The first project in this work used classical molecular dynamics to study the ice recrystallization inhibition potential of a series of carbohydrates and alcochols, using the hydration index, partial molar volumes and isothermal compressibilities as parameters for measuring their cryogenic efficacy. Unfortunately, after 8 months of testing, this work demonstrates that the accuracy and precision of the density extracted from simulations is not sufficient in providing accurate partial molar volumes. As a result, this work clearly demonstrates that current classical molecular dynamics technology cannot probe the volumetric properties of interest with sufficient accuracy to aid in the research and development of novel cryoprotectants.The second project in this work used molecular dynamics simulations to evaluate the Gibbs free energy change of substituting CO2 in sI clathrate hydrates by N2,CH4, SO2 and H2S flue gas impurities under conditions proposed for CO2 capture (273 K, 10 bar). Our results demonstrate that CO2 substitutions by N2 in the small sI cages were thermodynamically favored. This substitution is problematic in terms of efficient CO2 capture, since the small cages make up 25% of the sI clathrate cages, therefore a significant amount of energy could be spent on removing N2 from the flue gas rather than CO2. The thermodynamics of CO2 substitution by CH4, SO2 and H2S in sI clathrate hydrates was also examined. The substitution of CO2 by these gases in both the small and large cages were determined to be favorable. This suggests that these gases may also disrupt the CO2 capture by sI clathrate hydrates if they are present in large concentrations in the combustion flue stream. Similar substitution thermodynamics at 200 K and 10 bar were also studied. With one exception, we found that the substitution free energies do not significantly change and do not alter the sign of thermodynamics. Thus, using a lower capture temperature does not significantly change the substitution free energies and their implications for CO2 capture by sI clathrate hydrates.

SuperCritical-Water-cooled Reactors (SCWRs) are being developed as one of the Generation-IV nuclear-reactor concepts. SuperCritical Water (SCW) Nuclear Power Plants (NPPs) are expected to have much higher operating parameters compared to current NPPs, i.e., pressure of about 25 MPa and outlet temperature up to 625 oC. This study presents the heat transfer analysis of an intermediate Heat exchanger (HX) design for indirect-cycle concepts of Pressure-Tube (PT) and Pressure-Vessel (PV) SCWRs. Thermodynamic configurations with an intermediate HX gives a possibility to have a single-reheat option for PT and PV SCWRs without introducing steam-reheat channels into a reactor. Similar to the current CANDU and Pressurized Water Reactor (PWR) NPPs, steam generators separate the primary loop from the secondary loop. In this way, the primary loop can be completely enclosed in a reactor containment building. This study analyzes the heat transfer from a SCW primary (reactor) loop to a SCW and Super-Heated Steam (SHS) secondary (turbine) loop using a double-pipe intermediate HX. The numerical model is developed with MATLAB and NIST REFPROP software. Water from the primary loop flows through the inner pipe, and water from the secondary loop flows through the annulus in the counter direction of the double-pipe HX. The analysis on the double-pipe HX shows temperature and profiles of thermophysical properties along the heated length of the HX. It was found that the pseudocritical region has a significant effect on the temperature profiles and heat-transfer area of the HX. An analysis shows the effect of variation in pressure, temperature, mass flow rate, and pipe size on the pseudocritical region and the heat-transfer area of the HX. The results from the numerical model can be used to optimize the heat-transfer area of the HX. The higher pressure difference on the hot side and higher temperature difference between the hot and cold sides reduces the pseudocritical-region length, thus decreases the heat-transfer surface area of the HX. / UOIT

A detailed multi-zone thermodynamic simulation has been developed for the direct-injection (DI) diesel engine combustion process. For the purpose of predicting heterogeneous type combustion systems, the model explores the formation of pre-ignition radicals, start of combustion, and eventual heat release. These mechanisms are described based on the current understanding and knowledge of the diesel engine combustion acquired through advanced laser-based diagnostics. Six zones are developed to take into account the surrounding bulk gas, liquid- and vapor-phase fuel, pre-ignition mixing, fuel-rich combustion products as well as the diffusion flame combustion products. A three-step phenomenological soot model and a nitric oxide emission model are applied based on where and when each of these reactions mainly occurs within the diesel fuel jet evolution process. The simulation is completed for a 4.5 liter, inline four-cylinder diesel engine for a range of operating conditions. Specifically, the engine possesses a compression ratio of 16.6, and has a bore and stroke of 106 and 127 mm. The results suggest that the simulation is able to accurately reproduce the fuel jet evolution and heat release process for conventional diesel engine combustion conditions. The soot and nitric oxide models are able to qualitatively predict the effects of various engine parameters on the engine-out emissions. In particular, the detailed thermodynamics and characteristics with respect to the combustion and emission formation processes are investigated for different engine speed/loads, injection pressures and timings, and EGR levels. The local thermodynamic properties and energy, mass distributions obtained from the simulation offer some fundamental insights into heterogeneous type combustion systems. The current work provides opportunities to better study and understand the diesel engine combustion and emission formation mechanisms for conventional diesel engine combustion modes. The flexible, low computational cost features of this simulation result in a convenient tool for conducting parametric studies, and benefits for engine control and diagnostics.

The scope of this thesis was to study thermodynamics of lead oxide and cobalt oxide as the chemical looping agent for oxygen. Furthermore, the theoretical results were verified experimentally. Ellingham diagrams were constructed for the selected oxides. Then, detailed thermodynamic analysis was conducted for stability analysis at different temperatures and pressures. Equilibrium product compositions for various reactions involving these oxides were calculated via Gibbs free energy minimization analysis. Finally, it was shown that cobalt, lead and their oxide forms can be used for syngas production. In the experimental part PbOx, CoOx, Pt-doped CoOx and Pt-doped cobalt alumina, and mixed lead cobalt oxides were synthesized. In addition, technical grade cobalt oxide and lead rods were also used. XRD analysis indicated that Co3O4, Pb2O3 and &alpha / -PbO were the main crystal structures. Oxygen evolution from mixed oxides was monitored by TPD in a home built system. Re-oxidation of the reduced metals was successfully conducted using CO2 and H2O as oxidizing agents. Oxygen TPD studies indicated that oxygen evolution rates and amounts were higher and started at lower temperatures when two oxides were together. These observations were consistent with the predictions obtained from thermodynamics. In a series packed bed reactor, evolved oxygen from the mixed oxides were used to react with coal packed upstream of the oxides. It was found that coal oxidation can be achieved around 400oC and 600oC by using Pb/Co=3 (wt./wt.) looping media with almost no CO2 formation. It was also found that desired product selectivity (CO) can be increased by controlling reactive agent (O2) concentration in reaction environment.

This study gives our calculations for the temperature-pressure and temperature-concentration phase diagrams using the mean field models applied to ammonium halides (NH4Cl, ND4Cl), ammonium sulfate ((NH4)2SO4/H2O), lithium potassium rubidium sulfate (LiK1-xRbxSO4), potassium pyrosulfate-potassium hydrogensulfate (K2S2O7-KHSO4), cholestanyl myristate-cholesteryl myristate (CnM-CrM), cholestanyl myristate-cholesteryl oleate (CnM-CO), benzene (C6H6) and ice. The phase line equations are derived from the free energies expanded in terms of the order parameters and they are fitted to the experimental data. Some thermodynamic quantities are calculated close to phase transitions in these crystalline systems. We also calculate the specific heat CV using the Raman frequency shifts for NH4Br on the basis of an Ising model close to the lambda-phase transition. A linear relationship is obtained between the specific heat CP and the frequency shifts (1/v)(dv/dT)P near the lambda-point in NH4Br.

The specific heat Cp has been showed at various temperatures in the literature, which shows a sharp increase labeled as the lambda-transition at the critical temperature. This transition has been observed previously among the phases of solid-nematic-isotropic liquid in p-azoxyanisole (PAA) and anisaldazine (AAD), and among the phases of solid-smectic-cholesteric-isotropic liquid in cholesteryl myristate (CM). In this thesis work, we analyze the experimental data for the temperature dependence of Cp and the thermal expansion alpha_p and also pressure dependence of alpha_p by a power-law formula. From the analysis of pressure dependence of alpha_p, we calculate the temperature dependencies of specific heat Cp and of the isothermal compressibility kappa_T for the phase transitions considered in PAA, AAD and CM. Our calculations for the temperature dependence of the p and kappa_T can be compared with the experimental data when available in the literature. Polarization, tilt angle and the dielectric constant have been reported in the literature at various temperatures close to the solid-smectic C*-smectic A-isotropic liquid transition in the ferroelectric liquid crystals of A7 and C7. The mean field model with the free energy expanded in terms of the order parameters (polarization and tilt angle) has been reported in the literature previously. In this thesis work, we apply the mean field model first time by fitting the expressions derived for the temperature dependence of the polarization, tilt angle and the dielectric constant to the experimental data for A7 and C7 from the literature. Since the mean field model studied here describes adequately the observed behaviour of A7 and C7, the expressions for the temperature dependence of the polarization, tilt angle and the dielectric constant which we derive, can also be applied to some other ferroelectric liquid crystals to explain their observed behaviour.

We study in this thesis work the spectroscopic and thermodynamic quantities of some substances such as ammonium halides (NH4Cl, NH4I), ferroelectric crystals of tris-sarcosine calcium chloride (TSCC), tris-sarcosine calcium bromide (TSCB), organic compounds of carbon tetrachloride (CCl4) and s-triazine (C3N3H3) close to the phase transitions. Various physical and chemical properties of those materials have been measured near the critical points and have been reported in the literature. In this study, the spectroscopic parameters of the frequency shifts, intensity and bandwidths are calculated as functions of temperature or pressure near the phase transitions in ammonium halides using the experimental data from the literature. The spectroscopic parameters are related to the crystal volume and the specific heat in these compounds. The thermodynamic quantities of the specific heat, thermal expansion and the isothermal compressibility are also calculated in the solid and liquid phases of carbon tetrachloride using the experimental data. In another part of this thesis work, we analyze the temperature dependence of the spontaneous polarization and the dielectric susceptibility at fixed pressures for TSCC and TSCB by using the experimental data from the literature. The temperature dependence of the damping constant for the s-triazine is also calculated here close to the I-II transition. We use the theoretical models on the basis of the observations in the literature to calculate the critical behaviour of these physical quantities and we compare the results with the observed data. Various experimental studies in the literature give us the opportunity to find the proper way of fitting the calculated and observed results. This study gives us the chance of a better understanding of the critical behavior of the studied materials by verifying the values of some critical exponents and the types of transitions as expected by different theoretical models.

Limited worldwide energy supplies demand the improved utilization of thermal energy, which is the dominant form of all primary energy sources used today. Large quantities of waste heat are routinely exhausted wherever thermo-mechanical energy conversion occurs, providing an opportunity to improve utilization. Two waste-heat-driven cycles are analyzed: an absorption/compression cascade cooling cycle and a coupled Rankine/compression cycle. The absorption/compression cascade provides an environmentally-sound option for a common approach to thermal energy recovery: the use of absorption cycles for cooling applications. To achieve cooling at temperatures below 0ºC, ammonia-water is the overwhelming choice for the working fluid. However, concerns about the toxicity and flammability of ammonia sometimes limit its application in sensitive arenas. In this study, a lithium bromide-water absorption cycle is coupled with a carbon dioxide vapor compression cycle to realize the benefits of high-lift cooling without the concerns associated with ammonia. This cycle utilizes a waste heat stream at temperatures as low as 150°C to provide cooling at -40°C. The topping absorption cycle achieves a coefficient of performance (COP) of about 0.77, while the bottoming cycle achieves a COP of about 2.2. The coupled Rankine/compression cycle provides a mechanical expansion and compression approach to achieve thermally activated cooling, again driven by waste heat. The power produced in the turbine of the Rankine cycle is directly coupled to the compressor of a vapor-compression cooling cycle to generate cooling to be utilized for space-conditioning. The refrigerant R245fa is used throughout the cycle. Even with low grade waste heat sources, a Rankine cycle efficiency of about 11-12 percent can be achieved. When coupled to the bottoming compression cycle with a COP of about 2.7, this yields an overall waste heat to cooling conversion efficiency of about 32 percent at nominal conditions.

Im Gegensatz zur konventionellen adiabatischen Destillation erfolgt bei der diabatischen Destillation Wärmeaustausch nicht nur am Kondensator und Verdampfer, sondern auch innerhalb der Kolonne an den einzelnen Siebböden, was die Entropieproduktion (=Exergieverlust) des Destillationsprozesses stark reduziert. In dieser Arbeit werden Modellsysteme zur diabatischen Destillation von idealen binären Gemischen mittels numerischer Optimierung untersucht. Das Ausgangsmodell beschränkt sich auf die Minimierung der Entropieproduktion verursacht durch Wärme- und Massentransport im Inneren der diabatischen Destillationskolonne. Im zweiten Modell wird das diabatische Modell um die Irreversibilität bedingt durch den Wärmeaustausch mit der Umgebung erweitert. Im dritten Modellsystem wird anstelle der bis dahin voneinander unabhängig geregelten Bodentemperaturen eine diabatische Implementierung mit seriellen Wärmetauschern untersucht, die nur mehr vier Kontrollvariablen besitzt und besonders zur praktischen Anwendung geeignet ist. Für alle diabatischen Modelle werden die minimale Entropieproduktion und optimalen Betriebsprofile numerisch ermittelt, und mit konventionellen Destillationskolonnen verglichen. Alle Ergebnisse zeigen eine deutlich Reduktion der Entropieproduktion für den diabatische Fall, besonders bei Kolonnen mit vielen Böden. / Contrary to conventional adiabatic distillation, in diabatic distillation columns heat transfer not only happens at the condenser and reboiler but also at the intermediate trays which strongly reduces the entropy production (= exergy losses). In this work, model systems for the diabatic distillation of ideal binary mixtures are investigated numerically.The first model is restricted to the minimization of the entropy production due to heat and mass transfer inside the diabatic column. In the second approach the model is extended with the irreversibility due to heat transfer with the column's surroundings. Instead of independently controlled tray temperatures as in the latter models, we focus on a specific diabatic implementation with sequential heat exchangers, which has merely four controls and which is particularly suitable for practical application. For all diabatic models the minimum entropy production and resulting optimal operating profiles are determined numerically, and compared to the ones obtained for a conventional column. All results show an enormous reduction of the entropy production for the diabatic case, especially for columns with many trays.

This work investigates the volatilities of amine solvents used in post-combustion CO₂ capture from coal-fired power plants. Amine volatility is one of the key criteria used in screening an amine solvent for CO₂ capture: (1) amine losses up the stack can react in the atmosphere to form ozone and other toxic compounds; (2) volatility losses can result in greater solvent make-up costs; (3) high losses will require the use of bigger water wash units, and more water, to capture fugitive amines prior to venting - these translate to higher capital and operating costs; (4) volatilities need to be measured and modeled in order to develop more accurate and robust thermodynamic models. In this work, volatility is measured using a hot gas FTIR which can determine amine, water, and CO₂ in the vapor headspace above a solution. The liquid solution is speciated by NMR (Nuclear Magnetic Resonance). There are two key contributions made by this research work: (1) it serves as one of the largest sources of experimental data available for amine-water volatility; (2) it provides amine volatility for loaded systems (where CO₂ is present) which is a unique measurement not previously reported in the literature. This work studied the volatility of 20 alkanolamines in water at 0.5 - 1.1 molal (m) in water (< 1.5 mol% amine) at zero loading (no CO₂) from 40 ° - 70 °C. An empirical group contribution model was developed to correlate H[subscript 'amine'] to molecular structures of both alkylamines and alkanolamines. The model incorporated additional functional groups to account for cyclic structures and to distinguish between different types of alkyl groups based on the attached neighboring groups. This model represented the experimental H[subscript 'amine'], which spanned five orders in magnitude, to well within an order of magnitude of the measured values. The second component of this research involves upgrading the AspenPlus® v.7.3 model of MDEA-PZ-CO₂-H₂O system primarily by improving MDEA thermodynamics for MDEA-H₂O, MDEA-CO₂-H₂O, and MDEA-PZ-CO₂-H₂O. A key modification was made to include the carbonate (CO₃²⁻) species into the model chemistry set which greatly improved the fit of CO₂ solubility for MDEA-CO₂-H₂O at ultra lean loading ([alpha]) for 0.001 < [alpha] < 0.01. With MDEA-PZ-H₂O, no MDEA-PZ cross interaction parameters were needed to match the blend volatility. Ultimately, both the blend volatility, at unloaded and loaded conditions, along with speciation were adequately represented by the upgraded model. The final component of this research involves screening the volatilities of novel amines at unloaded and nominal lean loading condition from 40 ° - 70 °C (absorber operating conditions). The volatility of tertiary and hindered amines, such as MDEA and AMP, respectively, is not a strong function of loading because these amines are unable to form stable carbamates. Conversely, the volatility of mono-amines and of diamines decreases by ~3 and 5-20 times, respectively, due to a much greater extent of carbamate-forming speciation. PZ or a blend having a diamine promoted by PZ would be favorable for CO₂ capture due to the low volatility of the diamines in loaded solution. . Finally, in order of increasing degree of salting out as reflected by the increasing magnitude of the system asymmetric amine activity coefficient, 7 m MDEA < 4.8 m AMP ~ 7 m MDEA/2 m PZ < 8 m PZ < 7 m MEA. / text