Green Chemistry & Technology Letters

SANTOSH BAHADUR SINGH ([email protected])

Chemistry, University of Allahabad

May, 2010

Abstract

The present thesis entitled “Kinetic and Synthetic Study of Some Redox processes.” has been divided into two sections. Section A describes the oxidation of hydrocarbons (aromatic and alicyclic), alcohols (aromatic and alicyclic), aldehydes (aromatic), phenols and amines by sodium ferrate(VI) in the presence as well as in the absence of Cu-nano particles adsorbed on montmorillonite K10. The Section B exclusively deals with kinetic and mechanistic study of the oxidation of sodium arsenite by hexacyanoferrate(III) in aqueous alkaline medium in the presence as well as in the absence of iridium(III) chloride. The work presented in this thesis is important from the synthetic as well as from the kinetic point of views both. Synthetic part of the work opens a new avenue for the use of copper nano-particles as heterogeneous catalysts in the oxidation of various organic substrates. Iron in the form of sodium ferrate, which has been used as the oxidant is eco-friendly having no hazardous products. Hence the study is environmentally benign and can be safely extended for the industrial and laboratory synthesis. Kinetic part of the present work extends the use of transition metal ions as homogeneous catalysts in the oxidation of inorganic reactions also which are very important from the industrial point of view. IMPORTANCE OF THE PRESENT STUDY Great emphasis is now given to cost effective and eco-friendly synthetic methods. Fe(VI) can act as oxidant, coagulant, disinfectant, a selective oxidant and is useful in wastewater treatment processes. Novelty of the present study lies in the fact that without following the tedious and lengthy process of separation, the powerful oxidizing nature of in-situ prepared Fe(VI) and in-situ prepared nanoparticles adsorbed on montmorillonite K10 can be utilized in oxidizing various organic compounds. The present study also shows characterization and application of in-situ prepared copper nanoparticles adsorbed on solid clay support which may be used as effective catalysts in various redox processes under microwave irradiations. In the second part it has been shown that the presence of traces of transition metal ions can drastically enhance the rate of oxidation of arsenite, which is a major contaminant of drinking water. It also shows a method by which un-catalyzed reactions taking part along with the catalyzed ones can be separated graphically by studying the catalyzed reaction only. In the present scenario of deteriorating environmental conditions and the urgent need to save it, the present work is expected to be a mile-stone in the way leading to a clean and safe environment. REFERENCES 1. Cotton FA, Wilkinson G; “Advanced Inorganic Chemistry” Wiley Eastern Ltd., New Delhi 1976, p. 434. 2. Agrawal MC, Jindal VK, Mushran SP; J. Inorg. Nucl. Chem. 1970, 32, 1257. 3. Mohan D, Gupta D, Gupta YK; Inorg. Chem. 1977, 16, 1026. 4. Trakanosky WS (ed.), Oxidation of organic chemistry, Part B. Academic Press; New York, 1973. 5. Trost BM (ed.), Comprehensive organic synthesis (oxidation), vol. 7, Pergamon Press; New York, 1991. 6. Pavia DL, Lampman GM, Kriz GS, Engel RG; `Introduction to Organic Laboratory Techniques, A microscale approach`, Second Ed., Saunders College Publishing, 1995, 624. 7. Stiriner RL, Hermann CKE, Morrill TC, Curtin DY, Fuson RC; `The Systematic Identification of Organic Compounds`, Seventh Ed., John Wiley & Sons. Inc., New York, 1998, 307. 8. Stiriner RL, Hermann CKE, Morrill TC, Curtin DY, Fuson RC; `The Systematic Identification of Organic Compounds`, Seventh Ed., John Wiley & Sons. Inc., New York, 1998, 321 9. Hirai H, Wakabayashi H, Komiyama M; Chem. Lett. 1983, 1047. 10. Hirai H, Wakabayashi H, Komiyama M; Bull. Chem. Soc. Jpn. 1986, 59, 545.