Kinetic and Mechanistic Study of the Influence of Micelles on the Oxidation of Acetone by N-Bromophthalimide in Aqueous Acetic Acid Medium

Y. R. Katre; K. Tripathi; G. K. Joshi; A. K. Singh

doi:10.3139/113.110027

Published by De Gruyter April 2, 2013

Kinetic and Mechanistic Study of the Influence of Micelles on the Oxidation of Acetone by N-Bromophthalimide in Aqueous Acetic Acid Medium

Kinetik- und Mechanismus-Untersuchung über den Einfluss auf Mizellen bei der Oxidation von Aceton mit N-Bromphthalimid in wässriger essigsaurer Lösung

Y. R. Katre , K. Tripathi , G. K. Joshi and A. K. Singh

From the journal Tenside Surfactants Detergents

https://doi.org/10.3139/113.110027

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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 acetone by N-Bromophthalimide (NBP) was studied iodometrically at 308 K. In addition to 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 [Acetone] and [NBP] respectively. Cationic surfactant (CTAB) strongly catalysed the oxidation of acetone in aqueous acetic acid medium and typical k_obs and [CTAB] profile was observed i.e. with the progressive increase in [CTAB], the reaction rate increased, at higher concentration constancy in k_obs was observed, whereas anionic surfactant (SDS) was found to show no considerable effect on reaction rate. Mercuric acetate and phthalimide exhibited nil effect on the reaction rate. The presence of inorganic salts (KCl, KBr) exhibits positive effect in the reaction rate. The various activation parameters in presence of CTAB and SDS have been also evaluated. A suitable mechanism consistent with the experimental findings has been proposed. The binding constant with surfactants has been evaluated.

Kurzfassung

Der Einfluss kationischer Mizellen aus Cetyltrimethylammoniumbromid (CTAB) und anionischer Mizellen aus Natriumdodecylsulfat (SDS) auf die Oxidation von Aceton mit N-Bromphthalimid (NBP) wurde iodometrisch bei 308 K untersucht. Zusätzlich zu den Kinetikexperimenten wurden Leitfähigkeitsmessungen durchgeführt, um Angaben über die kritische Mizellbildungskonzentration und anderen thermodynamischen Eigenschaften zu bekommen. Die kinetischen Beobachtungen zeigen eine fraktionale Ordnung und eine Abhängigkeit erster Ordnung bezüglich [Acetone], bzw. [NBP]. Das kationische Tensid (CTAB) katalysiert stark die Oxidation von Aceton in wässriger essigsaurer Lösung, wobei ein typisches k_obs und [CTAB]-Profil beobachtet wurde, d.h. mit progressiver Erhöhung an [CTAB] steigt die Reaktionsgeschwindigkeit und bei höherer Konzentration wird eine Konstanz bei k_obs beobachtet, während das anionische Tensid (SDS) keinen bedeutenden Einfluss auf die Reaktionsgeschwindigkeit zeigte. Quecksilberacetat und Phthalimid besitzen gar keinen Effekt auf die Reaktionsgeschwindigkeit. Die Anwesenheit anorganischer Salze (KCl, KBr) übt einen positiven Effekt auf die Reaktionsgeschwindigkeit aus. Die verschiedenen Aktivierungsparameter in Gegenwart von CTAB und SDS wurden ebenfalls bewertet. Entsprechend der experimentellen Ergebnisse wurde ein geeigneter Mechanismus vorgeschlagen. Die Bindungskonstante mit Tensiden wurde bewertet.

Key words:: N-bromophthalimide; cetyltrimethylammonium bromide; sodium dodecyl sulphate; acetone; oxidation; kinetics

Stichwörter:: N-Bromphthalimid; Cetyltrimethylammoniumbromid; Natriumdodecylsulfat; Aceton; Oxidation; Kinetik

^∗ Dr. Y. R. Katre, Department of Chemistry, Kalyan P. G. College, Bhilai Nagar, Durg (C.G.), 490006, India, Phone: +91-788-2391124, Fax: +91-788-2223352, E-Mail: yokrajkatre@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 is 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 transition metal-ion catalysed oxidation kinetics as well as micellar oxidation kinetics. He is the author of more than 15 papers related to this field.

Mr. Ghanat K. Joshi received his M.Sc. in Physical Chemistry in 2001 from Government Arts and Science College, Durg, India and his M. Phil in Physical Chemistry in 2002 from Vikram University, Ujjain, India under the supervision of Dr. S. K. Solanki. He continues his 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. He was selected for Rajeev Gandhi National Fellowship from U.G.C., New Delhi, India. He is a member of American Chemical Society for the year 2007–08.

Ms. 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 is working as project scientist in Patent Cell which is a project of Department of Science and Technology, New Delhi, India. She continues 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: 2009-01-03

Revised: 2009-04-13

Published Online: 2013-04-02

Published in Print: 2009-07-01

Kinetic and Mechanistic Study of the Influence of Micelles on the Oxidation of Acetone by N-Bromophthalimide in Aqueous Acetic Acid Medium

Abstract

Kurzfassung

References

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