The kinetics of the reduction of silver amine complexes in aqueous solutions were investigated and found to be second order overall, the rate being proportional to silver complex and hydrogen concentrations. These systems were studied under conditions of essentially complete complexing and therefore the rates were independent of amine concentration. The rates were also shown to be independent of amine perchlorate concentration and thus of pH within a limited range. Enthalpies and entropies of activation were determined for each system and an attempt was made to correlate kinetic data with information on complex stability constants and amine basicities. The most prominent trend in the results was the inverse dependence of rate on complex stability constant. Two mechanisms are proposed both involving heterolytic cleavage of the hydrogen molecule. In the first mechanism, the proton released in the rate determining step is taken up by the basic ligand directly. In the second mechanism, a water molecule replaces the amine ligand and acts as the proton acceptor. The strength of the silver-ligand bond and the difficulty of ligand replacement by water account for the inverse dependence of rate on complex stability for each mechanism respectively. Arguments are presented to support both mechanisms. In general dibasic amine complexes activated hydrogen more readily and displayed a more negative entropy of activation than do the monoamine complexes. These observations are attributed to the presence of a free basic group in the ligand aiding the cleavage of the hydrogen molecule in the rate determining step. The proximity of the second basic group to the central silver atom also appears to be important. These effects and the possible role of the free basic group in the ligand are discussed. / Science, Faculty of / Chemistry, Department of / Graduate

Merocyanine dyes exhibit interesting changes in absorption spectra with changes in solvent polarity. For example solutions of 1-methyl-4- (oxocyclohexadienylidene) ethylidene -1,4-dihydropyridine (MOED) are yellow, red, violet, or blue, in water, ethanol, acetone or pyridine respectively.1 More striking effects are observed when aqueous solutions are diluted with various proportions of the organic co-solvents such as pyridine. The color varies across the whole spectrum from golden yellow to blue.These characteristic properties of merocyanine dyes in various organic solvents have been extensively studied and correlations between [see PDF file for formula]max and solvent polarity have been determined. In this work the visible absorption have been determined. In this work the visible absorption properties of merocyanine dyes were studied in cationic and anionic surfactants in order to investigate the behaviour of these dyes in micellar system and to use their electronic spectra as probes of the micellar environment. Since the description of the literature and discussion of the experimental results will involve certain terms and concepts from surfactant chemistry, it is necessary to introduce the subject.

No description available.

No description available.

Methods for the analysis of surfactants and proteins by Capillary Electrophoresis (CE) were investigated. Several modifications of the system to achieve detection and separation of these analytes were examined. These modifications included buffer additives, sample additives and surface treatment and modification of the fused silica capillary. For the analysis of anionic surfactants, the addition of an anionic IN absorbing compound to the buffer was investigated to achieve indirect detection of the non-absorbing surfactants. The effect on detection sensitivity and separation efficiency of the absorbing ion was examined. These parameters were affected by differences in the electrophoretic mobilities of the analytes in comparison to the absorbing ion. The use of organic modifiers was also investigated to minimize micelle formation of the surfactants which leads to zone spreading. For the analysis of serum and urine proteins, the use of high pH buffers was investigated to minimize solute/capillary surface interactions and achieve separation. At high pH's the proteins are negatively charged; therefore, they should be repelled by the negatively charged fused silica surface. To improve reproducibility of migration times of the proteins the addition of polyvinyl alcohol to the sample was also investigated. The polyvinyl alcohol improved reproducibility by reversibly covering the active sites on the capillary surface to minimize protein interactions. Migration time reproducibility was also improved by optimizing the capillary cleaning procedure. Lastly, the addition of methyl cellulose to the buffer to work as a dynamic molecular sieving medium was investigated to improve resolution. Analyte/ capillary surface interactions are a major limitation in CE especially for the analyses of proteins. The use of coated capillaries to eliminate these interactions has been widely investigated. However, reproducibility and degree of surface deactivation with these coating can be poor. In this work hydrothennal treatment of the fused silica capillary surface prior to deactivation was examined. Hydrothennal treatment was used to produce a homogenous surface prior to coating which leads to the production of more highly deactivated, reproducible columns. The effects of the treatment were studied by coating the surface with a silane and examining the influence of the coating on electroosmotic flow and analyte adsorption. / Ph. D.

High molecular weight polyether urea copolymers were synthesized using perfectly difunctional aromatic amine terminated polypropylene oxide (PPO) (2800 <Mn>) prepared via aluminum porphorin initiated coordination polymerization. The resulting segmented copolymer showed much higher tensile strength and better thermal stability than polyureas based on commercial PPO which contains some terminal unsaturation. This was attributed to the achievement of both higher molecular weight and to more extensive microphase separation between the segments. In addition, the surface structure of segmented polyether urea and polyurethane urea copolymers were modified in two ways: siloxane urea segmented copolymers were synthesized and physically blended into the system, and siloxane oligomers of controlled molecular weight and composition were incorporated into the copolymer backbone as a part of the soft segment. X-ray photoelectron spectroscopy (XPS) was used to obtain surface compositional information, while differential scanning calorimetry (DSC) and stress-strain analysis were used to characterize the bulk properties. In general, the surface enrichment of siloxane was observed in both solvent cast blends and siloxane incorporated systems. The surface siloxane concentration showed a small increase with siloxane segment length, content, and surface sensitive angle. Surface segregation of these systems was suppressed to a certain extent due to phase mixing within the copolymer bulk and by the anchoring of both ends of the siloxane segment with urea components. The bulk properties of these copolymer systems were not affected greatly when small amounts of siloxane ureas were added or when small amounts of siloxane blocks were incorporated. / Master of Science

The purpose of this investigation was to determine the effect of the positions and the molecular weight of surfactant hydrophilic functional groups on the rate of gas absorption. A quiescent unsteady-state absorption apparatus was used with carbon dioxide and water as the absorption system. Three surfactants with hydroxyl groups were selected for study, namely, n-octanol, 4-octanol and lauryl diglycol amide. Preliminary absorption tests were made using pure deionized water to determine the diffusion coefficient for the system. A value of 1.93 ± 0.05 x 10⁻⁵ square centimeters per second was obtained. The absorption tests were repeated with the three surfactant solutions at different concentrations. Then the interfacial resistance for each solution was calculated. The results of the surfactants were compared with each other and were also compared with the results of lauryl diethanol amide previous investigated. The octanol with hydroxyl group at a branched position was found to cause a higher interfacial resistance than those with hydroxyl groups at the end of the hydrophobic chain. It was also concluded that increasing the molecular weight of the hydrophilic group decreased the interfacial resistance. / Master of Science

Thesis (doctoral)--Lund University, 1998. / Thesis statement inserted. Includes bibliographical references.

Thesis (doctoral)--Lund University, 1998. / Thesis statement inserted. Includes bibliographical references.

An infiltration-wetting agent study, using the wetting agent "WATER-IN", was conducted in the ponderosa pine forest type of east central Arizona, near McNary, Arizona. An application rate of 10 gallons of wetting agent per surface acre was used both on bare mineral soil and on ponderosa pine litter. The infiltration rate was measured by a modified North Fork infiltrometer. It was found that "WATER-IN" significantly increased water runoff, when applied to litter, but when applied to bare mineral soil, "WATER-IN" caused a significant increase in water infiltration. The wetting agent did not significantly affect antecedent moisture, soil particle distribution, litter water holding capacity, or litter bulk density. It is presently hypothesized that the increase in water infiltration on treated bare mineral soil is due to a decrease in the average bulk density of the surface inch of soil. The data strongly suggests this hypothesis to be correct. The increase in runoff when litter is treated is probably due to an interaction, either physical, chemical, or both, between the humus layer and "WATER-IN", creating a hydrophobic condition where one did not exist before.