Coulometric generation of protons by oxidation of hydrogen dissolved in palladium, in non-aqueous media

Coulometric generation of H(+) ions by the oxidation of hydrogen dissolved in palladium, in media such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetic anhydride and acetic acid-acetic anhydride mixture, for use in titration of bases, has been investigated. The hydrogen is oxidized at potentials which are much more negative than those of the bases and other components present in the solution. Titrations of numerous bases have established that the oxidation is quantitative and proceeds with 100% current efficiency.     

Coulometric generation of hydrogen ions by oxidation of mercury in anhydrous acetone

The application of a mercury anode for the quantitative generation of H(+) ions in anhydrous acetone has been investigated. From the changes of anode potential with current density in 0.25M sodium perehlorate in anhydrous acetone it has been established that in this solvent mercury is oxidized at a potential which is much more negative than the oxidation potentials of the bases to be titrated, the indicator used and the solvent. Protons generated in this way have been used for titration of some organic bases, with either visual or potentiometric end-point detection. The oxidation of mercury in anhydrous acetone and the reaction of mercury ions with acetone have been found to proceed with 100% current efficiency.     

Coulometric generation of H+ ions by anodic oxidation of esters of gallic acid,phenols and ascorbic acid in propylene carbonate

The application of esters of gallic acid (methyl, ethyl, propyl, butyl, octyl and dodecyl gallate), phenols (pyrocatechol and pyrogallol) and ascorbic acid for the coulometric generation of H⁺ ions in propylene carbonate, is described. The current-potential curves recorded for these depolarizers, titrated bases, indicator and the solvent used showed that the investigated depolarizers are oxidized at lower potentials than the oxidation potentials of other components in the solution H⁺ ions formed by the oxidation of these depolarizers were used for the titration of organic bases (pyridine, piperidine and quinoline) with visual and potentiometric end-point detection. The current efficiency was 100%.     

Coulometric generation of hydrogen ions by oxidation of mercury in methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone

Mercury(II)-chloride reacts with anhydrous methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone in a precise stoichiometry ratio (1:2), and weakly ionized compounds of mercury with ketones are formed and equivalent quantity of HCl is released. The application of a mercury anode for the quantitative generation of H⁺ ions in 0.25 M sodium perchlorate in anhydrous methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone has been investigated. Current/potentials curves for the solvents, titrated bases, indicator and mercury showed that in these solvents mercury is oxidized at potentials much more negative than those for the titrated bases and other components present in the solution. The protons generated in this way have been used for the titration of some organic bases, with either visual or potentiometric end-point detection. The oxidation of mercury in methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone and the reaction of mercury ions with these solvents have been found to proceed with 100% current efficiency.     

Coulometric titration of D(+)-glucose using its enzymatic oxidation.

A definitive method is described for the indirect assay of milligram quantities of D(+)-glucose by coulometric titration. D(+)-Glucose was aerobically oxidized by glucose oxidase in an acetate buffer solution (pH 5.1). Subsequently, the enzymatically formed hydrogen peroxide was titrated coulometrically with electrogenerated hypobromite in sodium bromide-sodium tetraborate medium of pH 8.6, with biamperometric end-point detection. Parameters affecting the enzymatically catalyzed oxidation and coulometric titration were evaluated. The optimized conditions for the oxidation of up to 20 mg of D(+)-glucose include the addition of 4500 U of glucose oxidase and stirring over a 10-min interval at 25 degrees C. Under proposed conditions, the assay values of several commercial D(+)-glucose reagents were somewhat lower than the guaranteed minimum values, with RSDs (n = 5) of 0.071 - 0.106%.     

The anodic oxidation of alkanes in anhydrous hydrogen fluoride and related superacid media

The anodic oxidation of several alkanes in anhydrous hydrogen fluoride at various acidity levels, from “basic” media (KF) to “acid” media (SbF₅) has been studied to establish optimum conditions for the formation of carbenium ions. The oxidation potential of an alkane depends on structure and on the acidity level of the medium. Taking into account thermodynamical data, possible mechanisms for the anodic oxidation are proposed. Furthermore, it is shown that alkanes undergo spontaneous chemical oxidation in acid media (HF + SbF₅ which may be investigated in its kinetic and thermodynamic aspect by means of electroanalytical methods.     

Kinetics of the oxidation of hydrogen peroxide by aquosilver(II) ions in aqueous perchlorate media and comparison with oxidation by CoaqIII,MnaqIII, CeaqIV and FeaqIII

Detailed measurements on the kinetics and stiochiometry of the oxidation of hydrogen peroxide by aquosilver(II) ions are reported. Two Ag_aq^II ions are consumed for each H₂O₂ which disappears, and for [H₂O₂]>[Ag^II] the reaction is first order in Ag_aq^II and zero order in H₂O₂ with the rate independent of acidity in the range 2·0–4·8 M HClO₄. The activation energy for the decomposition of the Ag^IIH₂O₂ complex ∼zero, similar to the oxidations of H₂O₂ by Ce_aq^IV and Mn_aq^III. The contrasting orders in the oxidative reactivity towards H₂O₂ and in the redox potentials of the transition metal cations are discussed. It is suggested that, whereas Ag_aq^II, Ce_aq^IV, Mn_aq^III and Fe_aq^III oxidise H₂O₂ in one-electron transfers involving monomeric cations, the oxidation of H₂O₂ by Co_aq^III may involve a two-electron step with dimeric Co^III.     

Reversible sorption of hydrogen by colloidal palladium in aqueous solutions

Colloidal palladium was prepared by -irradiation or by H₂ reduction of Pd(NH₃)₄l₂ in aqueous solutions containing sodium polyacrylate as a stabilizer. The sots contain spherical particles 2–4 nm in diameter. Their optical spectra contain a band at 230 nm ( = 6.1 · 10³ L mol^–1 cm^–1) smoothly descending toward the visible range. The sots reversibly absorb chemically from 0.35 to 0.15 g-mol of H₂ per g-atom of Pd. The spectra of ultrafine metal particles saturated with molecular hydrogen exhibit an absorption band at 265 nm ( = 4.5 · 10³ L mol^–1 cm^–1). One-electron reduction of methylviologen by hydrogen is catalyzed by the colloidal palladium prepared.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 313–316, February, 1996.     

Rearrangements and hydrogen—deuterium exchange in ferrocenylcarbenium ions

The rearrangement of the t-butyl group in t-butylferrocenyl carbenium ions (VI) and the hydrogen—deuterium exchange in the methyl group of methylferrocenyl carbenium ions (XVI) has been studied. The reaction rates depend on the size of the substituents at the carbenium ion center, an increase in the size of the substituents causing an increase in the rate. This effect is attributed, on the basis of the Gleiter and Cais models of ferrocenyl substituted carbenium ions, to increased steric hindrance between the substituents and the unsubstituted cyclopentadienyl ring.     

Kinetics of the oxidation of isopropanol by aquosilver(II) ions in aqueous perchlorate media

A quantitative examination of the acetone produced from the oxidation of isopropanol by Ag_aq^II shows that two Ag_aq^IIions are consumed for each isopropanol molecule, and the kinetics show that the reaction involves the direct attack of an Ag_aq^II ion on an isopropanol molecule without involving intermediate Ag_aq^III. The overall reaction is insensitive to change in acidity, as found previously in the oxidation of secondary alcohols by direct attack of Mn_aq^III. To explain the effect of Ag^I on the rate, a back reaction is postulated, analogous to that found previously in the oxidation of methanol by Mn_aq^III. The free energy, energy and entropy of activation are compared with those found for the oxidation of isopropanol by other cations.     

Coulometric generation of H+ ions by oxidation of thiols at a platinum anode and by oxidation of mercury in acetic acid—acetic anhydride

The coulometric generation of hydrogen ions by anodic oxidation of propane-1-thiol, butane-1-thiol, 2-mercaptopropionic acid, heptane-1-thiol, 2-mercaptoethanol, methyl and ethyl thioglycollate and p-thiocresol in acetic acid—acetic anhydride (1 + 6 v/v) is described, together with the possibility of coulometric generation of protons by mercury oxidation in the presence of p-thiocresol in the same solvent system.Current-potential curves for the solvent, indicator, titrated bases, mercury and the investigated thiols showed that in acetic acid—acetic anhydride (5 + 95, v/v), mercury and the investigated thiols are oxidized at potentials which are much more negative than those of the titrated bases and other components present in the solution.Titration of potassium hydrogenphthalate and sodium acetate with protons generated by the oxidation of thiols, and of sodium acetate, lithium acetate and pyridine with protons generated by the oxidation of mercury, demonstrated that the oxidation of both thiols and mercury proceeds quantitatively with 100% current efficiency.     

Kinetics and mechanism of hydrogen peroxide oxidation of chromone-3-carboxaldehydes in aqueous acid and micellar media

Oxidation of chromone-3-carboxaldehyde (CCA) and substituted analogues by H₂O₂ has been carried out in aqueous acid (HCl and H₂SO₄) and micellar media. Reaction kinetics indicated order in [CCA] as well as [H₂O₂] to be unity while it is a fraction (1 > n > O) in [acid]. Reaction rates were found to be faster in the solvents of low-dielectric constant (D). Added salt (KCl or (NH₄)₂SO₄) increased the rate of oxidation marginally. On the basis of observed linearity of Amis plot and marginal positive salt effect, protonated CCA (enol form of CCA, a cation) and H₂O₂ (neutral molecule) were considered as reactive species in the rate limiting step. Reaction rates were found to be enhanced significantly in anionic and nonionic micellar (sodium dodecylsulfate (SDS) and Triton X-100 (Tx), respectively) media. However, cationic micelles [cetyl trimethyl ammonium bromide (CTAB)] indicated marginal retardation effect. Effect of anionic and cationic micelles has been interpreted in terms of electrostatic interactions, while that of nonionic micelles in terms of hydrophobic interactions. Structure-reactivity correlations have been interpreted by Hammett's equation. Negative “ρ” (reaction constant) values indicated cationic transition state. © 1996 John Wiley & Sons, Inc.     

Coulometric titration of salts of strong mineral acids in acetic anhydride by application of a hydrogen/palladium electrode

The application of H₂/Pd electrodes as generator and indicator electrodes is described for coulometric titrations of alkali metal halides and trivalent metal sulphates in acetic anhydride with potentiometric end-point detection. In acetic anhydride, sodium fluoride is a strong enough base to be titrated directly with H⁺ ions obtained by anodic oxidation of hydrogen dissolved in palladium. Other halides (NaCl, KCl, LiCl, KBr and NaBr) can be determined, after reaction of halides with mercury (II) acetate, by coulometric titration of the liberated base. Potentiometric end-point detection with a H₂/Pd-mercury(I) acetate electrode pair is satisfactory. Sulphates of Fe(III), Cr(III) and Al(III) are determined by back-titrating the excess of barium acetate after precipitation of barium sulphate. The errors in these determinations are < 1% for concentrations ranging from 0.001 to 0.003 M.     

Kinetics and mechanism of the oxidation of hydrogen peroxide by the octacyanotungstate(V) ion in alkaline aqueous media

Summary The oxidation of H₂O₂ by [W(CN)₈]^3– has been studied in aqueous media between pH 7.87 and 12.10 using both conventional and stopped-flow spectrophotometry. The reaction proceeds without generation of free radicals. The experimental overall rate law, , strongly suggests two types of mechanisms. The first pathway, characterized by the pH-dependent rate constant k _s, given by , involves the formation of [W(CN)₈· H₂O₂]^3–, [W(CN)₈· H₂O₂·W(CN)₈]^6– and [W(CN)₈· HO]^3– intermediates in rapid pre-equilibria steps, and is followed by a one-electron transfer step involving [W(CN)₈·HO]^3– (k _a) and its conjugate base [W(CN)₈·O]^4– (k _b). At 25 °C, I = 0.20 m (NaCl), the rate constant with H _a =40±6kJmol^–1 and S _a =–151±22JK^–1mol^–1; the rate constant with H _b =36±1kJmol^–1 and S _b =–136±2JK^–1mol^–1 at 25 °C, I = 0.20 m (NaCl); the acid dissociation constant of [W(CN)₈·HO]^3–, K ₅ =(5.9±1.7)×10^–10 m, with and is the first acid dissociation constant of H₂O₂. The second pathway, with rate constant, k _f, involves the formation of [W(CN)₈· HO₂]^4– and is followed by a formal two-electron redox process with [W(CN)₈]^3–. The pH-dependent rate constant, k _f, is given by . The rate constant k ₇ =23±6m ^–1 s ^–1 with and at 25°C, I = 0.20 m (NaCl).     

Coulometric generation of acetylions by oxidation of mercury in acetic anhydride and in acetic acid/acetic anhydride mixture

Coulometric generation of acetyl (CH₃CO⁺) ions by oxidation of mercury in acetic anhydride and in acetic acid/acetic anhydride (5:95, v/v) is described. Current/potential curves for solvents, titrated bases, indicator and mercury showed that in both these solvents mercury is oxidized at potentials which are much more negative than those for the titrated bases and other components present in the solution. Quinoline, triethanolamine, triethylamine, pyridine and quinolin-8-ol in acetic anhydride, as well as triethylamine, 2,2′-bipyridine, 2,4,6-collidine, pyridine and sodium acetate in acetic acid/acetic anhydride were titrated with acetyl ions generated by the oxidation of mercury. In this way, it was established that the oxidation of mercury to mercury (I) ions proceeds quantitatively with 100% current efficiency.     

The kinetics of polyolefin oxidation in aqueous media

The thermal oxidation, at 75–92°C, of antioxidant-free low-density polyethylene (LDPE) is faster in most aqueous environments than in air. The accelerative environments include water, solutions of sodium salts, and a basic buffer. However, an acidic buffer retards oxidation. Transition metal salts are not examined here since their catalytic effect is wellknown. The acceleration is predominantly a surface phenomenon, and so is most obvious in thin polymer films. For antioxidant-containing polyolefins, complications arise because of the possibility of extraction of stabilizers, but the trend in oxidative lifetime is similar to that of the antioxidant-free specimens, and the antioxidants are observed to react chemically during the aging process. For example, a commercial crosslinked polyethylene (XLPE) shows a reduction in thermo-oxidative lifetime of at least a factor of two in aqueous environments compared to air. High-density polyethylene (HDPE) and polypropylene (PP) show similar behavior, but the magnitude of the effect of aqueous environments is less. This phenomenon is discussed in terms of nucleophilic attack by peroxy anions on hydroperoxides.     

Flavin-catalyzed aerobic oxidation of sulfides in aqueous media

An aerobic, organocatalytic, and aqueous method for the oxidation of sulfides is described. Synthetic flavin, 5-ethyl-3,7,8,10-tetramethylisoalloxazinium perchlorate, acts as an efficient catalyst for the oxidation of sulfides in water under an oxygen atmosphere (1 atm) with the assistance of ascorbic acid as a reductant. This is an inexpensive, convenient, and environmentally benign method for the selective oxidative transformation of sulfides into sulfoxides.