18-Crown-6-potassium Ferricyanide Complex as a Potentiometric Titrant

Abstract

An oxidimetric titrant, 18-Crown-6-potassium ferricyanide complex, has been prepared in acetonitrile. This reagent is proposed for redox titrations in aqueous - acetonitrile media of some reductant compounds. The general analytical conditions for using this complex and the procedures for potentiometric determinations of oxalate, arsenic (III), thiocyanate, nitrite, sulfite, thiosulphate and iodide ions, as well as hydrazine sulphate and hydrogen peroxide are presented.     

The titrimetric determination of sulphate,thiosulphate and polythionates in mining effluents

A titrimetric procedure is described for the determination of various forms of sulphur (sulphate, sulphite, thiosulphate, dithionate, tri- and tetrathionates after conversion to sulphate) in mining effluents. Metal ions are removed, after an oxidizing step, by a cationexchange resin, and the sulphate is precipitated with a known excess of 0.01 M barium chloride at pH 3.5. The excess of barium is back-titrated with standard 0.01 M ethylenediaminetetraacetic acid (EDTA) solution to a o-cresolphthalein complexone end-point at pH 11.0. The results obtained are in good agreement with those obtained by lengthy gravimetric procedures. Indirectly, dithionate can be determined, and sulphate and oxidizable thio salts such as thiosulphate and di-, tri-, and tetrathionates can be distinguished.     

Oxidation of selenite by alkaline ferricyanide using osmium tetroxide as a catalyst

Summary Oxidation of selenite to selenate by alkaline ferricyanide catalysed by osmium tetroxide was followed by direct and indirect procedures. Either the ferrocyanide was titrated with selenite solution at 8–10% overall alkalinity or vice versa using amperometric or potentiometric end point. In the indirect procedure the excess ferricyanide was determined by amperometric titration with arsenious oxide at 10–15% alkalinity, and the ferrocyanide with ceric sulphate using o-phenanthroline or amperometric indicator. A cerimetric determination of ferricyanide based on this reaction is described.Sincere thanks of the authors are due to Dr. S. S. Joshi, D. Sc. (London), for kind interest in the work.     

Determination of thiosulphate in the presence of dithionite and sulphite

To determine thiosulphate in the presence of dithionite and sulphite, iodine dissolved in potassium bromide solution is used to oxidize thiosulphate to tetrathionate, and dithionite and sulphite to sulphate. The tetrathionate generated from the thiosulphate is then oxidized with potassium bromate-potassium bromide solution in the presence of hydrochloric acid. The bromine consumption of the tetrathionate is measured by titration of the excess of bromine with sodium thiosulphate after the addition of potassium iodide. For each equivalent of iodine used to determine thiosulphate by the Wollak method, fourteen equivalents of bromine are used to determine thiosulphate by this method.     

Gradient chromatographic elution of sulphur anions

The distribution coefficient of sulphide, sulphite, sulphate and thiosulphate anions between different concentrations of aqueous alkali metal chloride solutions and the anion exchanger Dowex 1X8 is studied. The obtained distribution deportment of these anions is explained in the light of water-water, anion-cation and ion-ion interactions as well as the different tendencies of the alkali ions to hydration. Based on the separation factors encountered between adjacent anions, a chromatographic method is adopted for isolation of the sulphur anions by gradient elution. This method is further compared with the chromatographic procedures so far reported for separation of the investigated anions.     

New iodometric methods for the microdetermination of arsenic in organic compounds

New methods are described for the iodometric microdetermination of arsenic in organic compounds after wet digestion or oxygen flask combustion. After evaporation of the arsenic solution to dryness and dissolution of the residue in water, acetone is added and the solution is treated with iodide-iodate and the iodine liberated (by the interfering acids and the first dissociation step of arsenic acid) is reduced with thiosulphate. The KH(2)AsO(4) left is then reacted with zinc sulphate in presence of excess of KI and KIO(3). Acetone is added and the liberated iodine is titrated with thiosulphate. This titration corresponds to the second and third dissociation steps of arsenic acid and is used to calculate the arsenic content of the compound. When arsenicals not containing sulphur are decomposed by the oxygen flask method, the arsenic acid solution obtained is reacted directly with zinc sulphate in presence of KI and KIO(3) and the iodine released is titrated with thiosulphate. In this case, the titration corresponds to all three dissociation steps of arsenic acid. The average recoveries obtained by the two methods are 99.5 and 99.9%, respectively.     

Vanadametry Estimation of Thiosulphate

1.(a) We have found that sodium thiosulphate is quantitatively oxidized to tetrathionate in five minutes at room temperature (28°) by excess sodium vanadate in a medium containing sulphuric acid at 0.06N to 0.1N concentration and a little copper sulphate as catalyst. (b) Quantitative emulation of sodium thiosulphate to tetrathionate has also been achieved by the action of excess sodium vanadate during five minutes at room temperature in a medium containing 2.0N—8.0N acetic acid and a little copper salt as catalyst. Further oxidation to sulphate does not occur, even if the mixture is heated to boiling. (c) The excess of unreacted vanadate in 1(a) and 1(b) can be titrated with a standard solution of ferrous ammonium sulphate using diphenylbenzidine as indicator, after adding the requisite quantity of syrupy phosphoric acid. 2. On the other hand, sodium thiosulphate is easily and quantitatively oxidized to sulphate at room temperature, when. acted upon by excess sodium vanadate in a medium containing hydrochloric acid at an overall concentration of 5-6N and 1.0 ml of iodine monochloride as catalyst. The time required for reaction is ten minutes. The unreacted vanadate can be estimated by titration with a standard solution of ferrous ammonium sulphate, using N-phenylanthranilic acid as indicator or with diphenylbenzidine as indicator after suitably diluting and adding phosphoric acid.     

The Use of μ-Oxo-ditrifluoroacetato-diphenyl-diiodine in Potentiometric Titrations

Abstract

The use of μ-oxo-ditrifluoroacetato-diphenyl-diiodine (μ-ODDD) in potentiometric titrations has been studied. This reagent is more powerful oxidizing agent and more stable than bis(trifluoroacetoxy) iodobenzene (BTIB). The general analytical conditions for using this oxidant and the procedures for potentiometric determinations of sulfite, thiosulphate, nitrite, selenocyanate, thiocyanate and iron(II)ions as well as hydrogen peroxide and hydrazine sulphate are described.

A simultaneous determination of hydrazine sulphate and nitrite ions and also of selôenocyanate and thiocyanate ions has been carried out.     

A systematic scheme for the analysis of common anions using the Weisz ring oven technique

Summary A systematic scheme for the identification of the common anions: sulphate, sulphite, nitrate, nitrite, fluoride, chloride, bromide, iodide, ferricyanide, ferrocyanide, thiocyanate, phosphate, sulphide, thiosulphate and borate in a mixture by the ring oven technique has been described.

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Zusammenfassung Ein systematischer Analysengang zum Nachweis folgender Anionen mit Hilfe des Ringofens wurde beschrieben: Sulfat, Sulfit, Nitrat, Nitrit, Fluorid, Chlorid, Bromid, Jodid, Cyanoferrat(III), Cyanoferrat (II), Rhodanid, Phosphat, Sulfid, Thiosulfat und Borat.

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Résumé On a décrit un plan d'identification systématique des anions usuels dans leurs mélanges: sulfate, sulfite, nitrate, nitrite, fluorure, chlorure, bromure, iodure, ferricyanure, ferrocyanure, thiocyanate, phosphate, sulfure, thiosulfate et borate, au moyen de la technique du four annulaire.

     

Oxidation of sulphide minerals-III determination of sulphate and thiosulphate in oxidised sulphide minerals

A method has been developed to determine sulphate and thiosulphate in small amounts of the oxidation products of sulphide minerals. The sample is treated with ammonium sulphide solution to promote ion-exchange between sulphide ion and the sulphur-bearing anions of the oxidation products. Sulphate is determined alone and then all other sulphoxy anions are oxidized to sulphate and determined as such. The non-sulphate anions are reported as thiosulphate. The relative error is about 10% or less for 2 mg or more of sulphoxy anion. Although this method does not yield exact results with respect to sulphite or polythionates, a clearer understanding of the oxidation of sulphide minerals is now available.     

Indirect determination of traces of thiosulphate by differential-pulse polarography

Two methods are reported for the indirect determination of thiosulphate down to ca. 0.02 microg/ml by differential-pulse polarography. Both methods involve prior oxidation of thiosulphate with iodine, either in acidic medium to tetrathionate or in alkaline medium to sulphate, whereby ultimately one and eight equivalents of iodate are obtained, respectively. The concentration of iodate in the resulting solution is then measured by differential-pulse polarography under optimum conditions. The average recovery for each method amounted to 100.1%, and the relative standard deviations were 1.3 and 1.4% for the two methods.     

The reduction of ferricyanides and a sensitive test for the detection of hydrogen peroxide

Yellow zinc ferricyanide is reduced by heating to white zinc ferrocyanide by hydrogen peroxide in the presence of zinc sulphate and sodium, acetate. Copper ferricyanide, however, is reduced to brown copper ferrocyanide at room temperature, by means of hydrogen peroxide in the presence of copper sulphate and sodium acetate. The latter reaction can be applied for the detection of extremely small quantities of hydrogen peroxide both in a test tube (2.5 γ in 1 ml) and as a spot test (0.5 to 1 γ).     

Molecular emission cavity analysis—a new flame analytical technique: Part V. The determination of some sulphur anions

An investigation of the MECA behaviour of sulphate, sulphite, metabisulphite, peroxodisulphate, thiocyanate, thiosulphate and sulphide ions, has shown that ng amounts of these anions may be determined in samples of a few μl. Metal ion interferences in the determination of sulphate and sulphite are removed by addition of phosphoric acid.     

Separation of oxyanions of sulphur by single-column ion-chromatography

After stabilization of sulphite by addition of a five-fold excess of formaldehyde, mixtures of sulphite, sulphate and thiosulphate are readily separated by HPLC. For use with Vydac columns (302IC or 300IC) a suitable eluent is 1-3mM phthalic acid (pH 5-6), and the eluted ions may be detected by means of the change in refractive index or the absorbance at 290 nm. With a flow-rate of 2 ml/min, anion elution times are about 2.7 (0.7) min for HOCH(2)SO(-)(3), 7.5 (2.6) min for SO(2-)(4) and 8.4 (5.2) min for S(2)O(2-)(3), the values in parentheses being those for the shorter 300IC column. Detection limits for sulphite and sulphate were around 1 mg/l., with relative standard deviations of 2-3% at higher levels. The sensitivity for S(2)O(2-)(3) was an order of magnitude lower. The proposed method has advantages over earlier procedures based on alkaline eluents.     

Volumetric studies in oxidation-reduction reactions: Reduction with ferrous ethylenediamine sulphate indirect determinations

Ferrous ethylenediamine sulphate has been. used as a reducing agent in acid medium for the indirect volumetric estimations of potassium chlorate, potassium bromate, potassium metaperiodate, potassium, dichromate, potassium ferricyanide, potassium permanganate, potassium persulphate, hydrogen peroxide and ceric sulphate. The excess of ferrous ethylenediamine sulphate added to each of the substances was titrated with standard potassium permanganate and also with. standard potassium dichromate solution. In case of potassium bromate or potassium metaperiodate the end-point was not sharp in potassium dichromate titrations; while accurate volumetric observations were made with standard potassium permanganate solution.     

Ion-Exchange Chromatographic Separation of Anions on Hydrated Bismuth Oxide Impregnated Papers

Abstract

A comparative study of the chromatographic behaviour of anions, iodide, sulphide, phosphate, arsenate, arsenite, vanadate, chroraate, dichromate, thiosulphate, thiocyanate, ferricyanide and ferrocyanide on papers impregnated with hydrated bismuth oxide and untreated Whatman no, 1 papers has been made by employing identical aqueous, non-aqueous and mixed solvent systems. Sharp and compact spots were obtained with impregnated papers whereas the opposite applied to plain papers. Various analytically important binary and ternary separations are reported.     

Titrimetric determination of thiocyanate and thiosulphate ions by oxidation with iodine in alkaline solution

Thiocyanate (2.7-90 mug) and thiosulphate (4.5-90 mug) ions are oxidized by iodine in alkaline media to sulphate ions. After acidification, the excess of iodine is extracted into chloroform, and the iodide ions formed in the redox reaction subjected to an amplification reaction. Either a titrimetric or a spectrophotometric finish may be used. Each thiocyanate and thiosulphate ion results in the ultimate production of 19 and 24 iodine molecules, respectively.     

Volumetric studies in oxidation-reduction reactions: Reduction with ferrous ethylenediamine sulphate ceric sulphate method

Ferrous ethylenediamine sulphate has been used as a reducing agent in acid medium for the indirect volumetric estimations of potassium chlorate, potassium bromate, potassium metaperiodate, potassium dichromate, potassium ferricyanide, potassium permanganate, potassium persulphate, hydrogen peroxide and ceric sulphate. The excess of ferrous ethylenediamine sulphate added to each of the substances in acid medium was titrated with standard ceric sulphate solution using ferroin as an indicator.     

Study of acid and reductant functions of hydrazine sulphate by iodate-iodide mixture

Summary Hydrazine sulphate was found to liberate two atoms of iodine per molecule, when treated with an excess of iodate and iodide, and this was determined by thiosulphate or arsenious oxide in borax-boric acid buffer. The study of the action of iodate-iodide mixture on hydrazine sulphate at different stages of neutralisation and decomposition was carried out and iodometric relationships were verified. An interesting titration involving hydrazine sulphate both as a titrant and the titrating solution following its different reactions towards iodate-iodide mixture and iodine, is described. Hydrazine sulphate is found to be a satisfactory standard for the titration of iodine in presence of an alkaline buffer.Sincere thanks of the authors are due to Dr. S. S. Joshi, D. Sc. (London), for kind interest in the work.     

Direct titration of potassium ferricyanide with hydrazine sulphate in presence of zinc sulphate determination of hydrazine

Operative conditions for direct titration of potassium ferricyanide solution with a solution of hydrazine sulphate which contains zinc sulphate are described. The results are comparable with those obtained by the standard iodate procedure. The chief advantages of the present method of estimating hydrazine are (1) titration in slightly acidic medium and (2) no indicator is required. Determination of substituted hydrazines, hydroxylamine and other reducing substances on similar lines is suggested.