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Current Physical Chemistry

Editor-in-Chief

ISSN (Print): 1877-9468
ISSN (Online): 1877-9476

Research Article

Kinetic and Mechanistic Pathway of Electron Transfer Reactions: Pyridine Oxidation by Peroxomonophosphoric Acid in Acidic Aqueous Medium

Author(s): A. Agarwal and A. Meena*

Volume 14, Issue 2, 2024

Published on: 26 January, 2024

Page: [133 - 142] Pages: 10

DOI: 10.2174/0118779468262862231220094220

Price: $65

Abstract

The kinetic and mechanistic pathways of pyridine oxidation by peroxomonophosphate has been studied in an acidic aqueous medium. Reactions of peroxomonophosphoric acid are the least exploited kinetically. This reaction has been attempted to understand the role of oxidation of pyridine and the reactivity pattern of peroxomonophosphate. The reaction has been second order and First-order concerning the oxidant and substrate, respectively. The reaction rate showed a decreasing effect with increasing hydrogen ion concentration. Considering peroxomonophosphate reactions as non-chain reactions and all the results, a feasible mechanism for the reaction has been suggested. The calculated energy of activation and entropy of activation has been observed conventionally to be 80 ± 5 kJ mol-1 and – 45 ± 6 JK-1 mol-1. The oxidation product was pyridine-N-oxide in this reaction.

Graphical Abstract

[1]
Kapoor, S.; Gupta, Y.K. Kinetics and mechanism of oxidations by peroxodiphosphate ions. Part 3. Oxidation of hypophosphite in aquous perchloric acid by the hydrolytic product peroxomonophosphate in a consecutive reaction. J. Chem. Soc., Dalton Trans., 1977, (9), 862.
[http://dx.doi.org/10.1039/dt9770000862]
[2]
Agarwal, A. Meena, kinetics and mechanism of electron transfer reactions: oxidation of pyridine by peroxomonosulphate in aqueous acid medium. Eur. Chem. Bull., 2023, 12(8), 988-1002.
[3]
Maruthamuthu, P.; Neta, P. Radiolytic chain decomposition of peroxomonophosphoric and peroxomonosulfuric acids. J. Phys. Chem., 1977, 81(10), 937-940.
[http://dx.doi.org/10.1021/j100525a001]
[4]
Goh, S.H.; Heslop, R.B.; Lethbridge, J.W. The hydrolysis of peroxophosphates. J. Chem. Soc. A, 1966, 1302-1306.
[5]
Bhardwaj, L.M.; Sharma, D.N.; Gupta, Y.K. Inorg, Kinetics and mechanism of oxidations by peroxydiphosphate. 2. Oxidation of bromide in aqueous perchloric acid solution. Chem, 1976, 15, 1695.
[6]
Kapoor, S.; Gupta, Y.K. Kinetics and mechanism of oxidations by peroxodiphosphate ions. Part I. Oxidation of arsenic(III) in aqueous perchloric acid. J. Chem. Soc., Dalton Trans., 1976, (5), 473.
[http://dx.doi.org/10.1039/dt9760000473]
[7]
Kapoor, S.; Gupta, Y.K. Kinetics and mechanism of oxidations by peroxodiphosphate—IV. J. Inorg. Nucl. Chem., 1977, 39(6), 1019-1021.
[http://dx.doi.org/10.1016/0022-1902(77)80256-X]
[8]
Patnaik, C.P.; Mohapatro, S.N.; Panigrahi, A.K.; Panda, R.S. Peroxy acid oxidations. I. A kinetic and mechanistic study of oxidation of acetylacetone by peroxomonophosphoric acid and hydrogen peroxide in alkaline medium. Bull. Chem. Soc. Jpn., 1987, 60(9), 3391-3395.
[http://dx.doi.org/10.1246/bcsj.60.3391]
[9]
Boyland, E.; Manson, D. J. Chem. Soc., 1957, 4869.
[10]
Mahapatra, S.N.; Panigrahi, G.P.; Panda, A.K. Cuer. Sci., 1980, 49, 227.
[11]
Panigrahi, G.P.; Panda, R. Oxidation studies with peroxomonophosphoric acid. II. A kinetic and mechanistic study of dimethyl sulfoxide oxidation in acid and alkaline media. Int. J. Chem. Kinet., 1980, 12(7), 491-499.
[http://dx.doi.org/10.1002/kin.550120705]
[12]
Panigrahi, G.P.; Panda, R. Oxidation studies with peroxomonophosphoric acid. III. A kinetic and mechanistic study of oxidation of dialkyl sulfides. Bull. Chem. Soc. Jpn., 1980, 53(8), 2366-2370.
[http://dx.doi.org/10.1246/bcsj.53.2366]
[13]
Mishra, D.K.; Dhas, T.P.A.; Sharma, P.D.; Bhargava, A.P.; Gupta, Y.K. Role of trace metal ions. Kinetics and mechanism of the copper(II)-catalysed oxidation of ascorbic acid with peroxodiphosphate in acetate buffers. J. Chem. Soc., Dalton Trans., 1990, (4), 1265. [and references cited therein].
[http://dx.doi.org/10.1039/dt9900001265]
[14]
Battagalia, C.J.; Edwards, J.O. The dissociation constants and the kinetics of hydrolysis of peroxymonophosphoric acid. Inorg. Chem., 1965, 4, 552.
[15]
Chatamrea, B.; Jones, A.S. 151. The permanganate oxidation of uracil and cytosine and their 1-substituted derivatives. J. Chem. Soc., 1963, 811-815.
[http://dx.doi.org/10.1039/jr9630000811]
[16]
Jones, A.S.; Walker, R.T. 669. The permanganate oxidation of nucleosides. J. Chem. Soc., 1963, 3554.
[http://dx.doi.org/10.1039/jr9630003554]
[17]
Jones, A.S.; Ross, G.W.; Takemura, S.; Thompson, T.W.; Walker, R.T. 66. The nucleotide sequence in deoxyribonucleic acids. Part VI. The preparation and reactions of permanganate-oxidised deoxyribonucleic acid. J. Chem. Soc., 1964, 373.
[http://dx.doi.org/10.1039/jr9640000373]
[18]
Soni, N.K.; Sailani, Riya.; Khandelwal, C. L.; Sharma, P. D. Kinetics and mechanism of oxidation of l-ascorbic acid by peroxomonophosphate in aqueous acid medium. Int. J. Chem. Kinetics, 2013, 45, 41-46.
[19]
Vijai, N.; Mala, D.; Khandelwal, C.L.; Sharma, P.D. Kinetics and mechanism of electron transfer reactions: Oxidation of glyoxylic acid by peroxomonophosphoric acid in acid perchlorate medium. J. Chem.-A, 2008, 47A(06)
[20]
Agrawal, A.; Sailani, R.; Sharma, P.; Khandelwal, C.L.; Sharma, P.D. Kinetics and mechanism of electron-transfer reactions: oxidation of pyridine by permanganate in aqueous acid perchlorate medium. Oxidation Commun., 2016, 39(2), 1273-1281.

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