101 resultados para Applications of some coordination polymers
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In this thesis we study the effect of rest periods in queueing systems without exhaustive service and inventory systems with rest to the server. Most of the works in the vacation models deal with exhaustive service. Recently some results have appeared for the systems without exhaustive service.
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The investigation of physical properties of matter has progressed so much during the last hundred years. Today physics is divided in to a large distinct group of special branches. These branches are distinguished by the particular area studied, method of investigation and so on. An independent and important branch that has developed is the physics ofthin films.Any object in solid or liquid form with one of its dimensions very much smaller than that of the other two may be called a thin film. It is having only one common property, namely, one of their dimensions is very small, though all their physical properties may be different. Thin layers of oil, floating on the surface of water, with their fascinating colours, have attracted men’s curiosity from time immemorial. The earliest application of thin films was the protective coatings in the form of paints. A thin layer of tin has been used from ancient times to protect copper utensils from corrosion. Indium thin films are used in certain applications on account of their good lubricating property. Relay contacts are coated with thin films of rare earth metals in order to prevent burning due to arcing. Hard coatings are also available using diamond like carbon (i-carbon). The basic properties of thin films are of considerable interest because of their potential applications in various fields of science and technology
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Catalysis research underpins the science of modern chemical processing and fuel technologies. Catalysis is commercially one of the most important technologies in national economies. Solid state heterogeneous catalyst materials such as metal oxides and metal particles on ceramic oxide substrates are most common. They are typically used with commodity gases and liquid reactants. Selective oxidation catalysts of hydrocarbon feedstocks is the dominant process of converting them to key industrial chemicals, polymers and energy sources.[1] In the absence of a unique successfiil theory of heterogeneous catalysis, attempts are being made to correlate catalytic activity with some specific properties of the solid surface. Such correlations help to narrow down the search for a good catalyst for a given reaction. The heterogeneous catalytic performance of material depends on many factors such as [2] Crystal and surface structure of the catalyst. Thermodynamic stability of the catalyst and the reactant. Acid- base properties of the solid surface. Surface defect properties of the catalyst.Electronic and semiconducting properties and the band structure. Co-existence of dilferent types of ions or structures. Adsorption sites and adsorbed species such as oxygen.Preparation method of catalyst , surface area and nature of heat treatment. Molecular structure of the reactants. Many systematic investigations have been performed to correlate catalytic performances with the above mentioned properties. Many of these investigations remain isolated and further research is needed to bridge the gap in the present knowledge of the field.
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This thesis is divided in to 9 chapters and deals with the modification of TiO2 for various applications include photocatalysis, thermal reaction, photovoltaics and non-linear optics. Chapter 1 involves a brief introduction of the topic of study. An introduction to the applications of modified titania systems in various fields are discussed concisely. Scope and objectives of the present work are also discussed in this chapter. Chapter 2 explains the strategy adopted for the synthesis of metal, nonmetal co-doped TiO2 systems. Hydrothermal technique was employed for the preparation of the co-doped TiO2 system, where Ti[OCH(CH3)2]4, urea and metal nitrates were used as the sources for TiO2, N and metals respectively. In all the co-doped systems, urea to Ti[OCH(CH3)2]4 was taken in a 1:1 molar ratio and varied the concentration of metals. Five different co-doped catalytic systems and for each catalysts, three versions were prepared by varying the concentration of metals. A brief explanation of physico-chemical techniques used for the characterization of the material was also presented in this chapter. This includes X-ray Diffraction (XRD), Raman Spectroscopy, FTIR analysis, Thermo Gravimetric Analysis, Energy Dispersive X-ray Analysis (EDX), Scanning Electron Microscopy(SEM), UV-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS), Transmission Electron Microscopy (TEM), BET Surface Area Measurements and X-ray Photoelectron Spectroscopy (XPS). Chapter 3 contains the results and discussion of characterization techniques used for analyzing the prepared systems. Characterization is an inevitable part of materials research. Determination of physico-chemical properties of the prepared materials using suitable characterization techniques is very crucial to find its exact field of application. It is clear from the XRD pattern that photocatalytically active anatase phase dominates in the calcined samples with peaks at 2θ values around 25.4°, 38°, 48.1°, 55.2° and 62.7° corresponding to (101), (004), (200), (211) and (204) crystal planes (JCPDS 21-1272) respectively. But in the case of Pr-N-Ti sample, a new peak was observed at 2θ = 30.8° corresponding to the (121) plane of the polymorph brookite. There are no visible peaks corresponding to dopants, which may be due to their low concentration or it is an indication of the better dispersion of impurities in the TiO2. Crystallite size of the sample was calculated from Scherrer equation byusing full width at half maximum (FWHM) of the (101) peak of the anatase phase. Crystallite size of all the co-doped TiO2 was found to be lower than that of bare TiO2 which indicates that the doping of metal ions having higher ionic radius into the lattice of TiO2 causes some lattice distortion which suppress the growth of TiO2 nanoparticles. The structural identity of the prepared system obtained from XRD pattern is further confirmed by Raman spectra measurements. Anatase has six Raman active modes. Band gap of the co-doped system was calculated using Kubelka-Munk equation and that was found to be lower than pure TiO2. Stability of the prepared systems was understood from thermo gravimetric analysis. FT-IR was performed to understand the functional groups as well as to study the surface changes occurred during modification. EDX was used to determine the impurities present in the system. The EDX spectra of all the co-doped samples show signals directly related to the dopants. Spectra of all the co-doped systems contain O and Ti as the main components with low concentrations of doped elements. Morphologies of the prepared systems were obtained from SEM and TEM analysis. Average particle size of the systems was drawn from histogram data. Electronic structures of the samples were identified perfectly from XPS measurements. Chapter 4 describes the photocatalytic degradation of herbicides Atrazine and Metolachlor using metal, non-metal co-doped titania systems. The percentage of degradation was analyzed by HPLC technique. Parameters such as effect of different catalysts, effect of time, effect of catalysts amount and reusability studies were discussed. Chapter 5 deals with the photo-oxidation of some anthracene derivatives by co-doped catalytic systems. These anthracene derivatives come underthe category of polycyclic aromatic hydrocarbons (PAH). Due to the presence of stable benzene rings, most of the PAH show strong inhibition towards biological degradation and the common methods employed for their removal. According to environmental protection agency, most of the PAH are highly toxic in nature. TiO2 photochemistry has been extensively investigated as a method for the catalytic conversion of such organic compounds, highlighting the potential of thereof in the green chemistry. There are actually two methods for the removal of pollutants from the ecosystem. Complete mineralization is the one way to remove pollutants. Conversion of toxic compounds to another compound having toxicity less than the initial starting compound is the second way. Here in this chapter, we are concentrating on the second aspect. The catalysts used were Gd(1wt%)-N-Ti, Pd(1wt%)-N-Ti and Ag(1wt%)-N-Ti. Here we were very successfully converted all the PAH to anthraquinone, a compound having diverse applications in industrial as well as medical fields. Substitution of 10th position of desired PAH by phenyl ring reduces the feasibility of photo reaction and produced 9-hydroxy 9-phenyl anthrone (9H9PA) as an intermediate species. The products were separated and purified by column chromatography using 70:30 hexane/DCM mixtures as the mobile phase and the resultant products were characterized thoroughly by 1H NMR, IR spectroscopy and GCMS analysis. Chapter 6 elucidates the heterogeneous Suzuki coupling reaction by Cu/Pd bimetallic supported on TiO2. Sol-Gel followed by impregnation method was adopted for the synthesis of Cu/Pd-TiO2. The prepared system was characterized by XRD, TG-DTG, SEM, EDX, BET Surface area and XPS. The product was separated and purified by column chromatography using hexane as the mobile phase. Maximum isolated yield of biphenyl of around72% was obtained in DMF using Cu(2wt%)-Pd(4wt%)-Ti as the catalyst. In this reaction, effective solvent, base and catalyst were found to be DMF, K2CO3 and Cu(2wt%)-Pd(4wt%)-Ti respectively. Chapter 7 gives an idea about the photovoltaic (PV) applications of TiO2 based thin films. Due to energy crisis, the whole world is looking for a new sustainable energy source. Harnessing solar energy is one of the most promising ways to tackle this issue. The present dominant photovoltaic (PV) technologies are based on inorganic materials. But the high material, low power conversion efficiency and manufacturing cost limits its popularization. A lot of research has been conducted towards the development of low-cost PV technologies, of which organic photovoltaic (OPV) devices are one of the promising. Here two TiO2 thin films having different thickness were prepared by spin coating technique. The prepared films were characterized by XRD, AFM and conductivity measurements. The thickness of the films was measured by Stylus Profiler. This chapter mainly concentrated on the fabrication of an inverted hetero junction solar cell using conducting polymer MEH-PPV as photo active layer. Here TiO2 was used as the electron transport layer. Thin films of MEH-PPV were also prepared using spin coating technique. Two fullerene derivatives such as PCBM and ICBA were introduced into the device in order to improve the power conversion efficiency. Effective charge transfer between the conducting polymer and ICBA were understood from fluorescence quenching studies. The fabricated Inverted hetero junction exhibited maximum power conversion efficiency of 0.22% with ICBA as the acceptor molecule. Chapter 8 narrates the third order order nonlinear optical properties of bare and noble metal modified TiO2 thin films. Thin films were fabricatedby spray pyrolysis technique. Sol-Gel derived Ti[OCH(CH3)2]4 in CH3CH2OH/CH3COOH was used as the precursor for TiO2. The precursors used for Au, Ag and Pd were the aqueous solutions of HAuCl4, AgNO3 and Pd(NO3)2 respectively. The prepared films were characterized by XRD, SEM and EDX. The nonlinear optical properties of the prepared materials were investigated by Z-Scan technique comprising of Nd-YAG laser (532 nm,7 ns and10 Hz). The non-linear coefficients were obtained by fitting the experimental Z-Scan plot with the theoretical plots. Nonlinear absorption is a phenomenon defined as a nonlinear change (increase or decrease) in absorption with increasing of intensity. This can be mainly divided into two types: saturable absorption (SA) and reverse saturable absorption (RSA). Depending on the pump intensity and on the absorption cross- section at the excitation wavelength, most molecules show non- linear absorption. With increasing intensity, if the excited states show saturation owing to their long lifetimes, the transmission will show SA characteristics. Here absorption decreases with increase of intensity. If, however, the excited state has strong absorption compared with that of the ground state, the transmission will show RSA characteristics. Here in our work most of the materials show SA behavior and some materials exhibited RSA behavior. Both these properties purely depend on the nature of the materials and alignment of energy states within them. Both these SA and RSA have got immense applications in electronic devices. The important results obtained from various studies are presented in chapter 9.
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The ability of aroylhydrazones to bind with transition metals is a developing area of research interest and the coordinating properties of hydrazones can be tuned by the appropriate choice of parent aldehyde or ketone and the hydrazide. So in the present work we selected four different aroylhydrazones as principal ligands. Introduction of heterocyclic bases like 1,10-phenanthroline, 2,2′-bipyridine, 3-picoline and pyridine leads to the syntheses of mixed ligand metal chelates which can cause different bonding modes, spectral properties and geometries in coordination compounds. The importance of aroylhydrazones and their complexes in various fields and their interesting coordinating properties stimulate our interest in the investigation of transition metal chelates with four different aroylhydrazones. The aroylhydrazones selected are 4-benzyloxy-2-hydroxybenzaldehyde-4-nitrobenzoylhydrazone dimethylformamide monosolvate, 5-bromo-2-hydroxy-3-methoxybenzaldehyde nicotinoylhydrazone dihydrate methanol monosolvate, 4-diethylamino-2- hydroxybenzaldehyde nicotinoylhydrazone monohydrate and 2-benzoylpyridine- 4-nitrobenzoylhydrazone. The selection of 4-benzyloxy-2-hydroxybenzaldehyde- 4-nitrobenzoylhydrazone was based on the idea of developing ligands having D-π-A general structure, so that the proligand and metal complexes exhibit NLO activity. Hence it is interesting to explore the coordinating capabilities of the synthesized hydrazones and to study the NLO activity of hydrazones and some of the metal complexes.
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The work embodied in this thesis was carried out by the author in the Department of Applied Chemistry, CUSAT, Kochi, during the period 2009-2012. The thesis is an introduction to our attempts to evaluate the coordination behavior of some compounds of our interest. The biological activities of semicarbazones and their metal complexes have been an active area of research during the past years because of their significant role in naturally occurring biological systems. Tridentate NNO and ONO semicarbazone systems formed from heterocyclic and aromatic carbonyl compounds and their transition metal complexes are wellauthenticated compounds in this field and their synthesis, crystal structures and spectral studies are well desirable. Hence, we decided to develop a research program aimed at the syntheses, crystal structures and spectral studies of new N4- phenylsemicarbazones derived from 2-formylpyridine and 3-ethoxysalicylaldehyde and their transition metal complexes and new transition metal complexes of 2- benzoylpyridine-N4-phenylsemicarbazone. In addition to various physicochemical methods of analysis, single crystal X-ray diffraction studies were also used for the characterization of the complexes.
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This study is about the analysis of some queueing models related to N-policy.The optimal value the queue size has to attain in order to turn on a single server, assuming that the policy is to turn on a single server when the queue size reaches a certain number, N, and turn him off when the system is empty.The operating policy is the usual N-policy, but with random N and in model 2, a system similar to the one described here.This study analyses “ Tandem queue with two servers”.Here assume that the first server is a specialized one.In a queueing system,under N-policy ,the server will be on vacation until N units accumulate for the first time after becoming idle.A modified version of the N-policy for an M│M│1 queueing system is considered here.The novel feature of this model is that a busy service unit prevents the access of new customers to servers further down the line.It is deals with a queueing model consisting of two servers connected in series with a finite intermediate waiting room of capacity k.Here assume that server I is a specialized server.For this model ,the steady state probability vector and the stability condition are obtained using matrix – geometric method.
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The thesis deals with some of the non-linear Gaussian and non-Gaussian time models and mainly concentrated in studying the properties and application of a first order autoregressive process with Cauchy marginal distribution. In this thesis some of the non-linear Gaussian and non-Gaussian time series models and mainly concentrated in studying the properties and application of a order autoregressive process with Cauchy marginal distribution. Time series relating to prices, consumptions, money in circulation, bank deposits and bank clearing, sales and profit in a departmental store, national income and foreign exchange reserves, prices and dividend of shares in a stock exchange etc. are examples of economic and business time series. The thesis discuses the application of a threshold autoregressive(TAR) model, try to fit this model to a time series data. Another important non-linear model is the ARCH model, and the third model is the TARCH model. The main objective here is to identify an appropriate model to a given set of data. The data considered are the daily coconut oil prices for a period of three years. Since it is a price data the consecutive prices may not be independent and hence a time series based model is more appropriate. In this study the properties like ergodicity, mixing property and time reversibility and also various estimation procedures used to estimate the unknown parameters of the process.
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The thesis deals with analysis of some Stochastic Inventory Models with Pooling/Retrial of Customers.. In the first model we analyze an (s,S) production Inventory system with retrial of customers. Arrival of customers from outside the system form a Poisson process. The inter production times are exponentially distributed with parameter µ. When inventory level reaches zero further arriving demands are sent to the orbit which has capacity M(<∞). Customers, who find the orbit full and inventory level at zero are lost to the system. Demands arising from the orbital customers are exponentially distributed with parameter γ. In the model-II we extend these results to perishable inventory system assuming that the life-time of each item follows exponential with parameter θ. The study deals with an (s,S) production inventory with service times and retrial of unsatisfied customers. Primary demands occur according to a Markovian Arrival Process(MAP). Consider an (s,S)-retrial inventory with service time in which primary demands occur according to a Batch Markovian Arrival Process (BMAP). The inventory is controlled by the (s,S) policy and (s,S) inventory system with service time. Primary demands occur according to Poissson process with parameter λ. The study concentrates two models. In the first model we analyze an (s,S) Inventory system with postponed demands where arrivals of demands form a Poisson process. In the second model, we extend our results to perishable inventory system assuming that the life-time of each item follows exponential distribution with parameter θ. Also it is assumed that when inventory level is zero the arriving demands choose to enter the pool with probability β and with complementary probability (1- β) it is lost for ever. Finally it analyze an (s,S) production inventory system with switching time. A lot of work is reported under the assumption that the switching time is negligible but this is not the case for several real life situation.
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This thesis is devoted to the study of some stochastic models in inventories. An inventory system is a facility at which items of materials are stocked. In order to promote smooth and efficient running of business, and to provide adequate service to the customers, an inventory materials is essential for any enterprise. When uncertainty is present, inventories are used as a protection against risk of stock out. It is advantageous to procure the item before it is needed at a lower marginal cost. Again, by bulk purchasing, the advantage of price discounts can be availed. All these contribute to the formation of inventory. Maintaining inventories is a major expenditure for any organization. For each inventory, the fundamental question is how much new stock should be ordered and when should the orders are replaced. In the present study, considered several models for single and two commodity stochastic inventory problems. The thesis discusses two models. In the first model, examined the case in which the time elapsed between two consecutive demand points are independent and identically distributed with common distribution function F(.) with mean (assumed finite) and in which demand magnitude depends only on the time elapsed since the previous demand epoch. The time between disasters has an exponential distribution with parameter . In Model II, the inter arrival time of disasters have general distribution (F.) with mean ( ) and the quantity destructed depends on the time elapsed between disasters. Demands form compound poison processes with inter arrival times of demands having mean 1/. It deals with linearly correlated bulk demand two
Commodity inventory problem, where each arrival demands a random number of items of each commodity C1 and C2, the maximum quantity demanded being a (< S1) and b(
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The levels and kinetic properties of arginase of the liver of s vertebrates : the fish otifg trhinea e)n, ztyhmee b ias thi(gPhteerro ipnu aslls tph.e), 3t hmeasmqumirarles lin(F cuonmampabruilsuosnp teon tnhaantt oi)f tahned p tohiek iglootahter(Cmaspra s(pC.)atalarec sattulad)i,edth. eT fhreo ga c(tRivaintya greater than that of the frog. The activity ; its activity in the fish is far in the bat and highest in the goat. in the bat is the same as in other mammals. The Km of the enzyme is lowest partially purified enzyme of vertebrates. significant difference in the inhibitory effect of glyoxylic acid on the partially purified enzyme of vertebrates.
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In this paper, two notions, the clique irreducibility and clique vertex irreducibility are discussed. A graph G is clique irreducible if every clique in G of size at least two, has an edge which does not lie in any other clique of G and it is clique vertex irreducible if every clique in G has a vertex which does not lie in any other clique of G. It is proved that L(G) is clique irreducible if and only if every triangle in G has a vertex of degree two. The conditions for the iterations of line graph, the Gallai graphs, the anti-Gallai graphs and its iterations to be clique irreducible and clique vertex irreducible are also obtained.
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Eigenvalue of a graph is the eigenvalue of its adjacency matrix. The energy of a graph is the sum of the absolute values of its eigenvalues. In this note we obtain analytic expressions for the energy of two classes of regular graphs.
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The objective of the present study is to understand the spatial and temporal variability of sea surface temperature(SST), precipitable water, zonal and meridional components of wind stress over the tropical Indian Ocean to understand the different scales of variability of these features of Indian Ocean. Empirical Orthogonal Function (EOF) and wavelet analysis techniques are utilized to understand the standing oscillations and multi scale oscillations respectively. The study has been carried out over Indian Ocean and South Indian Ocean. For the present study, NCEP/NCAR(National Center for Environmental Prediction National Center for Atmospheric Research) reanalyzed daily fields of sea surface temperature, zonal and meridional surface wind components and precipitable water amount during 1960-1998 are used. The principle of EOF analysis and the methodology used for the analysis of spatial and temporal variance modes.
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The present work is mainly concentrated on setting up a NIR tunable diode laser absorption (TDLA) spectrometer for high-resolution molecular spectroscopic studies. For successfully recording the high-resolution tunable diode laser spectrum, various experimental considerations are to be taken into account like the setup should be free from mechanical vibrations, sample should be kept at a low pressure, laser should be in a single mode operation etc. The present experimental set up considers all these factors. It is to be mentioned here that the setting up of a high resolution NIR TDLA spectrometer is a novel experiment requiring much effort and patience. The analysis of near infrared (NIR) vibrational overtone spectra of some substituted benzene compounds using local mode model forms another part of the present work. An attempt is made to record the pulsed laser induced fluorescence/Raman spectra of some organic compounds. A Q-switched Nd:YAG laser is used as the excitation source. A TRIAX monochromator and CCD detector is used for the spectral recording. The observed fluorescence emission for carbon disulphide is centered at 680 nm; this is assigned as due to the n, p* transition. Aniline also shows a broad fluorescence emission centered at 725 nm, which is due to the p,p* transition. The pulsed laser Raman spectra of some organic compounds are also recorded using the same experimental setup. The calibration of the set up is done using the laser Raman spectra of carbon tetrachloride and carbon disulphide. The observed laser Raman spectra for aniline, o-chloroaniline and m-chlorotoluene show peaks characteristics of the aromatic ring in common and the characteristics peaks due to the substitutuent groups. Some new peaks corresponding to low-lying vibrations of these molecules are also assigned