Alkylation of phenol with methanol over mixed oxides of tin with some rare earth elements

Alkylation of phenol with methanol has been carried out over Sn-La and Sn-Sm mixed oxides of varying compositions at 623 K in a vapour phase flow reactor. It is found that the product selectivity is greatly influenced by the acid-base properties of the catalysts. Ortho-cresol formation is favoured over catalysts with weak acid sites whereas formation of 2,6-xylenol occurs in the presence of stronger acid sites. The cyclohexanol decomposition reaction and titrimetric method using Hammett indicators have been employed to elucidate the acid-base properties of the catalysts.

Thermochemistry of Charge-Transfer Complexes of 7,7,8,8-Tetracyanoquinodimethane with Benzene and Its Chloro Derivatives

The enthalpies of formation of charge-transfer complexes of benzene, chlorobenzene, and 1,3-dichlorobenzene as donors with 7,7,8,8-tetracyanoquinodimethane as acceptor were determined. The thermochemical data show an increased stability of charge-transfer complexes of donors with permanent dipole moment. The results confirm the importance of electrostatic forces in bonding and stabilizing weak complexes. The approximate formation constants of the complexes are also reported.

Studies on the catalysis by sulfated mixed oxides of tin with some rare earth elements

A comparative study of acid-base properties and catalytic activity of Sn-La and Sn-Sm mixed oxides and their corresponding sulfate modified analogues are reported in this thesis. The catalytic activity and product selectivity in the decomposition of alcohols are correlated with the acid-base and redox properties of the catalyst systems under study The effect of catalyst preparation, pretreatment and various reaction parameters on the catalytic activity of sulfate modified oxides is investigated in the oxidative dehydrogenation reactions The experimental conditions are optimised to synthesise industrially important organic chemicals viz. 2,6 xylenol, o-cresol, N-methylanilne and N,N-dimethylaniline employing the mixed oxide systems. The effect of sulfate treatment on the catalytic activity of these systems in the alkylation reactions of phenol, anisole and aniline is also investigated and the merits and demerits of sulfate treatment are highlighted.

Surface Electron Donor Properties of Dy2O3,Y2O3 and Their Mixed Oxides with Alumina Catalyst

The limit of electron transfer in electron affinity from the oxide surface to the electron acceptor (EA) are reported from the adsorption of EA on DY203, mixed oxides of DY203 with alumina and mixed oxides of Y203 with y-alumina. The extent of electron transfer is understood from magnetic measurements.

(1−x)MgAl2O4-xTiO2 dielectrics for microwave and millimeter wave applications

The MgAl2O4 ceramics were prepared by the conventional solid-state ceramic route and the dielectric properties studied in the microwave frequency region (3–13 GHz). The phase purity and crystal structure were identified using the X-ray diffraction technique. The MgAl2O4 spinel ceramics show interesting microwave dielectric properties (εr = 8.75, Qux f = 68 900 GHz (loss tangent = 0.00017 at 12.3 GHz), τf =−75 ppm/◦C). The MgAl2O4 has high negative τf, which precludes its immediate use in practical applications. Hence the microwave dielectric properties of MgAl2O4 spinels were tailored by adding different mole fractions of TiO2. The εr and Q factor of the mixed phases were increased with the molar addition of TiO2 into the spinel to form mixtures based on (1−x)MgAl2O4-xTiO2 (x = 0.0−1.0). For x = 0.25 in (1−x)MgAl2O4-xTiO2, the microwave quality factor reaches a maximum value of Qux f = 105 400 GHz (loss tangent = 0.00007 at 7.5 GHz) where εr and τf are 11.035 and −12 ppm/◦C, respectively. The microwave dielectric properties of the newly developed 0.75MgAl2O4-0.25TiO2 dielectric is superior to several commercially available low loss dielectric substrates.

STANDARDIZATION OF PROCESS PARAMETERS FOR READY TO EAT FISH PRODUCTS IN INDIGENOUS POLYMER COATED TIN FREE STEEL CANS

In the present work, Indigenous polymer coated Tin Free Steel cans were analyzed fortheir suitability for thermal processing and storage of fish and fish products following standard methods. The raw materials used for the development of ready to eat thermally processed fish products were found to be of fresh condition. The values for various biochemical and microbiological parameters of the raw materials were well within the limits. Based on the analysis of commercial sterility, instrumental colour, texture, WB-shear force and sensory parameters, squid masala processed to F0 value of 8 min with a total process time of 38.5 min and cook value of 92 min was chosen as the optimum for squid masala in tin free steel cans while shrimp curry processed to F0 7 min with total process time of 44.0 min and cook value of 91.1 min was found to be ideal and was selected for storage study. Squid masala and shrimp curry thermally processed in indigenous polymer coated TFS cans were found to be acceptable even after one year of storage at room temperaturebased on the analysis of various sensory and biochemical parameters. Analysis of the Commission Internationale d’ Eclirage L*, a* and b* color values showed that the duration of exposure to heat treatment influenced the color parameters: the lightness (L*) and yellowness (b*)decreased, and the redness (a*) significantly increased with the increase in processing time or reduction in processing temperature.Instrumental analysis of texture showed that hardness-1 & 2 decreased with reduction in retort temperature while cohesiveness value did not show any appreciable change with decrease in temperature of processing. Other texture profile parameters like gumminess, springiness and chewiness decreased significantly with increase of processing time. W-B shear force values of mackerel meat processed at 130 °C were significantly higher than those processed at 121.1 and 115 °C. HTST processing of mackerel in brine helped in reducing the process time and improving the quality.The study also indicated that indigenous polymer coated TFS cans with easy openends can be a viable alternative to the conventional tin and aluminium cans. The industry can utilize these cans for processing ready to eat fish and shell fish products for both domestic and export markets. This will help in reviving the canning industry in India.

Studies on ocean surface layer responses to atmospheric forcing in the North Indian Ocean

The present study on upper ocean responses to atmospheric forcing (associated with cyclone passage) in North Indian Ocean revealed significant variability between AS and BoB. The analysis of cyclone frequency during 1947 to 2006 exhibited lesser frequency of cyclones in AS than that of BoB. The analysis also revealed significant reduction in cyclone frequency after the year 1976 with substantial reduction during monsoon season. The long term SST data at selected points in AS and BoB could not reveal any relation with reduction in cyclone frequency. However the SLP at same locations exhibited considerable increase during mid 1970’s, which could have contributed to the observed reduction in cyclone frequency after the year 1976.The response in waves during cyclone passage exhibited significant asymmetry on either side of the track in AS and BoB and the response is observed at 100’s of kilometers away from the track. The significant clockwise rotation in wave direction is observed on the right side of the track starting from near the track to far away locations, which existed for a longer duration. However, the anticlockwise rotation in wave direction is observed over a shorter distance on the left side of the track and dissipated immediately.Inertial oscillation is observed in surface current and in the mixed layer temperature associated with cyclone passage, which revealed the role of relative location(s) on either side of the track. The inertial peak closer to the local inertial period indicates maximum transfer of energy during the cyclone passage in both AS and BoB. The absence of strong inertial oscillation even with clockwise rotation in surface current and wind indicates the dominant role of duration of strong wind in generating inertial oscillation.The oceanic response associated with cyclone passage reveal the variable response(s) which depends on cyclone intensity, the proximity to track and cyclone translation speed. It is observed that resonance with wind generates higher response in surface current, wave and SST on the right side of the track and it lasts for a longer duration. The maximum oceanic response is observed at a few kilometers away on right side of the track. However lesser rightward bias in the location of maximum cooling is observed for cyclones with low cyclone translation speed. The response on the left side of the track is less and is limited over a shorter distance and dissipates immediately. It is observed that the ocean response, in general, increases with intensity of cyclones. However the differential cooling produced by the same intensity cyclones in AS and in BoB indicates the dominant role of low cyclone translation speed in oceanic response.The surface cooling exhibited strikingly differential responses between AS and BoB. The TMI-SST and buoy observations exhibited significant cooling for a longer duration in AS compared to that of BoB. The spatial extent of cooling is also much higher in AS than that of BoB. The wide spread cooling associated with cyclone passage in AS indicates the dominant role of thermal structure in oceanic response in AS than that of BoB.

Studies on Simple and Encapsulated Transition Metal Complexes of Schiff Bases Derived from Diaminonaphthalene

Schiff base complexes of transition metal ions have played a significant role in coordination chemistry.In the present study we have synthesized some new Mn(II),Co(II) and Cu(II) complexes of Schiff bases derived from 1,8-diaminonaphthalene.Even though we could not isolate theses Schiff bases (as they readily cyclise to form the perimidine compounds),we were able to characterize unequivacally the complexes synthesized from these compounds as complexes of Schiff Bases. We Synthesized three perimidine derivatives ,2-(quinoxalin-2-yl)-2,3-dihydro-1H-perimidine,2-(2,3-dihydro-1H-perimidin-2-yl)-6-methoxyphenol and 4-(2,3-dihyro-1H-perimidin-2-yl)-2-methoxyphenol by the condensation of 1,8-diaminonaphthalene with quinoxaline-2-carboxaldehyde,2- hydroxy-3-methoxybenzaldehyde or 4-hydroxy-3-methoxybenzaldehyde respectively.Theses compounds were used as precursor ligands for the preparation of Schiff base complexes.The complexes were characterized by using elemental analysis ,conductance and magnetic susceptibility measuremets ,infrared and UV-Visible spectroscopy ,thermogravimetric analysis and EPR spectroscopy .We also encapsulated the complexes in zeolite Y matrix and these encapsulated complexes were also characterized. We have also tried theses complexes as catalysts in the oxidation of cyclohexanol and decomposition of hydrogen peroxide.

Environmental impact of sand mining

This thesis Entitled Environmental impact of Sand Mining :A case Study in the river catchments of vembanad lake southwest india.The entire study is addressed in nine chapters. Chapter l deals with the general introduction about rivers, problems of river sand mining, objectives, location of the study area and scope of the study. A detailed review on river classification, classic concepts in riverine studies, geological work of rivers and channel processes, importance of river ecosystems and its need for management are dealt in Chapter 2. Chapter 3 gives a comprehensive account of the study area - its location, administrative divisions, physiography, soil, geology, land use and living and non-living resources. The various methods adopted in the study are dealt in Chapter 4. Chapter 5 contains river characteristics like drainage, environmental and geologic setting, channel characteristics, river discharge and water quality of the study area. Chapter 6 gives an account of river sand mining (instream and floodplain mining) from the study area. The various environmental problems of river sand mining on the land adjoining the river banks, river channel, water, biotic and social / human environments of the area and data interpretation are presented in Chapter 7. Chapter 8 deals with the Environmental Impact Assessment (EIA) and Environmental Management Plan (EMP) of sand mining from the river catchments of Vembanad lake.

Studies on the propagation of errors in physical oceanographic computations

The results of an investigation on the limits of the random errors contained in the basic data of Physical Oceanography and their propagation through the computational procedures are presented in this thesis. It also suggest a method which increases the reliability of the derived results. The thesis is presented in eight chapters including the introductory chapter. Chapter 2 discusses the general theory of errors that are relevant in the context of the propagation of errors in Physical Oceanographic computations. The error components contained in the independent oceanographic variables namely, temperature, salinity and depth are deliniated and quantified in chapter 3. Chapter 4 discusses and derives the magnitude of errors in the computation of the dependent oceanographic variables, density in situ, gt, specific volume and specific volume anomaly, due to the propagation of errors contained in the independent oceanographic variables. The errors propagated into the computed values of the derived quantities namely, dynamic depth and relative currents, have been estimated and presented chapter 5. Chapter 6 reviews the existing methods for the identification of level of no motion and suggests a method for the identification of a reliable zero reference level. Chapter 7 discusses the available methods for the extension of the zero reference level into shallow regions of the oceans and suggests a new method which is more reliable. A procedure of graphical smoothening of dynamic topographies between the error limits to provide more reliable results is also suggested in this chapter. Chapter 8 deals with the computation of the geostrophic current from these smoothened values of dynamic heights, with reference to the selected zero reference level. The summary and conclusion are also presented in this chapter.

Ligation properties of N4-phenylsemicarbazones towards transition metals: Synthesis and spectral studies

Semicarbazones and their transition metal complexes have been receiving considerable attention because of their biological relevance and applications in the field of analysis and in the field of organic NLO materials. Their structural diversity also attracted inorganic chemists. A good deal of work has been reported on the synthesis and structural investigation of semicarbazones and their complexes. This is due partially to their capability of acting as multidentate, NO, NNO, ONO and ONNO donors with the formation of either mono or bi or polynuclear complexes. Their chemistry and pharmacological applications have been extensively investigated. Appreciable biological applications as well as diverse stereochemistry of their metal complexes prompted us to synthesize two new tridentate ONO donor N4-phenyl semicarbazones derived from 2-hydroxy-4-methoxyacetophenone and 2-hydroxy-4-methoxybenzophenone and their transition metal complexes. These ketones were selected since they can provide a further binding site from phenolic–OH and can thus increase the denticity. Introduction of heterocyclic bases like 1,10-phenanthroline, 2,2′-bipyridine, 4,4′-dimethyl- 2,2′-bipyridine and 4-picoline and some pseudohalides like azide and thiocyanate ion can result in mixed ligand metal chelates with different geometries in coordination compounds In the present study, oxovanadium(IV), manganese(II), cobalt (II/III), nickel(II), copper(II) and zinc(II) complexes of 2-hydroxy-4- methoxyacetophenone-N4-phenylsemicarbazone (H2ASC) and 2-hydroxy-4- methoxybenzophenone-N4-phenylsemicarbazone (H2BSC) were synthesized and characterized.

Mono- and binuclear transition metal complexes of n(4)-substituted thiosel\licarbazones derived frol\i salicylaldehyde and 2-hydroxyacetophenone synthesis, spectral and structural studies

The work embodied in the thesis is divided into eight chapters. Chapter I gives a brief introduction about metal complexes of thiosemicarbazones, including their structural and bonding properties. Chapter 2 deals with the synthesis and single crystal X-ray diffraction studies of various thiosemicarbazones used up for the present investigations and various characterization techniques. Chapter 3 deals with synthesis, spectral and structural studies of Cu(U) complexes with ONS donor thiosemicarbazones. Chapter 4 deals with synthesis and spectral studies of Ni(II) complexes \vith 2-hydroxyacetophenone N(4)-cyclohexyl thiosemicarbazone as the ligand. Chapter 5 includes synthesis and spectral studies of Mn(II) complexes. Chapter 6 deals with synthesis, spectral and structural studies of Zn(II) complexes. Chapter 7 includes synthesis and spectral studies of oxovanadium(IV) complexes. Chapter 8 deals with synthesis, spectral and single crystal X-ray diffraction studies of dioxomolybdenum(VI) complexes.

Utilization of aquatic macrophyte Spirodela polyrhiza as phytotoxicological assessment and phytoremediation tool in selected polluted wetland sites in Ernakulam district

One of the objectives of the current investigation was to evaluate the effectiveness of Spirodela polyrhiza to remove heavy metals and other contaminants from the water samples collected from wetland sites of Eloor and Kannamaly under controlled conditions .The results obtained from the current study suggest that the test material S. polyrrhiza should be used in the biomonitoring and phytoremediation of municipal, agricultural and industrial effluents because of their simplicity, sensitivity and cost-effectiveness. The study throws light on the potential of this plant which can be used as an assessment tool in two diverse wetland in Ernakulum district. The results show the usefulness of combining physicochemical analysis with bioassays as such approach ensures better understanding of the toxicity of chemical pollutants and their influence on plant health. The results shows the suitability of Spirodela plant for surface water quality assessment as all selected parameters showed consistency with respect to water samples collected over a 3-monitoring periods. Similarly the relationship between the change in exposure period (2, 4 and 8 days) with the parameters were also studied in detail. Spirodela are consistent test material as they are homogeneous plant material; due to predominantly vegetative reproduction. New fronds are formed by clonal propagation thus, producing a population of genetically homogeneous plants. The result is small variability between treated individuals. It has been observed that phytoremediation of water samples collected from Eloor and Kannamaly using the floating plant system is a predominant method which is economic to construct, requires little maintenance and eco friendly.