Green Chemistry & Technology Letters

Priy Brat Dwivedi (priy.dwivedi@gmail.com)

Department of Chemistry, Central University of Allahabad

June, 2007

Senior Lecturer, Caledonian College of Engineering, Oman

Abstract

Oxidation of organic compounds by various oxidising agents, using certain selective catalysts is of considerable academic and industrial importance. Study, in my thesis; entitled ”Kinetic study of some redox processes in solution” has been performed keeping both applications of chemical kinetics in mind. Work in the thesis has been divided into two parts. Part-A In this part of the thesis contains study of the oxidation of benzyl alcohol, 2-phenyl ethanol and 2-methyl cyclohexanol by cerium(IV) sulphate in aqueous sulphuric acid medium catalyzed by iridium(III) chloride from the kinetic point of view. Study was performed at 360 nm wavelength (on Spectronic-20D) at which cerium (IV) absorbs strongly. Various Thermodynamic parameters viz. activation energy, free energy of activation and entropy of activation were also calculated. On the basis of experimental findings probable mechanism is also suggested. Final rate law based on proposed mechanism confirms our experimental findings. Part-B In this part of the thesis contains oxidation of p-chlorobenzaldehyde, p-nitro benzaldehyde, benzyl alcohol, p-methoxy benzyl alcohol, p-xylene and p-nitro toluene by cerium(IV) sulphate in aqueous acetic acid medium catalyzed by iridium(III) chloride from the synthetic point of view. Obtained products were identified by functional group analysis, thin layer chromatographic technique, formation of derivatives and by their IR and 1H-NMR spectral analysis. As all the reactions and reaction products are well studied from the kinetic and mechanistic point of view, therefore, we have tried to find out conditions for getting the maximum yield under most economical conditions. It may be pointed out that the present system is highly eco-friendly as the aqueous part contains only the traces of iridium (III) chloride (in the range of 10^-6 mmol) and acetic acid and hydrochloric acid. Acetic acid may be removed by distillation while hydrochloric acid was not present in such a quantity to damage the atmosphere. References Shriner, R. L., Hermann, C. K. F., Morill, T.C., Curtin, D.Y., Fuson, R.C. "The systematic identification of organic compound." 7th ed. John Wiley & Sons 1998. Forniss, B.S., Antony, J., Peter, H., Smith, W.J., Tatchel, A. R. "Vogel's text book of practical organic chemistry". Vth Edition, Reprinted 1996, Longman Group, UK Ltd. Pavia, D. L., Lampan, G. M., Kriz, G. S., Engel, R. G. "An Introduction to Organic laboratory techniques - A microscale approach" Saunders College Publishing & H. B. College Publishers, USA, 1995.