Kinetics and Mechanism of Electron-Transfer Reactions: Oxidation of Butanone and Cyclohexanone by Thallium (III) in Acid Perchlorate Medium- An Appraisal of Keto Form Reactivity

Shalini Hemkar; Riya Sailani; Chandra Lata Khandelwal; Prem Dutt Sharma

doi:doi:10.11648/j.ajpc.20130205.11

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Kinetics and Mechanism of Electron-Transfer Reactions: Oxidation of Butanone and Cyclohexanone by Thallium (III) in Acid Perchlorate Medium- An Appraisal of Keto Form Reactivity

Shalini Hemkar, Riya Sailani, Chandra Lata Khandelwal, Prem Dutt Sharma

Published in American Journal of Physical Chemistry (Volume 2, Issue 5)

Received: 8 August 2013 Published: 10 September 2013

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Abstract

The kinetics of oxidation of ketones by thallium (III) has been studied in acid perchlorate medium. The reaction does not indicate enolization to be the rate controlling step in the reaction mechanism. The kinetic rate law (1) has been observed. -d[TlIII] / dt= k1Kh [Tl(III)Ketone] / ([H+] + Kh) Where Kh is the hydrolysis constant of the oxidant. A plausible reaction mechanism is suggested conforming to the rate law (1). Activation parameters were evaluated.

Published in	American Journal of Physical Chemistry (Volume 2, Issue 5)
DOI	10.11648/j.ajpc.20130205.11
Page(s)	73-79
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), 2013. Published by Science Publishing Group

Keywords

Kinetics, Mechanism, Oxidation, Butanone, Cyclohexanone, Thallium (III)

References

[1]	M. Pechal, J. Vojtko, J. Kubena and M. Hrusovsky, "Kinetics of the oxidation of aliphatic ketones by thallic salts in sulfuric acid medium", React. Kinet. Catal. Lett., vol. 20, pp. 151-155, 1982.
[2]	K. Vijayamohan, P.R. Rao and E.V. Sundaram, "N-bromosaccharin as an oxidizing agent-A kinetic study using aliphatic and cyclic ketones in aqueous acetic acid", J. Ind. Chem. Soc., vol. 61, pp. 225-228, 1984.
[3]	M. Gupta, S.K. Saha and P. Banerjee, "Kinetics and mechanism of the oxidation of some cyclic and acyclic ketones by dodecatungstocobaltate(III)- A comparative study", Int. J. Chem. Kinet., vol. 22, pp. 81-94, 1990.
[4]	B. Singh, B.B.L. Saxena and A.K. Samant, "Kinetics and mechanism of the oxidation of some aliphatic ketones by n-bromoacetamide in acidic media", Tetrahderon, vol. 40, pp. 3321-3324, 1984.
[5]	D.S. Mahadevappa, K. Mohan and S. Ananda, "Oxidation of aliphatic ketones by bromamine-B; A kinetic study", Tetrahderon, vol. 42, pp. 4857-4866, 1986.
[6]	N.K. Murthy, C.H.S. Reddy and E.V. Sundaram, "Kinetics and mechanism of acid bromated oxidation of aliphatic, aralkyl & alicyclic ketones", Ind. J. Chem. Sect (A), vol. 28, pp. 288-291, 1989.
[7]	P. Manikyamba, "Structural effects in the oxidation of ketones by acid iodate", Collect. Czech. Chem. Commun., vol. 56, pp. 1279-1286, 1991.
[8]	K.K. Banerji, M.P. Nath and G.V. Bakore, "A kinetic investigation of oxidation of ethyl methyl ketone by manganese (III) sulphate", Bull. Chem. Soc. Jpn., vol. 43, pp. 2027-2029, 1970.
[9]	G. Manivannan and P. Maruthamuthu, "Kinetics and mechanism of oxidation of aliphatic and aromatic ketones by peroxomonosulphate", J. Chem. Soc. Perkin, Tran 2, pp. 565-568, 1986.
[10]	M.P. Nath and K.K. Banerji, "Kinetics & mechanism of oxidation of acetone, butanone, pentan-2-one, 3-methylbutan-2-one, hexan-2-one & 4-methylpentan-2-one by acid permanganate", Ind. J. Chem. Sec. (A), vol. 14, pp. 660-662, 1976.
[11]	M. P. Nath and K.K. Banerji, "Kinetics and mechanisms of the oxidation of methyl aryl ketones by acid permanganate", Aust. J. Chem., vol. 29, pp. 1939-1945, 1976.
[12]	P.S. Radhakrishnamurti and M.D.P. Rao, "Oxidation of aliphatic ketones, substituted acetophenones & cyclic ketones by potassium permanganate", Ind. J. Chem. Sect. (A), vol. 15, pp. 524-527, 1977.
[13]	P.K. Sen, G. Mukhopadhyay and K.K. Sengupta, "Kinetics and mechanism of the oxidation of alkyl and aryl methyl ketones by permanganate ion in aqueous ethanoic acid", Trans. Met. Chem., vol. 23, pp. 577-582, 1998.
[14]	A. Ramesh, B. Syamasunder and P.S. Radhakrishnamurti, "Kinetics and mechanism of oxidation of methyl ethyl ketone by iodine mono bromide catalyzed by Hg (II) and N-bromophthalimide in acid medium", Oxid. Commun., vol. 31 (3), pp. 554-560, 2008.
[15]	A. Gupta, M.K. Singh and H.S. Singh, "Iridium (III) chloride catalyzed oxidation of ketones by cerium (IV) sulfate in aqueous sulfuric acid medium. A kinetic study", Oxid. Commun., vol. 30 (3), pp. 633-640, 2007.
[16]	Liang. Jeng-Jong and Chen. Chun-Hsiang, "Catalytic oxidation of toluene and methyl ethyl ketone over La-Sr-Mn perovskite catalysts", Zhongguo Huanjing Gongcheny Xuekan, vol. 15 (2), pp. 111-119, 2005.
[17]	I.M. Kolthoff and R. Belcher, Volumetric Analysis, Interscience, New York, vol. 3, 1957, pp. 370.
[18]	H.G.S. Sengar, and Y.K. Gupta, "Kinetics of silver catalysed oxidation of Tl (I) by persulphate", J. Ind. Chem. Soc., vol. 43, pp. 223-234, 1966.
[19]	M. Latshaw, "A simple tangentimeter", J. Am. Chem. Soc., vol. 47, pp. 793-794, 1925.
[20]	A.G. Lee, Chemistry of Thallium, Elsevier, London, 1971.
[21]	G. Nord, "Oxidation of some tris (2,2’-bipyridyl) and tris (1,10-phenenthroline) osmium (II) salts by thallium (III) in aqueous acid", Inorg. Chem., vol. 15, pp. 1921-1925, 1976 and references cited therein.
[22]	J.O. Wear, "The oxidation of uranium (IV) by thallium (III) over an extended concentration range in aqueous perchloric acid solutions", J. Chem. Soc., pp. 5596-5601, 1965.
[23]	D.H. Irvine, "The Kinetics of the reduction of thallium (III) by the tris dipyridylosmium (II) ion in aqueous perchloric acid" J. Chem. Soc., pp. 1841-1845, 1957.
[24]	A.M. Armstrong and J. Halpern, "Kinetics of the oxidation of mercury (I) by thallium (III) in aqueous solution", Can. J. Chem., vol. 35, pp. 1020-1030, 1957 and references cited therein.
[25]	H.N. Halvorson and J. Halpern, "Kinetics of the reaction between formic acid and thallium (III) in aqueous solution", J. Am. Chem. Soc., vol. 78, pp. 5562-5566, 1956.
[26]	P.D. Sharma and Y.K. Gupta, "Reduction of chlorothallium (III) complexes by arsenic (III)", Aust. J. Chem., vol. 26, pp. 2115-2122, 1973.
[27]	P.D. Sharma and Y.K. Gupta, "Kinetics and mechanism of electron transfer reactions of aquo & coordinated thallium (III): Reduction of chloro-thallium (III) complexes by antimony (III)", Ind. J. Chem., vol. 12, pp. 100-102, 1974.
[28]	P.D. Sharma and Y.K. Gupta, "Kinetics and mechanism of the reduction of thallium (III) by arsenic (III) in perchlorate acid solution", J. Chem. Soc. Dalton Trans., pp. 52-55, 1972 and references cited therein.
[29]	W.M. Latimer, Oxidation Potentials, 2nd. ed., Prentice Hall, New York 1952.

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Shalini Hemkar, Riya Sailani, Chandra Lata Khandelwal, Prem Dutt Sharma. (2013). Kinetics and Mechanism of Electron-Transfer Reactions: Oxidation of Butanone and Cyclohexanone by Thallium (III) in Acid Perchlorate Medium- An Appraisal of Keto Form Reactivity. American Journal of Physical Chemistry, 2(5), 73-79. https://doi.org/10.11648/j.ajpc.20130205.11

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ACS Style

Shalini Hemkar; Riya Sailani; Chandra Lata Khandelwal; Prem Dutt Sharma. Kinetics and Mechanism of Electron-Transfer Reactions: Oxidation of Butanone and Cyclohexanone by Thallium (III) in Acid Perchlorate Medium- An Appraisal of Keto Form Reactivity. Am. J. Phys. Chem. 2013, 2(5), 73-79. doi: 10.11648/j.ajpc.20130205.11

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AMA Style

Shalini Hemkar, Riya Sailani, Chandra Lata Khandelwal, Prem Dutt Sharma. Kinetics and Mechanism of Electron-Transfer Reactions: Oxidation of Butanone and Cyclohexanone by Thallium (III) in Acid Perchlorate Medium- An Appraisal of Keto Form Reactivity. Am J Phys Chem. 2013;2(5):73-79. doi: 10.11648/j.ajpc.20130205.11

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@article{10.11648/j.ajpc.20130205.11,
  author = {Shalini Hemkar and Riya Sailani and Chandra Lata Khandelwal and Prem Dutt Sharma},
  title = {Kinetics and Mechanism of Electron-Transfer Reactions: Oxidation of Butanone and Cyclohexanone by Thallium (III) in Acid Perchlorate Medium- An Appraisal of Keto Form Reactivity},
  journal = {American Journal of Physical Chemistry},
  volume = {2},
  number = {5},
  pages = {73-79},
  doi = {10.11648/j.ajpc.20130205.11},
  url = {https://doi.org/10.11648/j.ajpc.20130205.11},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajpc.20130205.11},
  abstract = {The kinetics of oxidation of ketones by thallium (III) has been studied in acid perchlorate medium. The reaction does not indicate enolization to be the rate controlling step in the reaction mechanism. The kinetic rate law (1) has been observed. -d[TlIII] / dt= k1Kh [Tl(III)Ketone] / ([H+] + Kh) Where Kh is the hydrolysis constant of the oxidant. A plausible reaction mechanism is suggested conforming to the rate law (1). Activation parameters were evaluated.},
 year = {2013}
}

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TY  - JOUR
T1  - Kinetics and Mechanism of Electron-Transfer Reactions: Oxidation of Butanone and Cyclohexanone by Thallium (III) in Acid Perchlorate Medium- An Appraisal of Keto Form Reactivity
AU  - Shalini Hemkar
AU  - Riya Sailani
AU  - Chandra Lata Khandelwal
AU  - Prem Dutt Sharma
Y1  - 2013/09/10
PY  - 2013
N1  - https://doi.org/10.11648/j.ajpc.20130205.11
DO  - 10.11648/j.ajpc.20130205.11
T2  - American Journal of Physical Chemistry
JF  - American Journal of Physical Chemistry
JO  - American Journal of Physical Chemistry
SP  - 73
EP  - 79
PB  - Science Publishing Group
SN  - 2327-2449
UR  - https://doi.org/10.11648/j.ajpc.20130205.11
AB  - The kinetics of oxidation of ketones by thallium (III) has been studied in acid perchlorate medium. The reaction does not indicate enolization to be the rate controlling step in the reaction mechanism. The kinetic rate law (1) has been observed. -d[TlIII] / dt= k1Kh [Tl(III)Ketone] / ([H+] + Kh) Where Kh is the hydrolysis constant of the oxidant. A plausible reaction mechanism is suggested conforming to the rate law (1). Activation parameters were evaluated.
VL  - 2
IS  - 5
ER  -

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Author Information

Shalini Hemkar

Department of Chemistry, Government College, Churu, Rajasthan
Riya Sailani

Department of Chemistry, University of Rajasthan, Jaipur – 302055 (India)
Chandra Lata Khandelwal

Department of Chemistry, University of Rajasthan, Jaipur – 302055 (India)
Prem Dutt Sharma

Department of Chemistry, University of Rajasthan, Jaipur – 302055 (India)

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APA Style

Shalini Hemkar, Riya Sailani, Chandra Lata Khandelwal, Prem Dutt Sharma. (2013). Kinetics and Mechanism of Electron-Transfer Reactions: Oxidation of Butanone and Cyclohexanone by Thallium (III) in Acid Perchlorate Medium- An Appraisal of Keto Form Reactivity. American Journal of Physical Chemistry, 2(5), 73-79. https://doi.org/10.11648/j.ajpc.20130205.11

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ACS Style

Shalini Hemkar; Riya Sailani; Chandra Lata Khandelwal; Prem Dutt Sharma. Kinetics and Mechanism of Electron-Transfer Reactions: Oxidation of Butanone and Cyclohexanone by Thallium (III) in Acid Perchlorate Medium- An Appraisal of Keto Form Reactivity. Am. J. Phys. Chem. 2013, 2(5), 73-79. doi: 10.11648/j.ajpc.20130205.11

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AMA Style

Shalini Hemkar, Riya Sailani, Chandra Lata Khandelwal, Prem Dutt Sharma. Kinetics and Mechanism of Electron-Transfer Reactions: Oxidation of Butanone and Cyclohexanone by Thallium (III) in Acid Perchlorate Medium- An Appraisal of Keto Form Reactivity. Am J Phys Chem. 2013;2(5):73-79. doi: 10.11648/j.ajpc.20130205.11

Copy | Download

@article{10.11648/j.ajpc.20130205.11,
  author = {Shalini Hemkar and Riya Sailani and Chandra Lata Khandelwal and Prem Dutt Sharma},
  title = {Kinetics and Mechanism of Electron-Transfer Reactions: Oxidation of Butanone and Cyclohexanone by Thallium (III) in Acid Perchlorate Medium- An Appraisal of Keto Form Reactivity},
  journal = {American Journal of Physical Chemistry},
  volume = {2},
  number = {5},
  pages = {73-79},
  doi = {10.11648/j.ajpc.20130205.11},
  url = {https://doi.org/10.11648/j.ajpc.20130205.11},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajpc.20130205.11},
  abstract = {The kinetics of oxidation of ketones by thallium (III) has been studied in acid perchlorate medium. The reaction does not indicate enolization to be the rate controlling step in the reaction mechanism. The kinetic rate law (1) has been observed. -d[TlIII] / dt= k1Kh [Tl(III)Ketone] / ([H+] + Kh) Where Kh is the hydrolysis constant of the oxidant. A plausible reaction mechanism is suggested conforming to the rate law (1). Activation parameters were evaluated.},
 year = {2013}
}

Copy | Download

TY  - JOUR
T1  - Kinetics and Mechanism of Electron-Transfer Reactions: Oxidation of Butanone and Cyclohexanone by Thallium (III) in Acid Perchlorate Medium- An Appraisal of Keto Form Reactivity
AU  - Shalini Hemkar
AU  - Riya Sailani
AU  - Chandra Lata Khandelwal
AU  - Prem Dutt Sharma
Y1  - 2013/09/10
PY  - 2013
N1  - https://doi.org/10.11648/j.ajpc.20130205.11
DO  - 10.11648/j.ajpc.20130205.11
T2  - American Journal of Physical Chemistry
JF  - American Journal of Physical Chemistry
JO  - American Journal of Physical Chemistry
SP  - 73
EP  - 79
PB  - Science Publishing Group
SN  - 2327-2449
UR  - https://doi.org/10.11648/j.ajpc.20130205.11
AB  - The kinetics of oxidation of ketones by thallium (III) has been studied in acid perchlorate medium. The reaction does not indicate enolization to be the rate controlling step in the reaction mechanism. The kinetic rate law (1) has been observed. -d[TlIII] / dt= k1Kh [Tl(III)Ketone] / ([H+] + Kh) Where Kh is the hydrolysis constant of the oxidant. A plausible reaction mechanism is suggested conforming to the rate law (1). Activation parameters were evaluated.
VL  - 2
IS  - 5
ER  -

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