Kinetics and mechanism of oxidation of sulfanilic acid by periodate ion in aqueous medium

Results of kinetic studies of the sodium metaperiodate oxidation of sulfanilic acid in aqueous medium are discussed. A mechanism for the formation of azobenzene-4,4-disulfonic acid, isolated and characterized as its S-benzylisothiuronium derivative, is proposed.

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. -4,4- , S- .

     

Kinetics and mechanism of the oxidation of p-aminobenzoic acid by periodate ion in aqueous medium

Kinetic results of the oxidation of p-aminobenzoic acid by periodate ion in aqueous medium are discussed. A suitable mechanism based on kinetic evidence and product analysis is proposed.

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- . , .

     

Kinetics and mechanism of oxidation of 4-oxoacids by N-bromosuccinimide in aqueous acetic acid medium

Kinetics and mechanism of oxidation of substituted and unsubstituted 4-oxoacids (S) by N-bromosuccinimide (NBS) in aqueous acetic acid medium have been studied potentiometrically. The reaction follows first-order kinetics, each in 4-oxoacids, NBS and H⁺. The effect of changes in the electronic nature of the substrate reveals that there is a development of positive charge in the transition state. Based on the kinetic results and the product analysis, a suitable mechanism has been proposed for the reaction of NBS with 4-oxoacids.     

Kinetics and mechanism of oxidation of L-ascorbic acid by platinum(IV) in aqueous acid medium

The oxidation of l-ascorbic acid (H₂A) by platinum(IV) in aqueous acid medium exhibits overall second-order kinetics, being first order with respect to each reactant. Increasing both hydrogen and chloride ion concentrations inhibits the rate. The stoichiometry involves reaction of one platinum(IV) ion with H₂A to give dehydroascorbic acid. A reaction mechanism consistent with all the experimental observations is proposed.     

Manganese(III) oxidation of L‐serine in aqueous sulfuric acid medium: Kinetics and mechanism

Kinetics and mechanism of oxidation of L‐serine by manganese(III) ions have been studied in aqueous sulfuric acid medium at 323 K. Manganese(III) sulfate was prepared by an electrolytic oxidation of manganous sulfate in aqueous sulfuric acid. The dependencies of the reaction rate are: an unusual one and a half‐order on [Mn(III)], first‐order on [ser], an inverse first‐order on [H⁺], and an inverse fractional‐order on [Mn(II)]. Effects of complexing agents and varying solvent composition were studied. Solvent isotope studies in D₂O medium were made. The dependence of the reaction rate on temperature was studied and activation parameters were computed from Arrhenius‐Eyring plots. A mechanism consistent with the observed kinetic data has been proposed and discussed. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 525–530, 1999     

Kinetics and mechanism of oxidation of formic acid by bismuth(V) in aqueous phosphoric acid medium

The solution of bismuth(V) was prepared by digesting sodium bismuthate in aqueous phosphoric acid (3.0 mol dm⁻³), the resulting pink colour solution absorbs in the visible region at 530 nm (640 dm³ mol⁻¹ cm⁻¹). The stoichiometry of the oxidation of formic acid by bismuth(V) corresponds to the reaction as represented by the Eq. ( 1 ). (1) The observed kinetic rate law is given by the Eq. ( 2 ); (2) where Bi^V and [HCO₂H] are the gross analytical concentrations of bismuth(V) and formic acid respectively. A plausible reaction mechanism corresponding to the rate law (2) has been proposed. Also the pattern of reactivity of bismuth(V) in HCIOHF mixture and H₃PO₄ respectively has been compared. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 491–497, 2000     

Kinetics and mechanism of oxidation of malonic acid by chromium(VI) in aqueous perchlorate medium

The kinetics of oxidation of malonic acid, studied in aqueous acid perchlorate, conform to the rate law

Kinetics and mechanism of oxidation of antimony(III) by keggin‐type 12‐tungstocobaltate(III) in aqueous hydrochloric acid medium

The reaction between Sb(III) and [Co^IIIW₁₂O₄₀]^5? proceeds with two, one‐electron steps; formation of unstable Sb(IV) is the slow first step followed by its reaction with another oxidant in a fast step. The reaction rate is unaffected by the [H⁺] as there are no protonation equlibria involved with both the reactants, whereas the accelerating effect of chloride ion is due to the formation of an active chlorocomplex of the reductant, SbCl₆^3?. Increase in the ionic strength and decrease in the relative permittivity of the medium increases the rate of the reaction, which is attributed to the formation of an outer‐sphere complex between the reactants. The activation parameters were also determined and these values support the proposed mechanism. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 35: 9–14, 2003     

Kinetics and mechanism of oxidation of acetanilide by quinquevalent vanadium in acid medium

Summary The kinetics of the oxidation of acetanilide with vanadium(V) in sulphuric acid medium at constant ionic strength has been studied. The reaction is first order with oxidant. The order of reaction in acetanilide varies from one to zero. The reaction follows an acid catalyzed independent path, exhibiting square dependence in H⁺. A Bunnett plot indicates that the water acts as a nucleophile. The thermodynamic parameters have been computed. A probable reaction mechanism and rate law consistent with these data are given.

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Kinetik und Mechanismus der Oxydation von Acetanilid mit fünfwertigem Vanadium in saurem Medium

Zusammenfassung Es wurden kinetische Untersuchungen der Oxydation von Acetanilid mit Vanadium(V) in schwefelsaurem Medium bei konstanter Ionenstärke durchgeführt. Gegenüber dem Oxidans ist die Reaktion erster Ordnung, die Reaktionsordnung gegenüber Acetanilid variiert zwischen 1 und 0. Die Reaktion folgt einem von der Säurekatalyse unabhängigen Weg, wobei die Abhängigkeit von H⁺ quadratisch ist. Ein Bunnett-Plot zeigt, daß das Wasser als Nucleophil wirkt. Die thermodynamischen Parameter wurden berechnet. Ein möglicher Reaktionsmechanismus und ein Geschwindigkeitsnetz, das mit diesen Daten in Einklang ist, wird angegeben.

     

Kinetics and mechanism of the oxidation of nitrous acid by bromine in aqueous sulfuric acid

The kinetics and mechanism of the reaction between nitrous acid and bromine are studied in dilute sulfuric acid medium, using both the stopped‐flow method and conventional spectrophotometry. The partial reaction order with respect to Br₂ moderately differs from 1, showing a saturation at a higher concentration of bromine. The second order of the reaction towards nitrous acid has been observed. Hydrogen and bromide ions significantly suppress the rate of reaction. Despite the apparent simplicity, the mechanism is rather complex, with two reaction pathways proposed. The first one is represented by the reaction of bromine with the intermediate dinitrogen trioxide. A direct nucleophilic attack of NO₂⁻ ion towards the bromine molecule is suggested as the second pathway. The proposed mechanism accounts for the observed behavior; in almost all cases a satisfactory quantitative agreement with the experiments is obtained. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 279–285, 2000     

Kinetics and mechanism of the oxidation of L-α-amino-n-butyric acid by permanganate in acid medium

The kinetic study of the oxidation of L-α-amino-n-butyric acid by permanganate ions has been carried out in buffered acid medium at pH = 1–3, using a spectrophotometric technique. An auto-catalytic effect has been observed in all cases due to Mn²⁺ ions formed as a product of the reaction. A first-order reaction with respect to the amino acid and the permanganate ions in both processes, catalyzed and uncatalyzed was obtained. The influence of several factors (pH, temperature, ionic strength, and reactants concentration) on the rate constants has also been investigated. In this article we propose a reaction mechanism in accordance with the experimental results obtained. © 1996 John Wiley & Sons, Inc.     

Cu(II)氧化抗坏血酸的动力学和机理

本文在总离子强度I=1.00mol.dm^-^3、[Cu^2^+]>>[H2A]、[H^+]>>[H2A]、无氧及无缓冲剂存在的条件下, 研究Cu(II)氧化抗坏血酸(H2A)的动力学和机理. 发现Cu(II)与H2A不发生配位反应, 但以Cl^-存在的情况下, 确有Cu(II)的H2A配合物生成, Cu(II)氧化H2A反应的速率方程为r={a+b[Cl^-]}[Cu^2^+]{[H+]+Ka}^-^2, 25℃时a和b值分别为4.08×10^-^4s^-^1和0.555dm^3.s^-^1.mol^-^1. Cu(II)氧化H2A反应的表观活化能为68.1KJ.mol^-^1. 根据动力学结果, 提出了反应机理, 并给出了配合物ClCuHA的结构形式.     

Kinetics and mechanism of oxidation of dimethyl sulphoxide by sodium bromate-sodium bisulphite reagent in aqueous medium

Rates of oxidation of dimethyl sulphoxide (DMSO) by HOBr producedin situ from sodium bromate-sodium bisulphite reagent have been studied iodometrically in aqueous medium. The order in [DMSO] is one when [DMSO] < 001 mol dm^-3, fractional when [DMSO] is between 0.01 and 0.5mol dm^-3 and zero when (DMSO) > 0.5 mol dm^-3. Different rate laws are operative under these three conditions though HOBr is the effective oxidizing species in all the cases. A mechanism involving an intermediate four-membered cyclic transition state between DMSO and HOBr (formation constantK), which decomposes in a slow step with a rate constant(k) has been proposed. Thermodynamic parameters for the adduct formation step and activation parameters for the first-order decomposition of the adduct step have been evaluated in the temperature range 308–323 K. Activation parameters have also been determined while the orders in [DMSO] are unity and zero. The reaction product has been identified as dimethyl sulphone (DMSO₂).     

Kinetics of oxidation of ascorbic acid by methylene blue in acid solutions

We propose a kinetic scheme for reduction of methylene blue by ascorbic acid, characterized by the existence of two pathways: outer-sphere reduction of methylene blue according to a second-order reaction, and reduction through formation of a 11 complex with ascorbic acid.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 29, No. 5, pp. 424–429, September–October, 1993.     

Kinetics and mechanism of oxidation of malonic acid by permanganate and manganese dioxide in acid perchlorate medium

Summary The kinetics of oxidation of malonic acid by both [MnO₄]^– and MnO₂ have been studied in an HClO₄ medium. The oxidation product of the organic acid was found to be glyoxylic acid. A reaction mechanism assuming complexation between MnO₂ and malonic acid is suggested. The rate is independent of [H⁺].     

Kinetics and mechanism of the oxidation of L-ascorbic acid by 2,6-dichlorophenol-indophenol in aqueous solution

The kinetics of oxidation of L-ascorbic acid by 2,6-dichlorophenolindophenol in aqueous solution has been studied. The rate of the reaction decreases with increasing pH since the hydrogen ascorbate ion is less reactive than the unionized L-ascorbic acid. The rate constants for the oxidation of the two species have been evaluated and a plausible mechanism of the reaction is suggested.

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L- 2,6-- . pH, , L- . .

     

Kinetics and mechanism of oxidation of arsenious acid by tetrachloroaurate(III) in hydrochloric acid medium

Kinetics of the oxidation of arsenious acid by tetrahcloroaurate(III) have been studied spectrophotometrically in hydrochloric acid medium. Initial complex formation between As(III) and Au(III) followed by the decomposition of the intermediate complex to give products of the reaction is suggested. The empirical rate law is

k and K are found to be 13.9 × 10^?4 s^?1 and 24.2 M^?1 respectively at 30°C and μ = 1.0 M. ΔH³ and ΔS³ for k are found to be 49.2 kJ mol^?1 and - 137.2 JK^?1 mol^?1 whereas ΔH and ΔS associated with K are - 6.75 kJ mol^?1 and 4.14 JK^?1 respectively.     

Kinetics and mechanism of sulfite oxidation by permanganate in basic medium

The kinetics of the permanganate-sulfite redox reaction has been studied in the alkaline medium using a stopped-flow technique. In the pH range 10 to 12 the reaction was found to obey the rate expression: ?½d[MnO₄^?]/dt = (k₁ + k₂[OH^?]) [MnO₄^?] [SO₃^2?]. Mechanisms for the two paths involving the formation of a (O₃MnOSO₃)^3? complex prior to the rate-determining step are consistent with the data. © John Wiley & Sons, Inc.