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

Ferrous ethylenediamine sulphate has been used as a reducing agent to determine indirectly potassium dichromate, hydrogen peroxide, potassium permanganate, potassium persulphate, potassium chlorate, potassium bromate, and ceric sulphate by a potentiometric method. An excess of ferrous ethylenediamine sulphate added to each of the substances in an acid medium is titrated with a standard solution of potassium permanganate, using platinum foil as an oxidation-reduction electrode coupled with a saturated calomel electrode through an agar-agar potassium chloride bridge.     

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.     

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.     

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

Ferrous ethylenediamine sulphate has been used as a reducing agent to determine indirectly potassium permanganate, ceric sulphate, potassium chlorate, hydrogen peroxide, potassium persulphate, potassium dichromate and potassium bromate by a potentiometric method. An excess of ferrous ethylenediamine sulphate added to each of the substances in acid medium was titrated with a standard solution of ceric sulphate, using platinum foil as an oxidation-reduction electrode coupled with a saturated calomel electrode through an agar-agar potassium chloride bridge.     

The determination of small amounts of vanadium in the presence of large amounts of uranium

To eliminate the color interference of large amounts of uranium in the determination of vanadium by the Hamner method, the vanadium was separated prior to titration by the extraction of vanadium cupferrate with chloroform. The chloroform extract was evaporated with sulfuric acid and the excess cupferron removed by oxidation with nitric acid and perchloric acid. The vanadium was reduced with ferrous ammonium, sulfate solution, the excess ferrous ion oxidized with ammonium persulfate, and the vanadium (IV) titrated with 0.02 N potassium permanganate. As little as 1.02 mg of vanadium in the presence of 5 g of uranium oxide was determined accurately by this method.     

Dosage rapide du chrome et du vanadium

The two elements are supposed to be in solution in their maximum value. The total chromium + vanadium content is determined by direct titration in 23̄ 3 N sulphuric acid solution with a ferrous solution in the presence of sulphonated diphenyl amine as an oxydo-reduction indicator. Vanadium is titrated in the same solution after bringing it into its highest valence state by means of a slight excess of permanganate. After the destruction of the excess of oxidizing agent with sodium azide, the titration is completed with the ferrous solution in the presence of the same indicator.     

Sodium hypochlorite as volumetric reagent

Summary In presence of 5 N to 6 N hydrochloric acid, ferrous ethylenediamine sulphate was used as a reducing agent to determine indirectly potassium chlorate, potassium bromate, potassium metaperiodate, potassium dichromate, potassium ferricyanide, potassium permanganate, potassium persulphate, hydrogen peroxide, ceric sulphate and chloramine-T. An excess of ferrous ethylenediamine sulphate added to each of the substances in the acid medium was titrated with a standard solution of sodium hypochlorite. Iodine monochloride was used as catalyst and preoxidizer and chloroform was used as an indicator. Chloroform was coloured violet owing to the liberation of iodine during the titration and became very pale yellow at the end-point because of the formation of iodine monochloride.Part I: See Z. analyt. Chem. 160, 429 (1958).     

Determination of peroxydiphosphate in acid medium with oxalate (i) with silver(I) as catalyst and (ii) in the presence of excess of manganese(II)

Peroxydiphosphate can be determined with oxalate in acid medium in the presence of silver(I). Excess of oxalic acid along with the sample and silver (I) is heated to boiling and the excess of oxalic acid is titrated against standard permanganate. Another method involves boiling for 2 min a mixture consisting of the sample and excess of manganese(II), followed by titration of the resulting Mn(III) or MnO(2) with standard oxalic acid solution.     

Oxidations with potassium permanganate in the presence of fluoride

Summary The titration of ferrous iron in presence of fluoride ions in acid medium gives fleeting end points and erroneous results. A method is deviced to overcome this difficulty by oxidising the ferrous with an excess of KMnO₄ in alkaline medium. After mixing the reactants the excess of KMnO₄ is reduced by an excess of Hg₂ ²⁺ ions in presence of H₂SO₄ and fluoride. The remaining mercurous is then titrated with standard KMnO₄ solution.Part III: Issa, I. M., and M. Hamdy: Z. analyt. Chem. 174, 418 (1960).     

Differential titrimetric determination of mixtures of selenium and tellurium

Methods are described for the differential titrimetric determination at room temperature of mixtures of selenium(IV) and tellurium(IV). The test solution in 0.75-3.5M condensed phosphoric acid medium is oxidized with an excess of permanganate and the unreacted permanganate is titrated with iron(n), with ferroin as indicator, to indicate the total content of selenium and tellurium present. Then 10-20 ml of 10M sulphuric acid, 0.4 ml of 0.1% osmium tetroxide solution and an excess of arsenic(III) are added to the same solution and the unreacted arsenic(III) is titrated with permanganate (ferroin as indicator) to indicate the content of tellurium.     

Benzohydroxamic acid as a reductometric titrant: Determination of thorium

Milligram quantities of thorium can be accurately determined by precipitating it as oxalate, dissolving the precipitate in 11 sulphuric acid and oxidizing the liberated oxalic acid with a known excess of standard permanganate solution above 60 °C in sulphuric acid medium, and finally estimating the excess permanganate by titrating with a standard solution of benzohydroxamic acid either visually or potentiometrically. 10 mg quantities of thorium has been estimated with an error not exceeding 0.12%. The coefficient of variation for 10 estimations is found to be 0.06% and 0.12% for potentiometric and visual methods, resp.     

Colorimetric determination of traces of selenium, tellurium, manganese and cerium

Methods are described for the colorimetric determination of micro- and semi-micro quantities of selenium, tellurium, cerium and manganese. The test solution in 0.35-3M condensed phosphoric acid medium is oxidized with an excess of permanganate. The colour intensity of the unreacted permanganate is measured at 530 nm.     

The determination of organic substances by the oxidation with permanganate: XVIII. The oxidation of malonic acid

The oxidation of malonic acid with permanganate was studied under various acidity conditions. Analytical procedures, based on oxidation with excess reagent in a sodium carbonate medium and titration of the oxalate or manganese dioxide formed or of unconsumed permanganate, are proposed. On the basis of successive oxidation in sodium carbonate and sulfuric acid media, a titration determination, involving complete oxidation of malonic acid to carbon dioxide and water, was developed.     

Volumetric Studies In Oxidation-Reduction Reactions: Oxidation with ceric sulphate ferrous ethylenediamine sulphate method

Ceric sulphate has been used as an oxidizing agent in acid medium for the indirect volumetric determinations of ferrous ammonium sulphate, cuprous chloride, potassium thiocyanate, sodium thiosulpliate, sodiuin nitrite, hydrogen peroxide, sodium oxalate, hydroquinone and pyruvic acid. The excess of ceric sulphate added to each of the substances in acid medium was titrated with standard ferrous ethylenediamine sulphate solution using ferroin as an indicator.     

Oxidation of organic substances with compounds of trivalent manganese: XVII. Coulometric generation of the diphosphate complex of trivalent manganese in sulphuric acid medium and hexaaquomanganese(III) ions in perchloric acid medium

Conditions were found for the electrochemical generation of the diphosphate complex of trivalent manganese in a sulfuric acid medium and of hexaaquomanganese(III) ions in perchloric acid medium. Practical application of the studied reagents was verified by coulometric titration of the order of tenths of milligrams of ferrous ions and hydroquinone. Indirect determination of oxalic acid based on its oxidation with excess electrochemically produced trivalent manganese in perchloric acid medium and on coulometric back titration of the unreacted oxidizing agent with ferrous ions was also studied.     

The use of redox reactions in the analysis of dyes and dye intermediates : VI. Determination of 4,4′-dinitrostilbene-2,2′-disulfonic acid with potassium permanganate

Conditions were found for the electrochemical generation of the diphosphate complex of trivalent manganese in a sulfuric acid medium and of hexaaquomanganese(III) ions in perchloric acid medium. Practical application of the studied reagents was verified by coulometric titration of the order of tenths of milligrams of ferrous ions and hydroquinone. Indirect determination of oxalic acid based on its oxidation with excess electrochemically produced trivalent manganese in perchloric acid medium and on coulometric back titration of the unreacted oxidizing agent with ferrous ions was also studied.     

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.     

Spectrophotometric determination of micro amounts of tetrathionate via its oxidation with permanganate

The reaction conditions of tetrathionate with permanganate were investigated by varying reaction time, temperature and amounts of sulphuric acid and permanganate. Under the optimal conditions for the reaction of tetrathionate with permanganate, both penta- and hexathionate were also oxidised; each one mol of polythionates (S _x O ₆ ^2– x=4, 5 and 6) reacts with (x–1.5) mol of permanganate. The proposed method is based on the reaction of tetrathionate with a given excess amount of permanganate in a sulphuric acid medium and on the spectrophotometric measurement of the iodine as triiodide formed by the oxidation of iodide with the excess of permanganate. This method could be successfully applied to the determinations of tetrathionate (4 × 10^–7 to 2 × 10^–5 M), pentathionate (3 × 10^–7 to 1.43 × 10^–5 M) and hexathionate (2 × 10^–7 to 1.11 × 10^–5 M), and gave a higher sensitivity than any previous methods without solvent extraction.     

Potentiometric studies in oxidation-reduction reactions: Oxidation with chloramine-b. indirect determinations

Chloramine-B has been used as an oxidising agent to determine indirectly potassium iodate, potassium metaperiodate, potassium, bromate, potassium dichromate, hydrogen peroxide, chloramine-T and potassium permanganate by a potentiometric method. An excess of potassium iodide added to each of the substances in an acid medium is titrated back with a standard solution of chloramine-B, using platinum foil as an oxidation-reduction electrode coupled with a saturated calomel electrode through an agar-agar potassium chloride bridge.     

Precise and accurate determination of chromium in steel

Determination of chromium(VI) by addition of weighed amounts of solid ammonium ferrous sulfate in excess and back-titration with permanganate, using spectrophotometric end-point detection, is applied to the determination of chromium in steel. Except in the case of vanadium. and especially of vanadium + tungsten, very high selectivity and precision are claimed. Relative standard deviations of the order of 0.05% to 0.15% were found. Recoveries in excess of 99.95% were obtained in most cases. Results for the determination of chromium in standard samples of steel are given.