Thesis (Ph.D.)--Mississippi State University. Department of Mechanical Engineering. / Title from title screen. Includes bibliographical references.

<p> Inclement challenges of a changing climate and humanity's desire to explore extraterrestrial environments both necessitate efficient methods to obtain freshwater. To accommodate next generation water technology, there is a need for understanding and defining the energy efficiency for unconventional water sources over a broad range of environments. Exergy analysis provides a common description for efficiency that may be used to evaluate technologies and water sources for energy feasibility. This work uses robust thermodynamic theory coupled with atmospheric and planetary data to define water capture efficiency, explore its variation across climate conditions, and identify technological niches and development needs.  </p> <p><br></p> <p> We find that desalinating saline liquid brines, even when highly saline, could be the most energetically favorable option for obtaining water outside of Earth. The energy required to access water vapor may be four to ten times higher than accessing ice deposits, however it offers the capacity for decentralized systems. Considering atmospheric water vapor harvesting on Earth, we find that the thermodynamic minimum is anywhere from 0x (RH≥ 100%) to upwards of 250x (RH<10\%) the minimum energy requirement of seawater desalination. Sorbents, modelled as metal organic frameworks (MOFs), have a particular niche in arid and semi-arid regions (20-30%). Membrane-systems are best at low relative humidity and the region of applicability is strongly affected by the vacuum pumping efficiency. Dew harvesting is best at higher humidity and fog harvesting is optimal when super-saturated conditions exist. Component (e.g., pump, chiller, etc.) inefficiencies are the largest barrier in increasing process-level efficiency and strongly impact the regions optimal technology deployment. The analysis elucidates a fundamental basis for comparing water systems energy efficiency for outer space applications and provides the first thermodynamics-based comparison of classes of atmospheric water harvesting technologies on Earth.</p>

Many industrial processes have low-temperature waste heat sources that cannot be efficiently recovered. Low grade waste heat has generally been discarded by industry and has become an environmental concern because of thermal pollution. This has led to the lookout for technologies which not only reduce the burden on the non-renewable sources of energy but also take steps toward a cleaner environment. One approach which is found to be highly effective in addressing the above mentioned issues is the Organic Rankine Cycle (ORC), which can make use of low- temperature waste heat to generate electric power. Similar in principle to the conventional cycle, ORC is found to be superior performance-wise because of the organic working fluids used in the cycle. The focus of this study is to examine the ORC using different types of organic fluids and cycle configurations. These organic working fluids were selected to evaluate the effect of the fluid boiling point temperature and the fluid classification on the performance of ORCs. The results are compared with those of water under similar conditions. In order to improve the cycle performance, modified ORCs are also investigated. Regenerative ORCs are analyzed and compared with the basic ORC in order to determine the configuration that presents the best thermal efficiency with minimum irreversibility. The evaluation for both configurations is performed using a combined first and second law analysis by varying certain system operating parameters at various reference temperatures and pressures. A unique approach known as topological method is also used to analyze the system from the exergy point of view. Effects of various components are studied using the exergy-wheel diagram. The results show that ORCs using R113 as working fluid have the best thermal efficiency, while those using Propane demonstrate the worse efficiency. In addition, results from these analyses demonstrate that regenerative ORCs produce higher efficiencies compared to the basic ORC. Furthermore, the regenerative ORC requires less waste heat to produce the same electric power with a lower irreversibility.

Typescript (photocopy). / Digitized by Kansas Correctional Industries

Thesis (PhD)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: Recent developments in the atmospheric treatment of low-grade nickel laterite ores at Anglo American plc has culminated in the conceptual iron-focused laterite (ARFe) process. In addition to the recovery of nickel and cobalt from laterite ore, this process uniquely aims to recover iron as a saleable by-product. The reduction of soluble iron(III) (Fe(III)) by sulfur dioxide gas (SO2) is central to the ARFe concept and represents a complex, multiphase system involving simultaneous gas-liquid mass transfer, thermodynamic speciation and chemical reaction. The chemistry of iron-containing systems is generally poorly understood and accurately predicting their behaviour is challenging, especially under aggressive hydrometallurgical conditions. The primary objective of this work is the development of an engineering model capable of describing the rate and extent of ferric reduction with SO2 under conditions typical of the ARFe process. Thermodynamic considerations provide a rigorous framework for the interpretation of chemical reactions, however little experimental data are openly available for the associated solution species in acidic iron sulfate systems. A key contribution of this work, and critical for the development of the overall model, is the direct measurement of speciation in iron sulfate solutions. Raman and UV-vis spectroscopy were utilised to make direct speciation measurements in the various subsystems of the Fe2(SO4)3-FeSO4-H2SO4-H2O system that were previously unavailable in the open literature. The FeSO+4 and Fe(SO4)– 2 species were explicitly identified and measurements were supported and rationalised by static computational quantum mechanical calculations and ultimately permit the calibration of a robust, ion-interaction solution model with the explicit recognition of the important solution species up to 1.6 mol/kg Fe2(SO4)3, 0.8 mol/kg H2SO4 over 25 – 90 C. Batch and continuous Fe(III) reduction kinetics were measured and the effects of initial Fe2(SO4)3 and H2SO4 concentrations, temperature and in-situ neutralisation quantified. The retardation effect of sulfuric acid was observed to be the most significant factor influencing the initial reaction rate and the achievable extent of reduction at fixed residence time, which varied between about 20 and 80 % after 180 minutes of reaction. A reaction mechanism that is limited by the slow ligand-to-metal electron transfer in the FeIIISO+3 solution species’ decomposition is proposed and spectroscopic measurements and computational quantum mechanical calculations are used to support this mechanism. A kinetic model, comprising a system of differential mass-balance equations, is incorporated into the thermodynamic framework. This reaction model permits the prediction of kinetic profiles over the full range of experimental conditions and can be incorporated into more elaborate simulation models of the ARFe circuit. The specific original contributions of this work are • The direct measurement of aqueous speciation in the Fe2(SO4)3-H2SO4-H2O system by Raman and UV-vis spectroscopy • The development of a modelling framework to characterise speciation, activity coefficients and solubility in the mixed Fe2(SO4)3-FeSO4-H2SO4-H2O system. • The measurement of Fe(III) reduction kinetics using SO2 in concentrated sulfate solutions as a function of initial composition and temperature. • The development of a solution reaction model of Fe(III) reduction with SO2 that accurately predicts the solution speciation and reaction rate with time as a function of composition and temperature. Lastly, the vast complexity of industrial systems will nearly always result in a lack of specific experimental data that are required for the development of phenomenological models. This work emphasises the crucial role that engineering studies hold in the generation of such data to derive maximum practical value for industrial process development and optimisation. / AFRIKAANSE OPSOMMING: Onlangse ontwikkelinge in die atmosferiese behandeling van lae-graad nikkel lateriet erts by Anglo American plc het gelei tot die konseptuele yster gefokus lateriet (ARFe) proses. Bykommend tot die herwinning van nikkel en kobalt uit laterite erts is hierdie proses uniek en daarop gemik om yster te herwin as ’n verkoopbare by-produk. Die vermindering van oplosbare yster(III) (Fe(III)) met swaeldioksied (SO2) is sentraal tot die ARFe konsep en verteenwoordig ’n komplekse, multifase stelsel wat gelyktydige gas-vloeistof massa-oordrag, termodinamiese spesiasie en chemiese reaksie behels. Die oplossingschemie van ysterstelsels word, oor die algemeen, swak verstaan en om hul gedrag akuraat te voorspel is ’n uitdaging, veral onder aggressiewe hidrometallurgiese kondisies. Die primêre doel van hierdie werk is die ontwikkeling van ’n ingenieursmodel wat die tempo en omvang van yster(III) vermindering met SO2 onder tipiese ARFe proses toestande beskryf. Termodinamiese oorwegings stel ’n streng raamwerk voor vir die interpretasie van chemiese reaksies, alhoewel daar egter min eksperimentele data openlik beskikbaar is vir die gepaardgaande oplossing spesies in suur yster(III) sulfaat stelsels. ’n Belangrike bydrae van hierdie werk, en van kritieke belang vir die ontwikkeling van die algehele model, is die direkte meting van spesiasie in yster(III) sulfaat oplossings. Raman en UV-vis spektroskopie is gebruik om direkte spesiasie metings te maak in die verskillende subsisteme van die Fe2(SO4)3-FeSO4-H2SO4-H2O stelsel wat voorheen nie in die oop literatuur beskikbaar was nie. Die FeSO+4 en Fe(SO4)– 2 spesies is ekplisiet geïdentifiseer, terwyl die metings ondersteun en gerasionaliseer is deur statiese kwantummeganiese berekeninge wat uiteindelik die kalibrasie van ’n robuuste, ioon-interaksie model tot gevolg hê wat ook die belangrike oplossingspesies duidelik beklemtoon tot en met 1.6 mol/kg Fe2(SO4)3, 0.8 mol/kg H2SO4 en tussen 25 – 90°C. Enkellading en kontinue yster(III) verminderingskinetika is gemeet en die gevolge van die aanvanklike Fe2(SO4)3 en H2SO4 konsentrasies, temperatuur en in-situ neutralisasie is gekwantifiseer. Die waargeneemde vertragingseffek van swaelsuur is die mees beduidende faktor wat die aanvanklike reaksietempo en die haalbare reaksie omvangsvermindering na ’n vaste residensietyd van 180 minute bepaal, wat wissel tussen ongeveer 20 en 80%. ’n Reaksiemeganisme word voorgestel wat beperk word deur die stadige ligand-totmetaal elektronoordrag in ontbinding van die Fe(III)SO+3 oplossing-spesies en wat verder deur spektroskopiese metings en kwantummeganiese berekenings ondersteun word. A kinetiese model, wat bestaan uit ’n stelsel van gedifferensieerde massa-balans vergelykings, is in die termodinamiese raamwerk geïnkorporeer. Hierdie reaksie-model laat die voorspelling van kinetiese profiele toe oor die volle omvang van die eksperimentele toestande en kan in meer uitgebreide simulasie modelle van die ARFe proces geinkorporeer word. Die spesifieke en oorspronklike bydraes van hierdie werk is • Die direkte meting van die spesiasie in die Fe2(SO4)3-H2SO4-H2O stelsel deur Raman en UV-vis spektroskopie • Die ontwikkeling van ’n modelraamwerk om spesiasie, aktiwiteitskoëffisiënte en oplosbaarheid in die gemengde Fe2(SO4)3-FeSO4-H2SO4-H2O stelsel te karakteriseer. • Die meting van yster(III) vermideringskinetieka deur SO2 in gekonsentreerde sulfate oplossings te gebruik as ’n funksie van die aanvanklike samestelling en temperatuur. • Die ontwikkeling van ’n oplossingsreaksie-model van yster(III) vermindering met SO2 wat die oplossing-spesiasie en reaksietempo met die tyd as ’n funksie van samestelling en temperatuur akkuraat voorspel. Laastens, die oorgrote kompleksiteit van industriële stelsels sal byna altyd lei tot ’n gebrek van spesifieke eksperimentele data wat nodig is vir die ontwikkeling van fenomenologiese modelle. Hierdie werk beklemtoon die belangrike rol wat ingenieursstudies speel in die generasie van data wat sodanig tot maksimum praktiese waarde vir industriële prosesontwikkeling en optimalisering lei.

No description available.

Aqueous piperazine (PZ) blended with N-(2-aminoethyl) piperazine (AEP) is an attractive solvent for CO₂ capture from coal-fired power plants. Blending PZ with AEP can remediate the precipitation issue of concentrated PZ while maintaining its high CO₂ absorption rate, and high resistance to degradation. 5 m PZ/2 m AEP also shows a milder nitrosamine issue than concentrated piperazine. A rigorous thermodynamic model was developed in Aspen Plus® to predict properties of PZ/AEP/H₂O/CO₂, using the electrolyte-Nonrandom Two-Liquid (eNRTL) activity coefficient model. A sequential regression was performed to represent CO₂ solubility, speciation, and amine volatility data over operationally significant loading and temperature ranges. The model predicts a CO₂ cyclic capacity of 0.78 mol/kg (PZ + AEP + water) for 5 m PZ/2 m AEP, compared to 0.50 mol/kg for 7 m MEA and 0.86 mol/kg for 8 m PZ. The predicted heat of absorption is 75 to 80 kJ/mol CO₂ at the operating loading range (0.290-0.371 mol CO₂/mol alkalinity). Although 5 m PZ/2 m AEP has a slightly lower CO₂ capacity than 8 m piperazine, its higher heat of absorption may offset the negative effect on energy consumption. Speciation for PZ/AEP/H₂O at various CO₂ loading and temperature was also predicted, from which behavior of CO₂ in the amine system was proposed. / text

In a preamble, a quick summary of the line of thought from Noether's theorems to modern views on conserved charges in gauge theories is attempted. Most of the background material needed for the thesis is set out through a small survey of the literature. Emphasis is put on the concepts more than on the formalism, which is relegated to the appendices. The treatment of exact conservation laws in Lagrangian gauge theories constitutes the main axis of the first part of the thesis. The formalism is developed as a self-consistent theory but is inspired by earlier works, mainly by cohomological results, covariant phase space methods and by the Hamiltonian formalism. The thermodynamical properties of black holes, especially the first law, are studied in a general geometrical setting and are worked out for several black objects: black holes, strings and rings. Also, the geometrical and thermodynamical properties of a new family of black holes with closed timelike curves in three dimensions are described. The second part of the thesis is the natural generalization of the first part to asymptotic analyses. We start with a general construction of covariant phase spaces admitting asymptotically conserved charges. The representation of the asymptotic symmetry algebra by a covariant Poisson bracket among the conserved charges is then defined and is shown to admit generically central extensions. The asymptotic structures of three three-dimensional spacetimes are then studied in detail and the consequences for quantum gravity in three dimensions are discussed.

Le traitement et le diagnostic de maladies d'origine génétique suscite un grand intérêt à l'heure actuelle. De par leur spécificité d'appariement avec les acides nucléiques, les oligonucléotides possèdent un grand potentiel dans ce domaine. Ils se heurtent toutefois à des limitations majeures, dont leur faible stabilité en milieu physiologique et la difficulté qu'ils ont à franchir les membranes biologiques. De nombreuses équipes de recherche s'intéressent, afin de pallier ces limitations, à la conception et à la synthèse d'oligonucléotides chimiquement modifiés. Parmi ceux-ci, les Locked Nucleic Acids (LNA), présentant une modification qui consiste en l'insertion d'un pont −O−CH2− entre l'atome C2' et l'atome C4' du sucre, constituent une famille qui semble posséder les propriétés requises. Ils sont considérés comme des candidats très prometteurs en tant qu’agents thérapeutiques et qu’outils de diagnostic du génome. La caractérisation de la stabilité et de la sélectivité d'appariement entre les LNA et les acides nucléiques naturels est, dans ce contexte, important. Dans ce travail, nous avons étudié la stabilité, la sélectivité d'appariement ainsi que la dynamique de la structure double brin d'un oligonucléotide hybride LNA-DNA, et nous avons comparé ces propriétés à celles d'un oligonucléotide DNA-DNA de même séquence. Ce dernier est constitué de 11 paires de bases formées par l'appariement du brin 5'-GCGTGTGTGCG-3' avec le brin 3'-CGCACACACGC-5'. Dans le cas de l'hybride, les nucléotides du second brin sont tous remplacés par des LNA. La stabilité a été étudiée expérimentalement par différentes techniques : spectroscopie d'absorption UV, calorimétrie différentielle à balayage, résonance magnétique nucléaire et calorimétrie à titrage isotherme. Ces études montrent que la stabilité du duplexe hybride est plus importante que celle du naturel, et que ce phénomène s'explique par un terme entropique plus favorable pour la formation du duplexe LNA-DNA que pour la formation du duplexe DNA-DNA. La sélectivité d'appariement a été étudiée en comparant la stabilité des deux oligonucléotides étudiés avec celle d'oligonucléotides présentant un mésappariement dans la séquence. Nos résultats montrent que la sélectivité d'appariement du brin LNA n'est pas significativement différente de celle du brin DNA. Ce résultat ne doit cependant pas être généralisé car nous n'avons testé qu'une position centrale pour le mésappariement. L'étude de la dynamique de la structure des oligonucléotides a été effectuée par RMN et porte sur la caractérisation de la cinétique de l'ouverture individuelle des paires de bases. Nous observons que la durée de vie de l'état fermé des paires de bases G-C est supérieure dans l'oligonucléotide LNA-DNA, tandis que l'état fermé des paires A-T semble posséder une durée de vie supérieure dans l'oligonucléotide DNA-DNA. Au cours de ce travail de thèse nous avons pu caractériser les facteurs énergétiques à la base de la stabilité accrue des oligonucléotides chimiquement modifiés de type LNA. Nous avons montré que leur sélectivité d’appariement n’est pas toujours supérieure à celle des oligonucléotides naturels et dépend des séquences impliquées. Enfin, nous avons mis en évidence les différences entre la dynamique de la structure d’un oligonucléotide possédant des LNA et celle d’un duplexe DNA.

Water scarcity and high irradiance overlap in the southwestern United States. This thesis explores solar energy as a method to power desalination in the Southwest. Ten solar desalination plants were modeled using photovoltaic reverse osmosis and concentrated solar thermal multi-effect distillation. Seawater and brackish water were considered, as well as liquid and zero liquid discharge plants. Using borrowed capital amortization, levelized energy costs were estimated to be 0.067 $/kWh-electric for photovoltaic systems and 0.009 $/kWh-heat for thermal systems. Photovoltaic reverse osmosis with liquid plant waste showed the best short-term financials while optimal long-term solar desalination methods were shown to be arbitrary, limited by solar conversion and desalination thermodynamics. A conceptualization and proof of desalination minimum work is presented. This study concludes that solar desalination cost remains higher than conservation, but has considerable potential as a new source of water in the Southwest, filling the gap between overdraft and renewable supply.