Reproduction de : Thèse de doctorat : Chimie : Reims : 2004. / Titre provenant de l'écran titre. Bibliogr. p. 159-165.

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Measurements of relative densities and relative massic heat capacities have been made for several aqueous rare earth chloride and perchlorate systems. Densities and relative massic heat capacities of acidified aqueous perchlorates of yttrium, ytterbium, dysprosium, and samarium as well as the chlorides of yttrium, ytterbium, dysprosium, samarium and gadolinium have been measured at the temperatures 288.15, 298.15, 313.5 and 328.15 K. Using the density and massic heat capacity data, apparent molar volumes and apparent molar heat capacities have been calculated. These data have been modeled using the Pitzer ion interaction approach as well as the Helgeson, Kirkham and Flowers equations of state. Apparent molar volumes and apparent molar heat capacities previously presented in the literature have been compared to the data presented here. single ion apparent molar volume and apparent molar heat capacity contributions were calculated. Infinite dilution properties have been compared to existing models used to predict infinite dilution properties. Densities of aqueous perchloric acid and ytterbium perchlorate at the temperatures from 348.15 to 423.15 K and at pressured from 10.00 to 30.00 MPa were measured. Apparante molar volumes were calculated from the density measurements. The apparent molar volume data were modeled using Pitzer ion interaction theory as well as HKF equations of state. Models presented are compared to existing models. / xi, 149 leaves : ill. ; 29 cm.

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Aldehyde oxidase catalysed oxidation of various quinolinium and related cations has been studied in vitro. Oxidation products were identified by comparison of their spectral and chromatographic characteristics with those of authentic compounds. The N-heterocyclic cations and quinolones used required synthesis. Incubation of N-methylquinolinium, N-methyl-7,8-benzoquinolinium and N-phenylquinolinium yielded the corresponding 2- and 4-quinolones simultaneously. The ratio of 2- to 4-quinolone formation was found to be species dependent; the proportion of 4-quinolone was greater with guinea pig enzyme than with rabbit enzyme. Incubation of N-methyl-4-methylquinolinium, N-methyl-4-phenylquinolinium and N-methylphenanthridinium produced the expected 2-quinolones. Cations substituted adjacent to the ring nitrogen, i. e. N-methyl-2- methylquinolinium, N-methyl-2-phenylquinolinium and N-phenyl-2-phenylquinolinium, were oxidised to the corresponding 4-quinolones. Kinetic constants were determined spectrophotometrically. The Km values obtained with rabbit enzyme ranged from 1.6 x 10-3 M for N-methylquinolinium to <10-5 M for N-phenyl-2-phenylquinolinium. Quaternary compounds were found to be better substrates than their non-quaternary counterparts, except for N-methylisoquinolinium and N-methylphenanthridinium. In general, guinea pig aldehyde oxidase was shown to have a greater affinity for N-heterocyclic cations than rabbit enzyme. The substrate binding site has been discussed in the light of the results outlined below. Oxidation of N-methyl-4-phenylquinolinium (to the 2-quinolone) was competitively inhibited by N-methyl-2-phenylquinolinium (which yields the 4-quinolone), indicating that both these cations interact at the same active site. The ratio of 2- to 4-quinolone production from N-methylquinolinium was constant under various conditions, including purification of the enzyme but changed at high pH or in the presence of N-methylphenanthridinium. Inhibition studies indicated that both quaternary and non-quaternary compounds act at the same site on the enzyme. Km and Vmax values for phthalazine, N-methyl-2-phenylquinolinium and N-methylquinolinium were determined over the pH range 5.4 to 10.2. In each case, results indicated that the enzyme has an ionisable group at the active site with a pK ca. 8. Aldehyde oxidase was shown to catalyse the dehydrogenation of the pseudobases 3,4-dihydro-4-hydroxy-3-methyl-2-quinazolinone and 3,4-dihydro- 4-hydroxy-3-methylquinazoline.

The research provides data of pH and conductivity, some anions (e. g. fluoride, chloride, bromide, nitrate, phosphate and sulphate), monovalent cations (e. g sodium, ammonium and potassium), divalent cations (e. g calcium and magnesium) heavy metals (e. g. iron, copper, zinc, nickel, cobalt, cadmium and manganese) and organic compounds – from water samples of rivers of Brunei Darussalam, namely, Brunei River, Belait River, Tutong River and Temburong River. The higher values of certain parameters with respect to the acceptable standard limits for river water indicate the pollution in river water samples of the study area, make the waters unsuitable for various applications and do pose a human health hazard. The pH levels in Brunei Darussalam is quite reassuring and mostly safe. Although there are some stretches of rivers that show slightly lower levels of pH, there is no cause for any alarm as these waterways are not sources of drinking water. As for anions and cations, the only anion of significant levels detected in Brunei Rivers is chloride whereas only monovalent cation detected in significant levels, is sodium. The concentrations of chloride and sodium ions are below the standard concentrations. Brunei Rivers are still free from chloride and sodium pollution. For heavy metals, only iron is detected in Brunei Rivers. Brunei being a oil based country experiments were done to identify levels of a numbers of significant toxic organic compounds, including, toluene and benzene which have been detected in the waters of the oil mining district of Belait District but are within normal limits. The use of a photolytic cell system to achieve the photodegradation of benzene, toluene, ethylenediaminetetra-acetic acid (EDTA) and the surfactant – hexadecyltrimethyl-ammonium bromide (C19H42NBr) is reported. The system has been optimised by investigating the effects of the addition of hydrogen peroxide (H202) as an oxidant and the addition of titanium dioxide (TiO2) as a catalyst. The results show that the photolytic system can be used to achieve >99% degradation of organic contaminants. The research also includes a final chapter on management system which covers water protection, pollution control and solid waste management in Brunei. In addition to investigating various factors of the solid waste management in Brunei, the researcher has also exposed some of the weaknesses that need immediate addressing. Various measures have been suggested to make Brunei's water more efficient. Moreover, ways of preserving the high quality of Brunei's water figures in this chapter.

Studies of gas-phase ionic clusters have become an integral component in understanding microsolvation and catalysis by transition metal cations. Further interest in this field is due to the possibility of bridging the gap between the condensed and gas phases by developing our understanding of clusters and the possibility that small clusters can have unique chemical and catalytic properties. Most gas phase studies have focused on singly charged ions. Electrospray allows for the production of multiply charged ions solvated by a few solvent molecules. Understanding smaller reactive species such as metal centered clusters with well-defined, gas phase conditions also allows for detailed comparison between theory and experiments. In these studies the main focus is to understand bond activation by transition metal cations and solvation of transition metal dications. The gas phase ions of interest are studied using an electrospray-ionization or laser-ablation dual time-of-flight mass spectrometer and are characterized using photofragment spectroscopy in the visible and ultraviolet regions of the spectrum. Photofragment spectroscopy is a powerful method that can be used in gas phase studies to gather a wealth of information on the ions' bond strengths, spectroscopic constants, and dissociation kinetics and dynamics. The study of TiO + (CO 2 ) spectroscopy (Chapter 3) was a result of study of CO 2 bond activation by Ti + that went on to provide a wealth of information on the spectroscopy and dissociation kinetics of this molecule. An electronic transition of the TiO + chromophore was observed, 2 Π[arrow left] 2 Δ, revealing new information about the excited state and the effect of TiO + electronic state on the metal- CO 2 ligand interaction. The photodissociation spectrum of this molecule is well resolved and shows progressions in the covalent Ti-O stretch and metal-ligand stretch and rock. The lifetime of electronically excited TiO + (CO 2 ) was measured, and depends strongly on vibrational energy. Calculations on TiO + and TiO + (CO 2 ) were combined with experimental results on TiO + (CO 2 ) to predict spectroscopic transitions of TiO + , an astrophysically interesting molecule. The photodissociation dynamics of M 2+ (CH 3 CN)n(H 2 O)m where M = Co and Ni, (Chapter 4) is important in understanding the gas phase microsolvation of metal dications. The coordination number and type of solvent affect the dissociation pathways. M 2+ (CH 3 CN)n (n>2) primarily lose a solvent molecule. Electron transfer is a minor channel for n=3 and is the only channel observed for n=2. Mixed clusters M 2+ (CH 3 CN)n(H 2 O)m preferentially lose water. Loss of acetonitrile is a minor channel, as is proton transfer. Water is the proton donor. Replacing acetonitrile with water increases the proton transfer channel. Nickel and cobalt complexes show similar dissociation dynamics, with proton transfer more likely for nickel complexes. Methane activation by transition metal catalysts is industrially important as it can be used to produce gasoline from natural gas. We studied the products and intermediates of the reaction of laser-ablated platinum atoms with methane (Chapter 5). Photoionization efficiency curves were measured for PtCH 2 and the [H-Pt-CH 3 ] insertion intermediate using tunable vacuum ultraviolet light. The resulting ionization energies were combined with bond strengths for the cations to derive bond strengths for the neutrals. These were used to construct a potential energy surface for methane activation by platinum atoms.

Typescript. / Thesis (Ph. D.)--University of Hawaii at Manoa, 1974. / Bibliography: leaves 191-204. / xvii, 204 leaves ill

Membrane processes are increasingly used in water treatment. Experiments were performed using stirred cell equipment, polymeric membranes and synthetic surface water containing natural organics, inorganic colloids and their aggregates, and cations. All processes could remove a significant amount of natural organics. Pretreatment with ferric chloride was required to achieve significant organic removal with MF and high MWCO UF. Additionally, fouling mechanisms for the three processes were investigated. Crucial parameters were aggregate characteristics (fractal structure, stability, organic-colloid interactions), solubility of organics and calcium, and hydrodynamics. In MF, fouling by pore plugging was most severe. Variations in solution chemistry changed the aggregation state of the colloids and/or natural organic matter and dramatically affected rejection and fouling behaviour. UF membrane fouling was mainly influenced by pore adsorption and could improve natural organics rejection significantly. Coagulant addition shifted fouling mechanism from pore adsorption to cake formation. Aggregate structure was most significant for flux decline. In NF, rejection of natural organics involved both size and charge exclusion. Fouling was caused by precipitation of a calcium-organic complex. Fouling could be avoided by pretreatment with metal salt coagulants. Thorough chemical characterisation of the organics used demonstrated that only size and aromaticity can be related to fouling. The study is concluded with a process comparison based on a water quality parameter and a cost comparison. Treatment cost of microfiltration with chemical pretreatment was similar to that of nanofiltration at a comparable natural organics rejection.