Micellar effect on pentavalent vanadium  oxidation of formaldehyde to formic acid in aqueous acid media at room temperature

Sar, Pintu; Ghosh, Aniruddha; Saha, Rumpa; Saha, Bidyut

doi:10.1007/s11164-014-1635-4

Cited by 13 publications

(5 citation statements)

References 53 publications

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“…However, we can infer from chemical intuition that all cationic entities hydroxylate in an alkaline media and become neutral. These neutral entities can now interact with the surfactant through hydrogen bonding and ion–dipole interactions in the presence of OH − 48 . In alkaline CTAB micellar media, due to the extremely positively charged micellar surface, the negatively charged [Fe(CN) 6 ] 3− , OH − , and neutral Ru(III) complex (attached to the micellar surface) can approach the substrate molecule (in the stern layer) without any electrostatic repulsion (Figure 8).…”

Section: Resultsmentioning

confidence: 99%

“…These neutral entities can now interact with the surfactant through hydrogen bonding and ion-dipole interactions in the presence of OH − . 48 In alkaline CTAB micellar media, due to the extremely positively charged micellar surface, the negatively charged [Fe(CN) 6 ] 3− , OH − , and neutral Ru(III) complex (attached to the micellar surface) can approach the substrate molecule (in the stern layer) without any electrostatic repulsion (Figure 8). 36,49 CTAB thus facilitates and accelerates the oxidation of Glu by [Fe(CN) 6 ] 3− catalyzed by Ru(III) in an alkaline media.…”

Section: Mechanismmentioning

confidence: 99%

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Effect of cationic surfactant on Ru(III) catalyzed L‐glutamic acid oxidation by hexacyanoferrate(III)

Srivastava

Goswami

Dohare

et al. 2023

Int J of Chemical Kinetics

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In CTAB micellar medium, the kinetic investigation of Ru(III) promoted oxidation of L‐glutamic acid (Glu) by [Fe(CN)6]3− was carried out by recording the decline in absorbance at 420 nm, which corresponds to [Fe(CN)6]3−. By adjusting one variable at a time, the progression of the reaction has been inspected as a function of [OH−], ionic strength, [CTAB], [Ru3+], [Glu], [Fe(CN)63−], and temperature using the pseudo‐first‐order condition. The findings demonstrate that [OH−], [CTAB], and [Glu] are the key parameters that have a discernible impact on reaction rate. In the studied concentration range of Ru(III), [Fe(CN)6]3−, and at lower [Glu] and [OH−], the reaction displays first‐order kinetics. The incremental trend in reaction rate with electrolyte concentration demonstrates a positive salt effect. CTAB substantially catalyzes the process, and after reaching a maximum, the rate remains nearly constant at increased [CTAB]. The observed decline in the CMC of CTAB may be caused by the reduced repulsion between the positively charged heads of the surfactant molecules caused by the negatively charged OH−, and [Fe(CN)6]3−. The activation parameters also support the outer‐sphere electron transfer mechanism as recommended by us.

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Section: Resultsmentioning

confidence: 99%

Section: Mechanismmentioning

confidence: 99%

Effect of cationic surfactant on Ru(III) catalyzed L‐glutamic acid oxidation by hexacyanoferrate(III)

Srivastava

Goswami

Dohare

et al. 2023

Int J of Chemical Kinetics

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“…(a) A strong electrostatic or Coulombic interactions between the oppositely charged micelles and the accumulated active oxidant species at stern layer of micelle is another one forceful factor behind the micellar catalysis [81][82][83][84][85][86][87][88][89][90].…”

Section: In Oxidative Transformationsmentioning

confidence: 99%

Surfactant for better tomorrow: applied aspect of surfactant aggregates from laboratory to industry

et al. 2019

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Surfactant is a special kind of amphiphilic compound composed of water-loving and hating parts. The remarkable physical properties like interfacial tension, wettability, emulsifying and dispersing ability make the surfactant accessible for numerous applications from laboratory to commercial products. In recent years, the commercial applications of surfactant have led to greater relevance on account of the environmental concerns and market pressures of this compound. The utility of surfactants in global market increases steadily since its formulation with several beneficial aspects in pharmaceutical, detergent, cosmetic, paint, food science, gas hydrate, nanotechnology, petroleum recovery, bioremediation, chemical transformation and drug delivery. This review briefly discusses the applied aspect of surfactants in diverse area as well as catalytic effect of micelle in organic reactions from the recent literature survey. The trend of increasing use of bioderived surfactants in the modern field of research is also considered in this report. The recent advancement of surfactant-based organic transformations has been emphasized with the role of surfactant aggregates in course of different organic reactions.

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“…11,12 The study of the micelle-mediated oxidation kinetics of numerous substrates led by higher-valent metal ions has long been substantially illuminated. 13−17 On account of the high reduction potential value (E 0 ), metals like Cr(VI), 18,14 Mn(VII), 19 V(V), 20,21 Cu(III), 22−24 Ce(IV), 25−27 Fe(III), 28 Co(III), 29 and Ag(III) 30,16 have significant strength to oxidize many organic substrates. Chromium(VI) appeared as a renowned oxidant, used for various oxidation processes in organic synthesis over a long period, 31 for its distinct speciation and high E 0 (1.33 V) in acidic conditions despite having detrimental effects, such as the harmful impact of chromium drops after oxidation, since it itself reduces to Cr(III), which is kinetically inert and nontoxic.…”

Section: Introductionmentioning

confidence: 99%

“…The knowledge of critical micelle concentration (CMC) is essential in terms of the self-aggregation characteristic of surfactants by which micelle-like nanosized aggregates are produced in aqueous media. − In recent years, the unique catalytic activity of surfactants has long been gaining considerable attention from synthetic organic chemists, since in aqueous micellar media, the majority of organic reactions are accomplished with better solubilization, extensive reaction rate, and greater degree of product selectivity. − A lot of organic reactions are performed in an aqueous micellar medium to reduce the environmental impact of traditional organic synthesis. − Along with the elimination of hazardous solvents from organic synthesis, the use of water as a reaction medium also offers chemical processes simplified operations, allowing for mild reaction conditions. The oxidation reaction is one of the most studied organic reactions, which produces a large number of precursor compounds with significant industrial applications. , The study of the micelle-mediated oxidation kinetics of numerous substrates led by higher-valent metal ions has long been substantially illuminated. − On account of the high reduction potential value ( E 0 ), metals like Cr(VI), , Mn(VII), V(V), , Cu(III), − Ce(IV), − Fe(III), Co(III), and Ag(III) , have significant strength to oxidize many organic substrates. Chromium(VI) appeared as a renowned oxidant, used for various oxidation processes in organic synthesis over a long period, for its distinct speciation and high E 0 (1.33 V) in acidic conditions despite having detrimental effects, such as the harmful impact of chromium drops after oxidation, since it itself reduces to Cr(III), which is kinetically inert and nontoxic.…”

Section: Introductionmentioning

confidence: 99%

Influence of Chain Length and Concentration-Dependent Morphological Switching on Oxidation of Aromatic Alcohols in a Micellar Environment

Layek,

Karmakar,

Pal

et al. 2024

Ind. Eng. Chem. Res.

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Catalytic oxidation of benzyl alcohol (BA), p-chlorobenzyl alcohol (p-ClBA) and p-anisyl alcohol (p-OMeBA) in aqueous media has been investigated in the presence of two cationic surfactants, viz. cetylpyridinium chloride (CPCl) and dodecylpyridinium chloride (DPCl). The chromium(VI)governed oxidations of such aromatic compounds exhibit an unusual kinetics depending upon the concentration of CPCl and DPCl. Both the cationic surfactants catalyzed the oxidations at lower concentrations while retardation was noticed at higher concentrations. The catalytic and inhibitory functions of both the surfactants at the sub-and postmicellar levels have been enlightened based on the kinetic CMC (critical micellization concentration). The chain length of the two surfactants influences the kinetic profiles of the oxidation processes. Herein, the π−π interaction and the cation−π interaction play important roles in the solubilization process and therefore encourage the reaction rate. These strong interactions result in a maximum 12-fold catalytic enhancement for the oxidation of p-anisyl alcohol in the CPCl micellar environment, while the inhibitory effect of CPCl and DPCl on the oxidation kinetics have been analyzed based on the dilution effect. The morphological alteration of aggregates during the oxidation aids the interpretation of the inhibitory activity of both micelles produced by CPCl and/or DPCl. Berezin's model has been employed to reveal the inhibition caused by cationic micelles. Morphological alteration of both the cationic surfactants from spherical-to-cylindrical shape at variable concentrations in the absence and presence of substrate was supported by SAXS (small-angle X-ray scattering), TEM (transmission electron microscopy), and FE-SEM (field emission scanning electron microscopy) analysis.

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Micellar effect on pentavalent vanadium oxidation of formaldehyde to formic acid in aqueous acid media at room temperature

Cited by 13 publications

References 53 publications

Effect of cationic surfactant on Ru(III) catalyzed L‐glutamic acid oxidation by hexacyanoferrate(III)

Effect of cationic surfactant on Ru(III) catalyzed L‐glutamic acid oxidation by hexacyanoferrate(III)

Surfactant for better tomorrow: applied aspect of surfactant aggregates from laboratory to industry

Influence of Chain Length and Concentration-Dependent Morphological Switching on Oxidation of Aromatic Alcohols in a Micellar Environment

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