Synthesis, characterization and hydrodesulphurisation activity of CoMo/gama-Al2O3 catalyst prepared through molecular designed dispersion method

CoMo/gama-Al2O3 catalysts for hydrodesulphurisation activity were prepared by making use of the molecular designed dispersion (MDD) method. Molybdenum and cobalt pyrrolidine-N-carbodithioate (Pydtc) complexes were used for the incorporation of metals on the support. The catalysts were characterized by elemental analysis, low temperature oxygen chemisorption, temperature programmed reduction (TPR) and laser Raman spectroscopy. The hydrodesulphurisation activity of all the catalysts were carried out and results were compared with those of the catalysts prepared through the conventional method. Higher molybdenum dispersion, smaller molybdenum clusters, lower reduction temperature of catalyst and better hydrodesulphurisation activity were observed for the catalysts prepared through the MDD method

Solitons and their resonances on two-dimensional superfluid films

The dynamics of saturated two-dimensional superfluid4He films is shown to be governed by the Kadomtsev-Petviashvili equation with negative dispersion. It is established that the phenomena of soliton resonance could be observed in such films. Under the lowest order nonlinearity, such resonance would happen only if two dimensional effects are taken into account. The amplitude and velocity of the resonant soliton are obtained.

Studies on Spatial and Temporal solitons with varying dispersion,diffraction and nonlinearity

Department of Physics, Cochin University of Science and Technology

Closure of the Monte Carlo dynamical equation in the spherical Sherrington-Kirkpatrick model

We study the analytical solution of the Monte Carlo dynamics in the spherical Sherrington-Kirkpatrick model using the technique of the generating function. Explicit solutions for one-time observables (like the energy) and two-time observables (like the correlation and response function) are obtained. We show that the crucial quantity which governs the dynamics is the acceptance rate. At zero temperature, an adiabatic approximation reveals that the relaxational behavior of the model corresponds to that of a single harmonic oscillator with an effective renormalized mass.

Studies On The Dynamics And Water Quality Of The Muvattupuzha River In Relation To Effluent Discharge

The present study aims at the investigation of the 1ysico—chemical features of a tropical tidal river viz. we Muvattupuzha river. This river is expected to receive Jderate to heavy pollution loads in years to come, from we lone industrial unit, already set up on its bank. ilike other rivers, the geographical disposition of this Lver attains unique importance as regards its dynamics for 3) availability of natural runoff water from catchment :eas, which becomes very heavy during the monsoon season 3) regular steady availability of tail race water from a /dro—electric power station throughout the yearThe study also aims at arriving at the balancing forces of inherent self~purification of the river verses pollution loads from the factory effluents. The investigation period falls ahead of actual pollution occurrence and so the ambient conditions for a period of nearly one-and-a—half years were investigated, the analyses of which providflz to formulate the inter-relations of parameters varying with seasons. Tracer experiments were carried out which revealed the dispersion and dilution characteristics of the river in the vicinity of effluent outfall. The studv covers the trial—cum-capacity production periods of the factory during which effluents of various strength and quantity were discharged into the river; a few computed values arQ’cjmpgrQdl ... with the observed values. The base data along with the profiles of Oxygen sag equation have been utilized fb develop a mathematical model of the river with regard to its water quality

On the dielectric dispersion and absorption in nanosized manganese zinc mixed ferrites

The temperature and frequency dependence of dielectric permittivity and dielectric loss of nanosized Mn1−xZnxFe2O4 (for x = 0, 0.2, 0.4, 0.6, 0.8, 1) were investigated. The impact of zinc substitution on the dielectric properties of the mixed ferrite is elucidated. Strong dielectric dispersion and broad relaxation were exhibited by Mn1−xZnxFe2O4. The variation of dielectric relaxation time with temperature suggests the involvement of multiple relaxation processes. Cole–Cole plots were employed as an effective tool for studying the observed phenomenon. The activation energies were calculated from relaxation peaks and Cole–Cole plots and found to be consistent with each other and indicative of a polaron conduction

Synthesis, Characterization and Applications of Modified TiO2 Systems

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.

A generic polynomial solution for the differential equation of hypergeometric type and six sequences of orthogonal polynomials related to it

In this work, we present a generic formula for the polynomial solution families of the well-known differential equation of hypergeometric type s(x)y"n(x) + t(x)y'n(x) - lnyn(x) = 0 and show that all the three classical orthogonal polynomial families as well as three finite orthogonal polynomial families, extracted from this equation, can be identified as special cases of this derived polynomial sequence. Some general properties of this sequence are also given.

Experimentelle und numerische Untersuchungen zur Dispersion von Dichteströmungen in einem stochastischen Modellaquifer

Es ist bekannt, dass die Dichte eines gelösten Stoffes die Richtung und die Stärke seiner Bewegung im Untergrund entscheidend bestimmen kann. Eine Vielzahl von Untersuchungen hat gezeigt, dass die Verteilung der Durchlässigkeiten eines porösen Mediums diese Dichteffekte verstärken oder abmindern kann. Wie sich dieser gekoppelte Effekt auf die Vermischung zweier Fluide auswirkt, wurde in dieser Arbeit untersucht und dabei das experimentelle sowohl mit dem numerischen als auch mit dem analytischen Modell gekoppelt. Die auf der Störungstheorie basierende stochastische Theorie der macrodispersion wurde in dieser Arbeit für den Fall der transversalen Makodispersion. Für den Fall einer stabilen Schichtung wurde in einem Modelltank (10m x 1.2m x 0.1m) der Universität Kassel eine Serie sorgfältig kontrollierter zweidimensionaler Experimente an einem stochastisch heterogenen Modellaquifer durchgeführt. Es wurden Versuchsreihen mit variierenden Konzentrationsdifferenzen (250 ppm bis 100 000 ppm) und Strömungsgeschwindigkeiten (u = 1 m/ d bis 8 m/d) an drei verschieden anisotrop gepackten porösen Medien mit variierender Varianzen und Korrelationen der lognormal verteilten Permeabilitäten durchgeführt. Die stationäre räumliche Konzentrationsausbreitung der sich ausbreitenden Salzwasserfahne wurde anhand der Leitfähigkeit gemessen und aus der Höhendifferenz des 84- und 16-prozentigen relativen Konzentrationsdurchgang die Dispersion berechnet. Parallel dazu wurde ein numerisches Modell mit dem dichteabhängigen Finite-Elemente-Strömungs- und Transport-Programm SUTRA aufgestellt. Mit dem kalibrierten numerischen Modell wurden Prognosen für mögliche Transportszenarien, Sensitivitätsanalysen und stochastische Simulationen nach der Monte-Carlo-Methode durchgeführt. Die Einstellung der Strömungsgeschwindigkeit erfolgte - sowohl im experimentellen als auch im numerischen Modell - über konstante Druckränder an den Ein- und Auslauftanks. Dabei zeigte sich eine starke Sensitivität der räumlichen Konzentrationsausbreitung hinsichtlich lokaler Druckvariationen. Die Untersuchungen ergaben, dass sich die Konzentrationsfahne mit steigendem Abstand von der Einströmkante wellenförmig einem effektiven Wert annähert, aus dem die Makrodispersivität ermittelt werden kann. Dabei zeigten sich sichtbare nichtergodische Effekte, d.h. starke Abweichungen in den zweiten räumlichen Momenten der Konzentrationsverteilung der deterministischen Experimente von den Erwartungswerten aus der stochastischen Theorie. Die transversale Makrodispersivität stieg proportional zur Varianz und Korrelation der lognormalen Permeabilitätsverteilung und umgekehrt proportional zur Strömungsgeschwindigkeit und Dichtedifferenz zweier Fluide. Aus dem von Welty et al. [2003] mittels Störungstheorie entwickelten dichteabhängigen Makrodispersionstensor konnte in dieser Arbeit die stochastische Formel für die transversale Makrodispersion weiter entwickelt und - sowohl experimentell als auch numerisch - verifiziert werden.

Solution properties of the de Branges differential recurrence equation

In this 1984 proof of the Bieberbach and Milin conjectures de Branges used a positivity result of special functions which follows from an identity about Jacobi polynomial sums thas was published by Askey and Gasper in 1976. The de Branges functions Tn/k(t) are defined as the solutions of a system of differential recurrence equations with suitably given initial values. The essential fact used in the proof of the Bieberbach and Milin conjectures is the statement Tn/k(t)<=0. In 1991 Weinstein presented another proof of the Bieberbach and Milin conjectures, also using a special function system Λn/k(t) which (by Todorov and Wilf) was realized to be directly connected with de Branges', Tn/k(t)=-kΛn/k(t), and the positivity results in both proofs Tn/k(t)<=0 are essentially the same. In this paper we study differential recurrence equations equivalent to de Branges' original ones and show that many solutions of these differential recurrence equations don't change sign so that the above inequality is not as surprising as expected. Furthermore, we present a multiparameterized hypergeometric family of solutions of the de Branges differential recurrence equations showing that solutions are not rare at all.

Relativistic atomic level calculations with nuclei carrying additional fractional charges

One-electron energy levels and wavelengths have been calculated for Na-like ions whose nuclei carry quarks with additional charges ±e/3, ±2e/3. The calculations are based on relativistic self-consistent field procedures. The deviations from experimental values exhibit regularities which allow an extrapolation for the wavelengths of 3s - 3p, 3s - 4p, 3p - 3d, and 3p - 4s transitions for the nuclear charge Z = 11± 1/3, ±2/3. A number of transitions are found in the region of visible light which could be used in an optical search for quark atoms.