Oxyhalogen−Sulfur Chemistry:  Oxidation of Hydroxymethanesulfinic Acid by Chlorite

Salem, Mohamed A.; Chinake, Cordelia R.; Simoyi, Reuben H.

doi:10.1021/jp953795i

Cited by 16 publications

(29 citation statements)

References 38 publications

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“…With [H + ] 0 ≫ [ClO 2 − ] 0 ≫ [MV + ] 0 , the title reaction exhibits exponential kinetics. This departure from the nonlinear behavior 7, 8 and the highly selective catalytic efficiency of Ru(III) generated interest in the kinetic study of the reaction between MV + and acidic chlorite.…”

Section: Introductionmentioning

confidence: 99%

Uncatalyzed and ruthenium(III)‐catalyzed reaction of acidic chlorite with methylene violet

Jonnalagadda

Shezi

Pare

2003

Int J of Chemical Kinetics

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The kinetics and mechanism of the uncatalyzed and Ru(III)-catalyzed oxidation of methylene violet (3-amino-7-diethylamino-5-phenyl phenazinium chloride) (MV + ) by acidic chlorite is reported. With excess concentrations of other reactants, both uncatalyzed and catalyzed reactions had pseudo-first-order kinetics with respect to MV + . The uncatalyzed reaction had first-order dependence on chlorite and H + concentrations, but the catalyzed reaction had first-order dependence on both chlorite and catalyst, and a fractional order with respect to [H + ]. The rate coefficient of the uncatalyzed reaction is (5.72 ± 0.19) M −2 s −1 , while the catalytic constant for the catalyzed reaction is (22.4 ± 0.3) × 10 3 M −1 s −1 . The basic stoichiometric equation is as follows: 2MV + + 7ClO 2 − + 2H + = 2P + CH 3 COOH + 4ClO 2 + 3Cl − , where P + = 3-amino-7-ethylamino-5-phenyl phenazinium-10-N-oxide. Stoichiometry is dependent on the initial concentration of chlorite present. Consistent with the experimental results, pertinent mechanisms are proposed. The proposed 15-step mechanism is simulated using literature; experimental and estimated rate coefficients and the simulated plots agreed well with the experimental curves.

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Section: Introductionmentioning

confidence: 99%

Uncatalyzed and ruthenium(III)‐catalyzed reaction of acidic chlorite with methylene violet

Jonnalagadda

Shezi

Pare

2003

Int J of Chemical Kinetics

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“…The loop consists of three reactions, two of them irreversible and unopposed as shown below Subsequent to the publication of this mechanism, it was shown that reaction does not occur; so, the illegality of this reaction loop is no longer a concern. A related illegal loop appears in the mechanism proposed for the reaction of chlorite with hydroxymethanesulfinate, where step M10 above is considered to proceed irreversibly to the right, step M13 above produces HClO 2 and ClO 2 – instead of 2ClO 2 – , and the acid dissociation of HClO 2 is included …”

Section: Resultsmentioning

confidence: 99%

Systematic Application of the Principle of Detailed Balancing to Complex Homogeneous Chemical Reaction Mechanisms

Stanbury

Hoffman

2019

J. Phys. Chem. A

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It is not uncommon for proposed complex reaction mechanisms to violate the principle of detailed balancing. Here, we draw attention to three ways in which such violations can occur: reversible reaction loops where the rate constants do not attain closure, illegal loops, and reversible steps having rate equations in the forward and reverse directions that are inconsistent with the equilibrium expressions. We present two simple methods to test whether a proposed mechanism is consistent with the first two aspects of the principle of detailed balancing. Both methods are restricted to closed homogeneous isothermal reactions having mechanisms that consist of stoichiometrically balanced reaction steps. The first method is restricted to mechanisms in which all reaction steps are reversible; values of Δ f G°are assigned to all reaction species, equilibrium constants are then computed for all steps, and all rate constants for elementary steps are constrained by the relationship K eq = k f /k r . The second method is applicable to mechanisms that can consist of a series of reversible and/or irreversible reaction steps. One first examines the subset of reversible steps to determine whether any of these steps are stoichiometrically equivalent to a combination of any of the other steps. If so, the forward and reverse rate expressions must yield equilibrium constants that are in agreement with the stoichiometric relationships. Next, the complete set of steps is examined to look for "illegal reaction loops". Both of these procedures are performed by constructing matrices that represent the stoichiometries of the various reaction steps and then performing row reductions to identify basis sets of loops. A method based on linear programming is described that determines whether a mechanism contains any illegal loops. These methods are applied in the analysis of several published reaction mechanisms.

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“…The reasons for this discrepancy have not been elucidated. The interpretation 161,162 of the results of kinetic studies of the reactions of hydroxymethanesulfinate with bromate and chlorite in acid media is even more objectionable. Presumably, the reactions of HMS with any oxohalogen compounds either present initially or formed at intermediate stages (BrO 3 , HBrO 2 , HOBr, ClO À 2 , HOCl, ClO 2 , Cl 2 O 2 ) afford hydroxymethanesulfonate.…”

Section: The Kinetics and Mechanisms Of Reactions Involving Sulfur-co...mentioning

confidence: 99%

“…Presumably, the reactions of HMS with any oxohalogen compounds either present initially or formed at intermediate stages (BrO 3 , HBrO 2 , HOBr, ClO À 2 , HOCl, ClO 2 , Cl 2 O 2 ) afford hydroxymethanesulfonate. 161,162 As a result of oxidation, this product gives sulfate, i.e., as in the case of reactions involving thiourea, the C7S bond rupture takes place after the appearance of sulfonate. Meanwhile, it is known that hydroxymethanesulfonate is very stable in acid media and does not tend to participate in redox reactions.…”

Section: The Kinetics and Mechanisms Of Reactions Involving Sulfur-co...mentioning

confidence: 99%

“…7 Conversely, HMS rapidly decomposes in acid solutions, the products of its decomposition exhibiting strong reducing properties. Unfortunately, in the studies cited above, 161,162 no mention is even made of the HMS decomposition or the role of its products Ð sulfoxylate and formaldehyde (later, the same researchers demonstrated 163 that formaldehyde reacts with chlorite at a rather high rate). The results of study of Makarov et al 164 made it possible to introduce substantial changes to the schemes of reactions of halogens and oxohalogen compounds with thiourea, thiourea dioxide and hydroxymethanesulfinate.…”

Section: The Kinetics and Mechanisms Of Reactions Involving Sulfur-co...mentioning

confidence: 99%

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Recent trends in the chemistry of sulfur-containing reducing agents

Макаров¹

2001

Russ. Chem. Rev.

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Oxyhalogen−Sulfur Chemistry: Oxidation of Hydroxymethanesulfinic Acid by Chlorite

Cited by 16 publications

References 38 publications

Uncatalyzed and ruthenium(III)‐catalyzed reaction of acidic chlorite with methylene violet

Uncatalyzed and ruthenium(III)‐catalyzed reaction of acidic chlorite with methylene violet

Systematic Application of the Principle of Detailed Balancing to Complex Homogeneous Chemical Reaction Mechanisms

Recent trends in the chemistry of sulfur-containing reducing agents

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