The Behavior of the Glass Electrode in Hydrogen Peroxide Solutions

Kolczynski, J. R.; Roth, Evelin; Shanley, Edward S.

doi:10.1021/ja01560a009

Cited by 17 publications

(11 citation statements)

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“…From this we calculate 𝑘 𝑃 = 0.5. A similar estimate from the data in 65 yields 𝑘 𝑃 = 0.2. We find, in any case, that the value of this equilibrium constant makes no difference to our conclusions, and only affects Ẽ at low [NaOH].…”

Section: Appendix Ii: Ionic Diffusiophoresis Speed Calculationssupporting

confidence: 52%

Ionic effects in self-propelled Pt-coated Janus swimmers

2014

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Colloidal particles partially coated with platinum and dispersed in H2O2 solution are often used as model self-propelled colloids. Most current data suggest that neutral self-diffusiophoresis propels these particles. However, several studies have shown strong ionic effects in this and related systems, such as a reduction of propulsion speed by salt. We investigate these ionic effects in Pt-coated polystyrene colloids, and find here that the direction of propulsion can be reversed by addition of an ionic surfactant, and that although adding pH neutral salts reduces the propulsion speed, adding the strong base NaOH has little effect. We use these data, as well as measured reaction rates, to argue against propulsion by either neutral or ionic self-diffusiophoresis, and suggest instead that the particle's propulsion mechanism may in fact bear close resemblance to that operative in bimetallic swimmers.

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Section: Appendix Ii: Ionic Diffusiophoresis Speed Calculationssupporting

confidence: 52%

Ionic effects in self-propelled Pt-coated Janus swimmers

2014

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“…It has long been known that the pH meter readings in aqueous solutions of hydrogen peroxide are lower than the “real pH” (in water) and the difference, revealed by the glass−calomel electrode system as a shift in the E 0 value, increases with the increasing concentration of hydrogen peroxide. This behavior has been related 56 to the difference in free energy of solvation of the proton in water and in nearly anhydrous hydrogen peroxide (about 9 kcal/mol), which indicates that the proton is more firmly bound to water.…”

Section: Resultsmentioning

confidence: 99%

Efficient Oxidative Cleavage of Olefins to Carboxylic Acids with Hydrogen Peroxide Catalyzed by Methyltrioctylammonium Tetrakis(oxodiperoxotungsto)phosphate(3−) under Two-Phase Conditions. Synthetic Aspects and Investigation of the Reaction Course

et al. 1998

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The oxidative cleavage of alkenes to carboxylic acids with 40% w/v aqueous hydrogen peroxide catalyzed by methyltrioctylammonium tetrakis(oxodiperoxotungsto)phosphate(3-) (Ia) is reported to occur in high yields and selectivities under two-phase conditions in the absence of organic solvents. On the basis of a study of the reaction, two main reaction pathways leading to acids have been recognized, the first one involving the perhydrolysis and the second one the hydrolysis of the epoxide initially formed. The "perhydrolytic" reaction pathway appears to play a primary role in the oxidation of medium- and long-chain alkenes to acids, while it intervenes to a rather limited extent in the oxidation of arylalkenes and C(5)-C(7) cycloalkenes. The occurrence of this pathway has been proved by the isolation of the intermediate beta-hydroperoxy alcohols and their transformation into acids with H(2)O(2) and Ia. The course of this transformation, involving an initial oxidation (to alpha-oxo hydroperoxide) or decomposition (to carbonyl compounds) of the beta-hydroperoxy alcohol intermediate, is described. The primary oxidation products, alpha-hydroperoxy ketones, have been isolated in the case of internal beta-hydroperoxy alcohols, whereas their presence has been evidenced with terminal beta-hydroperoxy alcohols bearing a secondary hydroxy group. Hydrogen peroxide concentration appears to exert a remarkable influence on medium acidity, and its effects on the reaction efficiency are shown.

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“…The prewave at 1.14 V for the voltammetric reduction of S8 probably is due to the reduction of a protonated form of the S8 2" anion HSg-+ 2e~^H Sg3-£pC = -1.14 V (6) that results from proton abstraction from the solvent. The small oxidation wave at -0.75 V (Figure 1) appears to be due to the reverse of reaction 6.…”

Section: Discussionmentioning

confidence: 99%

Electrochemical reduction of sulfur in aprotic solvents

Martin¹,

Doub²,

Roberts³

et al. 1973

Inorg. Chem.

151

146

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The reduction of sulfur and the solution chemistry of the various polysulfide products have been investigated in dimethyl sulfoxide by cyclic voltammetry, controlled-potential electrolysis, and absorption spectroscopy. At a gold electrode sulfur is reduced by two electrons at a potential of -0.6 V vs. see to produce S8 2~a nd other polysulfides. These products yield, by a variety of reactions, a blue radical species, S3~, with an absorption maximum at 618 nm. Electrolytic reduction of sulfur yields a second process at a potential of -1.29 V with an overall stoichiometry of four electrons per Ss molecule; the major stable product is the S4 2~s pecies. The dissociation of S6 2" into S3" has a pX^v alue of 2.11 on the basis of spectrophotometric measurements. Equilibrium constants of other disproportionation and dissociation reactions for the various poly sulfides also have been evaluated.

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The Behavior of the Glass Electrode in Hydrogen Peroxide Solutions

Cited by 17 publications

References 0 publications

Ionic effects in self-propelled Pt-coated Janus swimmers

Ionic effects in self-propelled Pt-coated Janus swimmers

Efficient Oxidative Cleavage of Olefins to Carboxylic Acids with Hydrogen Peroxide Catalyzed by Methyltrioctylammonium Tetrakis(oxodiperoxotungsto)phosphate(3−) under Two-Phase Conditions. Synthetic Aspects and Investigation of the Reaction Course

Electrochemical reduction of sulfur in aprotic solvents

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