Ultramicrocoulometric determination of ammonia in serum, plasma, and blood

A method has been developed for the ultramicrodetermination of ammonia in as little as 0.01 ml of serum, plasma, or blood by coulometric titration with electrogenerated hypobromite using a sensitive amperometric endpoint. The only accurate volumetric measurement required is the pipetting of the sample. The sample is added to a 33-mm microdiffusion cell for 10 min to separate the ammonia; the ammonia is collected in 0.1 ml of 0.0025 M sulfuric acid in the center compartment. The separated ammonia is added to a coulometric generation cell where an excess amount of hypobromite has been generated. The decrease in amperometric current due to the utilization of the hypobromite by the ammonia is taken as a measure of the ammonia content; comparison is made with diffused standards. An optimum pH of 8.6 for the titration has been found to give reproducible results at all levels encountered. One-tenth-milliliter blood samples are routinely analyzed. When elevated ammonia levels are encountered, 0.01-ml samples can be used with accurate results. The time for the analysis is 10–15 min after initiating the diffusion.     

Analysis of hypobromite solutions by indicator titrations

A rapid titrimetric method is described for the determination of the three oxidizing components in 10^-1 N hypobromite solutions with only arsenic(III) as the standard reagent. Hypobromite is determined by titration with arsenic(III) in alkaline medium, with bromothymol blue, quinoline yellow or epsilon blue as reversible indicator. Bromite is determined by reaction with an excess of iodide in weakly alkaline medium, followed by titration of the formed triiodide with arsenic(III) solution and starch as indicator. Total hypobromite, bromite and bromate is determined by titration of arsenic(III) in hydrochloric acid medium, with quinoline yellow as reversible indicator. Bromate is calculated by difference.     

恒电流库仑滴定装置的自动化

介绍了恒电流库仑滴定装置的结构与原理,对电解电流的自动恒定以及利用计算机对库仑滴定过程进行自动控制做了探索。     

Influence of AgCl precipitates on the precipitation titration of sodium chloride by constant-current coulometry.

The precipitation titration of sodium chloride with electrogenerated silver ion was studied. The production of a precipitate of silver chloride had a significant effect on the titration results because the precipitate involved unreacted chloride or unreacted silver ion. The accuracy of the method was investigated by changing the introduction time of a sodium chloride solution to the coulometric cell during the process of electrolysis, and examining the dependency on the sample size. The accuracy of the measurement of the precipitation titration is discussed.     

Determination of hydrazine by direct titration with hypobromite

Summary A simple, accurate and rapid method is described for the determination of hydrazine by direct titration with hypobromite using Bordeaux B as indicator. The procedure can also be employed for the determination of hypobromite and bromate by titration with standard hydrazine.

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Zusammenfassung Zur Bestimmung von Hydrazin wird die direkte Titration mit Hypobromitlösung und Bordeaux B als Indicator empfohlen. Das Verfahren ist einfach, rasch durchführbar und liefert genaue Ergebnisse. Es kann auch zur Bestimmung von Hypobromit und Bromat durch Titration mit Hydrazinlösung verwendet werden.

     

Investigation on drying conditions and assays of amidosulfuric acid and sodium carbonate by acidimetric coulometric titration and gravimetric titration

Amidosulfuric acid and sodium carbonate as standards for acid–base titrimetry were assayed by coulometric titration and gravimetric titration. Amidosulfuric acid was directly assayed by coulometric titration with electrogenerated hydroxide ions, and sodium carbonate was assayed by gravimetric back-titration. For sodium carbonate, excess amount of sulfuric acid, whose concentration was determined by coulometric titration, was added to sodium carbonate, and then gravimetrically back-titrated using a sodium hydroxide solution whose concentration was determined by gravimetric titration using the sulfuric acid. The accuracy of the coulometric titration for amidosulfuric acid and sulfuric acid was evaluated by examining the current efficiency of pulse electrolysis, the amount of the electrolysis current used, and the time spent for a titration. In addition, the drying conditions for high purity primary standards have a significant effect on the titration results due to changes in the acid–base assay. The suitable drying conditions for amidosulfuric acid and sodium carbonate were evaluated by mass-change measurements, coulometric titration and gravimetric titration. The measurement uncertainties were estimated from the uncertainties on the titration processes. Finally, the assays of amidosulfuric acid and sodium carbonate were 99.986% ± 0.010% (k = 2) after drying at 50 °C for 2 h, and 99.970% ± 0.016% (k = 2) after drying at 280 °C for 4 h, respectively. In addition, the international consistency was confirmed by measuring certified reference materials (CRMs) available from different National Metrology Institutes, and the compatibility of values among CRMs was experimentally ascertained.     

A new method for the standardisation of hypobromite

Summary The oxidation of ferrocyanide by hypobromite and the optical density of the yellow colour of ferricyanide thus developed has been studied with the aid of a Hilger Spekker Absorptiometer Model H 760. A violet filter having maximum transmission in the range of 420–450 m was used. Series of experiments showed that quantitative oxidation of ferrocyanide occurred in the p_N range 8–8.5 (bicarbonate buffer) and the colorimetric titration may be used for the standardisation of hypobromite. The results compared favourably with those obtained by amperometric titration of hypobromite against sodium arsenite as a primary standard.Sincere thanks of the authors are due to Prof. S. S. Joshi, D. Sc. (London), F. R. I. C. (London), F. N. I., F. A. Sc. for kind interest and facilities for the work.     

Determination of the purity of acidimetric standards by constant-current coulometry, and the intercomparison between CRMs

The accuracy and uncertainty of the coulometric measurement results of reference materials for acidimetric titration were examined in this study. The results for amidosulfuric acid and potassium hydrogen phthalate are presented. The uncertainty was investigated by examining the dependency on the sample size and on the electrolysis current. Changes in the titration parameters did not result in any significant effects on the titration results. Acidimetric standards with the certified value linked to the SI were developed. In addition, the intercomparison of acidimetric standards was carried out by gravimetric titration, and the relationship between our coulometric results was determined. Furthermore, due to recent internationalization, not only the traceability to the SI but also the relationship and consistency of their analytical data have gained increasing importance. Our results were validated using certified reference materials (CRMs) obtained from different National Metrology Institutes (NMIs), and their relationships are presented. Presented at -- “BERM-10” -- April 2006, Charleston, SC, USA.     

Determination of the drug content of pharmaceuticals containing phenothiazine compounds by triangle programmed flow titration

Summary A flow-through triangle programmed coulometric titration technique is worked out for the determination of phenothiazine compounds. The oxidation reaction of phenothiazines with hypobromite ion served as titration reaction. A biamperometric detector cell has been used for following the titration process. The titration technique has been used for the determination of the drug content (average and individual) of chlorpromazine, promethazine, diethazine and trifluoperazine in pharmaceutical preparations. The relative standard deviation was in the range of 2.0 to 3.5%.

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Bestimmung des Wirkstoffgehaltes von Phenothiazin-haltigen Pharmazeutica mit Hilfe einer Dreieck-programmierten Durchflu\-Titration

     

流动注射电化学发光测定潘生丁

设计了一种应用于流通体系的电解池,以恒电流电解的方法,在线定量电生化学发光反应试剂次溴酸根。其可在碱性介质理米诺而产生强的化学发光。发现潘生丁对该电化学发光有很强的抑制作用。并建立了潘生丁的电化学发光方法。对影响潘生丁测定的实验条件进行了考察和优化。该方法测定潘生丁的一性范围为０．０１－２ｍｇ／Ｌ,检出限为０．００４ｍｇ／Ｌ,相对标准偏差为４．１％。雇学成功地用于片剂潘生丁样品的分析。     

Coulometric Titration of Free Cyanide with Electrogenerated Hypobromite

Abstract

A rapid and sensitive method is described for the direct determination of cyanide by coulometric titration with electrogenerated hypobromite. A biamperometric end point was utilized. From 0.498 – 9.980 ueq of cyanide were analyzed with an average error of 0.36% and an average standard deviation of 0.045.     

Evaluation of certified reference materials for oxidation-reduction titration by precise coulometric titration and volumetric analysis

The accuracy and uncertainty of coulometric titration of Japanese certified reference materials (CRMs) for oxidation-reduction titration were examined in this study. The results for potassium dichromate, sodium oxalate, and potassium iodate are presented. Potassium dichromate was directly determined by coulometric titration, and sodium oxalate and potassium iodate were determined by volumetric analysis using potassium dichromate assigned by coulometry.The uncertainty of the method was investigated by examining the dependency on the sample size and on the electrolysis current. Changes in the titration parameters did not result in any significant effects on the titration results. The coulometric system used primarily consists of a constant current source, timer, switching circuit, indicator unit, and voltmeter. They were controlled using the coulometry software by a PC/AT compatible computer. A highly automated coulometric system achieves repeatabilities of less than one part in 30,000 (k = 2) and uncertainties of less than one part in 15,000 (k = 2). In addition, using volumetric method, SI units traceable sodium oxalate and potassium iodate (purity standards for redox reaction) CRMs were developed.Reference materials for volumetric analysis are the most basic substances used in analytical chemistry. These materials are analyzed by several analytical methods and are produced globally; however, their purities have not been compared at the international level. Therefore, the relationship between the purity and reliability of these materials has not yet been established. In this paper, we determine the relationship between these parameters by titrating each material obtained from different laboratories.     

电生溴库仑滴定法直接测定渣油中硫醚硫的研究

本文提出了在甲苯－冰乙酸－乙醇－ＮａＢｒ电解液中电生溴库仑滴定电位法指示终点直接测定渣油中硫醚硫的新方法。该电解液对渣油样溶解性能好，终点电位突跃大，结果准确。     

Coulometric titration by a controlled-potential pulsed-charge potentiometric technique-II Acid-base, precipitation and homogeneous redox systems

An unconventional coulometric method, based on electrolysis at controlled potential by means of discrete charge-pulses, with end-point detection obtained by mathematical linearization of potentiometric data, has been applied to various systems. The results appear very satisfactory: very weak acids can be determined with high accuracy; in the case of precipitation reactions the selectivity is high enough to allow titration of the components of halide mixtures; for homogeneous redox systems some problems caused by irreversibility at the indicator electrode are overcome.     

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.     

Coulometric titration of D(+)-glucose using its enzymatic oxidation.

A definitive method is described for the indirect assay of milligram quantities of D(+)-glucose by coulometric titration. D(+)-Glucose was aerobically oxidized by glucose oxidase in an acetate buffer solution (pH 5.1). Subsequently, the enzymatically formed hydrogen peroxide was titrated coulometrically with electrogenerated hypobromite in sodium bromide-sodium tetraborate medium of pH 8.6, with biamperometric end-point detection. Parameters affecting the enzymatically catalyzed oxidation and coulometric titration were evaluated. The optimized conditions for the oxidation of up to 20 mg of D(+)-glucose include the addition of 4500 U of glucose oxidase and stirring over a 10-min interval at 25 degrees C. Under proposed conditions, the assay values of several commercial D(+)-glucose reagents were somewhat lower than the guaranteed minimum values, with RSDs (n = 5) of 0.071 - 0.106%.     

The determination of microgram quantities of organic nitrogen

A method is descriibed for the determination of microgram quantities of nitrogen in a wide variety of materials. This method involves the Kjeldahl procedure for the conversion of nitrogen to ammonium or amine sulphate. Digestion of the sample with concentrated sulphuric acid and catalyst, and, if necessary, pretreatment with hydriodic acid and red phosphorus, are followed by steam-distillation into a dilute acid solution. The final determination depends on the reaction of ammonia, in a suitably buffered solution, with sodium hypobromite reagent, and measurement of the excess reagent by titration of the iodine liberated by it from acidified potassium iodide, with a standard $\text{N}\text{500}$ sodium thiosulphate solution, using sodium starch glycollate indicator.Since sample size is relatively unrestricted and the final titration can measure 5 micrograms of nitrogen, the sensitivity of the method is very high.Reference is made to existing sub-micro methodes which, although sensitive, are time-consuming and specific in application.     

Evaluation of the Deacetylation Degree of Chitosan with Two‐Abrupt‐Change Coulometric Titration

The two‐abrupt‐change coulometric titration was proposed for the analysis of the degree of deacetylation of chitosan. The potential was indicated by an antimony electrode which could sensitively response to the variation of activity of hydrogen ion in the turbid and viscous chitosan solution. Through this new approach, the deficiency of combination pH glass electrode in that medium is successfully overcome. The degree of deacetylation of chitosan was obtained by the difference of electrolysis time between two inflection points in the electrolysis process. The measurement error, which is caused by the residual acid or alkali in the chitosan, could be eliminated. The degree of deacetylation of four chitosan samples were investigated by this new method, which found to be consist with those determined by proton nuclear magnetic resonance (¹H NMR). The standard deviations were found to be lower than 0.60 % and the whole experimental process can be completed within 15 min. With merit of simplicity, convenience, quickness, accuracy, the proposed new method would possess extensive practicability in scientific research and industrial production.     

零流电位法在酸碱滴定中的应用研究

探讨了零流电位法在酸碱滴定中的检测原理及应用,通过考察强碱滴定弱酸、强碱滴定强酸、强酸滴定弱碱以及强酸滴定强碱四种滴定体系,探明了零流电位法在酸碱滴定中的适用性。通过氢氧化钠滴定醋酸对本方法进行评价,实验结果表明:本法的相对误差为-0.4%,同一根电极的滴定值的相对标准偏差(RSD)为0.4%(n=5),同一根电极五天滴定值的RSD为0.6%,五根电极滴定值的RSD为0.5%。本方法具有较高的准确性、稳定性和重现性。     

The detection of formaldehyde in textiles using interdigitated microelectrode array diffusion layer titration with electrogenerated hypobromite

An interdigitated microelectrode array (IDA) was applied to the determination of formaldehyde released from textiles produced in industry. The proposed method is based on formaldehyde reaction with hypobromite which is formed in weakly basic media by control current electrooxidation of bromide on the generator segment of the IDA array. The unreacted hypobromite diffuses through the gap between individually polarisable IDA segments and it is amperometrically detected on the collector segment of the IDA. The efficiency of this nonconvective transfer process in the absence of formaldehyde was substantially higher (78%) in comparison with that when using the rotating ring disc electrode. The influence of the added formaldehyde on the transfer process can be utilised to develop a simple and sensitive analytical procedure for formaldehyde detection with a detection limit of 4×10⁻⁶ mol dm⁻³.