Kinetics of Cetyltrimethylammonium Bromide Catalysed Oxidation of Cyclopentanone by N-Bromophthalimide in Acidic Medium

Yokraj R. Katre; Kamalni Tripathi; Ajaya K. Singh

doi:10.3139/113.110295

Published by De Gruyter May 1, 2013

Kinetics of Cetyltrimethylammonium Bromide Catalysed Oxidation of Cyclopentanone by N-Bromophthalimide in Acidic Medium

Kinetik der von Cetyltrimethylammoniumbromid katalysierten Oxidation des Cyclopentanons durch N-Bromophthalimid im sauren Medium

Yokraj R. Katre , Kamalni Tripathi and Ajaya K. Singh

From the journal Tenside Surfactants Detergents

https://doi.org/10.3139/113.110295

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Abstract

The effect of cationic micelles of cetyltrimethylammonium bromide (CTAB) and anionic micelles of sodium dodecyl sulphate (SDS) on the kinetics of oxidation of cyclopentanone by N-bromophthalimide (NBP) was studied iodometrically at 308 K. In addition to the kinetic experiments, conductivity measurements have also been done to obtain critical micelle concentration and other thermodynamic properties. The kinetic observations indicate fractional order and first order dependence with respect to [cyclopentanone] and [NBP] respectively. Cationic surfactant (CTAB) strongly catalyses the oxidation of Cyclopentanone in aqueous acetic acid medium. Typical k_obs and [CTAB] profile were observed i. e. with the progressive increase in [CTAB], the reaction rate increased and at higher concentration of CTAB, constancy in k_obs was observed. Anionic surfactant (sodium dodecylsulphate, SDS), mercuric acetate and phthalimide did not influence the reaction rate. The presence of inorganic salts (KCl, KBr) exhibits a severe hike in the reaction rate. The various activation parameters in the presence of CTAB have been also evaluated. A suitable mechanism consistent with the experimental findings has been proposed.

Kurzfassung

Der Einfluss der kationischen Mizellen des Cetyltrimethylammoniumbromids (CTAB) und der anionischen Mizellen des Natriumdodecylsulfats (SDS) auf die Kinetik der Oxidationsreaktion des Cyclopentanons durch N-Bromophthalimid (NBP) wurde bei 308 K iodometrisch studiert. Zusätzlich zu den kinetischen Experimenten wurde Leitfähigkeitsmessungen durchgeführt, um die kritische Mizellbildungskonzentration und weitere thermodynamische Parameter zu bestimmen. Die Ergebnisse zeigen eine Kinetik gebrochener Ordnung in Hinblick auf die Cyclopentanonkonzentration und eine Kinetik Erster Ordnung hinsichtlich der N-Bromophthalimidkonzentration an. Das kationische Tensid CTAB katalysiert die Oxidation des Cyclopentanons im sauren wässrigen Medium stark. Die typischen k_obs- und [CTAB]-Profile wurden festgestellt, d. h. mit zunehmender Konzentration der CTAB-Konzentration steigt die Reaktionsgeschwindigkeit; bei höheren CTAB-Konzentrationen ist k_obs konstant. Das anionische Tensid SDS, Quecksilberacetat und Phthalimid beeinflussen die Reaktionsgeschwindigkeit dagegen nicht. Die Anwesenheit anorganischer Salze (KCl und KBr) liefern einen heftigen Anstieg der Reaktionsgeschwindigkeit. Es wurden die verschiedenen Aktivierungsparameter in Anwesenheit von CTAB berechnet. Ein geeigneter Mechanismus, der mit den experimentellen Ergebnissen konsistent ist, wurde vorgeschlagen.

Key words: N-bromophthalimide; cetyl trimethyl ammonium bromide; CTAB; sodium dodecyl sulphate; SDS; cyclo pentanone; oxidation; kinetics

Stichwörter: N-Bromphthalimid; Cetyltrimethylammoniumbromid; CTAB; Natriumdodecylsulphat; SDS Cyclopentanon; Oxidation; Kinetik

*Dr. Yokraj R. Katre, Department of Chemistry, Kalyan P. G. College, Bhilai Nagar, Durg (C.G.), 490006, India, E-Mail: yokrajkatre@rediffmail.com, E-Mail: ajayaksingh_au@yahoo.co.in, E-Mail: drkamalnitripathi@gmail.com

Dr. Yokraj Katre received his M. Sc. in 1977 from Sagar University, India, and his M. Phil in 1985 and Ph. D. in 1988 from Vikram University, Ujjain, India. He participated in the 8^th International Conference of Surfactants and presented a paper at the University of Florida, Gainesville, in 1990. He has been an assistant professor of chemistry in Kalyan P. G. Mahavidyalaya, Bhilai, since 1978. He continues his research related to micellar kinetics, including a current 2 year research project sanctioned by U.G.C. He attended the 233^rd American Chemical Society meeting in Chicago, USA and presented an oral paper in the Colloid and Surface Science Division in 25^th to 29^th March 2007. He was a member of American Chemical Society for the year 2007 – 08.

Dr. Ajaya K. Singh received his M. Sc. in inorganic chemistry from Poorvanchal University Jaunpur, India and his D. Phil in Physical Chemistry in 2002 from the University of Allahabad, Allahabad, India. He was selected as an assistant professor of chemistry in Government Science College, Mungeli, Bilaspur through the M. P. Public Service Commision, Indore in 1994. He presented an oral paper in the second Asian Conference on Colloidal and Interface Chemistry held on Shandong University, Ginan, China. He was awarded teacher research fellowship to complete his research in 2000 – 02. He is currently assistant professor of chemistry at Government V. Y. T. P. G. Autonomous College, Durg, India where he continues his research work, which is mainly related to solid thin films, transition metal-ion catalysed oxidation kinetics as well as micellar oxidation kinetics. He is the author of more than 70 papers related to this field.

Mrs. Kamalni Tripathi received her M.Sc. in Organic Chemistry in 1999 from Awadesh Pratap Singh University, Rewa, India and her B.Ed. in 2004 from Awadesh Pratap Singh University, Rewa, India. She has done her research work as a research scholar towards a Ph. D. at Kalyan Mahavidyalaya, Bhilai Nagar, India in the area of micellar oxidation kinetics under the supervision of Dr. Y. R. Katre.

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Received: 2013-07-28

Revised: 2013-10-11

Published Online: 2013-05-01

Published in Print: 2014-03-17

Kinetics of Cetyltrimethylammonium Bromide Catalysed Oxidation of Cyclopentanone by N-Bromophthalimide in Acidic Medium

Abstract

Kurzfassung

References

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