On the reduction of oxygen in aqueous solution by electrolytically precipitated cadmium

The reduction of oxygen in aqueous solution by electrolytically precipitated cadmium, used in a reductor column, has been studied in two ways. First, by analysis of the effluent for the hydrogen peroxide formed as a reaction intermediate, the conditions for quantitative reduction have been found. Attention is called to the fact that an effluent free from hydrogen peroxide also implies quantitative reduction of all dissolved oxygen. The practical consequences are pointed out. A comparison is also made with some other reductors. Secondly, the oxidation of electrolytically precipitated cadmium by hydrogen ion is strongly inhibited, so at pH 7 it is possible to determine oxygen as the equivalent amount of cadmium ion produced in the reductor column. The conditions of quantitative reduction of oxygen are determined and found to be in agreement with those obtained by the first method. From the results the solubility of oxygen in water in equilibrium with air is estimated and found to agree with a published result considered as reliable. An outline is given of a method for determination of oxygen in aqueous solution by measurement of the amount of cadmium ions produced.     

Re-Examination of the Cadmium Reduction Method and Optimisation of Conditions for the Determination of Nitrate by Flow Injection Analysis

The present paper re-examines the widely used flow injection method for nitrate which is based on heterogeneous reduction of nitrate with copperized cadmium followed by spectrophotometric detection of nitrite formed. The thorough investigation presented here has shown that the reduction step is very critical as far as conversion rate, possible further reduction of nitrite and long-term stability of the reductor column is concerned. The reasons for inconsistent and irreproducible results mentioned in original papers and often obtained in routine applications could be traced back to the way the reductor material had been prepared, the chemical conditions under which reduction takes place (i.e. pH and concentration of complexing agents) and the poisoning of the cadmium surface by sample constituents. The concomitant reduction of dissolved oxygen has been identified as a potential problem causing loss of pH control (due to in-situ generation of hydroxide). De-oxygenation of the carrier solution was found to be a means to overcome this problem with the additional advantages of increasing the lifetime of the reductor column and significantly reducing the concentration of cadmium ions in the waste stream. The role of particle size and column dimension as well as sample residence time within the reductor column on reduction efficiency and sample dispersion has also been investigated.     

Determination of thallium(III) by use of a mercury reductor

A convenient method has been developed for the determination of thallium(III) by using a mercury reductor. Thallium(III) is reduced to thallium(I) in 0.5–4N hydrochloric or sulphuric acid medium and the determination is completed by oxidative titration with potassium bromate. The method is extended to analysis of thallium(III)-thallium(I) and thallium(III)-iron(III) mixtures.     

Redox reactions on columns

In a study of redox reactions on columns, the work of Cerrai and Testa has been extended. It has been shown that insolubility of the redox compound is the most important factor and that adsorptive forces play little or no part. A useful redox column method for the determination of iron and vanadium, which compares favourably with that using a Jones reductor column, has been developed. The redox potentials of several substituted hydroquinones have been measured.     

还原剂与鲁米诺化学发光反应的研究(Ⅱ)——钒(Ⅱ)-鲁米诺化学发光反应

Fe(Ⅱ)和Ti(Ⅲ)与鲁米诺的化学发光反应已有报道,我们发现,Cr(Ⅱ)、Mo(Ⅲ)、W(Ⅲ)、U(Ⅲ)、CN^-、SO₃^2-、抗坏血酸等一大类还原剂均可与鲁米诺溶液作用产生化学发光,本文利用Jones还原柱产生V(Ⅱ),首次研究了V(Ⅱ)与鲁米诺的化学发光反应,在此基础上建立了钒的流动注射化学发光分析法,方法的检出限是8×10^-11g/mL钒,线性范围是4×10^-10～1×10^-5g/mL钒。测定的相对标准偏差小于2％,考察了20余种常见离子对测定的干扰情况,方法已用于水样中痕量钒的测定,初步探讨了发光反应的机理。     

A simple simultaneous flow injection method based on phosphomolybdenum chemistry for nitrate and nitrite determinations in water and fish samples

A direct spectrophotometric flow injection method for the simultaneous determination of nitrite and nitrate has been developed. The method is based on the oxidation of a phosphomolybdenum blue complex by the addition of nitrite and the decrease in absorbance of the blue complex is monitored at 820 nm. The injected sample is split into two segments. One of the streams was directly reacted with the above reagent and detected as nitrite. The other stream was passed through a copperised cadmium reductor column where reduction of nitrate to nitrite occurs, and the sample was then mixed with the reagent and passed through the cell of the spectrophotometer to be detected as nitrite plus nitrate. The conditions for the flow injection manifold parameters were optimised by experimental design and the concentration of nitrite and nitrate was determined in the linear range from 0.05 to 1.15 mug ml(-1) nitrite and 0.06 to 1.6 mug ml(-1) nitrate with a detection limit of 0.01 mug ml(-1) for nitrite and 0.025 mug ml(-1) for nitrate. The method is suitable for the simultaneous determination of nitrite and nitrate in fish and water samples with a sampling rate of 25+/-2 sample per hour.     

Indirect spectrophotometric determination of silicate

An indirect spectrophotometric method has been developed for trace determination of silicate in aqueous samples. The silicate is converted into silicomolybdic acid and extracted into a mixture of 1-butanol and butyl acetate. The silicomolybdic acid is then decomposed with sodium hydroxide and the molybdenum(VI) reduced to molybdenum(III) with a Jones reductor, followed by reoxidation to molybdenum(VI) with iron(III). The resulting iron(II) is complexed with ferrozine, and the absorbance of the complex measured at 562 run. In this manner, submicroamounts of silicate can be determined.     

Ion exchange separations in the analysis of bismuth base alloys : Binary alloys with uranium and thorium

Procedures are described for the determination of uranium (0.001–10%) and thorium (0.05–10%) in binary mixtures with bismuth. A preliminary separation of the bismuth is effected by the passage of a hydrochloric acid solution of the sample through a column of Deacidite FF For thorium contents greater than 1%, the determination is completed volumetrically with EDTA using pyrocatechol violet as indicator, smaller amounts are determined absorptiometrically with thoronol Similarly the higher uranium contents are determined volumetrically after reduction to the tetravalent state with a lead reductor, and an absorptiometric method based on the coloured complex formed by tetravalent uranium with thoronol is used for the smaller amounts.     

Flow-injection determination of nitrite and nitrate with biamperometric detection at two platinum wire electrodes

The flow-injection determination of nitrite is based on oxidation of iodide by nitrite. The triiodide formed is detected amperometrically in a flow-through cell with two teflonized graphite or platinum wire electrodes polarized with a voltage of 100 mV. More sensitive and faster response was observed with the platinum wire electrodes. The same detector is used for determination of nitrate after reduction to nitrite in a reductor column containing copperized cadmium. Detection limits under optimized conditions are 6 μg l^?1 for both nitrite- and nitrate-nitrogen. Effects of oxygen and interfering metal ions are discussed.     

Determination of traces of nitrite and nitrate in water by solid phase spectrophotometry

A simple and sensitive method for the determination of nitrite and nitrate in water using solid phase spectrophotometry is described. The method utilizes the quantitative and rapid sorption of the dye formed from nitrite, using the Griess reaction, into a thin layer of polyurethane foam (PUF) where a preconcentration factor of >140 has been achieved. Nitrate is pre-reduced using a cadmium reductor before applying the Griess reaction. The direct spectrophotometric measurement of the dye enriched in the solid foam phase has allowed the detection of as little as 5 and 40 ng ml⁻¹ nitrite and nitrate, respectively. Optimization of the parameters affecting the quantitative formation and sorption of the dye into PUF has been considered. Analysis of natural water samples has been performed.     

On the optimum conditions for the reduction of nitrate to nitrite by cadmium

The variables of direct importance in the reduction of nitrate to nitrite by a metallic reductant such as cadmium used in a reductor column are discussed with special reference to the determination of nitrate as nitrite in very dilute solutions, e.g., natural waters. As a result of these considerations the effect of flow-rate (expressed as bed-volumes min ), pH, temperature, chloride concentration and various types of reductor cadmium on the yield of nitrite is investigated. The effect of dissolved oxygen in the sample solution on pH and cadmium concentration in the reduced solution is demonstrated. At constant pH a maximum yield of nitrite is obtained at a certain flow-rate, which is explained as the result of a rapid formation and simultaneously proceeding slow reduction of nitrite. With increasing pH this maximum is shifted to lower flow-rates, and grows broader whilst the yield at maximum approaches 100%; at pH 9.5 a yield of 99.9 +/- 0.1% is obtained. The temperature has little effect on the reduction rate in the interval 20-30 degrees but at 10 degrees the reduction is noticeably slower. Chloride ions have a strongly retarding effect on the reduction rate but the yield at maximum is not affected. Electrolytically precipitated cadmium, filings of pure cadmium or amalgamated pure cadmium all give practically the same yield at maximum though some differences in reduction rate are observed. Impure cadmium or copper-cadmium and silver-cadmium, owing to the formation of galvanic cells with higher reducing power, give a high reduction rate, which also applies to nitrite, causing a poorer yield at maximum. The practical consequences of the results are thoroughly discussed.     

The formation of hydrogen peroxide in metallic reductors

The formation of hydrogen peroxide in various types of metallic reductors both in the presence and absence of oxygen has been studied. Only when oxygen is rigorously excluded is peroxide undetectable. The oxidimetric determination of iron is seriously affected by this peroxide when the test solution and reductor are open to atmospheric oxygen. Systems which are completely oxygen-free give satisfactory results.     

Comparative study of various methods of the heterogeneous reduction of nitrate ions

Working pH ranges of heterogeneous reductors of nitrate ions based on metallic cadmium, zinc, and brass as well as on cadmium-copper, cadmium-mercury, zinc-copper, and zinc-mercury galvanic couples were examined. Metallic cadmium and the cadmium-copper couple were selected as reductants; freshly prepared, these reductants provided the 100% reduction of nitrate ions to nitrite ions in the pH range from 3.4 to 9.5. A method was developed for prolonging the reducing properties of reductants based on metallic cadmium by permanently copper-plating these reductants. The relationship between the degree of reduction of nitrate ions in a cadmium reductor and the concentration of Cd²⁺ ions in the solution at the outlet of the reductor was determined.     

Flow injection chemiluminescent method for the successive determination of l-cysteine and l-cystine using photogenerated tris(2,2'-bipyridyl) ruthenium (III)

Flow injection configurations were developed for the individual determination of l-cysteine and l-cystine and for the mixture of both analytes. The method is based on the reaction of l-cysteine with tris(2,2'-bipyridyl) ruthenium (II) and peroxydisulphate under UV irradiation to produce chemiluminescence. Cystine is determined after reduction to cysteine in a copper-coated cadmium reductor mini-column in the flow system. The inclusion of a selection valve in the configuration allows the successive determination of the two analytes. Calibration was linear between 2x10(-6) and 5x10(-4) moll(-1) for cysteine and between 1x10(-6) and 2x10(-4) moll(-1) for cystine. When applied to pharmaceutical formulations, the procedure was free from interferences from common excipients. The results obtained for the assay of commercial formulations compared well with those obtained by an official method and demonstrated good accuracy and precision.     

Amperometric detection of nitrite and nitrate at tetraruthenated porphyrin-modified electrodes in a continuous-flow assembly

The modification of a glassy carbon surface by coating with an electrostatically assembled film of tetraruthenated cobalt porphyrin/(meso-tetra(4-sulphonatephenyl)porphyrinate zinc(II) yields an indicator electrode that allows the determination of nitrite to be performed with a limit of detection of 0.1 μM in a flow injection configuration. The dynamic range extends up to 1000 μM and the repeatability of the measurements was evaluated to be 1.5% with a throughput of 50 samples per hour. The efficiency of the bilayered film to mediate the electron transfer allows the determinations to be performed at a less positive potential (+0.75 V) with enhanced sensitivity. The coating also prevents the surface poisoning and its stability is maintained over several weeks. The same detector was used for determination of nitrate after reduction to nitrite in a reductor column containing copperised cadmium. This method was used for the determination of nitrate and nitrite in mineral water, saliva and cured meats, the results being in agreement with certified values and those obtained by using recommended procedures.     

光泽精与钨（Ⅲ）的流动注射－胶束增敏化学发光反应

采用了Jones柱在线还原钨（Ⅵ）为钨（Ⅲ），详细研究了钨（Ⅲ）与光泽精的化学发光反应，加入乳化剂OP能明显提高发光的信噪比，基于此建立了痕量钨的流动注射化学发光分析法。该法线性范围为1×10－6～1×10－2 g·L－1, 检出限为5×10－7 g·L－1 , 相对标准偏差为2.0％（5×10－5 g·L－1, n=11）。文中还探讨了反应机理。     

Ion exchange separation in the analysis of bismuth base alloys : Part II. Ternary alloys containing uranium and thorium

Procedures are described for the analysis of bismuth base alloys containing uranium and thorium in the range from 0.1 to 10%. The thorium is first separated by the passage of a solution of the sample in 5M hydrochloric acid through a column of Deacidite FF in the chloride form. For thorium contents greater than about 1%, the determination is completed volumetrically with EDTA using pyrocatechol violet as the indicator. Smaller amounts are determined absorptiometrically by the thoronol method. Uranium is recovered from the ion-exchange column in a quantity of 0.2M hydrochloric acid, bismuth still being retained by the column under these conditions. Uranium contents greater than about 1% are determined volumetrically after reduction to the tetravalent state with a lead reductor, whilst smaller amounts are determined polarographically using a tartrate base solution.     

Determination of uranium using a flow system with reagent injection. Application to the determination of uranium in ore leachates

The determination of uranium by a flow system with reagent injection is based on the reaction of U(IV) with Arsenazo III in 3.6 M HCl; U(IV) is generated by reduction of uranyl ion in a lead reductor minicolumn installed in the sample channel of the manifold. The interference effect caused by several ions is studied. The calibration graph is linear up to 1.0 × 10^?5 M (2.4 mg l^?1) and the detection limit is 2.8 × 10^?8 M (6.6 μg l^?1). The modification of the manifold by including a second valve to by-pass the reducing column allows the measurement of the difference in peak heights, which makes the method specific for uranium.     

Simple flow-injection system for the simultaneous determination of nitrite and nitrate in water samples

A novel spectrophotometric reaction system was developed for the determination of nitrite as well as nitrate in water samples, and was applied to a flow-injection analysis (FIA). The spectrophotometric flow-injection system coupled with a copperised cadmium reductor column was proposed. The detection was based on the nitrosation reaction between nitrite ion and phloroglucinol (1,3,5-trihydroxybenzene), a commercially available phenolic compound. Sample injected into a carrier stream was split into two streams at the Y-shaped connector. One of the streams merged directly and reacted with the reagent stream: nitrite ion in the samples was detected. The other stream was passed through the copperised cadmium reductor column, where the reduction of nitrate to nitrite occurred, and the sample zone was then mixed with the reagent stream and passed through the detector: the sum of nitrate and nitrite was detected. The optimised conditions allow a linear calibration range of 0.03–0.30 μg NO₂⁻-N ml⁻¹ and 0.10–1.00 μg NO₃⁻-N ml⁻¹. The detection limits for nitrite and nitrate, defined as three times the standard deviation of measured blanks are 2.9 ng NO₂⁻-N ml⁻¹ and 2.3 ng NO₃⁻-N ml⁻¹, respectively. Up to 20 samples can be analyzed per hour with a relative standard deviation of less than 1.5%. The proposed method could be applied successfully to the simultaneous determination of nitrite and nitrate in water samples.     

Rapid method for total iron determination in iron ores, sinter and related materials without use of mercury compounds

A rapid method for determining total iron in iron ores, sinter and related materials without use of mercury compounds is described. Fusion of the sample with sodium peroxide in a zirconium crucible and subsequent treatment with acid yields total decomposition and a solution amenable to direct reduction to ferrous iron with a silver reductor and subsequent titration with dichromate. Results for NBS, BCS and ISO reference standard ores demonstrate the universal applicability of the method both for routine and referee analysis. There is no interference from vanadium and two samples can be analysed in 30 min.