Carbon nanotubes (CNTs) have been one of the most studied nanoparticles and incorporated into various consumer products. It has been reported that CNTs can enter groundwater systems by accidental or intentional release into the subsurface. As transport mechanisms of CNTs are not well understood, investigation on mobility of CNTs in the subsurface will be helpful to define disposal regulations of CNTs. The objective in this study is to investigate the effect of solution chemistry (pH and ionic strength) and physical factors (collector grain size and flow rate) on the transport of multi-walled carbon nanotubes (MWCNTs). One-dimensional convection-dispersion model incorporated with collector efficiency for cylindrical nanoparticles was used to simulate the transport of MWCNTs in porous media. It was observed that higher pH led to increase in mobility of MWCNTs. The critical point of ionic strength for MWCNTs getting mobilized was narrowed down in the range of 2 to 5 mM. It was observed that the finer porous media could retain more nanoparticles. The decrease in pore water velocity resulted in a clear retardation, lowered the hydrodynamic force acting on the particles and led to more retention.

Excess molar volumes have been determined for four ternary chlorobenzene + dibutyl ether + alkane mixtures at 25°C. Results of these measurements are used to test the applications and limitations of BAB, Redlich-Kister, Kohler and Hwang et al. cubic models. For the systems studied, Redlich- Kister, Kohler and Cubic models were found to provide reasonable predictions. Differences between experimental and predicted ΔV^ex_123 values were about ±0.020 cm^3mol^-1 or less at most ternary compositions. Solubilities are reported for anthracene in binary mixtures containing propanol and butanol with alkanes at 25°C. Results of these measurements are used to test the NIBS/Redlich-Kister expression. The three-parameter form of this expression is found to provide reasonable mathematical representation with deviations between experimental and back-calculated values being less than ±1%.

Solvent-free reactions possess advantages compared to the solvent route, such as shorter reaction times, less use of energy, better yields, etc. Herein, the synthesis and characterization of bisferrocenylimines and arylbisamines are described. Reduction of the above compounds with LAH resulted in the formation of bisferrocenylamines and arylbisamines, respectively. The coordination chemistry of all the above compounds to rhodium(I) is also discussed in the prepared complexes [Rh(COD)(NN)]ClO4, where NN = bisferrocenylimines, and [Rh(COD)(NN)]BF4, where NN = bisferrocenylamines and arylbisamines. X-ray crystal structures of the complexes [Rh(COD)(NN)]ClO4 ([3.2] and [3.3]) have been obtained. Complexes of the type [Rh(COD)(NN)]BF4 were characterized with IR and UV-vis spectroscopy, cyclic voltammetry and conductometry. The catalytic activity of the complexes was also investigated: [Rh(COD)(NN)]ClO4 for the polymerization of phenylacetylene and [Rh(COD)(NN)]BF4 for the hydroformylation of styrene.

Variations in the yield, chemical composition, antibacterial, and antioxidant properties of the essential oils of Rosmarinus officinalis L. cultivated in Alice, Eastern Cape of South Africa over a period of 12 months using the solvent-free microwave extraction and traditional hydrodistillation methods were evaluated. The GC-MS analyses of the essential oils revealed the presence of 33 compounds with 1,8-cineole, a-pinene, camphor, verbenone, bornyl acetate and camphene constituting about 80 percent of the oils throughout the period of investigation, with the solvent-free microwave extraction method generally yielding more of the major components than the hydrodistillation method. Each of the major components of the oils varied in quantity and quality of yield at different periods of the year. The method of extraction and time of harvest are of importance to the quantity and quality of essential oil of Rosmarinus officinalis. Higher amounts of oxygenated monoterpenes such as borneol, camphor, terpene- 4-ol, linalool, a-terpeneol were present in the oil of SFME in comparison with HD. However, HD oil contained more monoterpene hydrocarbons such as a-pinene, camphene, β-pinene, myrcene, a-phellanderene, 1,8-cineole, trans- β-ocimene, γ-teprinene, and cis-sabinene hydrate than SFME extracted oil. Accumulation of monoterpene alcohols and ketones was observed during maturation process of Rosmarinus leaves. Quantitative evaluation of antibacterial activity, minimum inhibitory concentration values were determined using a serial microplate dilution method. The essential oils obtained using both methods of extraction were active against all the bacteria tested at a concentration of 10 mg mL-1. The minimum inhibitory concentrations for the SFME extracted oils ranged between 0.23 and 1.88 mg mL-1, while those of the HD extracted oils varied between 0.94 and 7.5 mg mL-1, thus suggesting that the oil obtained by solvent free microwave extraction was more active against bacteria than the oil obtained through hydrodistillation. The antioxidant and free radical scavenging activity of the obtained oils were tested by means of 1,1-diphenyl-2-picrylhydrazyl radical (DPPH+) assay and β- carotene bleaching test. In the DPPH+ assay, while the free radical scavenging activity of the oil obtained by SFME method showed percentage inhibitions of between 48.8 percent and 67 percent, the HD derived oil showed inhibitions of between 52.2 percent and 65.30 percent at concentrations of 0.33, 0.50 and 1.0 mg mL-1, respectively. In the β-carotene bleaching assay, the percentage inhibition increased with increasing concentration of both oils with a higher antioxidant activity of the oil obtained through the SFME than the HD method. Thin layer chromatography (TLC) was used to analyze the chemical composition of the extracts using three eluent solvent systems of varying polarities i. e. CEF, BEA and EMW and sprayed with vanillin-sulfuric acid. The chemical composition of the different extracts was similar with the exception of methanol and water extracts which had only one or two visible compounds after treating with vanillin-spray reagent. To evaluate the number of antibacterial compounds present in the fractions, bioautography was used against two most important nosocomial microorganisms. S. aureus (Gram positive) and E. coli (Gram negative). Nearly all the crude serial extraction fractions contained compounds that inhibited the growth of E. coli. The hexane extract had the most lines of inhibition followed by ethyl acetate. Bioassay-guided fractionation against E. coli was used to isolate antibacterial compounds. The largest number of antibacterial compounds occurred in the hexane fraction. Furthermore we tried to complete the characterization by extracting and studying other biologically important plant metabolites such as phenolic compounds to evaluate the antioxidant capacity of Rosmarinus extracts.

For the last fifteen years, research on students' conceptions of physical phenomena has been directing our attention to the value of knowing and considering children's prior ideas in science teaching. Although many who are concerned with science education are aware of and see wisdom in this perspective of teaching, there are many realities, including the content of the discipline, that pose great challenges in translating it into practice in science classes. Currently, in collaboration with teachers, science educators are actively conducting classroom studies. In this process, teachers as researchers are making reflective inquiries into their own students' learning. This study followed a similar framework of research at a microcosmic level. It entailed elicitation of thirteen Grade 11 students' individual prior conceptions of solubility and a teacher-researcher collaboration to incorporate these conceptions in the instruction of a unit on solution chemistry. Consequently, the study presents a phenomenography of solubility, narrates a story about classroom instruction which took students' conceptions into consideration, reports four case studies on students' conceptual growth and changes, and outlines some of the factors that facilitate or constrain collaborative teaching that focuses on student understanding of subject matter. The students' prior conceptions of solubility were categorized into six categories of description: 1. physical transformation from solid to liquid 2. chemical transformation of solute 3. density of solute 4. amount of space available in solution 5. properties of solute 6. size of solute particles With regard to learning chemistry, these conceptualizations made clear four issues: (1) students' explanations were bounded by their perceptions, (2) students extended macroscopic explanations to a microscopic level, (3) students made inappropriate links to previous chemistry learning, and (4) students used the language of chemistry non-discriminately. After studying a unit on solution chemistry, two more categories of description were added to the pre-instructional categories: 1. chemical structure of components 2. solution equilibrium After instruction, the students attributing to the initial six categories of description' diminished in number. The newly acquired conceptions of solubility reflected insufficient explanatory power and were merely overlaid with the chemical language. Learning the language of solution chemistry and acquiring some theoretical understanding of it were reflected in the change between pre- and post-instructional conceptions. This conceptual change can be considered as evolutionary. It was inferred that the abstract and ambiguous nature of chemical theories and principles sets limits to conceptual change teaching. The influences that facilitated the collaborative efforts include: (1) the teacher's attempts to incorporate students' conceptions, (2) the teacher's openness and willingness to assess her own methods of teaching chemistry, (3) the teacher's reflections about the researcher's constructivist teaching, and (4) the researcher's active participation in the classroom interactions. The four most important influences that seriously constrained the collaborative efforts to link students' conceptions with formal chemistry were: (1) the lack of time to devote to the topic of solution chemistry, (2) the lack of teacher time to plan lessons together in order to incorporate students' conceptions, (3) the lack of practical experience on the part of both the researcher and the teacher in developing specific teaching strategies which acknowledged students' prior belief in this content area, and (4) the lack of time to develop common perspectives and a shared language. This study has implications for both teachers and researchers. Specifically, it implies that students' conceptions form an integral component of chemistry instruction—as points of origin for lesson planning and development of curricular materials It also implies that through science educators' modelling and practising in their "teaching and learning" courses, pre- and in-service teachers be challenged to seek answers for epistemological questions such as: What is chemical knowledge? and, How is it acquired? A general implication is that both teachers and researchers, rather than being fence-makers, must strive to be bridge-builders so that they can be learners of each other's theoretical and practical experiences. / Education, Faculty of / Curriculum and Pedagogy (EDCP), Department of / Graduate

The dissertation consists of the following three sections: 1. Hydroxyapatite (HA) coatings. In this work, we deposited HA precursor films from weak basic electrolytic solution (pH= 8-9) via an electrochemical approach; the deposits were changed into crystallite coatings of hydroxyapatite by sintering at specific temperatures (600-800 ºC). The formed coatings were mainly characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). XRD patterns show well-defined peaks of HA when sintered under vacuum conditions. FTIR measurements indicate the existence of hydroxyl groups, which were confirmed by the characteristic intensity of the stretching and bending bands at ~3575 and ~630 cm-1, respectively. The SEM shows an adhesive, crack free morphology for the double-layer coating surface of the samples sintered in a vacuum furnace. 2. Silver/polymer/clay nanocomposites. Silver nanoparticles were prepared in layered clay mineral (montmorillonite)/polymer (PVP: poly (vinyl pyrrolidone)) suspension by an electrochemical approach. The silver particles formed in the bulk suspension were stabilized by the PVP and partially exfoliated clay platelets, which acted as protective colloids to prevent coagulation of silver nanoparticles together. The synthesized silver nanoparticles/montmorillonite/PVP composite was characterized and identified by XRD, SEM, and TEM (transmission electron microscopy) measurements. 3. Ce-doped lead zirconate titanate (PZT) thin films. In this study, we fabricated cerium-doped PZT films (molar ratio of Zr/Ti:: 0.5:0.5) via cathodic electrodeposition on the indium tin oxide ( ITO) coated glass substrate. In the preparation process, the PZT films were modified by adding a small amount of cerium dopants, which led to the formation of Ce-doped PZT films after sintering at high temperatures. The fabricated PZT films on the ITO coated glass substrate may be used as electro-optic devices in the industrial application.

It is the purpose of this work to study the solubility of naphthalene, the simplest polycyclic aromatic hydrocarbon as a function of the salt content and the temperature, in ranges that span those likely to be found in natural ecosystems. Another goal is to set up a high-pressure generator, to study the effect of pressure on the solubility of hydrocarbons.

The temperature dependence of the refractive index and the density of aqueous binary mixtures of water and ethyl alcohol (C₂H₅OH) were measured by using a modified Michelson interferometer and a narrow glass capillary tube over the temperature range of 278≤T≤353 K for solutions of 100, 75,65, 50, 25, 10 and 0 volume percent ethyl alcohol. The temperature was cycled over both increasing and decreasing directions to explore hysteresis in the cycling. The data are discussed and compared with the Lorentz-Lorenz (LL) formula. A more accurate formula which fits the experimental data better than the LL relation was derived. An attempt was made to determine the nature of the solvent-solute interaction through any changes that were found in the refractive index for He-Ne laser light and IR diode signals and to analyze the refractive index and density results to test the accuracy of the available mixing rules in predicting the refractive index values and the density of binary systems. Conductivity measurements (d. c.) over the temperature range 278≤T≤353 K of aqueous solutions of NaCl at various concentrations were made and used to establish transport properties of ions in solution. The dynamical properties of the electrolytes were used to establish the nature of hydrogen bonding in aqueous binary mixture systems. Rate equations for ion formation and recombination were used to establish the temperature ranges in which hydrogen bonding dominated in forming polymeric species. From experimental data on the binary mixtures with water, a better understanding of water in its different functions and aggregation is possible. The water molecule itself and its response to the environment are understood when suitable studies are made of the forces in the system. In this work, some qualitative aspects of the interactions and dynamics of the water molecule have been investigated. Classical molecular dynamics simulations were tried to explain some of the thermodynamical properties of the water molecule.

<p>    </p> <p>Surface functionalization of metallic nanoparticles is an attractive route to tailor the ensemble geometry and redox properties of active sites in heterogeneous catalysts. However, it is challenging to generate well-defined interfaces through conventional impregnation and one-pot colloidal synthesis methods. In this work, we utilize ligand exchange reactions for post synthetic surface modification of colloidal nanoparticles to generate unique core-shell and surface alloy structures. We use halometallate and metal chalcogenide complexes to create surface sites that are active for electrocatalytic hydrogen evolution reaction (HER). </p> <p>We synthesize a self-limiting monolayer of metal chalcogenides on colloidal Au nanoparticles through biphasic ligand exchange reaction between ammonium tetrathiomolybdate (NH₄)₂MoS₄ complex and Au nanoparticles. Through a combination of spectroscopy techniques and computational methods, we show that strong Au-S interactions introduce electronic and geometric distortion to the geometry and bond metrics of MoS₄^2-complex. Moreover, proximal MoS₄ units adsorbed on the Au surface interlink to form small MoSx oligomers with highly active bridging disulfide sites. Consequently, these core-shell AuMoS₄ nanoparticles exhibit significantly higher HER activity than MoS₄^2- supported on non-interacting carbon supports under highly acidic electrolyte conditions. Although post catalysis characterization reveals partial hydrolysis of surface adsorbed MoSx species, stable HER activity under bulk electrolysis condition indicates that active sites remain persistent. </p> <p>In an effort to extend these ligand exchange reactions to create metal/metal interfaces on other coinage metal nanoparticles such as Ag, we design metal-ligand coordination complexes to mitigate undesired galvanic replacement reactions. By varying the strength and number of coordinating ligands, we fine-tune the redox potential of oxidized noble metal precursors and confine the deposition of noble metals to a few surface layers of the Ag nanoparticles. We utilize organic amine and phosphine ligands to generate Ag@AgM core-shell nanoparticles, where M = Pd, Pt, and Au. Surface alloy or pure metal shells of Pd and Pt on Ag nanoparticles generated through this ligand-based strategy exhibited high precious metal atom utilization in electrocatalytic hydrogen evolution reaction. </p>

The purpose of this dissertation is to investigate the thermochemical properties of nonelectrolyte solutes dissolved in ternary solvent mixtures, and to develop mathematical expressions for predicting and describing behavior in the solvent mixtures. Forty-five ternary solvent systems were studied containing an ether (Methyl tert-butyl ether, Dibutyl ether, or 1,4-Dioxane), an alcohol (1-Propanol, 2-Propanol, 1-Butanol, 2-Butanol, or 2-Methyl-1-propanol), and an alkane (Cyclohexane, Heptane, or 2,2,4-Trimethylpentane) cosolvents. The Combined NIBS (Nearly Ideal Binary Solvent)/Redlich-Kister equation was used to assess the experimental data. The average percent deviation between predicted and observed values was less than ± 2 per cent error, documenting that this model provides a fairly accurate description of the observed solubility behavior. In addition, Mobile Order theory, the Kretschmer-Wiebe model, and the Mecke-Kempter model were extended to ternary solvent mixtures containing an alcohol (or an alkoxyalcohol) and alkane cosolvents. Expressions derived from Mobile Order theory predicted the experimental mole fraction solubility of anthracene in ternary alcohol + alkane + alkane mixtures to within ± 5.8%, in ternary alcohol + alcohol + alkane mixtures to within ± 4.0%, and in ternary alcohol + alcohol + alcohol mixtures to within ± 3.6%. In comparison, expressions derived from the Kretschmer-Wiebe model and the Mecke-Kempter model predicted the anthracene solubility in ternary alcohol + alkane + alkane mixtures to within ± 8.2% and ± 8.8%, respectively. The Kretschmer-Wiebe model and the Mecke-Kempter model could not be extended easily to systems containing two or more alcohol cosolvents.