Oxidation of thiocyanate by alkaline ferricyanide

Summary Oxidation of KSCN by alkaline K₃Fe(CN)₆ in presence of osmic acid has been studied quantitatively. The reaction proceeds at a measurable rate at ordinary temperature but is accelerated on refluxing the system on a water bath for a short time. The stoichiometry of the redox process suggests the formation of cyanate and sulphate as the products of oxidation. The quantity of thiocyanate is calculated by estimating the ferrocyanide formed and the ferricyanide consumed in terms of Ce(SO₄)₂ and Na₂S₂O₃ respectively. A kinetic study of the above reaction is under investigation.Sincere thanks of the author are due to Prof. S. S. Joshi for facilities and kind interest in the work. The award of a Scientific Man Power Committee Research Scholarship is also gratefully acknowledged.     

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.     

The oxidation of thallium(I) by alkaline ferricyanide

A simple method for the potentiometnc determination of thallium is described. Thus is based essentially on the precipitation of thallic hydroxide by alkaline ferricyanide and the back titration of excess K₃[FeCN)₆] by standard sodium arsemte according to Kolthoff's method Under thc specified experimental conditions. the reduction of trivalent thallium is not effected by As₂O₃ and the procedure offers therefore a unique advantage of simplicity and accuracy.     

Colorimetric titration of vanadium with alkaline ferricyanide

Summary The gradual disappearance of the yellow colour of ferricyanide with the addition of vanadyl ions in alkaline medium has been made the basis of the quantitative determination of both vanadium and ferricyanide. The colorimetric titrations were carried out with the aid of a Hilger Spekker Absorptiometer with a blue filter having maximum transmission in the range of 450–500 m. It is shown that the accuracy of the results compares favourably with those obtained by other standard procedures.     

Kinetics and mechanisms of oxidations by metal ions. Part 17. Oxidation of formate ion by alkaline osmium tetroxide

Summary The oxidation of formate ion by alkaline osmium tetroxide, such that [HCO _inf2 ^p– ] [Os^VII], exhibits first-order dependence in [Os^VII], an order less than unity in [HCO _inf2 ^p– ], and zero-order in [OH^–]. HCO^2– reacts as an ion-pair formed with an alkali metal ion and [OsO₄(OH)₂]^2– is the reactive species of Os^VII. The formation of an intermediate Os^VII-HCO₂M complex is substantiated by the rapid-scan spectra of the reaction mixture. Anions (Cl^–, ClO _inf4 ^p– ) have no effect on the rate. The close agreement between the observed k _H/k _D = 7.1 and the theoretically calculated value (7.0), based on the stretching frequencies of C-H and C-D bonds in the free molecule, indicates an outer-sphere mechanism.Author to whom all correspondence should be directed.     

Oxidation of lysine by ferricyanide in presence of osmium(VIII)

Osmium(VIII) catalysed oxidation of lysine by ferricyanide in excess ferrocyanide shows a complex kinetics. The order in lysine falls, from 1 to 0 while that in ferricyanide increases from 0 to 2 with large increase in lysine concentration. The rates were directly proportional to [Os(VIII)] and {Const.+[Fe(CN) ₆ ⁴ ]}. A suitable mechanism is proposed and discussed.

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Oxidation von lysin mittels ferricyanid in der gegenwart von osmium(VIII)

Zusammenfassung Die von Os(VIII) katalysierte Oxidation von Lysin mit Ferricyanid in überschüssigem Ferrocyanid zeigt eine komplexe Kinetik. Bei starker Steigerung der Lysinkonzentration fällt die Ordnung bezüglich Lysin von 1 auf 0, während bezüglich Ferricyanid eine Erhöhung, von 0 auf 2 festzustellen ist. Die Geschwindigkeitskonstanten waren direkt proportional zu [Os(VII)] und {Const.+[Fe(CN) ₆ ⁴ ]}. Es wird ein möglicher Mechanismus vorgeschlagen und diskutiert.

     

Oxidative determination of thiosulphate by alkaline ferricyanide using osmium tetroxide as a catalyst

Summary The catalytic action of osmium tetroxide has been utilised in the determination of thiosulphate by oxidation to sulphate with alkaline ferricyanide. Both direct and indirect procedures were developed. In the former the titration was carried out either ways using amperometric detection. In the latter, both the excess ferricyanide and ferrocyanide formed, were determined by arsenious oxide or iodometrically with thiosulphate, and by ceric sulphate respectively. The high conversion factor, availability of alternate procedures, use of potassium ferricyanide as a standard oxidant with a high molecular weight are characteristic features of this redox procedure.     

Electrometric titration of alkaline ferricyanide with hydrazine sulfate and arsenic (III)

Summary Potentiometric titrations of potassium ferricyanide with hydrazine sulfate and arsenic(III) are shown to be feasible at room temperature (25–30° C) and in an optimum alkali concentration of about 2 N when carried out in the initial presence of a few drops of osmic acid as catalyst. The method which is simple, rapid and accurate can be used in the estimation of hydrazine, arsenic(III) or ferricyanide.This work constituted, in part, the author's Ph. D. thesis (1956) at the Banaras Hindu University (India).     

Fabric‐based alkaline direct formate microfluidic fuel cells

Fabric‐based microfluidic fuel cells (MFCs) serve as a novel, cost‐efficient alternative to traditional FCs and batteries, since fluids naturally travel across fabric via capillary action, eliminating the need for an external pump and lowering production and operation costs. Building on previous research with Y‐shaped paper‐based MFCs, fabric‐based MFCs mitigate fragility and durability issues caused by long periods of fuel immersion. In this study, we describe a microfluidic fabric‐based direct formate fuel cell, with 5 M potassium formate and 30% hydrogen peroxide as the anode fuel and cathode oxidant, respectively. Using a two‐strip, stacked design, the optimized parameters include the type of encasement, the barrier, and the fabric type. Surface contact of the fabric and laminate sheet expedited flow and respective chemical reactions. The maximum current (22.83 mA/cm²) and power (4.40 mW/cm²) densities achieved with a 65% cotton/35% polyester blend material are a respective 8.7% and 32% higher than previous studies with Y‐shaped paper‐based MFCs. In series configuration, the MFCs generate sufficient energy to power a handheld calculator, a thermometer, and a spectrum of light‐emitting diodes.     

Mercurous salts as reductimetric reagents for titrations in alkaline medium : Titration of ferricyanide

For the first time the application of mercurous salt for reductimetric titrations in alkaline medium has been studied. In the presence of iodide the ferricyanide ion can be titrated accurately. The end-point can be determined potentiometrically or with barium diphenylamine sulphonate. The influence of the concentration of iodide, ferricyanide and alkali, temperature, acidity of the reagent, and time are considered. The greater advantage of this procedure lies in the fact that the reagent is stable to air and the titrations can be carried out without elimination of the latter.     

Oxidation of lignin in aqueous alkaline solution

Conclusions The hydrogenolysis and hydrolysis of lignin in an aqueous alkaline medium must be considered as an oxidative degradation of the lignin macromolecule by hydroxyl radicals. This process takes place even in a reducing medium in the presence of a catalyst. This was shown by a study of the hydrogenolysis process using model compounds. The oxidative processes in lignin are connected with the appearance in the system (lignin or its model) of alkali-induced quinoid structures which, being electron-acceptors, abstract electrons from hydroxyl ions and form hydroxyl radicals. The latter lead to oxidative processes through the the hydroxylation of the system. The correctness of this has been confirmed by studying the composition of the products, which shows the oxidative nature of the hydrogenolysis process.Scientific-Research Institute for the Chemistry and Technology of Cotton Cellulose, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 512–517, September–October, 1970.     

Oxidation of sulphides with alkaline potassium permanganate

Summary Sulphides are oxidised with potassium permanganate in alkaline medium to give dithionate. A method based upon this reaction is proposed for the determination of sulphides. The method consists in mixing the sulphide solution with an excess of permanganate in presence 1–2 M NaOH and 0.2 g telluric acid. The excess permanganate is then treated with ferrous ammonium sulphate in acid medium and the excess ferrous titrated with permanganate.     

Oxidation of lignin in aqueous alkaline solution

Chemistry of Natural Compounds - The hydrogenolysis and hydrolysis of lignin in an aqueous alkaline medium must be considered as an oxidative degradation of the lignin macromolecule by hydroxyl...     

Oxidation of chromium(III) by alkaline hexacyanoferrate(III)

Alkaline hexacyanoferrate(III) oxidation of freshly prepared solutions of Cr^III (pH>12) at 27°C follows the rate law, Equation 1:

Formic acid as a reagent for alkaline permanganate : Potentiometric determination of formate

Oxidation of formate with permanganate in alkaline solutions yields a mixture of MnO₄^-2 and MnO₂. The reaction occurs slowly without an abrupt change in potential at the end-point. In 0.1N NaOH, at 80° C in the presence ofAg⁺ions or NaCl,the reaction is accelerated and yields MnO₂. The concentrations of formic acid obtained by oxidation with permanganate are comparable with those obtained by neutralization down to 2.295·10^-2N.Reduction of permanganate in the presence of Ba⁺² ions (alkalinity = 0.5 — 1.5N) or in the absence of Ba⁺ ions (alkalinity = 0.5 — 2.5N), gave accurate results for the permanganate concentration comparable with the results of the acid oxalate method.Formic acid is preferred to sodium formate on account of the greater stability of its solutions.     

Oxidation of electrodeposited cobalt electrodes in an alkaline electrolyte

The oxidation of electrodeposited Co electrodes has been studied in 0.1 M KOH_aq at potentials more negative than ?880 mV vs. Hg|HgO by means of electrochemical quartz crystal microbalance (EQCM) and rotating ring disk electrode coupled with cyclic voltammetry (CV) and chronoamperometry (CA). Dissolution of cobalt was found to be insignificant and does not constitute a step in the overall process of formation of the oxidised layer. The irreversibility of the oxidation process depends on the electrode potential and oxidation time. The composition of the oxidised layer depends on the oxidation potential: Co(OH)₂ is formed at more negative potentials, while at more positive potentials CoO is the prevailing product. The results obtained by means of three techniques (CV, CA and EQCM) reveal that at potentials not higher than ?880 mV, the oxidation of Co follows a direct logarithmic law. The mechanism of the process is discussed.