Kinetics and mechanism of electron transfer reactions. Osmium(VIII) catalyzed oxidation of mannitol by hexacyanoferrate(III) in aqueous alkaline medium

Sharma, Manisha; Sharma, G. K.; Agrawal, Beena; Khandelwal, C. L.; Sharma, P. D.

doi:10.1007/s11243-005-0396-8

Cited by 8 publications

(5 citation statements)

References 20 publications

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“…The FTIR spectral analysis of this product indicated the product to be an aldehyde form of the substrate ( Fig. 1) [28]. The reaction stiochiometry has been ascertained by equilibrating the reaction mixture containing an excess of chromium(VI) over malonic acid (in varying ratio), …”

Section: Product Analysis and Stoichiometrymentioning

confidence: 99%

Combination of Sodium Dodecylsulfate and 2,2′-Bipyridine for Hundred Fold Rate Enhancement of Chromium(VI) Oxidation of Malonic Acid at Room Temperature: A Greener Approach

et al. 2016

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Chromic acid oxidation of malonic acid in aqueous media has been investigated spectrophotometrically at 303 K. The product glyoxylic acid has been characterized by 13 C-NMR and FTIR spectroscopy. Three representative N-heteroaromatic nitrogen base promoters, 2-picolinic acid, 2,2 0 -bipyridine (bpy) and 1,10-phenanthroline, in combination with the anionic surfactant sodium dodecylsulfate (SDS) enhanced the rate of the oxidation reaction compared to the unpromoted reaction. 2,2 0 -Bipyridine produced the maximum rate enhancement of the three promoters used. The mechanism of the reaction has been proposed with the help of kinetic results and spectroscopic studies. The observed net enhancement of rate effects has been explained by considering the hydrophobic and electrostatic interaction between the surfactants and reactants. The SDS and bpy combination is suitable for malonic acid oxidation.

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Section: Product Analysis and Stoichiometrymentioning

confidence: 99%

Combination of Sodium Dodecylsulfate and 2,2′-Bipyridine for Hundred Fold Rate Enhancement of Chromium(VI) Oxidation of Malonic Acid at Room Temperature: A Greener Approach

et al. 2016

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“…However, complications can arise when using HCF (III) in an acidic medium, as the oxidant can become complexed by one of the reduced products, hexacyanoferrate (II). While reactions in an alkaline medium have been found to be less prone to this complication, they are generally not as fast due to the reduced oxidation potential of the [Fe(CN) 6 ] 3À /[Fe(CN) 6 ] 4À redox couple [4] To address this issue, a range of transition metal ions have been used as catalysts in alkaline medium, including Osmium(VIII), [5,6] Ruthenium (III), [7,8] (IV), [9] (VI), [10] and (VIII), [11] Rhodium(III), [12] Iridium(III), [13] Paladium(II), [14] Molybdenum (IV), [15] and Cu (II), [16] Ru (III) [17] in micellar medium. HCF (III) is a potent one-electron oxidant and has redox potential of 0.36 V. It can act as a proton or electron abstracting reagent in oxidation reactions.…”

Section: Introductionmentioning

confidence: 99%

Experimental and Computational Kinetic Assessment of Ruthenium (III) Catalyzed Oxidation of Paracetamol by Hexacyanoferrate(III): A Mechanistic Pathway

Rolaniya,

Yadav,

Jain

et al. 2024

ChemistrySelect

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The ruthenium (III) catalyzed redox reaction of paracetamol with hexacyanoferrate (III) in an acidic medium has been investigated. The reaction shows fractional order dependence respecting paracetamol and first‐order dependence respecting the oxidant and ruthenium (III). It is enhanced by medium according to the equation kobs=a+b[H+]. The activation and thermodynamic parameters of the reaction have been estimated using the Arrhenius and Eyring equations. The oxidation product of paracetamol has been identified as quinone oxime through spectral analysis. Furthermore, the reaction has been examined in nine various organic solvents, and the solvents effect has been investigated by Taft's and Swain's multiparametric equations. The rate constants have been found to correlate well with Kamlet‐Taft's solvatochromic parameters (α, β, π*). The reaction constants have been found to be negative, suggesting that the reactivity is influenced mainly by the solute‐solvent interactions. On the basis of kinetic results, a plausible reaction mechanism has been proposed. The proposed mechanism is reinforced by additional evidence from density functional theory (DFT) computations conducted at b3lyp/6‐311*G (d,p) level, which demonstrate that the activation energy barriers align with the reactivity trend observed in the kinetics experiments. Therefore, these computational results provide further support for the proposed mechanism.

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“…The small reduction potential of the couple ([Fe(CN)6 3 − ]/[Fe(CN)6 4− ]: 0.356V) hinders [10] studies employing HCF(III) as an oxidant in acidic media. In acidic media, HCF(III) forms different species [11] . Iodometric techniques have been utilized to investigate the kinetics and mechanism of TCH oxidation in its free state and in its metal complex by Chloramin-T, Dichloramin-T, N-Bromo Succinimide, and N-Bromo acetamide [12] .…”

Section: Introductionmentioning

confidence: 99%

Kinetics and oxidation of thiocarbohydrazide by hexacyanoferrate(III) in aqueous perchloric acid medium

Seetharam,

Shastry,

Shashidhar

et al. 2023

Nano Carbons

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Hexacyanoferrate(III) [HCF(III)] was used to oxidize thiocarbohydrazide (TCH) in an aqueous perchloric acid (HClO4) medium, and the reaction kinetics were studied spectrophotometrically at 420 nm while keeping a constant ionic strength of 1.0 mol dm−3 and modulating the temperature between 298K–318K. The stoichiometry of the reaction among TCH and HCF in the HClO4 medium is 1:2. The reaction has a lower than unit order in both TCH and HClO4 and is of the first order in HCF. The impact of varying the ionic strength and dielectric constant of the medium on the rate has been investigated. The effect of temperature on the reaction rate was studied, and different activation parameters of reaction Ea, ΔH#, ΔS#, ΔG#, and log10 A were calculated. The products of oxidation were analyzed by simple qualitative analysis. On the basis of the collected data, the rate law has been derived, and a probable mechanism has been proposed.

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Kinetics and mechanism of electron transfer reactions. Osmium(VIII) catalyzed oxidation of mannitol by hexacyanoferrate(III) in aqueous alkaline medium

Cited by 8 publications

References 20 publications

Combination of Sodium Dodecylsulfate and 2,2′-Bipyridine for Hundred Fold Rate Enhancement of Chromium(VI) Oxidation of Malonic Acid at Room Temperature: A Greener Approach

Combination of Sodium Dodecylsulfate and 2,2′-Bipyridine for Hundred Fold Rate Enhancement of Chromium(VI) Oxidation of Malonic Acid at Room Temperature: A Greener Approach

Experimental and Computational Kinetic Assessment of Ruthenium (III) Catalyzed Oxidation of Paracetamol by Hexacyanoferrate(III): A Mechanistic Pathway

Kinetics and oxidation of thiocarbohydrazide by hexacyanoferrate(III) in aqueous perchloric acid medium

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