in an eluted molecule can be determined accurately from the response ratio if a standard reference compound is injected simultaneously.     

Flow-injection system with ion-exchange separation and potentiometric detection for the determination of three halides

The use of ion exchangers in flow-injection systems is reviewed briefly. In the method described, halides are separated on a short column of a strongly basic ion-exchange resin (Dowex 1-X8) placed in the flow-injection conduit, with a laboratory-made tubular silver/silver halide ion-selective electrode as potentiometric sensor. The response capabilities of the different halide-selective electrodes to a wide concentration range (20-5000 mg dm^?3) of single and mixed halide solutions with and without the incorporated ion-exchange column are compared. By careful selection of suitable concentrations of the potassium nitrate carrier/eluent stream to satisfy the requirements of both the ion-exchange column and the halide-selective electrode, it is possible to separate and determine chloride, bromide and iodide in mixed halide solutions with a detection limit of 5 mg dm^?3. The bromide-selective electrode is the most satisfactory detector.     

Hydrogen ion-selective poly(vinyl chloride) membrane electrode based on a calix[4]arene.

A hydrogen ion-selective poly(vinyl chloride) membrane electrode was constructed using 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetracyanomethoxycalix[4]arene as a neutral carrier. The electrode showed an apparent Nernstian response in the 2-11.5 pH range with a slope of 54.0 +/- 0.2 mV/pH at 20 +/- degrees C. This electrode showed a rapid response of the emf to changes in the pH, high ion selectivity with respect to lithium, sodium and potassium, and characteristics similar to those reported for the conventional pH glass membrane electrode. It can be used as a potentiometric indicator electrode in hydrofluoric acid solutions. The effects of iodide, thiocyanate, perchlorate and bromide on the characteristics of the electrode were also considered.     

Flow-injection potentiometric determination of residual chlorine in water

Residual chlorine is measured in water by using a potentiometric system composed of an iodide-selective electrode and a platinum electrode sensing the iodine-iodide ratio. When the sample is added to acidified iodide solution, the cell response is in a logarithmic relation to the iodine concentration which in turn depends on the concentration of residual chlorine. In the flow injection system evolved, 0.1–5.0 mg l^-1 residual chlorine can be determined at a rate of 40–60 samples per hour. The results of potentiometric determinations of residual chlorine in tap water compared to spectrophotometric results suggest that the presence of various organic substances is responsible for discrepancies between these measurements.     

Kinetic study of N-bromosuccinimide reactions and kinetic determination of pyridoxine using a bromide-selective electrode

The bromide released by the alkaline hydrolysis of N-bromosuccinimide and its reactions with bromide, pyridoxine and thiamine have been studied potentiometrically using a solid-state bromide-selective electrode to monitor the consumed or produced bromide ion. Potential-time indications are obtained using a microcomputer-controlled potentiometric system. The overall rate constants and the activation energies have been calculated. A kinetic-potentiometric procedure for the determination of pyridoxine in the presence of thiamine in pharmaceutical preparations, based on its reaction with N-bromosuccinimide, is presented.     

Flow injection determination of bromide ion in a developer using bromide ion-selective electrode detector

A potentiometric flow injection determination method for bromide ion in a developer was proposed, by utilizing a flow-through type bromide ion-selective electrode detector. The sensing membrane of the electrode was Ag(2)S-AgBr membrane. The response of the electrode detector as a peak-shape signal was obtained for injected bromide ion in a developer. A linear relationship was found to exist between peak height and the concentration of the bromide ion in a developer in a concentration range from 1.0x10(-3) to 1.0x10(-2) mol l(-1). The relative standard deviation for 10 injections of a 6x10(-3) mol l(-1) bromide ion in a developer was 1.3% and the sampling rate was ca 17-20 samples h(-1). The present method was free from the interference of an organic reducing reagent, an organic substance in a developer sample solution for the determination of bromide ion in a developer.     

Flow injection analysis for residual chlorine using Pb(II) ion-selective electrode detector

A simple flow injection analysis (FIA) system for residual chlorine in tap water has been developed by using a Pb(II) ion-selective electrode (ISE) detector. The method is based on a specific response of the Pb(II)-ISE to residual chlorine. The FIA system consists of a millivolt meter, a peristaltic pump, a Pb(II)-ISE detector and a recorder. A linear working curve between peak height and concentration of residual chlorine was obtained from 0.1 to 1 mg l(-1) for the developed FIA system. The relative standard deviation for repeated injections of a 0.2 mg l(-1) residual chlorine sample was 2%. The regression line and its correlation factor between the conventional o-tolidine colorimetric method and the present method were Y=0.75X+0.17 and 0.967, respectively, for this determination.     

PVC膜电极的研究(Ⅰ)——铋(Ⅲ)氯络阴离子选择性电极的研制

近几年,已有人研究过铋(Ⅲ)涂丝电极,该电极在10^-4-10^-1M铋(Ⅲ)浓度范围有近似线性的响应,斜率为36.5mV/pBi。本文以季铵盐7402-BiCl₄^-缔合物为电活性物质,以苯二甲酸二壬酯为增塑剂,研制成功了铋(Ⅲ)PVC膜电极。     

Performance of the Orion 97-70 total residual chlorine electrode at low concentrations and its application to the analysis of cooling waters

The performance characteristics of the Orion 97-70 total residual chlorine electrode have been determined and the electrode has been found to give a near-theoretical response down to chlorine concentrations in the range 1-5 mug/1. Within-batch relative standard deviations are about 6-8% at concentrations above 50 mug/1. and 10-15% at lower levels. The method is virtually free from interferences (only strong oxidizing agents such as permanganate interfere) but large variations in salinity affect the calibration by changing the conditional standard potential. The best performance at low concentrations (<50 mug/1.) is achieved only if the manufacturer's recommended procedure is changed, namely by using a more dilute iodide reagent, stirring constantly, adding the iodide reagent before the buffer solution and using chloramine-T as a standard.     

Kinetic-Potentiometric determination of ascorbic acid,biotin, pyridoxine hydrochloride and thiamine hydrochloride with N-bromosuccinimide

A kinetic-potenitometric method is proposed for the determination of ascorbic acid, biotin, pyridoxine hydrochloride and thiamine hydrochloride. The vitamin reacts with N-bromosuccinimide and the rate of production of bromide is monitored with a bromide-selective electrode. The method is simple, reliable and relatively free from interferences from common excipients and coexisting vitamins when applied to tablets and injections. The results obtained for the assay of commercial pharmaceutical preparations compare well with those obtained by official chemical methods and demonstrate good accuracy and precision.     

Calixazacrown ethers for copper(II) ion-selective electrode

Five novel 1,3-alternate calix[4]azacrown ethers having 2-picolyl, 3-picolyl, and benzyl unit on the nitrogen atom were synthesized and used as ionophores for transition metal-selective polymeric membrane electrodes. The electrode based on 2-picolyl armed 1,3-alternate calix [4] azacrown ether exhibited Nernstian response toward copper (II) ion over a concentration range (10(-4.5) M-10(-2.5) M). The detection limit was determined as 10(-5) M in pH 7 and the selectivity coefficients for possible interfering cations were evaluated. Anions in the sample solution strongly affected the electrode response.     

Cesium ion selective electrode based on calix[4]crown ether-ester

The potentiometric response characteristics of cesium ion selective PVC membrane electrode employing calix[4]crown ether-ester as an ionophore were investigated. The electrode exhibit a good response for cesium ion over wide concentration range of 5.0x10(-6)-1.0x10(-1) M with a Nernstian slope of 59 mV per decade. The detection limit of electrode is 5.0x10(-6) M. The electrode was found to have selectivity for cesium ion over alkali, alkaline and transition metals. The response time of the electrode is less than 20 s and can be used for more than 4 months without observing any divergence in potentiometric response. The electrode response was stable over wide pH range.     

Response mechanism of a neutral carrier Hg(II) polymeric membrane ion-selective electrode. SEM and EDAX study

Scanning electron microscopy (SEM) and energy dispersive atomic X-ray spectrometry (EDAX) were used to study the response mechanism of a previously reported new Hg membrane ion-selective electrode (ISE) based on 1,3-diphenylthiourea. These techniques allowed the study of the membrane surface characteristics, such as the morphological homogeneity and chemical composition. A 'twice Nernstian' response at pH > or = 7 was explained by the detection of the Hg(OH)+ cation. A normal Nernstian response was found at acidic pH values. Using these techniques, both coordination compounds, [Ligand-Hg-OH] at pH 7 and [Ligand-Hg-Ligand] at pH 4.5, were confirmed on the electrode membrane surface activated with Hg(NO3)2 solution at both pH values. These methods provide results which are independent of the potential measurement data and in agreement with them. A successful response model has explained both independent and unbiased sets of results. These conclusions confirm the proposed response mechanisms for this new Hg membrane sensor.     

表面活性剂对聚氯乙烯膜修饰电极电化学行为的影响

采用循环伏安法考察了所制备的聚氯乙烯(PVC)膜修饰电极的稳定性,结果表明,该修饰电极性能稳定,电极反应过程为扩散控制的过程。以循环伏安法、计时库仑法、稳态极化曲线法和交流阻抗法分别考察了阳离子(十六烷基三甲基溴化铵,CTMAB)、阴离子(十二烷基硫酸钠,SDS)和非离子(脂肪醇聚氧乙烯醚,AEO9)3种不同类型的表面活性剂对PVC膜-Ag[B(ph)4]修饰电极反应过程的影响。结果表明:加入CT-MAB或SDS后,PVC膜中Ag[B(ph)4]氧化态和还原态的扩散系数分别比电极在0.1mol/LKOH支持电解质中的扩散系数小,PVC膜修饰电极的反应过程受扩散控制的特征变得更明显,表明在此条件下膜中的电子转移速度加快,CTMAB或SDS对PVC膜修饰电极的电极反应过程有增敏作用。而加入AEO9后,PVC膜中的Ag[B(ph)4]氧化态和还原态的扩散系数比电极在0.1mol/LKOH支持电解质中的扩散系数大,并使电极反应的控制步骤从扩散控制转向含电子转移控制的扩散控制,表明在此条件下膜中的电子转移速度变慢,AEO9对PVC膜修饰电极的电极反应过程有抑制作用。     

Benzothiazoline derivatives. II. Preparation of N-substituted derivatives of 2-benzothiazolinethione by thiation of the 2-oxo analogs

Thuiation of the benzoate and acetate esters of 3-(2-hydroxyethyl)-2-benzothiazolinone (Ig) gave the corresponding thiones. The benzoate was then deblocked to yield 3-(2-hydroxyethyl)-2-benzothiazolinethione (Ik), a compound not accessible by direct addition or substitution. Attempts to introduce a chlorine (or bromine) atom in place of the hydroxy 1 group in the latter compound or its S-isomer, 2-(2-hydroxyethylthio)benzothiazole (11a), gave 2,3-dihydrothiazolo-[2,3-b ] benzothiazolium chloride (or bromide) (IIIa or b). The latter compound undergoes dihydrothiazolo ring opening when treated with sodium hydroxide or sodium sulfide to give bis[2-(2-benzolhiazolinon-,3-yl)ethyl]disulfide (IVc) or bis[2-(2-benzothiazolinethion-3-yl)ethyl] disulfide (lVb),respectively. 2-Benzothiazolinethione reacted with ethylenimine and with N-phenylethylenimine to give S-substituted derivatives. Addition to vinyl n-butyl ether gave the expected N-substituted derivative, which was found to undergo removal of the butyoxyethyl group when subjected to conventional conditions for ether cleavage.     

Application of neural network calibrations to an halide ISE array

The Neural Network (NN) technique was applied to the calibration of an ion selective electrode (ISE) array comprising a bromide selective electrode, two chloride ISEs and one thiocyanate ISE. The measured samples were synthetic mixture solutions of chlorides and bromides in concentration ranges such that interference occurs. The NN method allowed to perform the calibration without estimating the coefficients of the Nikolskii-Eisenman theoretical relation. Only the determination of bromide was detailed. The results obtained using this method were better than those obtained using linear multivariate calibration methods.     

Response of the jalpaite membrane copper(II) ion-selective electrode in marine waters

The response of the Orion 94-29 Cu^II ion-selective electrode (ISE) [employing a jalpaite membrane] in seawater has been related to levels of free Cu^II yielding results for the Derwent River and San Diego Bay that are 2 to 3 orders of magnitude higher than those for the Pacific Ocean. Response data for the electrode in acidified seawater at pH 2 are internally consistent with total Cu^II levels determined using differential pulse anodic stripping voltammetry (DPASV) and graphite furnace atomic absorption spectrometry (GFAAS). It has been found that, even in acidified seawater, the organic ligands influence the response of the electrode, and this effect can be compensated successfully by either analyzing UV-photooxidized seawater and/or using a standard addition technique. The assigned ISE results for total Cu^II in acidified seawater fall within ± (0.1–0.5) pCu unit of values determined using GFAAS. Electrode drift in seawater can be minimized by using a polished electrode that has been conditioned in seawater for 24 h. The improved response rate of a conditioned ISE minimizes electrode soaking times and sample contamination through membrane corrosion.     

Evaluating the Effect of four Hosting Ionophores on the Performance of Anion Selective Potentiometric Sensor

A systematically designed practical approach was carried out for the optimization of an anion selective electrode for the determination of an anionic laxative, docusate sodium (DS). The PVC membrane composition and the sensor assembly were systematically optimized. Different sensors were fabricated using tetradodecylammonium bromide (TDAB), tridodecylmethylammonium bromide, tetraheptylammonium bromide as ion exchangers. The effect of ionophore was evaluated using four different host‐guest ionophores, namely; calix[8]arene, β‐cylodextrin, hydroxypropyl‐β‐cylodextrin and carboxymethyl‐β‐cylodextrin to reach the optimum membrane composition. Sensors were constructed in both liquid membrane and solid contact sensor‐assemblies. The slope, linear range, LOQ and response time for each sensor was calculated to assess their performance characteristics. Best Nernstian slope of ?61.38 mV/decade and lowest quantification limit of 7.62×10^?7 M was achieved by the sensor containing TDAB as ion exchanger and Calix[8]arene as ionophore in the PVC matrix using the gold wire solid contact sensor assembly. Electrode selectivity was assured in the presence of DS potential degradation product, common interfering ions and industrial excipients of tablet and gel formulations. Validation was carried out regarding the ICH validation parameters.