Kinetics and mechanism of oxidation of hypophosphite by Waugh-type enneamolybdomanganate(IV) in perchloric acid

Gurame, Vashishtha M.; Gokavi, Gavisiddappa S.

doi:10.1016/j.poly.2008.02.028

Cited by 10 publications

(11 citation statements)

References 32 publications

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“…The synthesized polyoxometalate was characterized by FTIR and AAS to understand the structure and formula of the compound [23][24] . The reaction was followed by measuring the absorbance of the reaction mixture using Elico SL-177 spectrophotometer.…”

Section: Introductionmentioning

confidence: 99%

Oxidation of Hydroxylamine by Waugh Type POM, Enneamolybdomanganate(IV) ion (A Kinetic and Mechanistic Study)

Barge¹,

Gokavi²

2017

Orient. J. Chem

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ABSTARCTThe reaction between hydroxyl amine and Waugh-type polyoxometalate, enneamolybdomanganate(ΙV), was investigated under pseudo-first-order condition in aqueous perchloric acid. The product of the reaction was nitrous oxide as determined by studying the stoichiometry which requires one mol of oxidant per mole of hydroxylamine. The rate of reaction increases as hydrogen ion and oxidant, enneamolybdomanganate(ΙV), concentrations increase, while it remains unchanged as the hydroxylamine concentration is altered. The oxidant exists in both protonated and unprotonated form under the reaction conditions and both are active. The hydroxyl amine remains in the protonated form and reacts with the active forms of the oxidant with different rate constants. The proposed mechanism, in accordance with the kinetic results obtained, involves reaction between hydroxyl amine and oxidant in a slow step. The rate law derived as per the proposed mechanism is also verified kinetically. Change in ionic strength and solvent polarity did not affect the rate of the reaction while activation parameters were calculated by studying the reaction at different temperatures

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Section: Introductionmentioning

confidence: 99%

Oxidation of Hydroxylamine by Waugh Type POM, Enneamolybdomanganate(IV) ion (A Kinetic and Mechanistic Study)

Barge¹,

Gokavi²

2017

Orient. J. Chem

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“…In comparison with Keggin and Dawson type salts, less attention has been given to other types of POM anions. In continuation [4,14] of our interest in the electron transfer reactions involving POMs and their utilization as redox catalysts, the present study is concerned with the oxidation of benzoic acid hydrazide by bromate in the presence of octamolybdomanganate(II) ([MnMo 8 O 27 ] 4-). Octamolybdomanganate(II) has a sheet structure in which MoO 6 units are distributed around Mn(OH 2 ) 4 groups via common oxygen atoms [15].…”

Section: Introductionmentioning

confidence: 99%

Kinetics and mechanism of oxidation of benzoic acid hydrazide by bromate catalyzed by octamolybdomanganate(II)

Kadam

Supale

Gokavi

2008

Transition Met Chem

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Oxidation of benzoic acid hydrazide by bromate in the presence of octamolybdomanganate(II), [Mn II Mo 8 O 27 ] 4-, was studied in hydrochloric acid medium. The mechanism of the reaction involves oxidation of the catalyst to [Mn IV Mo 8 O 27 ] 2-by bromate which then forms a complex with the unoxidized catalyst. Both the complex and [Mn IV Mo 8 O 27 ] 2-react with the substrate in rate-determining steps to generate an intermediate acyl diimide, RCONNH.The reaction of water with the diimide then leads to the formation of benzoic acid and nitrogen as products through an NH-NH intermediate. There was no formation of free radical, indicating the involvement of only two-electron transfer steps in the mechanism. The order of more than unity in catalyst concentration is due to the formation of complex between the catalyst and the oxidized form of the catalyst. A rate law explaining all the kinetic results has been derived and verified. The effects of ionic strength and solvent polarity have also been studied, and the thermodynamic parameters were determined. A less solvated transition state as a result of interaction between the complex and oxidized form of the catalyst satisfactorily explains all the effects observed.

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“…Molybdenum, the major content of the oxidant used, is found in several tissues of the human body and is required for the activity of xanthine oxidase which is involved in the catabolism of purines [15]. In continuation of our earlier studies [6,7,16,17], oxidation of vitamin B6 by enneamolybdomanganate(IV) was carried All chemicals were of reagent grade and double-distilled water was used throughout the work. A solution of pyridoxine hydrochloride (vitamin B6)(Hi Media) was freshly prepared by dissolving an appropriate amount of sample in double-distilled water.…”

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confidence: 99%

“…The ammonium salt of Mn IV complex, (NH 4 ) 6 [Mn IV Mo 9 O 32 ] was prepared by reported method [18]. The oxidant was characterized by FTIR and AAS analysis as reported earlier [16,17].…”

mentioning

confidence: 99%

“…Therefore, in the acidic medium used in the present study pyridoxine is predominantly exists as monoprotonated form with formation of pyridinium cation. Polyoxometalates are known to undergo protonation and in acidic medium and enneamolybdomanganate(IV) ion is in the form of hexaprotonated species [17]. Therefore, under the reaction conditions, the oxidant exists as H 6 [MnMo 9 O 32 ] and it is in equilibrium with H 5 [MnMo 9 O 32 ] − ions as shown in equilibrium (2).…”

mentioning

confidence: 99%

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Kinetics and mechanism of oxidation of pyridoxine by enneamolybdomanganate(IV)

Nipane

Gurame

Gokavi

2011

Inorganic Chemistry Communications

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Kinetics and mechanism of oxidation of hypophosphite by Waugh-type enneamolybdomanganate(IV) in perchloric acid

Cited by 10 publications

References 32 publications

Oxidation of Hydroxylamine by Waugh Type POM, Enneamolybdomanganate(IV) ion (A Kinetic and Mechanistic Study)

Oxidation of Hydroxylamine by Waugh Type POM, Enneamolybdomanganate(IV) ion (A Kinetic and Mechanistic Study)

Kinetics and mechanism of oxidation of benzoic acid hydrazide by bromate catalyzed by octamolybdomanganate(II)

Kinetics and mechanism of oxidation of pyridoxine by enneamolybdomanganate(IV)

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