Skip to content
Licensed Unlicensed Requires Authentication 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

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 kobs and [CTAB] profile was observed i.e. with the progressive increase in [CTAB], the reaction rate increased, at higher concentration constancy in kobs 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 kobs und [CTAB]-Profil beobachtet wurde, d.h. mit progressiver Erhöhung an [CTAB] steigt die Reaktionsgeschwindigkeit und bei höherer Konzentration wird eine Konstanz bei kobs 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.


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:

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 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. 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 233rd American Chemical Society meeting in Chicago, USA and presented an oral paper in the Colloid and Surface Science Division in 25th to 29th 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.


References

1.Chiarini, M., Cerichelli, G., Foroudian, H. J., Gillitt, N. D., Yunes, S. F. and Bunton, C. A.: Langmuir20 (2004) 5201.10.1021/la0300885Search in Google Scholar

2.Chiarini, M. and Bunton, C. A.: Colloid Surf. A245 (2004) 177.10.1016/j.colsurfa.2004.07.016Search in Google Scholar

3.Chiarini, M., Gillitt, N. D. and Bunton, C. A.: Langmuir 18(10) (2002) 3836.10.1021/la0117404Search in Google Scholar

4.Chiarini, M. and Bunton, C. A.: Langmuir18 (2002) 8806.10.1021/la026156pSearch in Google Scholar

5.Makote, R. D. and Chatterjee, C.: Ind. J. Chem.37 A (1998) 21.10.1021/ie970752aSearch in Google Scholar

6.Panigrahi, G. P. and Mishra, S. K.: Ind. J. Chem.32 A (1993) 956.Search in Google Scholar

7.Hussain, M. and Ahmad, F.: Int. J. Chem. Kinet.22 (1990) 321.10.1002/kin.550220403Search in Google Scholar

8.Nagar, V., Solanki, S. K. and Shastry, V. R.: J. Ind. Chem. Soc.67 (1990) 956.Search in Google Scholar

9.Sanchez, F., Moya, M. L., Rodriguez, A., Jimenez, R., Herrera, C. G., Yanes, C. and Lopez-Cornejo, P.: Langmuir13 (1997) 3084.10.1021/la960989wSearch in Google Scholar

10.Khan, Z., Ali, S. I., Rafiquee, Md. Z. A. and Kabir-ud-Din: Ind. J. Chem.36 A (1997) 579.Search in Google Scholar

11.Panigrahi, G. P. and Swain, R.: Ind. J. Chem.40 A (2001) 1191.Search in Google Scholar

12.Panda, J. and Panigrahi, G. P.: Ind. J. Chem.42 A (7) (2003) 1636.Search in Google Scholar

13.Kabir-ud-Din, Salma U. and Khan, Z.: J. Surf. Sci. Technol.36 (2003) 101.Search in Google Scholar

14.Kabir-ud-Din, Salem J. K. and Kumar, S.: Ind. J. Chem.39 A (2000) 1019.Search in Google Scholar

15.Kabir-ud-Din, Morshed A. M. A. and Khan, Z.: J. Carbohydr. Chem.22 (2003) 843.10.1081/CAR-120026597Search in Google Scholar

16.Bhagwat, V. W., Pipada, M., Jonalagadda, S. B. and Pare, B.: Ind. J. Chem.42 A (2003) 1644.Search in Google Scholar

17.Gemeav, A. H., Mansour, I. A., El-Sharkawy, R. G. and Zaki, A. B.: J. Colloid Interface Sci.263 (2003) 228.10.1016/S0021-9797(03)00134-6Search in Google Scholar

18.Abou, O., Walash, M. I., El-Kerdawy, M. and El-Ashry: J. Drug Res.12 (1980) 77.Search in Google Scholar

19.Shorter, J.: J. Chem. Soc. (1962) 18681876.10.1039/jr9620001868Search in Google Scholar

20.Devi, K. L. and Chowdary, M. C.: J. Ind. Chem. Soc.76 (1999) 195.Search in Google Scholar

21.Panigrahi, G. P. and Sahu, B. P.: J. Ind. Chem. Soc.68 (1991) 239.Search in Google Scholar

22.Meenal, K. and Selvameena, R.: J. Ind. Chem. Soc.69 (1992) 822.Search in Google Scholar

23.Panda, R., Sahu, S. K. and Acharya, P. K.: J. Ind. Chem. Soc.80 (2003) 879.Search in Google Scholar

24.Jadhav, W. N., Bhusare, S. R., Pawar, R. P. and Arbad, B. R.: J. of Ind. Chem. Soc.78 (2001) 310.Search in Google Scholar

25.Rao, S. A. K., Syamasunder, B. and Radhakrishnamurti, P. S.: J. Ind. Chem. Soc.82 (2005) 710.Search in Google Scholar

26.Panda, J. and Panigrahi, G. P.: J. Ind. Chem. Soc.79 (2002) 58.Search in Google Scholar

27.Sewanee, J. P., Valechha, A., Singh, A. and Valechha, N. D.: J. Ind. Chem. Soc.70 (1993) 76.Search in Google Scholar

28.Annapoorna, S. R., Rao, M. P. and Sethuram, B.: J. Ind. Chem.40 A (2001) 283.Search in Google Scholar

29.Meenal, K. and Lalitha, S.: J. Ind. Chem. Soc.72 (1995) 693.Search in Google Scholar

30.Sing, V. P. and Saxena, S. B.: J. Ind. Chem. Soc.LXV (1988) 847.Search in Google Scholar

31.Selvaraj, K., Sankaran, S., Prema, B. and Ramarajan, K.: J. Ind. Chem. Soc.LXV (1988) 723.Search in Google Scholar

32.Panigrahi, G. P. and Sahu, B. P.: Int. J. Chem. Kinet.23 (1991) 989.10.1002/kin.550231104Search in Google Scholar

33.Mohan, K. and Mahadevappa, D. S.: Ind. J. Chem.27 A (1988) 702.10.1021/ie00076a029Search in Google Scholar

34.Gupta, K. C., Gupta, R. and Saxena, U.: Ind. J. Chem.28 A (1989) 253.Search in Google Scholar

35.Krishnamurthy, N., Reddy,CH. S. and Sundaram, E. V.: Ind. J. Chem28 A (1989) 288.Search in Google Scholar

36.Puttaswamy, and Mahadevappa, D. S.: Ind. J. Chem.32 A (1993) 409.Search in Google Scholar

37.Vijaymohan, K., Rao, P. R. and Sundaram, E. V.: J. Ind. Chem. Soc.LX (1984) 225.Search in Google Scholar

38.Siddiqui, M. A. A., Kumar,CH. S., Chandriah, U. and Kandlikar, S.: Ind. J. Chem.30 A (1991) 849.Search in Google Scholar

39.AnjumA. and Srinivas, P.: Asian. J. Chem.17 (1) (2005) 553.Search in Google Scholar

40.Nair, T. D. R. and Zachariah, A.: Asian. J. Chem.9 (2) (1997) 297.Search in Google Scholar

41.Panigrahi, A. K., Misra, S., Patra, M. and Sinha, B. K.: J. Ind. Chem. Soc.76 (1999) 395.Search in Google Scholar

42.Barkat, M. Z. and El-Wahab, M. F. A.: Anal. Chem.26 (1954) 1973.10.1021/ac60096a035Search in Google Scholar

43.Feigl, F.: Spot tests in organic analysis, 7th Eng. Edn, Elsevier Sci. Pub. (1966) 571.Search in Google Scholar

44.Lin, Z., Cai, J. J., Scriven, L. E. and Davis, H. T.: J. Phys. Chem.98 (1994) 5984.10.1021/j100074a027Search in Google Scholar

45.Bachofer, S. J. and Simonis, U.: Langmuir12 (1996) 1744.10.1021/la950612aSearch in Google Scholar

46.Joshi, G. K., Katre, Y. R. and Singh, A. K.: J. Surfact. Deterg.9 (2006) 231.10.1007/s11743-006-5002-3Search in Google Scholar

47.Katre, Y. R., Joshi, G. K. and Singh, A. K.: Kinet. and Catal. (2009) [In Press].Search in Google Scholar

48.Katre, Y. R., Joshi, G. K. and Singh, A. K.: Tenside Surf. Det.45 (2008) 4, 213.Search in Google Scholar

49.Katre, Y. R., Joshi, G. K. and Singh, A. K.: J. Disper. Sci. Tech. (10/12) (2009) 30 [In Press].Search in Google Scholar

50.Patil, S., Katre, Y. R. and Singh, A. K.: Colloids Surf. A: Physicochem. Eng. Aspects308 (2007) 6.10.1016/j.colsurfa.2007.05.015Search in Google Scholar

51.Patil, S., Katre, Y. R. and Singh, A. K.: J. Surfact Deterg.10 (2007) 175.10.1007/s11743-007-1028-4Search in Google Scholar

52.Katre, Y. R., Singh, M., Patil, S. and Singh, A. K.: Acta Phys.-Chim. Sin.25 (2) (2009) 319.10.3866/PKU.WHXB20090221Search in Google Scholar

53.Das, A. K.: Coordination Chem. Rev.248 (2004) 81.10.1016/j.cct.2003.10.012Search in Google Scholar

Received: 2009-01-03
Revised: 2009-04-13
Published Online: 2013-04-02
Published in Print: 2009-07-01

© 2009, Carl Hanser Publisher, Munich

Downloaded on 6.12.2022 from frontend.live.degruyter.dgbricks.com/document/doi/10.3139/113.110027/html
Scroll Up Arrow