Bestimmung organischer Stoffe durch Oxydation mit Permanganat

Zusammenfassung Die Wirkung von Permanganat, Mangan(IV)-oxid und dem Pyrophosphatkomplex des dreiwertigen Mangans auf Oxalsäure wurde verglichen. Die Oxydation zu Kohlendioxid und Wasser verläuft mit frisch bereitetem Mangan(IV)-oxid in einem breiten Aciditätsbereich sofort und quantitativ. Die Oxydation mit Permanganat und mit dem Pyrophosphatkomplex des dreiwertigen Mangans verläuft langsamer. Im Falle des letztgenannten Reagens wird ein quantitativer Verlauf der Reaktion in 2 N schwefelsaurer Lösung bei Laboratoriumstemperatur nach 20 min erreicht.

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Summary The effect of permanganate, manganese dioxide and of the pyrophosphate complex of trivalent manganese on oxalic acid has been compared. The oxidation of oxalic acid to carbon dioxide and water takes place immediately and quantitatively in a wide acidity range when freshly prepared manganese dioxide is used. Oxidation with permanganate and the manganese(III)-pyrophosphate complex is slower. With the latter reagent, a quantitative reaction is achieved only after 20 min at laboratory temperature in a medium of 2 N sulphuric acid.

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VII. Mitteilung: Mikrochim. Acta1968, 405.     

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.     

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.     

Chemiluminescence method with potassium permanganate for the determination of organic pollutants in seawater.

A chemiluminescence method with potassium permanganate was developed for use as an indicator of organic pollutants in fresh water. This method could be applied to the determination of organic pollutants in seawater as well. However, the flow chemiluminescence method suffered from the interference of chloride ions at the same concentration of seawater because of the production of manganese dioxide in the oxidation of chloride ions with permanganate. The conditions (concentrations of potassium permanganate and sulfuric acid and sample volume, i.e. flow injection method) were chosen to minimize the interference of chloride ions. The chemiluminescence method shows a good correlation with the chemical oxygen demand method on fresh water added artificial sea salt and seawater samples. Natural seawater was analyzed by the chemiluminescence method. The results obtained were compared with those obtained by chemical oxygen demand under the alkaline condition and total organic carbon methods. The chemiluminescence method has higher sensitivity and reproducibility than the conventional chemical oxygen demand and total organic carbon methods.     

A colorimetric determination of thorium

A colorimetric method for the determination of thorium is proposed. It is based upon the precipitation of thorium with a standard solution of oxalic acid and the subsequent reaction of the excess oxalic acid with a standard solution of potassium permanganate. The absorbancy of the remaining permanganate solution is directly proportional to the thorium present. The variables affecting this method have been critically studied. Reliable determinations can be made in the range of 3 to 30 mg of thorium in 1 cm cells when the colored solution is diluted to 250 ml. Most interfering substances can be removed by electrolysis in a mercury cathode cell or by the precipitation of thorium with potassium iodate.     

The Instability of Permanganate in orthophosphoric acid

Solutions of potassium permanganate in concentrated phosphoric acid (above 50%) are found to be unstable. The oxidation state of manganese is reduced from (VII) to (III) and oxygen is evolved during this process. The extent of decomposition of permanganate is found to be dependent on the concentration of the acid.     

Determination of organic substances by oxidation with permanganate : XIX. Analysis of mixtures of malonic and oxalic acids and of malonic and formic acids

A method for the analysis of mixtures of malonic and oxalic and malonic and formic acids has been developed. The method is based on stepwise oxidation with excess permanganate in alkaline [Eqs. (1) and (3)] and acid [Eq. (2)] media.     

Oxidation of organic substances with compounds of trivalent manganese: XIII. Oxidation of pyruvic acid with manganese(III) sulfate in a medium of sulfuric acid and with hexaquomanganese(III) ions in noncomplexing medium of perchloric acid

The oxidation of pyruvic acid with manganese(III) sulfate in a medium of sulfuric acid and with hexaquomanganese(III) ions in noncomplexing perchloric acid medium was studied. It was found that pyruvic acid is oxidized by both reagents to give acetic acid and carbon dioxide and the optimal conditions for the analytical application of this reaction on both a semimicro and micro level were found.     

Effect of oxidant type on the chemiluminescence intensity from the reaction of tris(2,2′-bipyridyl)ruthenium(III) with various organic acids

An investigation into the chemiluminescence of fourteen organic acids and tris(2,2′-bipyridyl)ruthenium(II) was undertaken. Particular emphasis was placed upon the method of production of the reagent, tris(2,2′-bipyridyl)ruthenium(III), with cerium(IV) sulfate, potassium permanganate, lead dioxide and electrochemical generation. Analytically useful chemiluminescence was observed when Ce(IV) or potassium permanganate were employed as oxidants. The kinetics of analyte oxidation was related to the intensity of the chemiluminescence emission, which increased by three orders of magnitude for tartaric acid after 40 h of oxidation.     

A contribution to the use of tetravalent manganese in solutions of sulfuric acid as an oxidimetric reagent

The preparation of solutions of manganese(IV) sulfate in 9 M sulfuric acid as well as the stability of these solutions was studied for 0.00501 M concentration of manganese(IV) ions. Potentiometric titration of solutions of primary standard substances, potassium iodide and sodium hexacyanoferrate, was recommended for determining the titer of 0.005 M reagent solutions. It was verified that manganese(IV) sulfate can be used for determining low concentrations of organic substances by direct titration determination of hydroquinone, p-aminophenol, and metol and by indirect determination of oxalic acid.     

Electrochemical generation of manganese (III) at glassy carbon electrode in acetic acid

Conditions were established for the electrochemical generation of manganese(III) at glassy carbon in acetic acid. In the oxidation of manganese-(II) in potassium acetate supporting electrolyte high current efficiencies were achieved in a wide range of current densities at the working electrode, whereas in the presence of sodium perchlorate a successful generation of manganese(III) could be performed only at low current densities. With increasing content of water in the anolyte the amount of generated manganese (III) was abruptly decreased and its stability in the solution was diminished. Procedures are given for a successful coulometric titration of reducing substances with anodically generated manganese (III); biamperometric, potentiometric and bipotentiometric methods for the location of the end-point were employed. The error of the determinations did not exceed ± 2%.     

Green Oxidations. Manganese(II) Sulfate Aided Oxidations of Organic Compounds by Potassium Permanganate

Summary. The oxidation of arenes and sulfides by potassium permanganate was accomplished in good yields under solvent free and heterogeneous conditions when manganese(II) sulfate is used as a solid support. After extraction of the organic products, the inorganic products can be reoxidized to permanganate. This result is important because it provides an approach to oxidation reactions that is, in theory, infinitely sustainable.     

Synthesis of metal-complexes and their reactivities: -The difference of reactivities among the manganese complexes-

Manganese chelates were prepared and the autoxidation of isopropyl benzene (IP) was carried out. (Mn-Chelate-1) showed a long induction period, but the other complexes (Mn-Chelate-2 and −3) which contain two or more magnesium ions in each molecule had shorter induction periods. The difference comes from the conformation around the manganese ion. Mn(III) acetate prepared from the oxidation of manganese (II) acetate with potassium permanganate in acetic acid was discussed.     

The use of alkaline permanganate in the preparation of biological materials for the determination of mercury by atomic absorption spectrometry

Biological materials when treated with 1.5 M potassium hydroxide, rapidly disintegrate, and become dispersed in the aqueous phase. Addition of potassium permanganate causes rapid and almost complete sample oxidation. Dissolution is completed by addition of sulphuric acid, and excess of oxidant is reduced with oxalic acid. The homogenization step allows representative subsampling. The procedure is applicable to human hair, fingernails, urine, fish products, plant material, rat fur, blood and liver.     

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.     

Volumetric estimation of potassium permanganate and potassium dichromate in mixtures with oxalic acid

1. A simple method has now been developed for the volumetric estimation of potassium permanganate and potassium dichromate in mixtures The method consists in taking an aliquot volume of the mixture in an Erlenmeyer flask, adding sufficient quantities of sulphuric acid and manganous sulphate (catalyst) and titrating with a standard solution of sodium oxalate or oxalic acid run in from the burette, until the colour changes from orange-red to yellow. The oxalic acid run ingives a measure of the permanganate present in the mixture Then the mixture in the flask is titrated with a standard solution of Mohr's salt using diphenylbenzidine as indicator. The volume of Fe⁺² solution run in the second stage gives a measure of the dichromate present in the original mixture. 2. The reverse titration does not give accurate results, because it is affected by the induced reaction between oxalic acid and dichromate which is induced by the reaction between oxalic acid and permanganate during the first stage of the reaction. This induced reaction has been studied in some detail.     

Oxidation of lactic acid by water soluble (colloidal) manganese dioxide

Spectrophotometric method has been used to characterize water‐soluble colloidal manganese dioxide obtained by the redox reaction between sodium thiosulphate and potassium permanganate in neutral aqueous medium which shows a single peak in the visible region with λ_max = 425 nm. The kinetics of the oxidation of lactic acid by colloidal manganese dioxide (oxidant) has been investigated spectrophotometrically under pseudo‐first‐order conditions of excess lactic acid. The rate of the noncatalytic reaction pathway was slow which increased with increasing lactic acid concentration. The reaction was first‐order with respect to [oxidant] as well as [lactic acid]. In presence of manganase(II) and fluoride ions, the noncatalytic path disappeared completely while the oxidation rate of autocatalytic path increased and decreased, respectively with increasing [Mn(II)] and [F^?]. A mechanistic scheme in conformity with the observed kinetics has been proposed with the rate‐law: © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 359–366 2004     

The application of strongly oxidizing agents in flow injection analysis : Part 2. Manganese(III)

The application of manganese(III) as a powerful oxidizing agent in flow injction analysis is described. Manganese(III) is generated electrochemically in the flowing system at a working electrode consisting of a packed bed of gold powder. Spectrophotometric detection is used at 490 nm, where manganese(III) in sulphuric acid solution absorbs strongly. Undr the experimental conditions, the generation of manganese(III) can be accompanied by generation of manganese(IV) and permanganate; manganese(III) alone can be generated by a proper selection of the generating current and the flow rate. Results are presented for the determinatin of various organic and inorganic substances by means of manganese(III), usually at concentrations in the 10^?4—10^? mol l^?1 range. Unlike permanganate and manganese(IV), manganese(III) does not react with chloride, so that oxidizable compounds can be determined in the presence of large amounts of this species.     

Oxidation of organic substances with compounds of trivalent manganese: XXIII. Preparation,stability, and determination of the titer of standard solutions of the fluoride complex of trivalent manganese

A method of preparation of 10^?2 ?10^?3M standard solutions of the fluoride complex of manganese(III) by the reaction of manganese(II) with permanganate in a medium of potassium fluoride acidified with sulfuric acid has been developed. It has been found that in a medium of 1 M sulfuric acid, 0.5 M manganese(II) sulfate, and 0.1 M potassium fluoride these solutions are sufficiently stable for both direct and indirect titrimetric determinations. The titer was determined using potassium iodide as a primary standard and potentiometric, bipotentiometric, or biamperometric titration.