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Solution of perborate in glacial acetic acid generates peracetic acid on aging and the peracetic acid oxidation of diphenylamine is fast. Hydrogen peroxide in glacial acetic acid does not yield peracetic acid on standing; also, the hydrogen peroxide oxidation rate is only two-third of perborate. The aging effect was overcome by dissolving perborate in 1,2-diols. The oxidation in 1,2-diols-acetic acid is zero order in the oxidizing agent, whereas the same oxidation with fresh solution of perborate in acetic acid is first order with respect to the oxidizing agent. However, the rate of the former and the specific rate of the latter show first order dependence on [perborate]0. The reactions proceed via two paths, one is first order and the other is zero order in diphenylamine. In 1,2-diols-acetic acid, the perborate oxidation is slower than hydrogen peroxide. The reaction mechanism is discussed and the rate laws derived.
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Rocznik
Tom
Strony
1019--1029
Opis fizyczny
Bibliogr. 15 poz., rys.
Twórcy
autor
- Department of Chemistry, Annamalai University, Annamalainagar 608002, India
autor
- Department of Chemistry, Annamalai University, Annamalainagar 608002, India
autor
- Department of Chemistry, Annamalai University, Annamalainagar 608002, India
Bibliografia
- 1.Cotton F.A. and Wilkinson G., Advanced Inorganic Chemistry, 5th ed., Wiley Interscience, NY, 1988, p. 172.
- 2.Karunakaran C. and Muthukumaran B., Transition Met. Chem., 20, 460 (1995).
- 3.Karunakaran C. and Muthukumaran B., React. Kinet. Catal. Lett., 60, 387 (1997).
- 4.Karunakaran C. and Palanisamy P.N., Synth. React. Inorg. Met.-Org. Chem., 28, 1115 (1998).
- 5.Karunakaran C., Ramachandran V. and Palanisamy P.N., Int. J. Chem. Kinet., 31, 675 (1999).
- 6.Karunakaran C. and Kamalam R., Synth. React. Inorg. Met.-Org. Chem., 29, 1463 (1999).
- 7.Muzart J., Synthesis, 1325 (1995).
- 8.McKillop A. and Sanderson W.R., Tetrahedron, 51, 6145 (1995).
- 9.McKillop A. and Sanderson W.R., J. Chem. Soc., Perkin Trans., 1, 471 (2000).
- 10.Dasgupta G. and Mahanti M.K., Indian J. Chem., 25A, 958 (1986).
- 11.Sidhu K.S., Bansal W.R. and Sukhjeet Kaur, Indian J. Chem., 26A, 740 (1987).
- 12.Gupta P.K. and Dahmiwal N.R., Indian J. Chem., 33A, 722 (1994).
- 13.Dean J.A., Handbook of Organic Chemistry, McGraw-Hill, NY, 1987.
- 14.Fumiss B.S., Hannaford A.J., Rogers V., Smith P.W.G. and Tatchell, A.R., Vogel’s Textbook of Practical Organic Chemistry Including Qualitative Organic Analysis, 4th ed., ELBS, London, 1978.
- 15.Ogata Y. and Shimizu H„ Bull. Chem. Soc. Jpn., 52, 635 (1979).
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Bibliografia
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bwmeta1.element.baztech-article-BUJ1-0019-0010