Effect of vanadia on physico-chemical and catalytic characteristics of dysprosia

Physico-chemical characterization of DY203/V2O5 systems prepared through wet impregnation method has been carried out using various techniques like EDX, XRD, FTIR. thermal studies, BET surface area, pore volume and pore size distribution analysis. The amount of vanadia incorporated has been found to influence the surface properties of dysprosia. The spectroscopic results combining with X-ray analysis reveal that vanadia species exist predominantly as isolated amorphous vanadyl units along with crystalline dysprosium orthovanadate. Basicity studies have been conducted by adsorption of electron acceptors and acidity and acid strength distribution by temperature programmed desorption of ammonia. Cyclohexanol decomposition has been employed as a chemical probe reaction to examine the effect of vanadia on the acid base property of Dy2O3. Incorporation of vanadia titrates thc Lewis acid and base sites of Dy2O3, while an enhancement of Bronsted acid sites has been noticed. Data have been correlated with the catalytic activity of these oxides towards the vapour phase methylation of phenol

Structural and biological investigations of metal complexes of some substituted thiosemicarbazones

Department of Applied Chemistry, Cochin University of Science and Technology

Structural and catalytic investigation of vanadia supported on ceria promoted with high surface area rice husk silica

Rice husk silica was utilized as the promoter of ceria for preparing supported vanadia catalysts. Effect of vanadium content was investigated with 2–10 wt.% V2O5 loading over the support. Structural characterization of the catalysts was done by various techniques like energy dispersive X-ray (EDX), X-ray diffraction (XRD), BET surface area, thermal analysis (TGA/DTA), FT-infrared spectroscopy (FT-IR), UV–vis diffused reflectance spectroscopy (DR UV–vis), electron paramagnetic spectroscopy (EPR) and solid state magnetic resonance spectroscopies (29Si and 51V MASNMR). Catalytic activity was studied towards liquid-phase oxidation of benzene. Surface area of ceria enhanced upon rice husk silica promotion, thus makes dispersion of the active sites of vanadia easier. Highly dispersed vanadia was found for low V2O5 loading and formation of cerium orthovanadate (CeVO4) occurs as the loading increases. Spectroscopic investigation clearly confirms the formation of CeVO4 phase at higher loadings of V2O5. The oxidation activity increases with vanadia loading up to 8 wt.% V2O5, and further increase reduces the conversion rate. Selective formation of phenol can be attributed to the presence of highly dispersed active sites of vanadia over the support.

Photoacoustic signal saturation and optical limiting in C70-toluene solution

Pulsed photoacoustic studies in solutions of C70 in toluene are made using the 532-nm radiation from a frequency-doubled Nd:YAG laser. It is found that contrary to expectation, there is no photoacoustic (PA) signal enhancement in the power-limiting range of laser fluences. Instead, the PA signal tends to saturate during optical power-limiting phenomenon. This could be due to the enhanced optical absorption from the photoexcited state and hence the depletion of the ground-state population. PA measurements also ruled out the possibility of multiphoton absorption in the C70 solution. We demonstrate that the nonlinear absorption leading to optical limiting is mainly due to reverse saturable absorption.

A Study of Photoacoustic Effects and Optical Limiting in the Solution of C60 in Toluene

Pulsed photoacoustic studies in solution of C60 in toluene have been made using the 532 nm radiation from a frequency doubled Nd:YAG laser. Though C60 is found to exhibit the phenomenon of optical limiting, the results on photoacoustic measurements do not give any indication of multiphoton transitions as suggested in some of the earlier works. Results of photoacoustic measurements show that excited state absorption is the dominant process responsible for optical limiting while phenomena like nonlinear scattering may contribute to a lesser extent.

Dielectric and optical properties of europium oxide films

The dielectric properties of vacuum-deposited europium oxide films have been investigated in the frequency range from 1 kHz to 1 MHz at various temperatures (300-543 K). The dielectric constant is found to depend on film thickness and it attains a constant value beyond 1000 Å. Films deposited at higher substrate temperatures (above 423 K) exhibit improved dielectric properties owing to the recovery of stoichiometry. The frequency variation of the loss factor exhibits a minimum which increases with rise in temperature. The breakdown field strength (about 106V cm-1) is found to be thickness dependent and it varies in accordance with the Forlani-Minnaja relation. The films exhibit ohmic conduction with an activation energy of 0.86 eV at low electric fields but at higher fields the conductivity becomes space charge limited. X-ray studies show that the films are amorphous in nature. The a.c. conductivity is proportional to ω at low frequency, whereas a square law dependence is observed at higher frequencies. The optical constants n, α and k and optical band gap are calculated from the UV-visible-near-IR spectra.

Excitation and Emission Characteristics of Pretreated SrS:Mn:Ce Phosphors

Excitation and emission spectra of SrS : Mn : Ce phosphors have been studied in detail at various Mn and Ce concentrations. In order to study the effect of external pressure on phosphors, the samples were pretreated under various pressures. Four bands around 470 nm, 530 nm, 310 nm and 620 nm were observed, when the samples were excited with 265 nm radiation. The effect of pressure is to reduce the fluorescence ability of the phosphors, and the luminescence vanishes above O· 1 ton m-2 pressure. The fluorescence ability, however, can be regained on retiring the sample. The emission mechanism has been attributed to two luminescentcenters in the forbidden gap. An appreciable amount of photocurrent has also been observed for the sample.

Impact of zinc substitution on the structural and magnetic properties of chemically derived nanosized manganese zinc mixed ferrites

Mn1-xZnxFe2O4 nanoparticles (x=0-1) were synthesized by wet chemical co-precipitation techniques. X-ray diffraction, transmission electron microscopy and high-resolution transmission electron microscopy were effectively utilized to investigate the different structural parameters. The elemental analysis was conducted using energy-dispersive spectrum and inductively coupled plasma analysis. The magnetic properties such as magnetization and coercivity were measured using vibrating sample magnetometer. The observed magnetization values of the nanoparticles were found to be lower compared to the bulk counterpart. The magnetization showed a gradual decrease with zinc substitution except for a small increase from x=0.2 to 0.3. The Curie temperature was found to be enhanced in the case of ferrites in the nanoregime. The variation in lattice constant, reduced magnetization values, variation of magnetization with zinc substitution, the presence of a net magnetic moment for the zinc ferrite and the enhancement in Curie temperature in Mn1-xZnxFe2O4 all provide evidence to the existence of a metastable cation distribution together with possible surface effects at the nanoregime.

Studies on ASE, Lasing and NLO characteristics in Certain Laser Dyes

Observing the wide possibilities of fluorescent dyes, an exhaustive investigation is done in laser dyes mainly focusing on Coumarin 540 which has a very strong emission in the green region. The photophysics of the dye is studied in detail in a good number of solvent environments. The results of the amplified spontaneous emission and lasing behaviour in both dye solution and different polymer solid state matrices and the ptotostability of the these matrices are investigated using the photoacoustic technique and the same are also included in this thesis. The energy transfer behaviour in dye mixtures which could be utilized for laser studies and bio-analysis are also presented. The nonlinear characterization of Coumarin540 forms the last part of the experimental investigations presented in the thesis.

A Study Of The Strength And Compressibility Characteristics Of Cochin Marine Clays

With the advent of urbanisation and consequent search for more and more habitable land, it was imperative that the large tracts of marine clays, considered inhabitable earlier, had to be reclaimed and developed. These marine clays, wellknown for its high compressibility and poor shear strength, posed numerous problems to the builders and Cochin was no exception. It is only less than a decade since active research work was initiated on marine clays in general and Cochin marine clays in particular. Eventhough some systematic studies are available on compressibility characteristics, attempts to study the shear strength aspects and development of techniques to improve it have been very limited. This work is an investigation on the consolidation and shear strength characteristics of Cochin marine clays including methods to improve the same

Spectral and statistical characteristics of shoaling waves of Alleppey West coast of India

Some investigations on the spectral and statistical characteristics of deep water waves are available for Indian waters. But practically no systematic investigation on the shallow water wave spectral and probabilistic characteristics is made for any part of the Indian coast except for a few restricted studies. Hence a comprehensive study of the shallow water wave climate and their spectral and statistical characteristics for a location (Alleppey) along the southwest coast of India is undertaken based on recorded data. The results of the investigation are presented in this thesis.The thesis comprises of seven chapters

Studies on Catalysis by Nano Titania Modified with Metals and Nonmetals

Semiconductor photocatalysis has received much attention during last three decades as a promising solution for both energy generation and environmental problems. Heterogeneous photocatalytic oxidation allows the degradation of organic compounds into carbon dioxide and water in the presence of a semiconductor catalyst and UV light source. The •OH radicals formed during the photocatalytic processes are powerful oxidizing agents and can mineralise a number of organic contaminants. Titanium dioxide (TiO2), due to its chemical stability, non-toxicity and low cost represents one of the most efficient photocatalyst. However, only the ultraviolet fraction of the solar radiation is active in the photoexcitation processes using pure TiO2 and although, TiO2 can treat a wide range of organic pollutants the effectiveness of the process for pollution abatement is still low. A more effective and efficient catalyst therefore must be formulated. Doping of TiO2 was considered with the aim of improving photocatalytic properties. In this study TiO2 catalyst was prepared using the sol-gel method. Metal and nonmetal doped TiO2 catalysts were prepared. The photoactivity of the catalyst was evaluated by the photodegradation of different dyes and pesticides in aqueous solution. High photocatalytic degradation of all the pollutants was observed with doped TiO2. Structural and optical properties of the catalysts were characterized using XRD, BET surface area, UV-Vis. DRS, CHNS analysis, SEM, EDX, TEM, XPS, FTIR and TG. All the catalysts showed the anatase phase. The presence of dopants shifts the absorption of TiO2 into the visible region indicating the possibility of using visible light for photocatalytic processes.

Spatial and temporal characteristics of rain intensity in the peninsular Malaysia using TRMM rain rate

The present study is focused on the intensity distribution of rainfall in different classes and their contribution to the total seasonal rainfall. In addition, we studied the spatial and diurnal variation of the rainfall in the study areas. For the present study, we retrieved data from TRMM (Tropical Rain Measuring Mission) rain rate available in every 3 h temporal and 25 km spatial resolutions. Moreover, station rainfall data is used to validate the TRMM rain rate and found significant correlation between them (linear correlation coefficients are 0.96, 0.85, 0.75 and 0.63 for the stations Kota Bharu, Senai, Cameron highlands and KLIA, respectively). We selected four areas in the Peninsular Malaysia and they are south coastal, east coastal, west coastal and highland regions. Diurnal variation of frequency of rain occurrence is different for different locations. We noticed bimodal variation in the coastal areas in most of the seasons and unimodal variation in the highland/inland area. During the southwest monsoon period in the west coastal stations, there is no distinct diurnal variation. The distribution of different intensity classes during different seasons are explained in detail in the results

Spectral, Structural And Biological Studies Of Some Metal Complexes Of ‘Nsubstituted 2-Benzoylpyridine Thiosemicarbazones

Aqua complex ions of metals must have existed since the appearance of water on the earth, and the subsequent appearance of life depended on, and may even have resulted from the interaction of metal ions with organic molecules. Studies on the coordinating ability of metal ions with other molecules and anions culminated in the theories of/\lfred Werner. Thereon the progress in the studies of metal complex chemistry was rapid. Many factors, like the utility and economic importance of metal chemistry, the intrinsic interest _in many of the compounds and the intellectual challenge of the structural problems to be solved, have contributed to this rapid progress. X—ray diffraction studies further accelerated the progress. The work cited in this thesis was carried out by the author in the Department of Applied Chemistry during 2001-2004. The primary aim of these investigations was to synthesise and characterize some transition metal complexes of 2-benzoylpyridine N(4)-substituted thiosemicarbazones and to study the antimicrobial activities of the ligands and their metal complexes. The work is divided into eight chapters