This thesis includes a description of modifications of the Hilger atomic absorption apparatus, which was used for most of the work. These modifications were restricted to the atomiser and burner, which were replaced by a modified "Eel" flame. photometer atomiser-burner and resulted in improved sensitivity and instrumental stability for the atomic absorption of magnesium. A comparison of the performance of this unit with that of the unmodified Hilger apparatus is given. A "Handigas" butane-propane mixture)-air flame was used for most of this work, but a coal-gas-air flame was also studied and found to give slightly greater sensitivity. The method was found to be subject to interference from many elements. Strontium salts, employed as releasing agents to overcome the effect of other elements, were not completely effective as milligram amounts of several elements interfered even when strontium was present. Among the more serious interfering elements are: aluminium, iron, manganese and zirconium (less than 20 p.p.m. interfere); the alkali and alkaline earth metal salts (more than 200-500 p.p.m. interfere); phosphate (more than 100 p.p.m. P₂0₅ uranium (more than 4,000 p.p.m.); arsenate and vanadate. An attempt is made to explain the mechanism of some of these interfering effects. A combination of strontium salt and acetyl acetone was found to over-come the effects of small amounts of several elements that form complexes with acetyl acetone (e.g. iron and aluminium) far more effectively than strontium alone. Larger amounts of many interfering elements are removed by a solvent extraction procedure employing acetyl acetone and chloroform. Elements which cannot be removed by this means may be separated by anion-exchange, volatilisation, electrolysis or precipitation. A spiking technique, which compensates JT/GB for the effects of small amounts of interfering elements, is described and enables many samples to be analysed without prior separations. The method described has good sensitivity (the limit of determination is approximately 1 microgram of magnesium in 50 ml. of solution). It has been applied to the analysis of clay samples, iron ore, limestone and uranium metal, oxides and processing solutions. The coefficient of variation of the method was determined using two clay samples and results of 2.0 and 4.6 percent, at magnesium oxide concentrations of 0.65 and 0.22 percent respectively, wore obtained. The speed of the method compares favourably with others described for the determination of microgram amounts of magnesium, but increases if large amounts of interfering elements are present.

The major criticism of the human skin blanching assay is the subjective nature of grading the response. Recently the American FDA released a Guidance document for topical corticosteroid bioequi valence testing. The guidelines require the use of a chromameter as a reliable method to estimate skin blanching. The purpose of this study was to evaluate the recommendations of this document for appropriateness by comparing visual and chromameter data. The visually-assessed blanching assay methodology routinely practised in our laboratories was modified to comply with the specifications of the Guidance. The preliminary trial indicated that the training period that is required for a novice to be classified as an experienced observer is not a major problem. The major trend that emerged from the pilot study was that visual assessment was better than the chromameter. Longer dose durations were found to be more discriminatory than shorter durations. The visual data were best described by the sigmoid Emax model and the chromameter data were best described by the simple Emax model. The pivotal results indicated that the D2/Dj criterion to determine sample size of "acceptable blanchers" produced only few subjects suggesting that the validity of this criterion requires extensive investigations. The estimates of the Locke's confidence interval method were simiJar to those for the general simple formula. However, due to undefined parameters of the Locke's method in the Guidance, the validity of the Locke's method requires evaluation. The chromameter b-scale parameter was the least sensitive in estimating skin blanching whereas the a- and L-scale parameters produced similar results. Poor correlation between visual and chromameter was noted indicating that the visual method is still the best method.

Introduction: Part 1. Greenhouse studies were conducted to investigate the absorption of sodium, potassium, calcium and magnesium by lemon seedlings. The plants were grown in controlled nutrient solutions and analysis of the plant material was made to determine the relationship between the four cations in the different plant organs. Results of the experiment may be summarized as follows:- The occurrence of leaf burn appeared to be associated with a low calcium content, together with a high sodium, potassium or sodium + potassium content. The development of the seedlings was shown to be markedly influenced by the level of calcium supply and to a much lesser degree by the level of potassium supplied. The concentration of sodium, potassium, calcium and magnesium in the stem and leaf varied with position of the tissues on the main axis. The level of sodium was found to influence the distribution of sodium in the leaves, and the sodium content of the leaf, stem and root tissues gave a good reflection of the level of sodium supplied. The effect of the sodium treatment on the uptake of potassium appeared to be dependent on the calcium content of the tissues. Sodium treatment was found not to affect the leaf calcium content. In the stem and root tissues the calcium content was reduced when the calcium level in the nutrient medium was low, and increased the calcium content of these two tissues at the higher level of calcium supply. The sodium supply was shown to reduce the leaf magnesium only slightly, and its affect on the magnesium content of the stem and root tissues was shown to be dependent on the level of calcium supplied. The potassium content of the leaves, stems and roots increased when the supply of potassium was raised. Increasing the potassium level in the nutrient supply was found to cause a very slight reduction in the sodium content of the leaf, but did not affect the sodium content of the stem and root. Potassium did not affect the calcium content of the leaves and increased the stem calcium when sodium was not present in the nutrient media in high concentrations. In the roots potassium only increase the calcium content at the upper level of calcium supply. The magnesium content of the leaf and stem tissues was reduced as the potassium supply was increased. In the roots the general trend was for the magnesium content to increase when the level of potassium treatment was raised. The calcium content of all the plant parts increased with a rise in the calcium supply, the stem and root tissues having a greater percentage increase than the leaves. The sodium content of the plant tissue was reduced as the level of calcium supply was raised. The leaf potassium content decreased with a higher calcium level of supply. In the stem and roots the potassium content was increased by doubling the calcium supply. The calcium treatment had no influence on the magnesium content of the foliage, but in the stem and root tissues a decrease in magnesium content resulted from an increase in the calcium supply. Part II Potato tuber tissue and carrot root tissue were used as experimental material in the investigation of sodium9 potassium9 and calcium uptake by storage tissue. It was shown that when the tissue disks are transferred from distilled water to a solution of salts there is a rapid initial uptake of cation which is neither particularly selective, nor related to metabolism, but dependent on the external concentration. On the other hand, the prolonged active accumulation of cation exhibits selectivity. Potassium absorption by potato tuber tissue was shown to be stimulated by sodium9 whereas the potassium and calcium absorption by carrot root tissue was shown to be reduced by sodium. Similarly the sodium absorption by the carrot root tissue was reduced by potassium, thus suggesting that the cations compete with one another for the same absorption mechanism.

Tubes of glass reinforced thermosetting resins have been tested in axial compression between steel platens with one end chamfered to prevent critically high loads causing catastrophic centre failure. By testing in such a manner these tubes crush in a progressive and controlled manner, and are capable of exhibiting high levels of energy absorption, particularly when related to the material mass involved. Polymers are known to display viscoelastic behaviour and polymer composites are similarly sensitive to test speed and temperature. Energy absorption in tube crushing has been shown to be speed and temperature sensitive and the purpose of this project has been to understand the variability of the energy absorption and the associated mechanisms. The main aim has been to show how the two variables interrelate. The materials used have been produced by hot rolling of pre-preg cloth or by resinjection into closed moulds. Reinforcement has consisted of woven glass cloth or random glass mat; matrix materials have been epoxy and polyester resins. Trends to higher values of specific energy absorption with increasing speed have been observed for epoxy matrix tubes, while polyester matrix tubes have shown less certain trends and give lower values of specific energy absorption at high speeds. All the tubes have shown a rapid drop in specific energy absorption with increasing temperature above normal room temperature, with changes in crush mode being very apparent. At temperatures in excess of about 100 degrees C the tubes have failed by centre buckling, the transition temperature from normal crushing to buckling being sensitive to the crush speed. The interrelation between speed and temperature effects has been examined. Three factors that prevent simple interrelation have been identified; these are inertial effects of crush debris, residual stresses in the hoop direction of the tube and frictional heating in the crush zone. Speed sensitivity of the energy absorption has been determined over a range of temperatures and various features of these responses related to the responses of the material properties. Frictional temperature rises have been modelled mathematically and the predictions have been shown to be reasonably consistent with experimental measurements. These temperature rises have been shown to be important in determining the speed sensitive behaviour of the energy absorption levels, particularly for polyester resin matrix tubes tested at high speeds.

The fluorescence and absorption spectra of anthracene in the near ultra-violet were investigated in n-heptane, fluorene, biphenyl and n-hexane matrices at low temperature. The assignment of the excited electronic state as ‘Biu was confirmed. In the ground electronic state eight Qg and five b₃g, and in the 'Bᵢᵥ upper electronic state seven Qg and five b₃g fundamentals were assigned. It was deduced that the potential surfaces of the 'Ag and the 'Bᵢᵥ states were similar in shape as there was an approximate agreement between the values of corresponding fundamental vibrations in the two electronic states. The potential surfaces were unusually harmonic for a polyatomic molecule, at least along the normal co-ordinates available to this study. No evidence for the presence of anharmonicity was found in even the highest overtone (the third) measured, although several possible examples of Fermi resonance between vibrational modes were observed both in fluorescence and in absorption. The Fermi resonances were assigned primarily on the basis of intensity transfer between lines rather than line shifts. The presence of a weaker long-axis polarized transition ( 'B₂ᵥ- 'Ag ) in anthracene predicted by theory was not detected. The lowest energy electronic transition in fluorene was found to be polarized along the long axis of this molecule. / Science, Faculty of / Chemistry, Department of / Graduate

. The kinetics of the absorption of carbon monoxide by basic solutions was studied at 80°C and carbon monoxide pressures up to 30 atmospheres. The reaction was followed by the rate of decrease of carbon monoxide pressure in a closed system. The observed kinetics in potassium hydroxide solutions yield a rate law of the form (formula omitted) No influence from Li⁺, Na⁺, K⁺ ions was detected and no catalytic effect from Ag(I),- Cu(II), T1(I), N0₃⁻, Mn0₄⁻ was observed. The kinetics are consistent with a mechanism which includes the insertion of a carbon monoxide molecule into the hydroxyl bond,viz. (formula omitted) The rate-controlling step above 90°C was found to be the mass transfer of carbon monoxide from the gas phase into the liquid phase under the conditions involved in this study. / Applied Science, Faculty of / Materials Engineering, Department of / Graduate

Two soil types, the Ladner silty clay loam and the Nicomekl loam, located in the Lower Fraser Valley, representing the modal profile characteristics were selected to study the permeability and the factors affecting it. Undisturbed core samples and fragmented samples were procured for laboratory characterization of the soils. Measurement of the soil permeability in the laboratory confirmed the field observations that the Nicomekl soil was more permeable than the Ladner soil. There was a good correlation in the soil permeability and the soil macroporosity as determined by tension table at 40 cm. water tension. The texture of the two soils, as determined by pipette method, was not sufficiently different to account for the permeability differences. The variations in the organic matter content, as determined by wet combustion method, seemed to have little effect on the permeability behaviour of these soils. The nature of exchangeable cations, as extracted by the ammonium acetate method and quantitatively determined by flame photometry and versenate titration, in the two soils, were found to be very different; the exchangeable cations, Na⁺, K⁺ and Mg⁺⁺, in the Ladner soil seemed responsible for the lower permeability in comparison with the Nicomekl soil which had very low percent base saturation and appeared to have mostly Al⁺⁺⁺ ions present in the exchange complex. The poorer physical conditions of the Ladner were also, perhaps, due to the differences in the exchangeable cations. The X-ray identification of clay minerals, using oriented "aggregate technique", monochromatic copper radiation and surface reflection method, revealed that the Ladner and Nicomekl soils were qualitatively similar in their clay content. Both soils contained montmorillonite, micaceous mineral, chlorite, feldspar and quartz; the presence of kaolinite and vertniculite could not be established. In an intricate mixture of clays as above, quantitative estimation of clay minerals was not performed; hence the effect of clay minerals on the permeability of the two soil types could not be evaluated. Permeability measurements on soil mixtures containing reference clay minerals, using air pressures in a water permeameter, revealed that Na-Bentonite even in small quantities rendered soil highly impermeable. The permeability of soil mixtures containing clays with exchangeable calcium improved with the application of Krilium while the clays with exchangeable sodium did not respond to similar treatment. The effect of Al⁺⁺⁺ ion and weak acids on the flocculation behaviour of Na-Bentonite suggested that the presence of both Al⁺⁺⁺ ions and weak acids promoted soil permeability. X-ray diffraction diagrams using unflitered cobalt radiation indicated that weak acids formed heat stable complexes with bentonite. The bentonite treated with aluminum chloride as well as phosphoric acid plus aluminum gave diffraction patterns indicating that increased c-spacing was due to the complexes formed with bentonite; the deposition of these complexes at the interlayer positions prevented the complete collapse of lattice at elevated temperatures. / Land and Food Systems, Faculty of / Graduate

The Bose-Einstein distribution is derived, and from this the mean values and fluctuations of the thermodynamic quantities describing a volume V of black body radiation at absolute temperature T, are calculated. The problem of the energy fluctuation of a body of emissivity ε in thermodynamic equilibrium with a volume of black body radiation, is considered from a statistical approach. The result var E = kT ²C , known to be correct from thermodynamics, is obtained. The zero point energy difficulty in the mean energy of the radiation is discussed in detail. Arguments are presented supporting the inclusion of the zero point energy in the thermal radiation theory. The problem of the number of distinguishable levels that can be obtained from a certain signal power in a resonator is discussed in this section. Finally the results of the theory above are employed to determine the ultimate sensitivity of radiation detectors. Care is taken to isolate factors which are not fundamental properties of the detector, from the treatment of the detector sensitivity. A bolometer and a phototube, energy and quantum detectors respectively, are discussed in detail. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

This thesis describes the photochemical synthesis of silver nano particles, several ways to make these particles as well as control the size and shape of the colloidal particles. Understanding the primary reactions in photochemical nanoparticle formation has lead to important contributions to the overall mechanism of metal nanoparticle synthesis. The size and shape control of the particles is shown to have important implications for the Raman spectrum of surface bound molecules. The particles have also been used in antibacterial properties where it was shown that silver nanoparticles are more antibacterial than the corresponding silver cation, while remaining non-toxic to several common cell lines. The particles were also shown to have some interesting properties that can be exploited in lithography and optoelectronics.

Gas absorption with chemical reaction is an important unit operation in the chemical and petroleum industries for the selective removal of components from industrial gas streams. Apart from choosing absorption media, the most difficult problems facing the design engineer are the sizing and performance prediction of the absorption tower due to the scarcity of fundamental design data, especially when novel absorption media and/or packings are used. The solubility of carbon dioxide in 2 and 3 M solutions of 2-amino-2-methyl-1-propanol (AMP), which is a newly introduced absorbent, was determined at 20, 40, 60 and 80 °C and for CO₂ partial pressures ranging from approximately 1 to 100 kPa. The results were interpreted with a modified Kent-Eisenberg model which predicted the present and previous experimental results well. The absorption capacities of AMP and monoethanolamine (MEA) solutions were also compared. Detailed concentration and temperature measurements were reported for the absorption of carbon dioxide from air into NaOH, MEA and AMP solutions. A full-length absorber (0.1 m ID, packed with 12.7 mm Berl Saddles up to heights of 6.55 m) was used. It was operated in countercurrent mode and at 30 to 75 % flooding velocities which are typical for gas absorber operations. The following ranges of operating conditions were employed: superficial gas flow rate 11.1 to 14.8 mol/m² s; superficial liquid flow rate 9.5 to 13.5 m³/m² h; feed CO₂ concentration 11.5 to 19.8 %; total absorbent concentration 1.2 to 3.8 kmol/m³; liquid feed temperature 14 to 20 °C; total pressure 103 kPa. The measurements for the CO₂-NaOH and CO₂-MEA systems were compared with predictions from a previously developed mathematical model. Generally good agreement was obtained except at high CO₂ loadings of MEA solutions. Compared with MEA, AMP was found to have superior CO₂ absorption capacities and inferior mass transfer rates. A new procedure, called the Pilot Plant Technique (PPT), for designing gas absorbers with chemical reactions has been developed. The PPT is primarily intended for designing absorbers for which fundamental design information is lacking. It is based on the premise that full-length absorption columns can be sized by making a minimum number of tests using a small-scale pilot plant. Two special features of the PPT are (i) the details of hydrodynamic parameters (i.e. mass transfer coefficients, effective interfacial area and liquid hold-up) and the physico-chemical information of the system (e.g. reaction mechanism, reaction rate constants) need not be known and (ii) complex calculations are avoided. Using the PPT to size the height or to predict the performance of a given full-length absorber, the specific absorption rate, which is the essential information, can be measured directly using the pilot plant model (PPM) column if both columns have the same hydrodynamic conditions. This can be achieved by using the same type and size of packing in the PPM and the full-length columns and ensuring that the end and wall effects are negligible. The PPM column must also be operated at the same superficial fluid velocities as those of the full-length column. The specific absorption rate was then obtained from the gradient of the fluid composition profile along the PPM column. The validity of the PPT was demonstrated by determining the height and predicting the performance of the full-length column in which carbon dioxide was absorbed from air by aqueous solutions of NaOH and AMP at various operating conditions; good agreement was obtained. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate