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Kinetics and mechanism of 2,4,6-trimethylaniline oxidation

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Abstract

The kinetics of oxidation of 2,4,6-trimethylaniline hydrochloride with ammonia peroxydisulfate in an aqueous solution was studied by the potentiometric method. It was shown that the reaction proceeds as the second order process. The rate constants of one-electron transfer from 2,4,6-trimethylaniline molecule to peroxydisulfate ion were determined and are 1.46, 2.3, and 3.17 l/(mol.sec) at 30, 35 and 40° С , respectively. The activation energy of one-electron transfer from 2,4,6-trimethylaniline molecule to peroxydisulfate ion is 61 kJ/mol, the entropy of activation is –63 J/(mol К ), and the enthalpy of activation is 58.5kJ/mol. It was determined that 2,4,6-trimethylaniline is not prone to oxidative polymerization. This indicates that cation-radicals of aromatic amines which act as active centers of aniline oxidative polymerization are formed. The fact that there is no autoacceleration during oxidation of 2,4,6-trimethylaniline hydrochloride indicates that the oxidative polymerization of aniline is an autocatalytical process.

About the Authors

Ya. O. Mezhuev
D.I. Mendeleyev University of Chemical Technology of Russia, Moscow, 125047 Russia
Russian Federation


Yu. V. Korshak
D.I. Mendeleyev University of Chemical Technology of Russia, Moscow, 125047 Russia
Russian Federation


I. S. Strakhov
D.I. Mendeleyev University of Chemical Technology of Russia, Moscow, 125047 Russia
Russian Federation


M. I. Shtilman
D.I. Mendeleyev University of Chemical Technology of Russia, Moscow, 125047 Russia
Russian Federation


T. A. Vagramyan
D.I. Mendeleyev University of Chemical Technology of Russia, Moscow, 125047 Russia
Russian Federation


References

1. Gospodinova N., Terlemezyan L. / Conducting polymers prepared by oxidative polymerization: Polyaniline / Prog. Polymers Sci. 1998. V. 23. P.1443–1483.

2. Mav I., Zigon M. 1H NMR study of the kinetics of substituted aniline polymerization // J. Polymer. Sci. 2001. V. 39. P. 2471–2481.

3. Межуев Я.О., Коршак Ю.В., Штильман М.И., Коледенков А.А., Устинова М.С. Новые аспекты механизма окислительной полимеризации анилина // Пластические массы. 2011. № 3. С. 26–31.

4. Wei Y., Tang X., Sun Y. A study of the mechanism of aniline polymerization // J. Polymer Sci. 1989. V. 27. P. 2385–2396.

5. Каррер П. Курс органической химии. – Л.: Гос. научно-техн. изд-во хим. лит-ры, 1960. 1216 с.

6. Реутов О.А., Курц А.Л., Бутин К.П. Органическая химия. В 4-х т. – М.: Бином. Лаборатория знаний, 2004. Т. 3. 543 с.

7. Minami H., Okubo M., Murakami K., Hirano S. The oxidative dispersion polymerization of 3,5-xylidine // J. Polymer Sci. Part A. 2000. V. 38. P. 4238–4246.

8. Bolton P.D., Hall F.M. Substituent effects on the thermodynamic functions of ionization of metasubstituted anilinium ions // Austral. Chem. 1967. V. 20. P. 1797– 1781.


For citation:


Mezhuev Y.O., Korshak Yu.V., Strakhov I.S., Shtilman M.I., Vagramyan T.A. Kinetics and mechanism of 2,4,6-trimethylaniline oxidation. Fine Chemical Technologies. 2013;8(1):62-65. (In Russ.)

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ISSN 2410-6593 (Print)
ISSN 2686-7575 (Online)