Abstract
The kinetics and mechanism of ruthenium(III) catalyzed oxidation of tetrahydrofurfuryl alcohol (THFA) by cerium(IV) in sulfuric acid media have been investigated spectrophotometrically in the temperature range 298–313 K. It is found that the reaction is first-order with respect to CeIV, and exhibits a positive fractional order with respect to THFA and RuIII. The pseudo first-order ([THFA]≫[CeIV]≫[RuIII]) rate constant k obs decreases with the increase of [HSO −4 ]. Under the protection of nitrogen, the reaction system can initiate polymerization of acrylonitrile, indicating the generation of free radicals. On the basis of the experimental results, a reasonable mechanism has been proposed and the rate equations derived from the mechanism can explain all the experimental results. From the dependence of k obs on the concentration of HSO −4 , \({{\rm Ce}({\rm SO}_{4})_{2}}\) has been found as the kinetically active species. Furthermore, the rate constants of the rate determining step together with the activation parameters were evaluated.
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References
Shan J.H., Wang L. and Shen S.G. (2001). J. Hebei Univ. 21(Natural Science Edition): 53
Song W.Y. and Liu H.M. (2000). Chinese J. Inorg. Chem. 16: 607
Shan J.H., Qian J. and Zhai T.Y. (2003). Chinese J. Inorg. Chem. 19: 843
Lakshmi S. and Renganathan R. (1996). Int. J. Chem. Kinet. 28: 713
Chimatadar S.A., Koujalagi S.B. and Nadibewoor S.T. (2002). Indian J. Chem. 41: 316
Halligudi N.N., Deasai S.M. and Nadibewoor S.T. (1999). Indian J. Chem. 38: 943
Song W.Y., Jiang Q.M. and Liu Y.D. (2004). J. Hebei Univ. 24(Natural Science Edition): 594
Das A.K. and Das M. (1995). Int. J. Chem. Kinet. 27: 7
Das A.K. and Das M. (1995). Indian J. Chem. 34: 866
Kong F.Z., Tian J.H. and Jin Z.L. (2002). Petro. Tech. 31: 387
Feigl F. (1956). Spot test in organic analysis. Elsevier pulishing Co., New York, 334
Department of Chemistry, Hangzhou University. Handbook of analytical chemistry, Chemical Industry Press, Beijing, 618 (1982).
Moore J.W. and Pearson R.G. (1981). Kinetics and mechanism. John Willey and Sons, New York, 379
Mishra S.K. and Gupta Y.K., J. Chem. Soc. (A), 2918 (1970)
Song W.Y., Li Z.H. and Wang A.Z. (1997). Chem. J. Chin. Univ. 18: 1842
Mondal S.K., Kar D. and Das M. (1998). Indian J. Chem. 37: 765
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Zhai, Y., Liu, H., Liu, B. et al. Kinetics and mechanism of ruthenium(III) catalyzed oxidation of tetrahydrofurfuryl alcohol by cerium(IV) in sulfuric acid media. Transition Met Chem 32, 570–575 (2007). https://doi.org/10.1007/s11243-007-0198-2
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DOI: https://doi.org/10.1007/s11243-007-0198-2