Oxidation by chloramine-T

Murthy, A. R. Vasudeva; Rao, B. Sanjiva

doi:10.1007/bf03172477

Cited by 16 publications

(14 citation statements)

References 5 publications

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“…In general, these monohalomines undergo two-electron changes in their reactions [2]. The oxidation potential of haloamine-sulfonamide redox couple is pH-dependent [30] and it decreases with increase in pH of the medium. Because organic haloamines exhibit similar Table 3.…”

Section: Discussionmentioning

confidence: 99%

Ruthenium(III)-catalyzed mechanistic investigation of oxidation of an azo dye by sodium N-haloarenesulfonamidates in acid medium: A comparative spectrophotometric kinetic study

Puttaswamy

Jagadeesh

2005

Applied Catalysis A: General

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Section: Discussionmentioning

confidence: 99%

Ruthenium(III)-catalyzed mechanistic investigation of oxidation of an azo dye by sodium N-haloarenesulfonamidates in acid medium: A comparative spectrophotometric kinetic study

Puttaswamy

Jagadeesh

2005

Applied Catalysis A: General

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“…Therefore, the possible oxidizing species in acid medium are RNHX, RNX 2 , HOX, and probably H 2 OX ϩ , and in alkaline solutions RNHX, HOX, RNX Ϫ , and OX Ϫ . The oxidation potential of haloamine-sulfonamide system is pH dependent and decreases with increase in pH of the medium [25]. In alkaline solutions of haloamine, dihaloamine does not exist, and the possible species are the anions RNX Ϫ , and OX Ϫ which could be transformed into the more reactive oxidizing species RNHX and HOX in the course of reaction in alkaline medium.…”

Section: Discussionmentioning

confidence: 99%

“…In the present case, the observed solvent isotope effect of kЈ (H 2 O)/kЈ (D 2 O) Ͼ 1 is due to the greater basicity of OD Ϫ compared to OH Ϫ . However, the magnitude of retardation in D 2 O is small (expected value is ϳ2 -3 times greater [25]) due to the hydrolysis step, which tends to make the normal kinetic isotope effect k H /k D Ͼ 1 for the slow step of Scheme I, and also fractional negative order dependence on [OH Ϫ ]. Hence, this observation supports the proposed mechanism.…”

Section: Scheme IImentioning

confidence: 99%

Oxidation of isoniazid by N-haloarenesulfonamidates in alkaline medium: A kinetic and mechanistic study

Puttaswamy

Anuradha

Ramachandrappa

et al. 2000

Int. J. Chem. Kinet.

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The kinetics of oxidation of Isoniazid (INH) by sodium N‐haloarenesulfonamidates, chloramine‐T (CAT), bromamine‐T (BAT), chloramine‐B (CAB), and bromamine‐B (BAB), has been studied in alkaline medium at 303 K. The oxidation reaction follows identical kinetics with a first‐order dependence on each [oxidant] and [INH] and an inverse fractional‐order on [OH−:]. Addition of the reaction product (p‐toluenesulfonamide or benzenesulfonamide) had no significant effect on the reaction rate. Variation of ionic strength and addition of halide ions have no influence on the rate. There is a negative effect of dielectric constant of the solvent. Studies of solvent isotope effects using D2O showed a retardation of rate in the heavier medium. The reaction was studied at different temperatures, and activation parameters have been computed from the Arrhenius and Eyring plots. Isonicotinic acid was identified as the oxidation product by GC‐MS. A two‐pathway mechanism is pro‐posed in which RNHX and the anion RNX− interact with the substrate in the rate‐limiting steps. The mechanism proposed and the derived rate laws are consistent with the observed kinetics. The rate of oxidation of INH increases in the order: BAT > BAB > CAT > CAB. This effect is mainly due to electronic factors. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 221–230, 2000

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“…If [oxidant] t represents the total concentration of the oxidant, then from steps (i) and (ii) of Scheme In the present investigations, disparity of dielectric constant of the medium does not have an effect on the rate appreciably. The effect of varying solvent composition and dielectric constant on the rate of reaction has been described in several studies [30][31][32][33][34]. For limiting case of zero angle of approach between two dipoles or an ion-dipole system, Amis [33] has shown that a plot of log k / versus 1/D, gives a straight line with a negative slope for a reaction between a negative ion and a dipole or between two dipoles, where a positive slope results for a positive ion-dipole interaction.…”

Section: Kinetic Rate Lawmentioning

confidence: 99%

Kinetics and mechanism of oxidative decolorization of azo dye acid orange 8 by sodium N-halo-p-tolenesulfonamides in acid medium: spectrophotometric approach

Shubha¹,

Vinutha²,

Dinamani³

et al. 2014

IOSRJAC

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The kinetics of oxidative decolorization of acid orange 8 (AO8) by chloramine-T and bromamine-T in HClO 4 medium has been investigated spectrophotometrically (λ max = 490 nm) at 298 K. Kinetic runs were executed under pretend first-order conditions of [oxidant] o >> [AO8] o. Under identical experimental conditions, reactions with both the oxidants follow identical kinetics with a first-order dependence on each [oxidant] o and [AO8] and a fractional-order dependence on [HClO 4 ]. Stoichiometry of the reaction was found to be 1:1 and the oxidation products were identified. The reaction was studied at dissimilar temperatures and activation parameters have been computed. Effects of p-toluenesulfonamide, halide ions, ionic strength and dielectric constant of the medium have been investigated. Reaction mixture fails to induce polymerization of acrylonitrile. The rate of oxidation of AO8 is about twofold faster with BAT as compared to CAT. This may be endorsed to the diversity in electrophilicities of Cl + and Br + ions and also the van der Waal's radii of chlorine and bromine. Authentic mechanism and associated rate law have been deliberated for the observed kinetics.

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Oxidation by chloramine-T

Cited by 16 publications

References 5 publications

Ruthenium(III)-catalyzed mechanistic investigation of oxidation of an azo dye by sodium N-haloarenesulfonamidates in acid medium: A comparative spectrophotometric kinetic study

Ruthenium(III)-catalyzed mechanistic investigation of oxidation of an azo dye by sodium N-haloarenesulfonamidates in acid medium: A comparative spectrophotometric kinetic study

Oxidation of isoniazid by N-haloarenesulfonamidates in alkaline medium: A kinetic and mechanistic study

Kinetics and mechanism of oxidative decolorization of azo dye acid orange 8 by sodium N-halo-p-tolenesulfonamides in acid medium: spectrophotometric approach

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