Perbenzoic acid as volumetric reagent

Summary Perbenzoic acid (0.05 M) chloroform solution is used as volumetric reagent for the determination of potassium ferrocyanide, arsenious oxide, tartar emetic, sodium sulphite, stannous chloride, hydrazine sulphate and sodium thiosulphate atph 4.0 to 4.5 in sodium acetate and acetic acid buffer solutions, using iodine as catalyst and preoxidiser. Appearance of faint violet colour in chloroform layer indicates the end point in visual titrations. In potentiometric titrations bright platinum foil is used as an oxidation-reduction electrode and it is coupled with saturated calomel electrode. At the equivalence point there is a sharp jump in potential in each titration.     

Studies in bivalent chromium salts

Summary It has been shown that methylene blue, indigo carmine, neutral red, methyl red and phenosafranine serve as excellent internal indicators for the titration of ferric solution against chromous sulphate. It has been further demonstrated that in the presence of a large concentration of hydrochloric acid cupric salts are reduced quantitatively to the cuprous state. The latter titration can also be carried out with the help of visual indicators. The strengths of the chromous solutions calculated from titrations with ferric and cupric salts are in agreement within experimental error (±0.5%).The authors' thanks are due to Dr. R. N. Singh, Professor of Chemistry, B. R. College, Agra, for providing laboratory facility and encouragement.     

A new volumetric method for the determination of molybdenum(VI)

Summary A new volumetric method has been developed for the determination of molybdenum(VI). The method consists in the reduction of molybdenum(VI) by heating with a slight excess of hydrazine sulphate in 1 to 2 M hydrochloric acid medium for ten minutes on a water bath. The mixture is cooled and the molybdenum(V) obtained determined by titration with a standard solution of ceric sulphate at an overall acidity of 4 N hydrochloric acid, using diphenyl benzidine as indicator and adding 5 ml of syrupy phosphoric acid for 50 ml of the mixture. Alternately the molybdenum(V) can be titrated with a standard solution of ceric sulphate at an overall acidity of 3 N hydrochloric acid using ferroin as indicator and adding 5 ml of syrupy phosphoric acid for 50 ml of the titration mixture. The molybdenum(V) can also be titrated with a standard solution of sodium vanadate in 8 N sulphuric acid medium, using N-phenyl anthranilic acid as indicator. Alternately, the titration with sodium vanadate can be made with diphenyl benzidine as indicator in 4 N acid medium, adding 5 ml of syrupy phosphoric acid and 1 ml of 1.0 M oxalic acid to catalyse the indicator action. The method now proposed is much more convenient than the methods currently available. It is simple because it does not require any costly chemicals or complicated apparatus. Furthermore, it has the advantages of great rapidity and excellent precision.     

Quinquevalent tungsten as a reducing agent in potentiometric titrations

Qmnquevalcnt tungsten prepared by the electrolytic reduction of tungstate in ION HC1 is sufficiently stable when kept in strong acid solutions under COg to be used as an effective reducing agent in potcntiometric titrations. It can be accurately standardised with dichromate. The formal redox potentials of the $\text{W}{}^{\mathrm{+6}}\text{W}{}^{\mathrm{+5}}$ system as determined at different acidities indicate that quinquevalent tungsten is more reducing than the corresponding molybdenum compound.Quinquevalent tungsten can be applied successfully as a volumetric reagent in the potentiometric titration of ferric iron in 8-ioN HC1 or in a mixture of HCl and H3PO4 0.5.N each and of cupric copper in 8N HCl at 80° C. It can also be applied for the estimation of iodate, provided that the latter is used as the titrant.     

Use of brucine as an oxidation-reduction indicator in cerimetry

Summary Brucine has been found to work satisfactorily as an inside indicator in the titration of molybdenum(V) and hydroquinone with ceric sulphate. It does not give a good indication of the end point in the titration of arsenic(III) in sulphuric acid medium, using osmium tetroxide as a catalyst or in hydrochloric acid medium using iodine monochloride as a catalyst. Brucine cannot also be used in the titration or uranium(IV) with ceric sulphate. A 0.1 per cent solution of brucine in 2 N–3 N acetic acid has been found to be stable for nine months without showing any discoloration.     

Ferrimetric determination of uranium using rhodamine 6G as fluorescent indicator

Experimental conditions have been developed for the titration of uranium^IV with iron^III alum solution, using Rhodamine 6G as a fluorescent indicator. The titration is best carried out at 98–100° in a 2–3N hydrochloric acid medium, under filtered ultraviolet light, using 2.0 ml of 0.05% Rhodamine 6G solution for 30 ml of the titration mixture. A slight excess of iron^III solution quenches the greenish-yellow fluorescence of the dye through inner filter action. With the titration assembly described here, it is possible to determine uranium^IV with an accuracy of about 0.4%. This method appears to be more convenient than the potentiometric titration or the method employing potassium thiocyanate as internal indicator.

Evidence is also presented to show that the reaction between uranium^IV and iron^III is slow at room temperature.     

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.     

Acid-base strengths in 1,2-dichloroethane

The pK_a value of hydriodic acid in 1,2-dichloroethane was determined from conductivity measurements. A glass electrode was calibrated for dichloroethane in the potentiometric titration of hydriodic acid with tetramethylguanidine. From potentiometric titrations, the pK_a values in dichloroethane of hydrobromic acid, hydrochloric acid, picric acid and some sulfonphthaleins as well as some protonated nitrogen bases were determined. In the curves of the titrations of the carboxylic acids and the hydrogen halides with TMG, evidence was found for the formation of the complex B(HX)₂.     

Determination of Na(2)O from sodium aluminate NaAlO(2)

The aim of the work was to find a suitable method and conditions for determining Na(2)O wt.% from NaAlO(2). Problems were encountered while titrating NaAlO(2) with hydrochloric acid. The problematic area was the pH range 4-10 where aluminum precipitates as hydroxides. The different species of the aluminate solution were determined using potentiometric and complexometric titrations. The equivalent point of the potentiometric titration was detected using Gran's plotting method. Precipitation of aluminum hydroxides did not interfere with titrations, because in potentiometric titrations the pH value was over 10 and in complexometric titrations the pH was 4. The results were accurate and determinations were easy to carry out. Sodium was also determined by DCP-AES.     

Mercurimetrische Titrationen von aromatischen Borverbindungen

Summary Direct titrations of the aromatic compounds of boron, containing 1–4 phenyl groups attached to the boron atom, with the solutions of mercuric nitrate and perchlorate are described. The titrations were performed using potentiometric and polarometric techniques. All the compounds, containing more than 1 phenyl group (tetraphenylboron compounds, triphenylboron, diphenylboric acid) react with mercuric ions in two distinct steps. In the first step phenylboric acid and diphenylmercury are formed, whereas in the later course of the titration both these products react with mercuric ions to form the corresponding phenylmercuric salt. Reverse titrations of mercuric ions with the solutions of sodium tetraphenylboron or with phenylboric acid are possible too. The results are presented in the figures and a short discussion follows.

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Der Firma Heyl & Co in Hildesheim und Herrn Dr. Büechl persönlich habe ich für die freundliche Überlassung der Präparate Kalignost und Flavognost herzlichst zu danken.     

Thermometric titration of some molybdates,molybdic acid,and molybdenum trioxide

A thermometric titrator equipped with differential thermistor is used for the titration of molybdenum in sodium molybdate, potassium molybdate, magnesium molybdate, tetramethylammonium molybdate, and tetraethylammonium molybdate, based on their reactions with hydrochloric acid, and in ammonium paramolybdate, molybdic acid, and molybdenum trioxide, based on their reactions with sodium hydroxide. Orthomolybdates and ammonium paramolybdate were determined in the 0.5–0.005 M range; sufficient solid molybdic acid or molybdenum trioxide was taken to give a final 0.01–0.5 M solution in 20 ml of water. The method is simple and very quick. The standard deviation varies from 0.5 to 1.5% depending on the amount of sample taken.     

Back titration with mercuric ntrate in alkaline medium; potentiometric estimation of aluminium and manganese

Summary Mercuric nitrate has been successfully used for back titrating excess EDTA amounts than required for chelation with Al³⁺ or Mn²⁺ ions. This principle was the basis underlying the potentiometric determination of small amounts of both metals in the range of 10 g to 6 mg. End points are attended within 0.01 to 0.02 ml of titrant with fair accuracy and reasonable jumps ranging from 35 to 88 mv per 0.1 ml of titrant.     

自动电位滴定法测定冷轧薄板酸洗液中总酸度

自动电位滴定法测定酸液中总酸度具有简单、快捷、不受其他元素干扰等优点。用硫代硫酸钠掩蔽铁离子,利用自动电位滴定仪测定冷轧薄板酸洗液的总酸度(以盐酸量计)。当电位突变达30mV以上时,仪器自动判定滴定终点。自动电位滴定法测定冷轧薄板酸洗液中总酸度结果与酸碱中和滴定方法具有较好的一致性。相对标准偏差小于0.6%,能够满足生产检验的要求。     

Comparison between amperometric and true potentiometric end-point detection in the determination of water by the Karl Fischer method

A rapid and sensitive method using true potentiometric end-point detection has been developed and compared with the conventional amperometric method for Karl Fischer determination of water. The effect of the sulphur dioxide concentration on the shape of the titration curve is shown. By using kinetic data it was possible to calculate the course of titrations and make comparisons with those found experimentally. The results prove that the main reaction is the slow step, both in the amperometric and the potentiometric method. Results obtained in the standardization of the Karl Fischer reagent showed that the potentiometric method, including titration to a preselected potential, gave a standard deviation of 0.001(1) mg of water per ml, the amperometric method using extrapolation 0.002(4) mg of water per ml and the amperometric titration to a pre-selected diffusion current 0.004(7) mg of water per ml. Theories and results dealing with dilution effects are presented. The time of analysis was 1-1.5 min for the potentiometric and 4-5 min for the amperometric method using extrapolation.     

Trivalent molybdenum as volumetric reducing agent

Summary The purpose of the present investigation is to introduce trivalent molybdenum as a new analytical reducing agent, in hydrochloric as well as sulphuric acid media.The solution is prepared in 9N acid by electrolytic or mercuryreduction of the hexavalent form. It is preferentially stocked and used in high acid concentrations, whereby its stability in air is optimal, falling to half its titer after nearly two months. It has been tested with success as reductant for ceric, dichromate, ferric and vanadate. It has the advantage of being used in ordinary opened burettes. Titrations were followed potentiometrically in general, and alternately visually in decinormal media, whereby molybdenum blue appears at the end-point. The percentage error in fifteen discussed experiments never surpassed ±1%. Some oxidation titrations were also undertaken using iodate and bromate, with the same degree of accuracy, provided they were conducted in 6N acid. In weaker acid concentrations, equilibria were more slowly attained, with a more or less pronounced deviation, due to some oxidisability that necessitates controlled inert atmosphere.     

Stability constants of zinc(II), cadmium(II), and cobalt(II) complexes of trimethylenediamine-<Emphasis Type="Italic">N,N,N′,N′</Emphasis>-tetraacetic acid

Stability constants of Zn²⁺, Cd²⁺, and Co²⁺ complexes of trimethylenediamine-N,N,N′,N′-tetraacetic acid were determined at 298.15 K and ionic strengths of 0.1, 0.5, and 1.0 by potentiometric titration. Potassium nitrate and chloride were used as supporting electrolytes. The results obtained were extrapolated to the zeroth ionic strength using an equation with one individual parameter, and the thermodynamic stability constants of the complexes were calculated. The results are compared with the corresponding data on related compounds.     

Estimation of benzidine by non-aqueous titration

Summary It has been shown that the potentiometric titration of benzidine in propyleneglycol: chloroform (13) with hydrochloric acid in propyleneglycol gives two inflexions for the successive neutralisation of the two amino groups, a phenomenon not observed frequently in the case of weak bases. It has also been demonstrated that benzidine can be estimated in glacial acetic acid/chloroform (13) by visual titration.

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Zusammenfassung Benzidin gibt bei der potentiometrischen Titration in Propylenglykol/ Chloroform (13) mit Salzsäure in Propylenglykol zwei getrennte Potentialsprünge für die beiden Aminogruppen, eine Erscheinung, die bei so schwachen Basen selten ist. Visuell kann Benzidin in Eisessig/Chloroform (13) titriert werden.

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Grateful thanks are due to Prof. M. V. C. Sastri for his constant encouragement during the course of the work.     

Studies in ferrimetry

Summary We have found that ferric alum oxidises hydroxylamine quantitatively and rapidly to nitrous oxide, even at the room temperature, if 1 ml of 5% copper sulphate is used as catalyst per 50 ml of reaction mixture. The resultant ferrous salt can be determined by titration with a standard solution of sodium vanadate.     

Macro and semimicro determination of inorganic bromide by cerium(IV) oxidimetry

Aqueous solutions containing 1-200 mg of inorganic bromide in 25-100 ml of solution are quantitatively analysed at room temperature by direct titration with ammonium hexanitratocerate(IV) in 2M perchloric acid. The titration medium is perchloric acid at a concentration of at least 4M. End-points are determined from potentiometric (Pt vs. S.C.E. electrodes) titration plots, the potential break at the end-point being 300 mV. Iodide up to at least 0.02N and sulphate up to 0.01N do not interfere. Chloride depresses the end-point potential break but a satisfactory titration curve is still obtained in the presence of 0.04N chloride. Standard deviations are +/- 0.068 mg of bromide in the 1- to 20-mg range [0.02M cerium(IV) titrant] and +/- 0.45 mg of bromide in the 20- to 200-mg range [0.1M cerium(IV) titrant].