Studies on Catalysis by Titania

Scientists throughout the world are in search of a better methodology to reduce the use of environmentally hazardous chemicals common in industries .A significant contribution in this field is given by different redox catalysts in oxidation reactions. The oxidation of organic substrates represents one of the most important industrial chemical reactions, explaining the significant efforts invested in the research and development of new heterogeneous catalysts with increased activities and selectivities in these type reactions[l-4|. Hence liquid phase reactions like epoxidation of cylcohexene and hydroxylation of phenol were carried out with a new outlook in the challenge using CeO2/TiO;; and CuO/TiO2 catalysts denoted as TiO2-Ce as TiO2-Cu respectively in this work. Also different wt% of metals incorporated titania catalysts like 3, 6, 9 wt% CeO2/TiO; and CuO/TiO;were subjected to the present study .The interaction between metal oxides and the oxide supports have attracted much attention because of the wide applications of supported metal oxide systems[7,8]. It is well known that supported oxides of transition metals are widely used as catalysts for various reactions. Titania as well its metal modified catalysts systems afford high activity and selectivity in the liquid phase epoxidation of cyclohexene[9]. Cyclohexene epoxide is obtained as the major product during the reaction with small amounts of allylic substitution products.This chapter gives an idea about the liquid phase oxidation reactions like epoxidation of cylcohexene and hydroxylation of phenol in which many industrially important products are formed. Here discusses about the redox properties of the ceria and copper incorporated titania catalysts.The epoxidation of cyclohcxene is carried out efficiently over the prepared systems with the selective formation of cyclohexane epoxide. This reaction hints that it might be possible to create cleaner nylon chemistry. The total acidity of the prepared systems plays an important role in determining the catalytic activity in the dehydrogenation of cyclohexane and cyclohexene. The total acidity of the prepared systems plays an important role in determining the catalytic activity in the dehydrogenation of cyclohexane and cyclohexene.

Studies on nonlinear dynamics of certain reaction systems

The nonlinear dynamics of certain important reaction systems are discussed and analysed in this thesis. The interest in the theoretical and the experimental studies of chemical reactions showing oscillatory dynamics and associated properties is increasing very rapidly. An attempt is made to study some nonlinear phenomena exhibited by the well known chemical oscillator, the BelousovZhabotinskii reaction whose mathematical properties are much in common with the properties of biological oscillators. While extremely complex, this reaction is still much simpler than biological systems at least from the modelling point of view. A suitable model [19] for the system is analysed and the researcher has studied the limit cycle behaviour of the system, for different values of the stoichiometric parameter f, by keeping the value of the reaction rate (k6) fixed at k6 = l. The more complicated three-variable model is stiff in nature.

Hydrogeology and hydrochemistry of the aquifer systems of Kuttanad area, Kerala: Their role in understanding the evolution of groundwaters

This is an attempt to understand the important factors that control the occurrence, development and hydrochemical evolution of groundwater resources in sedimentary multi aquifer systems. The primary objective of this work is an integrated study of the hydrogeology and hydrochemistry with a view to elucidate the hydrochemical evolution of groundwater resources in the aquifer systems. The study is taken up in a typical coastal sedimentary aquifer system evolved under fluvio-marine environment in the coastal area of Kerala, known as the Kuttanad. The present study has been carried out to understand the aquifer systems, their inter relationships and evolution in the Kuttanad area of Kerala. The multi aquifer systems in the Kuttanad basin were formed from the sediments deposited under fluvio-marine and fluvial depositional environments and the marine transgressions and regressions in the geological past and palaeo climatic conditions influenced the hydrochemical environment in these aquifers. The evolution of groundwater and the hydrochemical processes involved in the formation of the present day water quality are elucidated from hydrochemical studies and the information derived from the aquifer geometry and hydraulic properties. Kuttanad area comprises of three types of aquifer systems namely phreatic aquifer underlain by Recent confined aquifer followed by Tertiary confined aquifers. These systems were formed by the deposition of sediments under fluvio-marine and fluvial environment. The study of the hydrochemical and hydraulic properties of the three aquifer systems proved that these three systems are separate entities. The phreatic aquifers in the area have low hydraulic gradients and high rejected recharge. The Recent confined aquifer has very poor hydraulic characteristics and recharge to this aquifer is very low. The Tertiary aquifer system is the most potential fresh water aquifer system in the area and the groundwater flow in the aquifer is converging towards the central part of the study area (Alleppey town) due to large scale pumping of water for water supply from this aquifer system. Mixing of waters and anthropogenic interferences are the dominant processes modifying the hydrochemistry in phreatic aquifers. Whereas, leaching of salts and cation exchange are the dominant processes modifying the hydrochemistry of groundwater in the confined aquifer system of Recent alluvium. Two significant chemical reactions modifying the hydrochemistry in the Recent aquifers are oxidation of iron in ferruginous clays which contributes hydrogen ions and the decomposition of organic matter in the aquifer system which consumes hydrogen ions. The hydrochemical environment is entirely different in the Tertiary aquifers as the groundwater in this aquifer system are palaeo waters evolved during various marine transgressions and regressions and these waters are being modified by processes of leaching of salts, cation exchange and chemical reactions under strong reducing environment. It is proved that the salinity observed in the groundwaters of Tertiary aquifers are not due to seawater mixing or intrusion, but due to dissolution of salts from the clay formations and ion exchange processes. Fluoride contamination in this aquifer system lacks a regional pattern and is more or less site specific in natureThe lowering of piezometric heads in the Tertiary aquifer system has developed as consequence of large scale pumping over a long period. Hence, puping from this aquifer system is to be regulated as a groundwater management strategy. Pumping from the Tertiary aquifers with high capacity pumps leads to well failures and mixing of saline water from the brackish zones. Such mixing zones are noticed from the hydrochemical studies. This is the major aquifer contamination in the Tertiary aquifer system which requires immediate attention. Usage of pumps above 10 HP capacities in wells taping Tertiary aquifers should be discouraged for sustainable development of these aquifers. The recharge areas need to be identified precisely for recharging the aquifer systems throughartificial means.

Studies on some supported transition metal complex and metal oxide catalysts for oxidation reactions

Zeolite encapsulated transition metal complexes have received wide attention as an effective heterogenized system that combines the tremendous activity of the metal complexes and the attractive features of the zeolite structure. Zeolite encapsulated complexes offer a bright future for attempts to replace homogeneous systems retaining its catalytic activity and minimizing the technical problems. especially for the partial oxidation of organic compounds. Studies on some zeolite encapsulated transition metal complexes are presented in this thesis. The ligands selected are technically important in a bio-mimetic or structural perspective. Attempts have been made in this study to investigate the composition, structure and stability of encapsulated complexes using available techniques. The catalytic activity of encapsulated complexes was evaluated for the oxidation of some organic compounds. The recycling ability of the catalyst as a result of the encapsulation was also studied.Our studies on Cu-Cr/Al2O3, a typical metal oxide catalyst. illustrate the use of design techniques to modify the properties of such conventional catalysts. The catalytic activity of this catalyst for the oxidation of carbon monoxide was measured. The effect of additives like Ce02 or Ti02 on the activity and stability of this system was also investigated. The additive is potent to improve the activity and stability ofthe catalyst so as to be more effective in commercial usage.

“A comparative study of medium and large pore zeolites in alkylation reactions”

Zeolites have established themselves as industrial catalysts for over two decades for a variety of hydrocarbon processing reactions where acidity and shape selectivity are important factors. As solid catalysts, zeolites may be advantageous and superior compared to their homogenous counterparts due to their characteristic properties. It is only in recent years that the utility of zeolites for organic synthesis is recognized for producing specific organic intermediates and fine chemicals in high selectivity. In this thesis an attempt has been made to compare the catalytic activity of some medium and large pore zeolites in a few alkylation and acylation reactions. The work reported in the present study is basically centered around the following zeolites namely, ZSM-5, mordenite, zeolite Y and beta. The major reactions carried out were benzoylation of o-xylene, propionylation of toluene and anisole and benzylation of oxylene. . The programme involves the synthesis, modifications and characterization of the zeolite catalysts by various methods. The influence of various parameters such as non-framework cations, Si/Al ratio of zeolites, temperature of the reaction, catalyst concentration, molar ratio of the reactants and recycling of the catalysts were also examined upon the conversion of reactants and the formation of the desired products in the alkylation/ acylation reactions. The general conclusions drawn by us from the results obtained are summarized in the last chapter of the thesis. Zeolite beta ofi'ers interesting opportunities as a potential catalyst in alkylation reactions and the area of catalysis by medium and large pore zeolites is very fascinating and there is plenty of scope for further research in this field. Moreover, zeolite based catalysts are effective in meeting current industrial processing and more stringent environment pollution limits.

Novel [3+2] annulation reaction of nitrones with Burgess reagent and a few related reactions

Burgess reagent first prepared by E. M. Burgess in 1968, is a mild and selective dehydrating agent for secondary and tertiary alcohols and due to the amphipolar nature it is gainfully employed in a number of creative synthetic ventures. A close examination of the structure of Burgess reagent reveals that it can act as a 1,2-dipole. To the best of our knowledge, no attempts have been made to tap full synthetic potential of the amphipolar nature of this reagent and no reports on 1,3-dipolar addition to a σ-bond in acyclic systems are available in literature. In this context, we propose to unravel novel applications of Burgess reagent based on its amphipolar nature. Rich and multifaceted chemistry of nitrones form the basis of many successful chemical transformations used in attractive synthetic strategies. For the last 50 years special attention has been given to nitrones due to their successful application as building blocks in the synthesis of various natural and biologically active compounds. Our interest in nitrones stems out of its unique character: i.e. it is a 1,3-dipole exhibiting distinct nucleophilic activity. We reasoned that 1,3-dipole possessing significant nucleophilicity should react with amphipolar Burgess reagent with elimination of triethylamine to give the corresponding five-membered ring product by formal dipolar addition to a σ bond. To test this hypothesis we studied the reaction of nitrones with Burgess reagent. This thesis reveals our attempts to explore the [3+2] annulation reaction of nitrones with Burgess reagent which was found to be followed by a rearrangementinvolving C-to-N aryl migration, ultimately resulting in diarylamines and carbamates. We have also examined the reaction of cyanuric chloride with nitrones in DMF with a view to exploit the nucleophilicty of nitrones and to unravel the migratory aptitude, if any, observed in this reaction