The kinetics of oxidations of caffeine by permanganate ion in both perchloric and sulfuric acids solutions have been investigated spectrophotometrically at a constant ionic strength of 1.0 mol dm-3 and at 25°C. In both acids, the reaction-time curves were obtained with a sigmoid profile suggesting an autocatalytic effect caused by Mn(II) ions formed as a reaction product. Both catalytic and non-catalytic processes were determined to be first order with respect to the permanganate ion and caffeine concentrations, whereas the orders with respect to [H+] and [Mn(II)] were found to be less than unity. Variation of either ionic strength or dielectric constant of the medium had no significant effect on the oxidation rates. Spectroscopic studies and Michaelis-Menten plots showed no evidence for the formation of intermediate complexes in both acids suggesting that the reactions point towards the outer-sphere pathway. The reactions mechanism adequately describing the kinetic results was proposed. In both acids, the main oxidation products of caffeine were identified as 1,3,7-trimethyluric acid. Under comparable experimental conditions, the oxidation rate of caffeine in perchloric acid was slightly higher than that in sulfuric acid. The constants involved in the different steps of the reactions mechanism have been evaluated. With admiration to the rate-limiting step of these reactions, the activation parameters have been evaluated and discussed.
| Published in | Science Journal of Chemistry (Volume 4, Issue 2) |
| DOI | 10.11648/j.sjc.20160402.12 |
| Page(s) | 19-28 |
| Creative Commons |
This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited. |
| Copyright |
Copyright © The Author(s), 2024. Published by Science Publishing Group |
Caffeine, Oxidation, Permanganate, Acid, Kinetics, Mechanism
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APA Style
Ahmed Fawzy, Ishaq A. Zaafarany, Khalid S. Khairou, Layla S. Almazroai, Tahani M. Bawazeer, et al. (2016). Oxidation of Caffeine by Permanganate Ion in Perchloric and Sulfuric Acids Solutions: A Comparative Kinetic Study. Science Journal of Chemistry, 4(2), 19-28. https://doi.org/10.11648/j.sjc.20160402.12
ACS Style
Ahmed Fawzy; Ishaq A. Zaafarany; Khalid S. Khairou; Layla S. Almazroai; Tahani M. Bawazeer, et al. Oxidation of Caffeine by Permanganate Ion in Perchloric and Sulfuric Acids Solutions: A Comparative Kinetic Study. Sci. J. Chem. 2016, 4(2), 19-28. doi: 10.11648/j.sjc.20160402.12
AMA Style
Ahmed Fawzy, Ishaq A. Zaafarany, Khalid S. Khairou, Layla S. Almazroai, Tahani M. Bawazeer, et al. Oxidation of Caffeine by Permanganate Ion in Perchloric and Sulfuric Acids Solutions: A Comparative Kinetic Study. Sci J Chem. 2016;4(2):19-28. doi: 10.11648/j.sjc.20160402.12
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author = {Ahmed Fawzy and Ishaq A. Zaafarany and Khalid S. Khairou and Layla S. Almazroai and Tahani M. Bawazeer and Badriah A. Al-Jahdali},
title = {Oxidation of Caffeine by Permanganate Ion in Perchloric and Sulfuric Acids Solutions: A Comparative Kinetic Study},
journal = {Science Journal of Chemistry},
volume = {4},
number = {2},
pages = {19-28},
doi = {10.11648/j.sjc.20160402.12},
url = {https://doi.org/10.11648/j.sjc.20160402.12},
eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.sjc.20160402.12},
abstract = {The kinetics of oxidations of caffeine by permanganate ion in both perchloric and sulfuric acids solutions have been investigated spectrophotometrically at a constant ionic strength of 1.0 mol dm-3 and at 25°C. In both acids, the reaction-time curves were obtained with a sigmoid profile suggesting an autocatalytic effect caused by Mn(II) ions formed as a reaction product. Both catalytic and non-catalytic processes were determined to be first order with respect to the permanganate ion and caffeine concentrations, whereas the orders with respect to [H+] and [Mn(II)] were found to be less than unity. Variation of either ionic strength or dielectric constant of the medium had no significant effect on the oxidation rates. Spectroscopic studies and Michaelis-Menten plots showed no evidence for the formation of intermediate complexes in both acids suggesting that the reactions point towards the outer-sphere pathway. The reactions mechanism adequately describing the kinetic results was proposed. In both acids, the main oxidation products of caffeine were identified as 1,3,7-trimethyluric acid. Under comparable experimental conditions, the oxidation rate of caffeine in perchloric acid was slightly higher than that in sulfuric acid. The constants involved in the different steps of the reactions mechanism have been evaluated. With admiration to the rate-limiting step of these reactions, the activation parameters have been evaluated and discussed.},
year = {2016}
}
TY - JOUR T1 - Oxidation of Caffeine by Permanganate Ion in Perchloric and Sulfuric Acids Solutions: A Comparative Kinetic Study AU - Ahmed Fawzy AU - Ishaq A. Zaafarany AU - Khalid S. Khairou AU - Layla S. Almazroai AU - Tahani M. Bawazeer AU - Badriah A. Al-Jahdali Y1 - 2016/05/03 PY - 2016 N1 - https://doi.org/10.11648/j.sjc.20160402.12 DO - 10.11648/j.sjc.20160402.12 T2 - Science Journal of Chemistry JF - Science Journal of Chemistry JO - Science Journal of Chemistry SP - 19 EP - 28 PB - Science Publishing Group SN - 2330-099X UR - https://doi.org/10.11648/j.sjc.20160402.12 AB - The kinetics of oxidations of caffeine by permanganate ion in both perchloric and sulfuric acids solutions have been investigated spectrophotometrically at a constant ionic strength of 1.0 mol dm-3 and at 25°C. In both acids, the reaction-time curves were obtained with a sigmoid profile suggesting an autocatalytic effect caused by Mn(II) ions formed as a reaction product. Both catalytic and non-catalytic processes were determined to be first order with respect to the permanganate ion and caffeine concentrations, whereas the orders with respect to [H+] and [Mn(II)] were found to be less than unity. Variation of either ionic strength or dielectric constant of the medium had no significant effect on the oxidation rates. Spectroscopic studies and Michaelis-Menten plots showed no evidence for the formation of intermediate complexes in both acids suggesting that the reactions point towards the outer-sphere pathway. The reactions mechanism adequately describing the kinetic results was proposed. In both acids, the main oxidation products of caffeine were identified as 1,3,7-trimethyluric acid. Under comparable experimental conditions, the oxidation rate of caffeine in perchloric acid was slightly higher than that in sulfuric acid. The constants involved in the different steps of the reactions mechanism have been evaluated. With admiration to the rate-limiting step of these reactions, the activation parameters have been evaluated and discussed. VL - 4 IS - 2 ER -
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