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.

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.

Studies on the macrobenthic community of Cochin backwaters with special reference to culture of Eriopisa chilkensis (Gammaridae-Amphipoda)

This thesis Entitled studies on the macrobenthic community of cochin backwaters with special reference to culture of eriopisa chilkensis (Gammaridae- amphipoda).Benthic organisms are usually studied for environmental impact assessment, pollution control and resource conservation. The benthic monitoring component has three major objectives: 1) characterize the benthic communities to assess the estuarine health, 2) determine seasonal and spatial variability in benthic communities, and 3) detect changes in the estuarine community through examination of changes in abundances of specific indicator taxa and other standard benthic indices.Cochin backwaters situated at the tip of the northern Vembanad lake is a tropical positive estuarine system. The backwaters of Kerala support as much biological productivity and diversity as tropical rain forest and are responsible for the rich fishery potential of Kerala. Backwaters also act as nursery grounds for commercially important prawns and fishes.The thesis has been subdivided into seven chapters. The first chapter gives a general introduction about the topic and also highlights the scope and purpose of the study. The second chapter covers the methodology adopted for the collection and analysis of water quality parameters, sediment and the macrobenthic fauna.Chapter 3 deals with hydrographic features, sediment characteristics and the spatial variation and abundance of macrobenthic fauna in the Cochin estuary.Chapter 4 explains the impact of organic enrichment on macrobenthic popUlation in the Cochin estuary and includes the comparison of the present data with the earlier work in this region.Chapter 5 deals with seasonal variability in abundance of macrobenthic species in the estuary. The study was conducted from 9 stations during three seasons (pre-monsoon, monsoon and post-monsoon) in 2003.Chapter 6 deals with Life history and Population Dynamics of Eriopisa chilkensis Chilton (Gammaridae-Amphipoda). The life cycle of the gammarid amphipod Eriopisa chilkensis from the Cochin estuary, south west coast of India was studied for the first time under laboratory conditions.

Synthesis, characterization and properties of Conductive elastomeric composites based on Polypyrrole and short Nylon-6 fiber

The search for new materials especially those possessing special properties continues at a great pace because of ever growing demands of the modern life. The focus on the use of intrinsically conductive polymers in organic electronic devices has led to the development of a totally new class of smart materials. Polypyrrole (PPy) is one of the most stable known conducting polymers and also one of the easiest to synthesize. In addition, its high conductivity, good redox reversibility and excellent microwave absorbing characteristics have led to the existence of wide and diversified applications for PPy. However, as any conjugated conducting polymer, PPy lacks processability, flexibility and strength which are essential for industrial requirements. Among various approaches to making tractable materials based on PPy, incorporating PPy within an electrically insulating polymer appears to be a promising method, and this has triggered the development of blends or composites. Conductive elastomeric composites of polypyrrole are important in that they are composite materials suitable for devices where flexibility is an important parameter. Moreover these composites can be moulded into complex shapes. In this work an attempt has been made to prepare conducting elastomeric composites by the incorporation of PPy and PPy coated short Nylon-6 fiber with insulating elastomer matrices- natural rubber and acrylonitrile butadiene rubber. It is well established that mechanical properties of rubber composites can be greatly improved by adding short fibers. Generally short fiber reinforced rubber composites are popular in industrial fields because of their processing advantages, low cost, and their greatly improved technical properties such as strength, stiffness, modulus and damping. In the present work, PPy coated fiber is expected to improve the mechanical properties of the elastomer-PPy composites, at the same time increasing the conductivity. In addition to determination of DC conductivity and evaluation of mechanical properties, the work aims to study the thermal stability, dielectric properties and electromagnetic interference shielding effectiveness of the composites. The thesis consists of ten chapters.

A PVC plasticized membrane sensor for nickel ions

A new PVC membrane sensor, which is highly selective towards Ni (II) ions, has been developed using a thiophene-derivative Schiff base as the ionophore. The best performance was exhibited by the membrane having the composition percentage ratio of 5:3:61:31 (ionophore:NaTPB:DBP:PVC) (w=w), where NaTPB is the anion excluder, sodium tetraphenylborate and DBP is the plasticizing agent (dibutyl phthalate). The membrane exhibited a good Nernstian response for nickel ions over the concentration range of 1.0 10 1– 5.0 10 6M (limit of detection is 1.8 10 6 M) with a slope of 29.5 1.0mV per decade of activity. It has a fast response time of<20 s and can be used for a period of 4 months with good reproducibility. The sensor is suitable for use in aqueous solutions of a wide pH range of 3.2–7.9. The sensor shows high selectivity to nickel ions over a large number of mono-, bi- and trivalent cations. It has been successfully used as an indicator electrode in the potentiometric titration of nickel ions against EDTA and also for direct determination of nickel content in real samples – wastewater samples from electroplating industries and Indian chocolates.

A PVC Plasticized Membrane Sensor for Nickel Ions

A new PVC membrane sensor, which is highly selective towards Ni (II) ions, has been developed using a thiophene-derivative Schiff base as the ionophore. The best performance was exhibited by the membrane having the composition percentage ratio of 5:3:61:31 (ionophore:NaTPB:DBP:PVC) (w=w), where NaTPB is the anion excluder, sodium tetraphenylborate and DBP is the plasticizing agent (dibutyl phthalate). The membrane exhibited a good Nernstian response for nickel ions over the concentration range of 1.0 10 1– 5.0 10 6M (limit of detection is 1.8 10 6 M) with a slope of 29.5 1.0mV per decade of activity. It has a fast response time of<20 s and can be used for a period of 4 months with good reproducibility. The sensor is suitable for use in aqueous solutions of a wide pH range of 3.2–7.9. The sensor shows high selectivity to nickel ions over a large number of mono-, bi- and trivalent cations. It has been successfully used as an indicator electrode in the potentiometric titration of nickel ions against EDTA and also for direct determination of nickel content in real samples – wastewater samples from electroplating industries and Indian chocolates.

(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.

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.

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.

Studies On The Biology Of The Clam Sunetta Scripta (Linne), From The Subtidal Waters Of Cochin

Enhancement and culture of bivalves presents an opportunity to maximise and even increase production of many growing areas. Clam culture is less intensive both for capital and labour, involves simple farming and management techniques and is considered an efficient means of protein production. Clams are efficient converters of primary production and growth rate is fast with maximum production in 5-6 months. with culture, production is less influenced by poor recruitment. Stable production facilitates market development. Rivalves are being increasingly used in bio-medical research. Culture practices would ensure uninterrupted supplies of experimental material. Paucity of biological data restricts the development of efficient management and culture techniques of bivalves. This study was undertaken with a view to provide information on some aspects of biology of the bivalve S_. scripta which have hitherto been uninvestigated.

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.

Temporal pattern of fish production in a microtidal tropical estuary in the south-west coast of India

The status of fisheries and seasonal variation in fish diversity in the Kodungallur-Azhikode Estuary (KAE) were investigated. Total annual average fish production in the estuary declined significantly to 908.6 t with average yield of 5.4 kg ha-1 day-1, when compared to earlier study; where 2747 t was reported. During the present study, 60 species of finfishes (belonging to 34 finfish families), 6 species of penaeid shrimps, 2 species of palaemonid prawns, 2 species of crabs (4 crustacean families), 6 species of bivalves and 2 species of edible oysters (3 molluscan families) were noticed. Finfishes were the major group that contributed 69.62% of total fishery in the estuary and crustaceans (23.47%), bivalves (6.84%) and oysters (0.07%) also formed good fishery. Many of the fish species in the estuary were observed as threatened (Horabagrus brachysoma, Channa striatus, Channa marulius, Clarias batrachus, Heteropneustes fossilis and Wallago attu). The major fishing gears employed in the estuary were gillnets, cast nets, stake nets, scoop nets, ring nets, traps and Chinese dip nets. Gillnets contributed 45% of the total fish catch. Gillnets also showed highest catch per unit effort (CPUE) of 6.91 kg h -1 followed by cast nets (1.85 kg h -1), Chinese dip nets (3.20 kg h -1), stake nets (3.05 kg h -1), ring nets (1.27 kg h -1), hooks and lines (1.35 kg h -1) and scoop nets (0.92 kg h -1). The study implies that temporal changes in fish landing pattern of the KAE was mainly due to environmental variability, habitat modification and fish migration; under the influence of south-west monsoon and anthropogenic activities in the KAE. Results of the study suggest that spatio-temporal variations in the fish community structure could be an indicator for anthropogenic stress and it should be considered for restoration programmes.

Studies on the use of Nanokaolin, MWCNT and Graphene in NBR and SBR

The current research investigates the possibility of using unmodified and modified nanokaolin, multiwalled carbon nanotube (MWCNT) and graphene as fillers to impart enhancement in mechanical, thermal, and electrical properties to the elastomers. Taking advantage of latex blending method, nanoclay, MWCNT and graphene dispersions, prepared by ultra sound sonication are dispersed in polymer latices. The improvement in material properties indicated better interaction between filler and the polymer.MWCNT and graphene imparted electrical conductivity with simultaneous improvement in mechanical properties. Layered silicates prepared by microwave method also significantly improve the mechanical properties of the nanocomposites. The thesis entitled ‘Studies on the use of Nanokaolin, MWCNT and Graphene in NBR and SBR’ consists of ten chapters. The first chapter is a concise introduction of nanocomposites, nanofillers, elastomeric matrices and applications of polymer nanocomposites. The state-of-art research in elastomer based nanocomposites is also presented. At the end of this chapter the main objectives of the work are mentioned. Chapter 2 outlines the specifications of various materials used, details of experimental techniques employed for preparing and characterizing nanocomposites. Chapter3 includes characterization of the nanofillers, optimsation of cure time of latex based composites and the methods used for the preparation of latex based and dry rubber based nanocomposites. Chapter4 presents the reinforcing effect of the nanofillers in XNBR latex and the characterization of the nanocomposites. Chapter5 comprises the effect of nanofillers on the properties of SBR latex and their characterization Chapter 6 deals with the study of cure characteristics, mechanical and thermal properties and the characterization of NBR based nanocomposites. Chapter7 is the microwave studies of MWCNT and graphene filled elastomeric nanocomposites. Chapter 8 gives details of the preparation of layered silicates, their characterization and use in different elastomeric matrices. Chapter 9 is the study of mechanical properties of nanoclay incorporated nitrile gloves .Chapter 10 presents the summary and conclusions of the investigation.

Community Participation in Ecotourism: An Inclusive Development Option for Kerala

The inferences obtained from the study are presented in coherent area-specific levels so as to understand the ecotourism and its sub-sector areas for the researchers and policy makers about the issues, importances and potentialities of the sector. An analysis of the tourism sector in Kerala has shown tremendous growth both in terms of tourist arrivals and in terms of revenue generation from direct and indirect sources. The foreign tourist visitors in Kerala in 2014 was 9,23,336 which shows 7.60 percent increase from the last year and the domestic tourist visitors were 1,16,95,411 which again shows 7.71 percent increase, is a clear evidence of its potential. In 2014 the industry contributed revenue of 24885.44 crores from direct and indirect sources giving rise to an increase of 12.11 percent from the last year. A dichotomy of tourists and ecotourists shows that tourists in the ecotourism destinations come to 42.6 percent of the total, shows the scope, significance and its potential. Correlation of zone-wise tourist arrivals based on the ecotourism destinations highlights the fact that with only 19 of the 64 destinations that come in the central zone are the most preferred centres (around 54 percent) for the domestic as well as foreign tourists. The north zone encompassing 6 districts with rich biodiversity shows that the tourists‟ arrival patterns exhibit less promising results. Though the north zone has 31 ecotourism destinations of the state receives only 6.19 percent of the foreign visitors. The ecotourism activities in the state are primarily managed by the Eco-Development Committees (EDCs) and the Vana Samrakshana Samithies (VSS) under the Forest Development Agency of Kerala. Social class-wise categorization of membership shows that 13142 families have membership in 190 EDCs with SC (28 percent), ST (33 percent) and other marginalised communities (39 percent). But this in the VSS shows that 400 VSS have 59085 members actively engaged in ecotourism activities and social category of the VSS makes clear that majority are from the other marginalized fringe households with 62 percent where as the participation of SC is 12 percent and ST is 26 percent. An evaluation of the socio-economic and demographic matrix of the community members involved in ecotourism activities brings out region specific differences. About 75.70 percent of the respondents are males and the rest are females. Majority of the respondents (about 60 percent) are in the age group of 20 to 40 years, followed by the age group of 40-50 (20 percent). The average age of respondents in the three zones is between 35 and 37 years. The majority of the respondents are married, a few are unmarried. Average family size is 4-5 members and differences are identified among zones. Average number of adults per household is 3 and child per household is 2. Majority have an education of 10th class and below i.e. about 60 percent of the sample have only basic school education like primary, secondary and high school (i.e. up to SSLC but not passed) level. About 18 percent are SSLC passed, 10 percent are undergraduates whereas 6 percent constitute respondents having qualification of graduation and above. Majority of the „graduates and above‟ are from south and central zone. Inter-zone differences in educational profile are also identified with lesser number of „graduates and above‟ are identified in the north zone compared to the other two zones. Investigating into the income and livelihood options of the respondents gives insight about the prominence of ecotourism as an employment and livelihood option for the community members, as more than 90 percent of the respondents have cited tourism sector as their main employment option. Most (49.30 percent) of respondents get 100 percent income from tourism related activities, followed by 37.30 percent of community members have income between 75-99 percent from tourism whereas the rest (13 percent) have less than 74 percent of their income from tourism and there exists difference between zones and percentage of income. Financial habit shows that about 49.7 percent hold active bank accounts, 61 percent have savings behaviour and 73.8 percent have indebtedness. Analysis about the ownership of house brings to light that 37 percent of respondents live in their own house followed by 25.7 percent in government funded/provided house and 21 percent in their parent‟s house and 3.5 percent in rented house. About 12 percent of the respondents have other kinds of accommodation facilities such as staff quarters, etc. But in the case of north zone majority i.e. 52 percent primarily depend on the government funded house indicating the effectiveness of government housing programme. Standard of living measured in SLI frameworks shows that majority of the respondents have medium SLI values (42.3 percent); the remaining 47.7 percent have low SLI and 10 percent have high SLI. The community members have been benefitted immensely from forest and its resources. Since the ecotourism destinations are located amidst the wildlife settings, majority of them depend on forest for their livelihood. The information on the tourist‟s demographic characteristics like age, sex, educational qualification and annual income show that the age category of domestic and foreign tourists falls below the age group of less than 35 years (about 65 percent), whereas only 16 percent of tourists are aged above 46 years. The age group below 25 years consists of more international tourists (31.3 percent) compared to the proportion of domestic tourists (12.5 percent). Male-female ratio shows that the males constitute 56 percent of the sample and females with 44 percent. The factors determining the impact of ecotourism programmes in the community was evaluated with the aid of a factor analysis with 12 selected statements. The worries and concerns of the community members about the impact of ecotourism on the environment are well understood from this analysis. It can be drawn that environment protection and the role of ecotourism in improving the income and livelihood options of the local communities is the most important factor concerning the community members.