Maxwell&rsquo / s thought experiment on a demon performing microscopic actions and violating the second law of thermodynamics has been a challenging paradox for a long time. It is finally resolved in the seventies and eighties by using Landauer&rsquo / s principle, which state that erasing information is necessarily accompanied with a heat dumped to the environment. The purpose of this study is to describe the heat dumped to the environment associated with erasure operations on quantum systems. To achieve this, first a brief introduction to necessary tools like density matrix formalism, quantum operators and entropy are given. Second, the Maxwell&rsquo / s demon and Szilard model is described. Also the connection between information theory and physics is discussed via this model. Finally, heat transfer operators associated with quantum erasure operations are defined and all of their properties are obtained.

Thesis (Sc. D.)--University of Michigan, 1960. / Abstracted in Dissertation abstracts, v. 21 (1960) no. 8, p. 2220. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--University of Chicago, Department of Physics, December 2003. / Includes bibliographical references. Also available on the Internet.

Thesis (Ph. D.)--University of Chicago, Department of Physics, December 2003. / CD-ROM contains entire thesis in PDF format. Includes bibliographical references. Also available on the Internet.

Hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂) is one of the most abundant materials in mammal bone. It crystallizes in an aqueous environment within spaces between tropocollagen protein chains. However, despite its abundance and possible usefulness in the medical field this complex physical system remains poorly understood to date. We present a theoretical study of the energetics of hydroxyapatite, its electronic, mechanical and thermodynamic properties. Our mechanical and thermodynamic properties from first principles are in excellent agreement with the rare available experimental data. The monoclinic and hexagonal phases are lowest in energy. A comparison of the phonon dispersions of these two phases reveals that a phase transition occurs due to a difference in vibrational free energy. The transition is of order-disorder type. Our calculated phase transition temperature is 680 K, in decent agreement with the experimentally determined 470 K. An alternative theoretical model yields 882 K. The phase transition is mediated by OH libration modes. We also report for the first time on a peculiarity in the phonon spectrum of hexagonal and monoclinic HA. When studying the Lyddane-Sachs-Teller shifts in the spectrum close to the [Gamma]-point we identify two vibration modes showing a systematically increasing Lyddane-Sachs-Teller shift in frequency with decreasing dielectric constant. In experiment, the dielectric constant varies between 5 and 20 depending on the Ca/P ratio in the sample. The frequency shifts in the affected modes are as large as 20 cm⁻¹ as one spans the range of the dielectric constant. Thus, a simple spectroscopic analysis of a sample of bone may determine the quality of the sample in a physiological sense. We also identify the chemically stable low energy surface configurations as function of the OH, PO₄ and Ca concentration. In the experimentally relevant OH-rich regime we find only two surfaces competing for lowest energy. The surface most stable over almost the entire OH-rich regime is OH-terminated, and is currently being investigated in the presence of water and atomic substitutions on the HA surface. / text

The Electrolyte Nonrandom Two-Liquid Activity Coefficient model in Aspen PlusTM 2006.5 was used to develop a rigorous and consistent thermodynamic representation for the base sub-component systems associated with aqueous combinations of K₂CO₃, KHCO₃, MEA, and piperazine (PZ) in a mixed-solvent electrolyte system for the application of CO₂ absorption/stripping from coal fired power plants. We developed a new vapor-liquid equilibrium apparatus to measure CO₂, amine, and H2O vapor pressures at 40 and 60 oC. We found that the volatility of MEA and PZ can be approximated at 50 and 20 ppmv at 40°C for any solvent composition studied in this work, over the CO₂ partial pressure range from 0.01 to 0.1 kPa. Very few solvent compositions exhibited a greater differential capacity than 7 m MEA at 60°C; specifically 11 m MEA, 3.5 m MEA + 3.6 m PZ, 7 m MEA + 2 m PZ, 7 m MEA + 3.6 m PZ, and 5 m K+ + 7 m MEA + 3.6 m PZ. Piperazine exhibited a possible maximum differential capacity of 2.21 mole CO₂/kg-H₂O at a concentration of 7.3 m. At the Norwegian University of Science and Technology, Inna Kim determined the differential enthalpy of CO₂ absorption for aqueous combinations of K₂CO₃, KHCO₃, MEA, PZ, and CO₂, based on a consistent experimental method developed for MEA, from 40 to 120°C for use in this work. In addition, we developed a consistent method to measure the specific heat capacity for a number of similar solvent combinations. We found that the enthalpy of CO₂ absorption increased with temperature because the apparent partial heat capacity of CO₂ may be considered small. Finally, by using a differential scanning calorimeter, we determined the dissolution temperature for aqueous mixtures of unloaded piperazine, which inferred an effective operating range for solutions of concentrated piperazine, greater than 5 m PZ, over a loading range between 0.25 to 0.45 mole CO₂/2·mol PZ. Through unit cell x-ray diffraction, we were able to identify and characterize the presence of three solid phases (PZ·6H₂O, KHCO₃, and KvPZ(COO)₂) in aqueous mixture combinations of K₂CO₃, KHCO₃, PZ, and CO₂. / text

In addition to their potential use at low to moderate temperatures in mobile fuel cell technologies, metal hydrides may also find application as high temperature tritium getterers in the U.S. DOE Next Generation Nuclear Plant (NGNP). We use Density Functional Theory to identify metal hydrides capable of sequestering tritium at temperatures in excess of 1000 K. First we establish the minimum level of theory required to accurately capture the thermodynamics of highly stable metal hydrides and determine that isotope effects can be neglected for material screening. Binary hydride thermodynamics are largely well established, and ternary and higher hydrides typically either do not form or decompose at lower temperatures. In this thesis we investigate anomalous systems with enhanced stability in order to identify candidates for the NGNP application beyond the binary hydrides. Methods implemented in this work are particularly useful for deriving finite temperature phase stability behavior in condensed systems. We use grand potential minimization methods to predict the interstitial Th−Zr−H phase diagram and apply high throughput, semi-automated screening methodologies to identify candidate complex transition metal hydrides (CTMHs) from a diverse library of all known, simulation ready ternary and quaternary CTMHs (102 materials) and 149 hypothetical ternary CTMHs based on existing prototype structures. Our calculations significantly expand both the thermodynamic data available for known CTMHs and the potential composition space over which previously unobserved CTMHs may be thermodynamically stable. Initial calculations indicate that the overall economic viability of the tritium sequestration system for the NGNP will largely depend on the amount of protium rather than tritium in the metal hydride gettering bed feed stream.

Thesis (MTech. degree in Chemistry)--Tshwane University of Technology, 2008. / This work is aimed at experimental verification of the theory about the advantages of the two-step sample vapour release in a fast-heated ballast furnace. The term “ballast” was introduced earlier in electrothermal atomic absorption spectrometry, as an alternative to a platform to describe a compact body of refractive material loosely located on the bottom of a tube furnace atomiser. The thermal behaviour of the ballast furnace is similar to that of the platform, but without restriction created by the platform area. Compared with the flat or concave platform, a compact ballast of similar mass to the platform should have less impact on gas temperature because of the smaller surface area. The theoretical predictions concerning atomisation efficiency in the fast-heated ballast furnace were examined by the determination of metals in organic and inorganic matrices using a Quantum Z.ETA atomic absorption spectrometer. The instrument provided fast heating of the tube atomizer, 10 K ms-1. It is shown that in the employed ballast furnace the vapour released into the gas phase occurs after interim condensation on the ballast. For the samples of tetraethyllead, base oil and aqueous solutions of various metals, analytical signals are observed after stabilisation of tube temperature, independent of volatility of the analyte and level of temperature setting. For those samples, a high gas phase temperature provides complete recovery of the analyte without involvement of chemical modifiers and the reduction of spectral interferences from chloride matrices.

Temperature, pressure, and length scale dependence of the solvation of simple solvophobic solutes is investigated in the Jagla liquid, a simple liquid consisting of particles that interact via a spherically symmetric potential combining hard and soft core interactions. The results are compared with identical calculations for a model of a typical atomic liquid, the Lennard-Jones (LJ) potential, and with predictions for hydrophobic solvation in water using the recently developed cavity equation of state and the extended simple point charge model. We find that the Jagla liquid captures the qualitative thermodynamic behavior of hydrophobic hydration as a function of temperature and pressure for both small and large length scale solutes. In particular, for both the Jagla liquid and water, we observe temperature-dependent enthalpy and entropy of solvation for all solute sizes as well as a negative solvation entropy for sufficiently small solutes at low temperature. This feature of water-like solvation is distinct from the strictly positive and temperature independent enthalpy and entropy of cavity solvation observed in the Lennard-Jones fluid. The results suggest that a competition between two energy scales that favors low-density, open structures as temperature is decreased is an essential interaction of a liquid that models hydrophobic hydration. In addition the Jagla liquid dewets surfaces of large radii of curvature less readily than the Lennard-Jones liquid, and the so-called ``length scale crossover'' in solvation, whereby solvation free energies change from scaling with the solute volume to scaling with the solute surface area, occurs at length scales that are larger relative to the solvent size. Both features reflect a greater flexibility or elasticity in the Jagla liquid structure than that of a typical liquid, similar to water's ability to maintain its hydrogen bond network. The implications of the differences in crossover behavior between water-like and typical liquids are examined in the context of a simple thought experiment on the aggregation of solvophobic solutes that builds on ideas from Chandler and Rajamani et al. We find that water-like crossover behavior exposes a size range of solvophobic aggregates to destabilization upon cooling and pressurizing, which may thereby precipitate phenomena such as cold and pressure denaturation of proteins. Statistics of density fluctuations, void space, and pair distributions are analyzed for molecular-scale volumes. The pair distribution functions are used to provide an estimate of the size of the Jagla particle with a physical basis. The void distributions are observed to be distinct in the three liquids, with low temperature distributions in the LJ and Jagla liquids demonstrating a high degree of skewness. The void distributions observed in LJ liquid are hard sphere-like, while those of water and the Jagla liquid exhibit a higher degree of density inhomogeneity relative to a hard sphere system. The well-known Gaussian behavior of density fluctuations in molecular volumes in water is not generally observed in other liquids, as evidenced by the fact that this behavior is not consistently observed in either the LJ or the Jagla liquids. An exploratory study of the effects of explicit solvent on the sequence energy landscape of model heteropolymers has been performed. For a fixed set of configurations, the energy landscape of all possible sequences taken from a two letter alphabet consisting of only solvophilic and solvophobic monomers is characterized at different solvent temperatures. Non-trivial solvent and temperature effects are manifest in the distribution of sequences, confirming that the negation of these effects may have profound consequences on designability. / text

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