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.     

Analysis of mixtures of citric and oxalic acids based on their oxidation with potassium permanganate and manganese(III) sulfate

A determination of mixtures of citric and oxalic acids has been developed based on quantitative oxidation of the two substances with excess potassium permanganate to carbon dioxide and water and on quantitative oxidation of oxalic acid to carbon dioxide and water and of citric acid to carbon dioxide and formic acid with excess manganese(III) sulfate. The content of the two substances in mixtures can be calculated from the different consumption in these two oxidimetric determinations; a single standard solution of potassium permanganate can also be used for the preparation of manganese(III) sulfate.     

电位滴定测定富锂锰基正极材料中锰

采用盐酸、硝酸溶解样品,加入焦磷酸钠溶液并调节溶液pH为6.0~7.0。用高锰酸钾标准溶液滴定至电位滴定仪上,根据消耗的高锰酸钾标准溶液的体积计算样品中的锰含量。探究了焦磷酸钠用量、溶液pH、共存元素等对测定锰含量的影响。在最优的实验条件下,方法的相对标准偏差在0.13%~0.22%之间,加标回收率在99.8%~100.5%之间。本方法是富锂锰基正极材料中质量分数10%~60%的锰测定的理想方法。     

Volumetric studies in oxidation-reduction reactions: Oxidation with chloramine-t. indirect determinations

Chloramine-T has been used as an oxidizing agent in hydrochloric acid medium for the indirect volumetric determination of hydrogen peroxide, lead dioxide, selenium dioxide, sodium formate, potassium meta-periodate, potassium permanganate and potassium dichromate using iodine monochloride as a catalyst, prcoxidizer and an indicator. Chloroform is coloured pink owing to the liberation of iodine during the titration and becomes very pale yellow at the end-point because of the formation of iodine monochloride.     

Titrimetric determination of some organic acids by xenon trioxide oxidation

Aqueous xenon trioxide in acidic or neutral solutions oxidises carboxylic acids quantitatively to carbon dioxide and water. Micro and semimicro amounts of carboxylic acids may be determined by the iodometric titration of the excess of xenon trioxide remaining in the reaction mixture. The optimum time and temperature for the reaction depend on the structure of the acid ; dicarboxylic and hydroxy-carboxylic acids react faster than corresponding monocarboxylic acids. Oxalic and polyhydroxy acids are oxidised within 20 min at room temperature while acetic, maleic, succinic, malonic acids require 2 hr at 40 degrees . Carboxylic acids in amounts less than 100 mug are determined with a coefficient of variation of 4%, which decreases to 1 % for amounts over 250 mug.     

Carbon Dioxide Measurements with and without Barium Peroxide in Electrolytic Studies with and without a Supporting Electrolyte

Abstract

This research deals with the quantitative formation of carbon dioxide in electrolytic oxidation reactions. The electrolytic reactions were run with barium peroxide to generate the superoxide anion at the anode. With the organic compounds used in these electrolytic studies we needed to develop a method where we could determine the amount of carbon dioxide liberated from these compounds with the superoxide anion. This method degasses an acidified solution with dry nitrogen, which carries the carbon dioxide to a standard solution of sodium hydroxide. Titration of the sodium hydroxide solution with standardized hydrochloric acid revealed the amount of carbon dioxide formed in the reaction after precipitation of the carbonate ions with barium chloride. Blank runs with the apparatus using anhydrous sodium carbonate produced 99% plus results of recovered carbon dioxide from the sodium carbonate.     

Investigation on drying conditions and assays of amidosulfuric acid and sodium carbonate by acidimetric coulometric titration and gravimetric titration

Amidosulfuric acid and sodium carbonate as standards for acid–base titrimetry were assayed by coulometric titration and gravimetric titration. Amidosulfuric acid was directly assayed by coulometric titration with electrogenerated hydroxide ions, and sodium carbonate was assayed by gravimetric back-titration. For sodium carbonate, excess amount of sulfuric acid, whose concentration was determined by coulometric titration, was added to sodium carbonate, and then gravimetrically back-titrated using a sodium hydroxide solution whose concentration was determined by gravimetric titration using the sulfuric acid. The accuracy of the coulometric titration for amidosulfuric acid and sulfuric acid was evaluated by examining the current efficiency of pulse electrolysis, the amount of the electrolysis current used, and the time spent for a titration. In addition, the drying conditions for high purity primary standards have a significant effect on the titration results due to changes in the acid–base assay. The suitable drying conditions for amidosulfuric acid and sodium carbonate were evaluated by mass-change measurements, coulometric titration and gravimetric titration. The measurement uncertainties were estimated from the uncertainties on the titration processes. Finally, the assays of amidosulfuric acid and sodium carbonate were 99.986% ± 0.010% (k = 2) after drying at 50 °C for 2 h, and 99.970% ± 0.016% (k = 2) after drying at 280 °C for 4 h, respectively. In addition, the international consistency was confirmed by measuring certified reference materials (CRMs) available from different National Metrology Institutes, and the compatibility of values among CRMs was experimentally ascertained.     

On the oxidation of malonic acid by ceric ions

The oxidation of malonic acid by ceric ions has been investigated in sulfuric acid solution under a variety of conditions. The initial rate at low ceric ion concentrations is first order in each of the two reactants and has an activation energy of 11.6 kcal/mol; the instantaneous rate constant increases somewhat with time during a single run. At higher concentrations of ceric ion, semilogarithmic plots are sigmoid with a reduced rate constant at long times. The rate decreases slightly with increasing sulfuric acid concentration. Rates of carbon dioxide evolution may be much less than rates of ceric ion reduction because of supersaturation effects. The observations can be explained if dissolved oxygen reacts with organic radicals to catalyze the rate of initial attack on malonic acid, but oxygen must also be consumed irreversibly during these reactions. Computations with plausible rate constants have simulated the experimental observations. These oxygen effects can rationalize peculiar almost discontinuous changes in rate when bromomalonic acid is oxidized by ceric ion. These effects may also explain the previously puzzling observation that some Belousov–Zhabotinsky solutions are oscillatory in bulk but become quiescent but excitable when spread in a thin film in contact with air.     

Kinetics and mechanisms of the permanganate oxidation of L-valine in neutral aqueous solutions

The permanganate oxidation of L-valine has been studied by visible spectrophotometry in neutral aqueous solutions. Under these conditions, both the zwitterionic and anionic forms of the amino acid are oxidized, the reaction being autocatalyzed by soluble colloidal manganese dioxide. Kinetic data for both the uncatalyzed and autocatalytic reaction pathways have been obtained, and reaction sequences consistent with the experimental findings are proposed.     

A wet chemical method for the estimation of carbon in uranium carbides

A wet chemical method for the estimation of carbon in uranium carbides has been developed, based on oxidation with a saturated solution of sodium dichromate in 9M sulphuric acid, absorption of the evolved carbon dioxide in a known excess of barium hydroxide solution, and titration of the excess of barium hydroxide with standard potassium hydrogen phthalate solution. The carbon content obtained is in good agreement with that obtained by combustion and titration.     

A one-pot sulfide to sulfone oxidation with m-chloroperoxybenzoic acid and sodium permanganate

A synthetic strategy towards [2-(1H-indol-5-yl)-6-morpholin-4-ylpyrimidin-4-yl]methylsulfones is described, utilising m-chloroperoxybenzoic acid and sodium permanganate in a one-pot sulfide-sulfone oxidation.     

Kinetics and mechanisms of the oxidation by permanganate of L-Phenylalanine

The oxidation of L-Phenylalanine by permanganate ion in aqueous phosphate buffers is autocatalized by the inorganic reaction product, which is stabilized in solution by adsorption of phosphate ions on its surface. This product is a soluble form of colloidal manganese dioxide. The rate of the noncatalytic reaction pathway is first-order in both the oxidizing and reducing agent. It is not affected by potassium chloride addition to the solution, but by phosphate addition. The rate increases with the pH of the medium. The autocatalytic pathway is first-order in both permanganate ion and colloidal manganese dioxide, (the permanganate ion according to the Langmuir isotherm). The autocatalytic rate increases with reductant concentration (follows the Langmuir adsorption isotherm). It is not affected by potassium chloride addition to the solution, whereas an increase in the phosphate concentration results in an increase in the rate with the same pH of the medium. Mechanisms consistent with the experimental data are proposed.     

Deuterium kinetic isotope effect in the oxidation of sodium (2-D2)propionate with permanganate in water solutions

Kinetic parameters characterizing the oxidation of sodium(2-¹H₂) propionate and the oxidation of sodium (2-²H₂) propionate with permanganate in water solutions have been determined and compared with kinetic parameters derived from the investigation of the deuterium isotope effect on the activation parameters in the permanganate and manganate oxidation of sodium (2-³H₂) propionate in water solutions of sodium hydroxide.     

The oxidation of benzidine, o,o′-tolidine and o,o′-dianisidine by manganese dioxide

The oxidation of benzidine, o,o′-tolidine, and o,o′-dianisidine by manganese dioxide was studied in an acidic medium. It has been shown that the studied substances are quantitatively oxidized by the reagent to the corresponding quinonediimines and that this reaction can be utilized for the indirect titrimetric determination of benzidine and o,o′-tolidine, based either on ferrometric titration of unconsumed manganese dioxide or on ascorbinometric titration of the quinonediimine formed.     

Mechanism of the oxidation of d-glucose onto colloidal MnO2 surface in the absence and presence of TX-100 micelles

Aqueous colloidal manganese dioxide (MnO₂) was prepared via titration by using potassium permanganate and sodium thiosulphate in aqueous neutral medium. The kinetics of oxidation of d-glucose onto the surface of colloidal MnO₂ have been studied spectrophotometrically. The results show that the rate of initial stage (nonautocatalytic path) increases with increasing the [d-glucose], [H⁺], and temperature and also upon addition of nonionic surfactant Triton X-100 (TX-100), which indicates that the surfactant enhances the concentration of d-glucose at the surface of the colloidal MnO₂. Hydrogen bonding interaction seemingly arises between –OH groups of d-glucose and oxygen of the ether linkages of polyoxyethylene chain of TX-100. A possible mechanism of the oxidative degradation of d-glucose is discussed in terms of d-glucose/TX-100 and colloidal MnO₂ interaction.     

The use of pyridine-2-azo-p-dimethylaniline as an indicator in glacial acetic acid

Pyridine-2-azo-p-dimethylaniline is suggested as an indicator in the titration of amines (aniline, butylamine, p-phenylenediamine and ethylenediamine) with perchloric acid in glacialacetic acid medium. The precision obtainable is much better than that with crystal violet indicator. The pyridine dye can also be used satisfactorily in the titration of sodium carbonate and sodium acetate.     

Evidence of competitive mechanisms during oxidation of CS(2)N(-)(3) by permanganate ion in alkaline solution

The oxidation of the 1,2,3,4-thiatriazole-5-thiolate ion, CS(2)N(-)(3), by permanganate ions in alkaline medium has been investigated over a wide range of oxidant concentrations. With a moderate excess of permanganate ion a 17-electron reaction takes place, yielding sulphate, nitrogen and carbon dioxide. With a high permanganate concentration the pseudohalide undergoes a 26-electron reaction yielding sulphate, carbon dioxide and nitrite as final products. These two different stoichiometries arise from the existence of competitive mechanisms and the ratio C(MnO(-)(4))/C(CS(2)N(-)(3)) will determine the course of the reaction.     

The mechanism of permanganate oxidation of sulfides and sulfoxides

Coupled-cluster (CCSD) and density functional computations are used to investigate historically competing mechanisms for the permanganate oxidation of sulfides and sulfoxides. The calculations all lead to a mechanism of 1,3-dipolar cycloaddition of permanganate, as opposed to historical mechanisms of attack of the sulfur atom by one O or by Mn. Such a mechanism, reminiscent of ozonolysis, may prevail in most permanganate oxidations. The ab initio activation enthalpies are in reasonable agreement with the experimental data; the ab initio activation entropies are not, possibly because of problems with Eyring equation assumptions.     

Kinetics and mechanism of oxidation of malonic acid by permanganate and manganese dioxide in acid perchlorate medium

Summary The kinetics of oxidation of malonic acid by both [MnO₄]^– and MnO₂ have been studied in an HClO₄ medium. The oxidation product of the organic acid was found to be glyoxylic acid. A reaction mechanism assuming complexation between MnO₂ and malonic acid is suggested. The rate is independent of [H⁺].     

Low temperature oxidation of oxalic acid with potassium permanganate

Summary Oxidation of oxalate and oxalic acid with permanganate was studied at ordinary temperature. In the presence of mixtures of Mn²⁺ and Cu²⁺ ions the reaction is sufficiently rapid for a visual titration. The end point is attained when a lilac or a faint violet colour appears. A blank experiment is necessary as Cu²⁺ consumes some permanganate before the end point can be perceived. Other catalysts including Zn²⁺, Cd²⁺, Hg²⁺ and Ag⁺ ions were tried but were less efficient.