Stopped Flow Kinetics of MnII Catalysed Periodate Oxidation of 2, 3- dimethylaniline - Evaluation of Stability Constant of the Ternary Intermediate Complex

DOI: https://doi.org/10.9767/bcrec.10.1.7621.78-87
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Submitted: 03-10-2014
Published: 27-02-2015
Section: Original Research Articles
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The formation of ternary intermediate unstable complex during the oxidation of aromatic amines by periodate ion catalysed by MnII has been proposed in case of some anilines. This paper is the first report on stopped-flow kinetic study and evaluation of stability constant of ternary complex forming in the MnII - catalysed periodate oxidation of 2, 3-dimethylaniline (D) in acetone-water medium. Stop-flow spectrophotometric method was used to study the ternary complex formation and to determine its stability constant. The stop-flow trace shows the reaction to occur in two steps. The first step, which is presumably the formation of ternary complex, is relatively fast while the second stage is relatively quite slow. The stability constant evaluated for D - MnII - IO4- ternary complex by determining  equilibrium absorbance is (2.2 ± 1.0) × 105. Kinetics of ternary complex formation was defined by the rate law(A)  under pseudo first order conditions.

ln{[C2]eq / ( [C2]eq -[C2])} = kobs . t (A)

where, kobs is the pseudo first order rate constant, [C2] is concentration of ternary complex at given time t, and [C2]eq is the equilibrium concentration of ternary complex. © 2015 BCREC UNDIP. All rights reserved

Received: 3rd October 2014; Revised: 4th December 2014; Accepted: 15th December 2014

How to Cite: Kaushik, R.D., Agarwal, R., Tyagi, P., Singh, O., Singh, J. (2015). Stopped Flow Kinetics of MnII Catalysed Periodate Oxidation of 2,3-dimethylaniline - Evaluation of Stability Constant of the Ternary Intermediate Complex. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (1): 78-87. (doi:10.9767/bcrec.10.1.7621.78-87)

Permalink/DOIhttp://dx.doi.org/10.9767/bcrec.10.1.7621.78-87

Keywords

Stopped flow kinetics; Stability constant; Ternary complex; MnII catalysed; Periodate oxidation; 2, 3- dimethylaniline

  1. Rajneesh Dutt Kaushik 
    Department of Chemistry, Gurukul Kangri University, Haridwar-249404,, India
    Professor & Head, Department of Chemistry; Dean, Faculty of Science; Dean, Faculty of Engineering & Technology, Gurukul Kangri University, Haridwar (Uttarakhand)-249404,
  2. Richa Agarwal 
    Department of Chemistry, Gurukul Kangri University, Haridwar-249404,, India
  3. Priyanka Tyagi 
    Department of Chemistry, Gurukul Kangri University, Haridwar-249404,, India
  4. Om Singh 
    Department of Chemistry, Gurukul Kangri University, Haridwar-249404,, India
  5. Jaspal Singh 
    Department of Chemistry, Gurukul Kangri University, Haridwar-249404,, India
  1. Mortensen, S.K., Trier, X.T., Foverskov, A., Petersen, J.H. (2005). Specific determination of 20 primary aromatic amines in aqueous food stimulants by liquid chromatography-electrospray ionization-tendem mass spectrometry. J. Chromatogr. A., 1091: 40-50.
  2. Pinheiro, H.M., Touraud, E., Thomas, O. (2004). Aromatic amines from azo dye reduction: status review with emphasis on direct UV spectrophotometric detection in textile industry wastewaters. Dyes and Pigments. 61: 121-139.
  3. Dupret, J.M., Dairou, J., Busi, F., Silar, P., Martins, M., Mougin, C., Lima, F.R., Cocaign, A. (2011). Pesticide-Derived Aromatic Amines and Their Biotransformation, in: Stoytcheva, M., (Ed.), Pesticides in the Modern World - Pests Control and Pesticides Exposure and Toxicity Assessment. InTech, Croatia, 601- 614.
  4. Gupta, V.K. (1985). Kinetics and mechanism of oxidation of p-substituted anilines by peroxydisulphate ion in acetic acid-water medium. React. Kinet. Catal. Lett., 27: 207-211.
  5. Mansoor, S.S., Shafi, S.S. (2014). Oxidation of some para-substituted anilines by benzimida-zolium fluorochromate in aqueous acetic acid medium-A kinetic and mechanistic study. Arab. J. Chem., 7: 171-176.
  6. Pavolva, V.K., Sevchenko, Ya.S., Yatsimiriskii, K.B. (1970). Kinetics and mechanism of oxidation of diethylaniline by perio- date. Zh. Fiz. Khim., 44: 658-663.
  7. Kaushik, R.D., Kumar, V., Arya, R.K., Singh, D. (2000). Periodate oxidation of o-toluidine in acetone-water medium - A kinetic and mechanistic study. Asian J. Chem., 12: 1123-1128.
  8. Kaushik, R.D., Singh, R.P., Shashi. (2003). A kinetic-mechanistic study of periodate oxida- tion of p-chloroaniline. Asian J. Chem., 15: 1485-1490.
  9. Kaushik, R.D., Malik, R., Kumar, A. (2010). Kinetics and Mechanism of periodate oxidation of o-anisidine in acetone-water medium. J. Indian Chem. Soc., 87: 317-323.
  10. Kaushik, R.D., Kumari, R., Kumar, T., Singh, P. (2010). Periodate oxidation of N,N-dimethylaniline and N,N- diethylaniline. Asian J. Chem., 22: 7959-7968
  11. Kaushik, R.D., Arya, R.K., Kumar, S. (2000). Periodate oxidation of aromatic amines: Kinetics and Mechanism of oxidation of N-ethylaniline in acetone-water medium. Asian J. Chem., 12: 1229-1234
  12. Kaushik, R.D., Kumar, V. Kumar, S. (1999). Periodate oxidation of N-methylaniline in acetone-water medium-A kinetic and mechanistic study. Asian J. Chem., 11: 633-638
  13. Kaushik, R.D., Joshi, R. Singh, D. (1998). Periodate oxidation of aromatic amines - studies on the role of substituents and linear free energy relationships. Asian J. Chem., 10: 567- 572
  14. Kaushik, R.D., Oswal, S.D., Singh, D. (2000). A kinetic and mechanistic study of periodate oxidation of o-ethylaniline in acetone-water medium. Asian J. Chem., 12: 1129-1134
  15. Kaushik, R.D., Singh, D., Joshi, R., Kumar, S. (1998). Kinetics of periodate oxidation of aro- matic amines - studies on the kinetic parameters and isokinetic relationship for few ani- lines. Asian J. Chem., 10: 573-576
  16. Kaushik, R.D., Joshi, R. (1997). Kinetics and mechanism of periodate oxidation of m – tolu- idine in acetone – water medium. Asian J. Chem., 9: 527-532
  17. Kaushik, R.D., Singh, J., Manila, Kaur, M., Singh, P. (2014). Kinetics and Mechanism of MnII Catalyzed Periodate Oxidation of p- anisidine: Effect of pH. Bull. Chem. React. Eng. Catal. 9(3): 182-191 (DOI: 10.9767/bcrec.9.3.6823.182-191 )
  18. Kaushik, R.D., Shashi, Amrita, Devi, S. (2004). Kinetics and mechanism of Mn(II) catalysed periodate oxidation of 4-chloro-2- methyl aniline. Asian J. Chem.16: 818-822.
  19. Kaushik, R.D., Kumar, D., Kumar, Anuj., Kumar, Ajay. (2010). Manganese(II) catalysed oxidation of 2,4-xylidine by periodate-A kinetic-mechanistic study. J. Indian Chem. Soc., 87: 811-816.
  20. Kaushik, R.D., Kaur, M., Malik, R., Kumar, A. (2010). Studies on Manganese(II) catalysed oxidation of N-methylaniline by periodate ion. Int. J. Chem. Sci., 8: 1379-1388.
  21. Kaushik, R.D., Kumar, A., Kumar, T., Singh, P. (2010). Manganese(II) catalysed periodate oxidation of p-toluidine-A kinetic-mechanistic study. React. Kinet. Mech. Catal., 101: 13-23.
  22. Kaushik, R.D., Malik, R., Kumar, T., Singh, P. (2012). Manganese(II) catalysed periodate oxidation of 2-amino-m-xylene-A Kinetic- Mechanistic Study. Oxid. Commun., 35: 316- 326.
  23. Kaushik, R.D., Malik, R., Agarwal, R., Singh, J. (2014). Kinetics and Mechanism of MnII catalyzed periodate oxidation of 2, 3-xylidine in acetone-water medium. Res. J. Pharm. Biol. Chem. Sci., 5: 1644-1653.
  24. Britton, H.T.S. (1956). Hydrogen ions, D. Von Nostrand Co. 354.
  25. Conklin, M.H., Hoffmann, M.R. (1988). Metal Ion-Sulfur (IV) Chemistry. 3. Thermodynamics and Kinetics of Transient Iron(III)-Sulfur( IV) Complexes. Environ. Sci. Technol., 22: 899-907.
  26. Gupta, K.S., Jain, U., Singh, A., Dhayal, Y., Rani, A. (2012). Kinetics of palladium(II)- catalysed oxidation of sulfur(IV) by oxygen. J. Indian Chem. Soc., 89: 1035-1043.