Kinetics and mechanism of urea - formaldehyde and related reactions

Urea-formaldehyde resins find numerous applications in adhesive, textile finishing and moulded plastic industries. Kinetic investigations of the reactions of urea and its related compounds with formaldehyde in aqueous acid, alkaline and neutral media have been carried out. A thin—layer chromatographic method was developed for the separation and estimation of the products of these reactions. Using this technique the various initial steps in the reactions were analysed and the rate constants have been determined.

Determination of the nature of the diperiodatocuprate(III) species in aqueous alkaline medium through a kinetic and mechanistic study on the oxidation of iodide ion

The nature of the diperiodatocuprate(III) (DPC) species present in aqueous alkaline medium has been investigated by a kinetic and mechanistic study on the oxidation of iodide by DPC. The reaction kinetics were studied over the 1.0 ´ 10)3±0.1 mol dm)3 alkali range. The reaction order with respect to DPC, as well as iodide, was found to be unity when [DPC] [I)]. In the 1.0 ´ 10)3±1.0 ´ 10)2 mol dm)3 alkali region, the rate decreased with increase in the alkali concentration and a plot of the pseudo-®rst order rate constant, k versus 1/[OH)] was linear. Above 5.0 ´ 10)2 mol dm)3, a plot of k versus [OH)] was also linear with a non-zero intercept. An increase in ionic strength of the reaction mixtures showed no e ect on k at low alkali concentrations, whereas at high concentrations an increase in ionic strength leads to an increase in k. A plot of 1/k versus [periodate] was linear with an intercept in both alkali ranges. Iodine was found to accelerate the reaction at the three di erent alkali concentrations employed. The observed results indicated the following equilibria for DPC.

Thermodynamics of transfer of polar nonelectrolytes from water to aqueous salt solutions

The Setschenow parameter and thermodynamic parameters of transfer of a number of monosubstituted benzoic acids from water to different salt solutions have been reported. The data have been rationalized by considering the structure breaking effects of the ions of the salts, the localised hydrolysis model, the internal pressure theory and Symons' theory of water structure.

Second Order Fit for Mercuric Chloride Catalysed Solvolysis of Alkyl Chlorides in Aqueous DMSO Solvents

Kinetics of mercuric chloride catalysed solvolysis of l-butyl chloride, benzyl chloride. p-methylbenzyl chloride, l-phenylethyl chloride and triethylcarbinyl chloride have been studied in aq. DMSO, aq. acetonitrile and aq. ethanol. The kinetic data fit a second order rate equation in aq. DMSO. The calculated values of the second order rate coefficients increase in the case of aq. acetonitrile and aq. ethanol. The order in catalyst in 95%(v/v) aq. DMSO is less than unity.

Mercuric Chloride Catalysed Solvolysis of Benzyl Chloride in Water & Highly Aqueous Organic Solvent Systems

Kinetics of mercuric chloride catalysed solvolysis of benzyl chloride have been studied in water. 10% aq. ethanol, 10,20 and 30% aq. acetone and 20% aq. DMSO. The results confirm the operation of a mass law effect.

Thermodynamic Parameters of Transfer of 2-Nitrobenzoic Acid & 3-Nitrobenzoic Acid from Water to Aqueous Salt Solutions

The Setschenow parameters of solubility in salt solutions and the thermodynamic parameters (25·C) of transfer from aqueous solution to aqueous salt solutions for 2-nitrobenzoic acid and 3-nitrobenzoic acid have been reported. The data have been rationalized on the basis of the localized hydrolysis model and the structure breaking action of ions of the electrolytes.

Thermodynamics of Transfer of Aminobenzoic Acids from Water to Aqueous Salt Solutions

The Setschenow parameter and thermodynamic parameters of transfer of 2- and 4-aminobenzoic acids from water to salt solutions have been reported. The results are discussed in terms of the structure- breaking effects of the ions of the salts, the localized hydrolysis model, and the internal pressure theory.

Investigation of nonlinear absorption and aggregation in aqueous solutions of rhodamine B using thermal lens technique

Thermal lensing effect was studied in aqueous solutions of rhodamine B using 532 nm, 9 ns pulses from a Nd:YAG laser. A low intensity He-Ne laser beam was used for probing the thermal lens. Results obtained show that it is appropriate to use this technique for studying nonlinear absorption processes like two photon absorption or excited state absorption and for analyzing dimerization equilibria.

Studies of nonlinear absorption and aggregation in aqueous solutions of rhodamine 6G using a transient thermal lens technique

Dual-beam transient thermal lens studies were carried out in aqueous solutions of rhodamine 6G using 532 nm pulses from a frequency-doubled Nd:YAG laser. The analysis of the observed data showed that the thermal lens method can effectively be utilized to study the nonlinear absorption and aggregation which are taking place in a dye medium.

Aqueous Sol-gel Process for Nanocrystalline Photocatalytic Titania, Transparent Functional Coatings and Ceramic Membrane

The present thesis develops from the point of view of titania sol-gel chemistry and an attempt is made to address the modification of the process for better photoactive titania by selective doping and also demonstration of utilization of the process for the preparation of supported membranes and self cleaning films.A general introduction to nanomaterials, nanocrystalline titania and sol-gel chemistry are presented in the first chapter. A brief and updated literature review on sol-gel titania, with special emphasis on catalytic and photocatalytic properties and anatase to rutile transformation are covered. Based on critical assessment of the reported information the present research problem has been defined.The second chapter describes a new aqueous sol-gel method for the preparation of nanocrystalline titania using titanyl sulphate as precursor. This approach is novel since no earlier work has been reported in the same lines proposed here. The sol-gel process has been followed at each step using particle size, zeta potential measurements on the sol and thermal analysis of the resultant gel. The prepared powders were then characterized using X-ray diffraction, FTIR, BET surface area analysis and transmission electron microscopy.The third chapter presents a detailed discussion on the physico-chemical characterization of the aqueous sol-gel derived doped titania. The effect of dopants such as tantalum, gadolinium and ytterbium on the anatase to rutile phase transformation, surface area as well as their influence on photoactivity is also included. The fourth chapter demonstrates application of the aqueous sol-gel method in developing titania coatings on porous alumina substrates for controlling the poresize for use as membrane elements in ultrafiltration. Thin coatings having ~50 nm thickness and transparency of ~90% developed on glass surface were tested successfully for self cleaning applications.

Synthesis of Bio-Compatible SPION–based Aqueous Ferrofluids and Evaluation of RadioFrequency Power Loss for Magnetic Hyperthermia

Bio-compatible magnetic fluids having high saturation magnetization find immense applications in various biomedical fields. Aqueous ferrofluids of superparamagnetic iron oxide nanoparticles with narrow size distribution, high shelf life and good stability is realized by controlled chemical co-precipitation process. The crystal structure is verified by X-ray diffraction technique. Particle sizes are evaluated by employing Transmission electron microscopy. Room temperature and low-temperature magnetic measurements were carried out with Superconducting Quantum Interference Device. The fluid exhibits good magnetic response even at very high dilution (6.28 mg/cc). This is an advantage for biomedical applications, since only a small amount of iron is to be metabolised by body organs. Magnetic field induced transmission measurements carried out at photon energy of diode laser (670 nm) exhibited excellent linear dichroism. Based on the structural and magnetic measurements, the power loss for the magnetic nanoparticles under study is evaluated over a range of radiofrequencies.

Anti–white spot syndrome virus activity of Ceriops tagal aqueous extract in giant tiger shrimp Penaeus monodon

White spot syndrome virus (WSSV), the most contagious pathogen of cultured shrimp, causes mass mortality, leading to huge economic loss to the shrimp industry. The lack of effective therapeutic or prophylactic measures has aggravated the situation, necessitating the development of antiviral agents. With this objective, the antiviral activity in the aqueous extract of a mangrove plant Ceriops tagal in Penaeus monodon was evaluated. The Ceriops tagal aqueous extract (CTAE) was non-toxic to shrimps at 50 mg/ml when injected intramuscularly at a dosage of 10 lL/animal (0.5 mg/animal) and showed a protective effect against WSSV at 30 mg/ml when mixed with WSSV suspension at a 1:1 ratio. When the extract was administered along with the diet and the animals were challenged orally, there was a dose-dependent increase in survival, culminating in 100 % survival at a concentration of 500 mg/kg body weight/day. Neither hypertrophied nuclei nor the viral envelope protein VP28 could be demonstrated in surviving shrimps using histology and indirect immunofluorescence histochemistry (IIFH), respectively. To elucidate the mode of action, the temporal expression of WSSV genes and shrimp immune genes, including antimicrobial peptides, was attempted. None of the viral genes were found to be expressed in shrimps that were fed with the extract and challenged or in those that were administered CTAE-exposed WSSV. The overall results suggest that the aqueous extract from C. tagal can protect P. monodon from white spot syndrome virus infection.

Process Improvement of Coir Pith Degradation Involving White Rot Fungi By Substitution of Urea With Nitrogen Fixing Bacteria and Application of Biodegraded Coir Pith as Plant Growth Medium

In this study, a novel improved technology could be developed to convert the recalcitrant coir pith into environmental friendly organic manure. The standard method of composting involves the substitution of urea with nitrogen fixing bacteria viz. Azotobacter vinelandii and Azospirillum brasilense leading to the development of an improved method of coir pith. The combined action of the microorganisms could enhance the biodegradation of coir pith. In the present study, Pleurotus sajor caju, an edible mushroom which has the ability to degrade coir pith, and the addition of nitrogen fixing bacteria like Azotobacter vinelandii and Azospirillum brasilense could accelerate the action of the fungi on coir pith. The use of these microorganisms brings about definite changes in the NPK, Ammonia, Organic Carbon and Lignin contents in coir pith. This study will encourage the use of biodegraded coir pith as organic manure for agri/horti purpose to get better yields and can serve as a better technology to solve the problem of accumulated coir pith in coir based industries

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.