Abstract

No description available.

Herein we describe a straight-forward and reproducible method for the preparation of homogeneous, multicomponent cocrystals and supramolecular solid solutions. We prepared these multicomponent materials based on small organic molecules that employ a two-point supramolecular hydrogen bond synthon. We report the creation and characterization of two, three, four, five, and seven component crystals containing a variety of 2-aminopyridines and monosubstituted benzoic acids. These systems exhibit the ability to accommodate multiple components in varying proportions while coordinating into an identical packing structure. The flexibility of the system to incorporate multiple components also gives rise to gradual modulation of physical properties.

This thesis is submitted as a portfolio of peer-reviewed publications. / For many geochemical systems, reaction kinetics determines the system's current status and evolution. It might also be the key to unraveling their thermal history. In metal sulfide systems, kinetic studies have been carried out on four sets of solid-state transitions/transformations in Fe-Ni-S and Ni-S systems. In this work, a new kinetic model, the Refined Avrami method, has been developed to account for reactions involving changes in reaction mechanisms. Nonstoichiometric compounds are commonly present in these reactions. The exsolution of pentladite from the monosulfide solid solution (mss) is an important reaction in the formation of nickel ores. For near equimolar mss compositions, the reaction rate is rapid even in the low temperature ranges. For bulk composition Fe₀.₇₇ Ni₀.₁₉ S, the experimental results show the reaction rates ( mss → pentlandite ) vary from 1.6x10⁻⁵ to 5.0x10⁻⁷ s⁻¹ at 200 °C and from 9.4x10⁻⁵ to 4.1x10⁻⁷ s⁻¹ at 300 °C. The activation energy, E [subscript a], varies during the course of reaction from 49.6 kJ.mol⁻¹ at the beginning of reaction (nucleation mechanism is dominant) to 20.7 kJ.mol⁻¹ at the end (crystal growth mechanism is dominant). Monosulfide solid solution (mss) is a common intermediate phase observed during the oxidation of nickel ores, such as violarite and pentlandite. The investigation of mss oxidation is of benefit in understanding the thermal behavior of economically important metal sulfides during smelting. The oxidation products of mss vary in our samples depending on their compositions. Apart from the common oxidation products hematite and Ni₁ ₇ S₁₈, Fe₂ (SO₄) ₃ was observed during the oxidation of Fe₇ . ₉ S₈ and pentlandite for Fe₆ . ₁ ₅Ni₁ . ₅₄ S₈ . The activation energy was determined using a model-free method. The oxidation of Fe₆.₄ Ni₁.₆ S₈ exhibited a higher E [subscript a] than Fe₆ . ₁ ₅Ni₁ . ₅₄ S₈ over the course of the reaction. The E [subscript a] increases with reaction extent (y) from 67.1 to 103.3 kJ.mol⁻¹ for mss composition Fe₆ . ₁ ₅Ni₁ . ₅₄ S₈ and from 76.1 to 195.0 kJ.mol⁻¹ for Fe₆.₄ Ni₁.₆ S₈ . The kinetic study of the α - Ni₁₋ ₓ S → β - NiS transition shows that initial compositions of α - Ni₁₋ ₓ S plays an important role in the kinetics of the transition. The activation energy ( E [subscript a] ) for this α - to β - phase transition is 16.0 ( ± 0.5 ) kJ.mol⁻¹ for NiS in the temperature range 70 to 150 °C, and 13.0 (± 0.5) kJ.mol⁻¹ in the temperature range 250 to 350 °C. For Ni₀. ₉₇ S, however, E [subscript a] deceases from 73.0 ( ± 0.5 ) to 17.0 ( ± 0.5 ) kJ.mol⁻¹ over the course of the reaction in the temperature range 300 to 320 °C. The relationship between E [subscript a] and extent of transition (y) for the initial bulk Ni₀. ₉₇ S was derived using the Refined Avrami method. For Ni deficient compositions, α - Ni₁₋ₓ S, the transformation to β-NiS is accompanied by the exsolution of either a progressively more Ni deficient α-Ni₁₋ₓ S and Ni₃ S₄ , and the reactions become more sluggish for more metal deficient compositions. The study of oxidation kinetics of α-NiS is of metallurgical interest, as α-NiS related phases may occur when nickel ores are flash smelted to produce nickel matte. In an open air environment, the oxidation mechanisms of α-NiS are constant at 670 and 680 °C, dominated by the direct oxidation of α-NiS → NiO. The dominant oxidation mechanism changes to a chain reaction : α-NiS → [superscript k] ₁ Ni₃ S₂ → [superscript k] ₂ NiO at 700 °C. Therefore, different kinetic models need to be applied to these two distinct reaction mechanisms. Activation energy for the oxidation, α-NiS → NiO, in the temperature range 670 to 680 °C was calculated to be 868.2 kJ.mol⁻¹ using Avrami/Arrhenius method. Rate constant k₁ and k₂ are approximated to be 3 x 10⁻⁴ s⁻¹ and 5 x 10⁻⁴ s⁻¹ for the first part and second part of the chain reaction respectively at 700 ° C. The study of the variation in reaction rate with oxidation time illustrates the optimum oxidation time zone for each temperature, where NiO can be produced at the fastest rate. / Thesis (Ph.D.) -- University of Adelaide, School of Chemical Engineering, 2005.

The jarosite group of minerals is part of the alunite supergroup, which consists of more than 40 different mineral species that have the general formula AB3(TO4)2(OH, H2O)6. There is extensive solid-solution in the A, B and T sites within the alunite supergroup. Jarosite group minerals are common in acid mine waste and there is evidence of jarosite existing on Mars. Members of the jarosite - natrojarosite – hydronium jarosite (K,Na, H3O)Fe3(SO4)2(OH)6 solid-solution series were synthesized and investigated by Rietveld analysis of X-ray powder diffraction data. The synthesized samples have full iron occupancy, where in many previous studies there was significant vacancies in the B site. Well-defined trends can be seen in the unit cell parameters, bond lengths A – O and Fe - O across the solid-solution series in the synthetic samples. Based on unit cell parameters many natural samples appear to have full iron occupancy and correlate well with the synthetic samples from this study. In addition, the infrared spectra of the samples were analyzed. The atomic structure of ammoniojarosite, (NH4)Fe3(SO4)2(OH)6, has been solved using single-crystal X-ray diffraction to wR 3.64% and R 1.4%. The atomic coordinates of the hydrogen atoms of the NH4 group have been located and it was found that the ammonium group has two different orientations with equal probability. Samples in the ammoniojarosite – hydronium jarosite solid-solution series were synthesized and analyzed using powder X-ray diffraction and Rietveld refinement. It was found that an incomplete solid-solution series exists between jarosite and plumbojarosite, Pb[Fe3(SO4)2(OH)6]2, based on experimental and mineralogical data. At the studied synthesis conditions, lead solubility in jarosite is extremely limited with occupancy of 2% in the potassium site. Increased Pb in the iv starting solution resulted in no increased substitution of Pb into jarosite, but an increased substitution of H3O+. The stable isotope (H) geochemistry of hydronium jarosite, (H3O,K)Fe3(SO4)2(O,OH)6, and the effect that the presence of hydronium in the crystal structure has on exchange rates of stable isotope values of jarosite with hydronium substitution has been investigated in this study. / Thesis (Ph.D, Geological Sciences & Geological Engineering) -- Queen's University, 2008-05-07 18:21:45.136

This thesis is submitted as a portfolio of peer-reviewed publications. / For many geochemical systems, reaction kinetics determines the system's current status and evolution. It might also be the key to unraveling their thermal history. In metal sulfide systems, kinetic studies have been carried out on four sets of solid-state transitions/transformations in Fe-Ni-S and Ni-S systems. In this work, a new kinetic model, the Refined Avrami method, has been developed to account for reactions involving changes in reaction mechanisms. Nonstoichiometric compounds are commonly present in these reactions. The exsolution of pentladite from the monosulfide solid solution (mss) is an important reaction in the formation of nickel ores. For near equimolar mss compositions, the reaction rate is rapid even in the low temperature ranges. For bulk composition Fe₀.₇₇ Ni₀.₁₉ S, the experimental results show the reaction rates ( mss → pentlandite ) vary from 1.6x10⁻⁵ to 5.0x10⁻⁷ s⁻¹ at 200 °C and from 9.4x10⁻⁵ to 4.1x10⁻⁷ s⁻¹ at 300 °C. The activation energy, E [subscript a], varies during the course of reaction from 49.6 kJ.mol⁻¹ at the beginning of reaction (nucleation mechanism is dominant) to 20.7 kJ.mol⁻¹ at the end (crystal growth mechanism is dominant). Monosulfide solid solution (mss) is a common intermediate phase observed during the oxidation of nickel ores, such as violarite and pentlandite. The investigation of mss oxidation is of benefit in understanding the thermal behavior of economically important metal sulfides during smelting. The oxidation products of mss vary in our samples depending on their compositions. Apart from the common oxidation products hematite and Ni₁ ₇ S₁₈, Fe₂ (SO₄) ₃ was observed during the oxidation of Fe₇ . ₉ S₈ and pentlandite for Fe₆ . ₁ ₅Ni₁ . ₅₄ S₈ . The activation energy was determined using a model-free method. The oxidation of Fe₆.₄ Ni₁.₆ S₈ exhibited a higher E [subscript a] than Fe₆ . ₁ ₅Ni₁ . ₅₄ S₈ over the course of the reaction. The E [subscript a] increases with reaction extent (y) from 67.1 to 103.3 kJ.mol⁻¹ for mss composition Fe₆ . ₁ ₅Ni₁ . ₅₄ S₈ and from 76.1 to 195.0 kJ.mol⁻¹ for Fe₆.₄ Ni₁.₆ S₈ . The kinetic study of the α - Ni₁₋ ₓ S → β - NiS transition shows that initial compositions of α - Ni₁₋ ₓ S plays an important role in the kinetics of the transition. The activation energy ( E [subscript a] ) for this α - to β - phase transition is 16.0 ( ± 0.5 ) kJ.mol⁻¹ for NiS in the temperature range 70 to 150 °C, and 13.0 (± 0.5) kJ.mol⁻¹ in the temperature range 250 to 350 °C. For Ni₀. ₉₇ S, however, E [subscript a] deceases from 73.0 ( ± 0.5 ) to 17.0 ( ± 0.5 ) kJ.mol⁻¹ over the course of the reaction in the temperature range 300 to 320 °C. The relationship between E [subscript a] and extent of transition (y) for the initial bulk Ni₀. ₉₇ S was derived using the Refined Avrami method. For Ni deficient compositions, α - Ni₁₋ₓ S, the transformation to β-NiS is accompanied by the exsolution of either a progressively more Ni deficient α-Ni₁₋ₓ S and Ni₃ S₄ , and the reactions become more sluggish for more metal deficient compositions. The study of oxidation kinetics of α-NiS is of metallurgical interest, as α-NiS related phases may occur when nickel ores are flash smelted to produce nickel matte. In an open air environment, the oxidation mechanisms of α-NiS are constant at 670 and 680 °C, dominated by the direct oxidation of α-NiS → NiO. The dominant oxidation mechanism changes to a chain reaction : α-NiS → [superscript k] ₁ Ni₃ S₂ → [superscript k] ₂ NiO at 700 °C. Therefore, different kinetic models need to be applied to these two distinct reaction mechanisms. Activation energy for the oxidation, α-NiS → NiO, in the temperature range 670 to 680 °C was calculated to be 868.2 kJ.mol⁻¹ using Avrami/Arrhenius method. Rate constant k₁ and k₂ are approximated to be 3 x 10⁻⁴ s⁻¹ and 5 x 10⁻⁴ s⁻¹ for the first part and second part of the chain reaction respectively at 700 ° C. The study of the variation in reaction rate with oxidation time illustrates the optimum oxidation time zone for each temperature, where NiO can be produced at the fastest rate. / Thesis (Ph.D.) -- University of Adelaide, School of Chemical Engineering, 2005.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第20603号 / 理博第4318号 / 新制||理||1620(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 北川 宏, 教授 竹腰 清乃理, 教授 吉村 一良 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第21248号 / 理博第4418号 / 新制||理||1634(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 北川 宏, 教授 吉村 一良, 教授 竹腰 清乃理 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

The adsorption and desorption behavior of trace element contaminants was evaluated solids—goethite and ruthenium oxide. The importance of anion displacement as a mechanism responsible for arsenic release from iron oxides was investigated on goethite. The adsorption and polymerization of silicate on goethite was examined as a function of surface concentration determine the influence of adsorbed silicate monomers and polymers on arsenite adsorption desorption. A kinetic model was employed to describe arsenite adsorption and desorption absence and presence of silicate. The potential environmental impacts of the research discussed. Hydrous and crystalline ruthenium oxides were extensively characterized traditional colloidal surface characterization techniques, dissolution experiments, and macro- spectroscopic experiments. The two ruthenium oxide phases exhibited large specific areas, a high density of reactive surface functional groups and the presence of multiple oxidation states in both solids. Enhanced dissolution of hydrous ruthenium oxide occurred presence of oxalate and ascorbate. While enhanced dissolution of the crystalline phase only in the presence of oxalate at pH 3. Results from the dissolution experiments were develop possible mechanisms for the oxalate and ascorbate promoted dissolution of ruthenium oxides. Macroscopic adsorption studies of arsenate adsorption on both ruthenium oxides examined over a broad pH (3-10) and initial solution concentration range (0.01 to Results from the adsorption studies indicate arsenate forms a stable surface complex with ruthenium oxide phases. Extended x-ray absorption fine structure spectroscopy and Pressure-jump relaxation studies indicates arsenate is specifically adsorbed the ruthenium oxide Chromate adsorption on ruthenium oxides was investigated as a function of pH and chromate solution concentration. Macroscopic adsorption studies and zeta measurements suggest chromate forms an inner-sphere surface complex with both oxide X-ray absorption near edge spectroscopy data indicates chromate (Cr(VI)) is reduced chromium (Cr(III)) on the ruthenium oxide surface. Modeling of the first Cr shell indicated two oxygen backscattering distances similar to the Cr-O atomic distances reported for coordinated to Cr(VI) and Cr(III) providing additional evidence for Cr(VI) reduction. / Ph. D.

Doctor of Philosophy / Department of Mechanical and Nuclear Engineering / Douglas S. McGregor / Strengthening the crystal lattice of lanthanide halides, which are brittle, anisotropic, ionic crystals may increase the availability and ruggedness of these scintillators for room-temperature γ-ray spectroscopy applications. Eight dopants for CeBr[subscript]3, including CaBr[subscript]2, SrBr[subscript]2, BaBr[subscript]2, ZrBr[subscript]4, HfBr[subscript]4, ZnBr[subscript]2, CdBr[subscript]2, and PbBr[subscript]2, were explored at two different doping levels, 500ppm and 1000ppm, in an effort to identify potential aliovalent strengthening agents which do not adversely affect scintillation performance. All dopants and doping levels exhibited improved ingot yields over the undoped case, indicating an improvement in the ease of crystal growth. Scintillation performance was gauged using four key metrics. Scintillation emission spectra or, rather, radioluminescence spectra were recorded using x-ray irradiation. Total light yield was estimated through pulse height comparison with bismuth germanate (BGO) scintillators. Scintillation kinetics were checked by measuring single interaction pulses directly output by a fast response PMT. Finally, light yield proportionality was measured using a Compton coincidence system. Samples from each ingot were harvested to benchmark their performance with the four metrics. Of the eight dopants explored, only BaBr[subscript]2 and PbBr[subscript]2 clearly altered scintillation spectral emission characteristics significantly. The remaining dopants, CaBr[subscript]2, SrBr[subscript]2, ZrBr[subscript]4, HfBr[subscript]4, CdBr[subscript]2 and ZnBr[subscript]2, altered scintillation performance to a lesser degree. No dopant appeared to affect light yield proportionality, nor did any drastically alter the light decay characteristics of CeBr[subscript]3. HfBr[subscript]4 and ZnBr[subscript]2-doped CeBr[subscript]3 exhibited the highest light yields, significantly higher than the undoped CeBr[subscript]3 samples tested. Finally, aliovalent doping appeared to greatly improve CeBr[subscript]3 ingot yields, regardless of the dopant, thus it is a promising method for improving crystal strength while not deleteriously affecting scintillation performance. HfBr[subscript]4 and ZnBr[subscript]2 both demonstrated high performance without any noticeable negative side-effects and are prime candidates for future study.