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Effect of Micellar Aggregates on the Kinetics of Dextrose Oxidation by N-Bromosuccinimide

Einfluss mizellarer Aggregate auf die Kinetik der Dextroseoxidation durch N-Bromsuccinimid
Y. Katre , M. Singh and A. K. Singh

Abstract

The kinetics of oxidation of dextrose by N-bromosuccinimide (NBS) has been investigated in the presence of cationic cetyltrimethylammonium bromide (CTAB) surfactant in sulfuric acid (H2SO4) medium. Similarly in absence of CTAB solution, the reaction followed fractional-, first-, and negative fractional-order kinetics with respect to [dextrose], [NBS] and [H2SO4], respectively. Although the reaction mechanism remained unaltered by micelles, a typical kψ-[CTAB] profile was observed, that is, with a progressive increase in [CTAB], the reaction rate increased, reached a maximum value, and then decreased. The results are treated quantitatively in terms of Berezin's model. Activation parameters were also evaluated and a negative value of ΔS# shows the formation of well-structured activated complex. The influence of salts on the reaction rates has also been seen. On the basis of product analysis, a pertinent mechanism is proposed.

Kurzfassung

Die Oxidationskinetik von Dextrose durch N-Bromsuccinimid (NBS) wurde in Anwesenheit des kationischen Tensids Cetyltrimethylammoniumbromid (CTAB) im schwefelsauren Medium (H2SO4) untersucht. Ähnlich zur Reaktion in Abwesenheit von CTAB, folgte die Reaktion in Bezug auf [Dextrose], [NBS] und [H2SO4], einer gebrochenen, einer ersten und einer negativ gebrochenen Ordnung. Obwohl der Reaktionsmechanismus von den Mizellen unverändert war, wurde ein typisches kψ-[CTAB]-Profil beobachtet, d.h. mit einem progressiven Anstieg der [CTAB]-Konzentration nimmt die Reaktionsgeschwindigkeit zu und fällt bei Erreichen eines Maximalwerts ab. Die Ergebnisse wurden quantitativ mit dem Berezin-Modell ausgewertet. Aktivierungsparameter wurden ebenfalls ermittelt und ein negativer Wert von ΔS# zeigt die Entstehung eines strukturierten Aktivierungskomplexes. Der Einfluss von Salz auf die Reaktionsgeschwindigkeit wurde ebenfalls untersucht. Auf Basis einer Produktanalyse wird ein geeigneter Mechanismus vorgeschlagen.


Yokraj Katre, Department of Chemistry, Kalyan Post Graduate College, Bhilai Nagar, Durg, (C.G.) – 490006, India. E-Mail:

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, under the guidance of Dr. S. K. Solanki. He participated in 8th 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. College, Bhilai, since 1978. He continues his research related to micellar kinetics, including a current two-year research project sanctioned by U. G. C.

Miss Minu Singh received her M. Sc. in organic chemistry in 2006 from Bhilai Mahila Mahavidyalaya, Bhilai, India. She continues her research work as a research scholar toward a Ph. D. at Kalyan P. G. College, Bhilai, India, in the area of micellar oxidation kinetics, under the supervision of Dr. Y. R. Katre.

Dr. Ajaya Kumar 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, India, under the supervision of Dr. Ashok Kumar Singh. He was selected as an assistant professor of chemistry at Government Science College, Mungeli, Bilaspur, through M. P. Public Service Commission, Indore in 1994. He was awarded a Teacher Research Fellowship to complete his research work in 2000–2002. 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-catalyzed oxidation kinetics as well as micellar oxidation kinetics. He is the author of more than 10 papers related to this field.


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Received: 2009-06-23
Published Online: 2013-04-05
Published in Print: 2010-03-01

© 2010, Carl Hanser Publisher, Munich

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