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Oxidation of 2-(2-Methoxyethoxy)ethanol and 2-(2-Ethoxyethoxy)ethanol by Diperiodatocuprate(III) in Alkaline Medium-A Kinetic and Mechanistic Study
Corresponding Author(s) : Jinhuan Shan
Asian Journal of Chemistry,
Vol. 25 No. 15 (2013): Vol 25 Issue 15
Abstract
The kinetics of oxidation of 2-(2-methoxyethoxy)ethanol and 2-(2-ethoxyethoxy)ethanol by diperiodatocuprate(III) (DPC) in alkaline liquids had been investigated spectrophotometrically in the temperature range of 20 ºC to 40 ºC. It was found that the reaction was pseudo-first order in [DPC] and 1 < nap < 2 in the concentration of reductants. The pseudo-first order rate constant kobs decreased rapidly with an increase in [OH–] to a certain value, then increasing with the continuous increase in [OH–]. In addition, the kobs decreased with an increase in [IO4–]. There was no salt effect. The rate of 2-(2-ethoxyethoxy)ethanol was higher than 2-(2-methoxyethoxy)ethanol in stronger alkaline medium. A plausible mechanism involving pre-equilibriums before the rate controlling step and a free radical mechanism was proposed from the kinetics study. The rate equations derived from mechanism can explain all experimental phenomena. Moreover, the activation parameters at 298.2 K along with rate constants of the rate-determining step were calculated.
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- J.H. Shan, L.P. Wang and H.W. Sun, Turkish J. Chem., 27, 265 (2003).
- J.H. Shan, Y.P. Liu and J.Y. Zhang, Chin. J. Chem., 29, 639 (2011).
- K.B. Reddy, Transition Metal Chem., 15, 9 (1990).
- P.J. Timy and M.T. Suresh, J. Mol. Struct., 827, 137 (2007).
- A. Kumar, P. Kumar and P. Ramamurthy, Polyhedron, 18, 773 (1999).
- V.H. Chanabasayya, T.S. Kiran and S.T. Nandibewoor, J. Mol. Catal. A, 248, 163 (2006).
- T.R. Prasad, B. Sethuram and T.N. Rao, Indian J. Chem., 21A, 169 (1982).
- H.L. Yang, Z.Z. Yan, H.L. Zhang and L.D. Kui, Eur. Polym. J., 38, 1619 (2002).
- F. Feigl, Spot Tests in Organic Anaiysis; Elsevier, New York, 208 (1956).
- K.B. Reddy, B. Sethuram and T.N. Rao, Indian J. Chem., 20A, 272 (1981).
- P.K. Jaiswal and K.L. Yadava, Indian J. Chem., 11, 837 (1973).
- F. Feigl, Spot Tests in Organic Anaiysis, Elsevier, New York, p. 196 (1966).
- J. Aveston, J. Chem. Soc. (A), 273 (1996).
- C.E. Crouthamel, H.V. Meek, D.S. Martin and C.V. Banks, J. Am. Chem. Soc., 71, 3031 (1949); 73, 82 (1951).
- J.H. Shan, S.M. Li, S.Y. Huo, S.G. Shen and H.W. Sun, Chinese J. Chem., 24, 478 (2006).
References
J.H. Shan, L.P. Wang and H.W. Sun, Turkish J. Chem., 27, 265 (2003).
J.H. Shan, Y.P. Liu and J.Y. Zhang, Chin. J. Chem., 29, 639 (2011).
K.B. Reddy, Transition Metal Chem., 15, 9 (1990).
P.J. Timy and M.T. Suresh, J. Mol. Struct., 827, 137 (2007).
A. Kumar, P. Kumar and P. Ramamurthy, Polyhedron, 18, 773 (1999).
V.H. Chanabasayya, T.S. Kiran and S.T. Nandibewoor, J. Mol. Catal. A, 248, 163 (2006).
T.R. Prasad, B. Sethuram and T.N. Rao, Indian J. Chem., 21A, 169 (1982).
H.L. Yang, Z.Z. Yan, H.L. Zhang and L.D. Kui, Eur. Polym. J., 38, 1619 (2002).
F. Feigl, Spot Tests in Organic Anaiysis; Elsevier, New York, 208 (1956).
K.B. Reddy, B. Sethuram and T.N. Rao, Indian J. Chem., 20A, 272 (1981).
P.K. Jaiswal and K.L. Yadava, Indian J. Chem., 11, 837 (1973).
F. Feigl, Spot Tests in Organic Anaiysis, Elsevier, New York, p. 196 (1966).
J. Aveston, J. Chem. Soc. (A), 273 (1996).
C.E. Crouthamel, H.V. Meek, D.S. Martin and C.V. Banks, J. Am. Chem. Soc., 71, 3031 (1949); 73, 82 (1951).
J.H. Shan, S.M. Li, S.Y. Huo, S.G. Shen and H.W. Sun, Chinese J. Chem., 24, 478 (2006).