The study of excess thermodynamic properties of liquid mixtures is very important for designing the thermal separation processes, developing solution theory models and to have a better understanding of molecular structure and interactions involved in the fluid mixtures. In particular, heat of mixing or excess molar enthalpy data of binary and ternary fluid mixtures have great industrial and theoretical significance. In this connection, the experimental excess molar enthalpies for seventeen binary and nine ternary systems involving hydrocarbons, ethers and alcohol have been measured at 298.15K and atmospheric conditions for a wide range of composition by means of a flow microcalorimeter (LKB 10700-1). The binary experimental excess molar enthalpy values are correlated by means of the Redlich-Kister polynomial equations and the Liebermann - Fried solution theory model. The ternary excess molar enthalpy values are represented by means of the Tsao-Smith equation with an added ternary term and the Liebermann-Fried model was used to predict ternary excess molar enthalpy values. The Liebermann-Fried solution theory model was able to closely represent the experimental excess enthalpy data for most of the binary and ternary systems with reasonable accuracy. The correlated and predicted excess molar enthalpy data for the ternary systems are plotted in Roozeboom diagrams

Thesis (Ph. D.)--California Institute of Technology, 1995. / "UMI number: 9539115"--P. [i]. Includes bibliographical references. Available on microfilm and online via the World Wide Web.

Orientador: Artur Zaghini Francesconi / Dissertação (mestrado) - Universidade Estadual de Campinas. Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-04T22:34:23Z (GMT). No. of bitstreams: 1 Galvao_AlessandroCazonatto_M.pdf: 4286598 bytes, checksum: 5343225ecef9d45c563d1805d234599e (MD5) Previous issue date: 2005 / Resumo: Resumo: Este trabalho compreende o estudo experimetal da entalpia molar em excesso em função da composição de soluções líquidas binárias contendo 1-pentanol + acetonitrila e 1- hexanol + acctonitrila às temperaturas de 288,15, 298,15, 313,15 e 323,15K e pressão atmosférica. O método experimental utilizado para determinação da entalpia molar em excesso foi a calorimetria. O ponto de partida foi a determinação experimental do efeito térmico provocado na solução pela mistura de dois reagentes puros. Os modelos ERAS e PFP foram ampliados na tentativa de correlacionar os dados experimentais. Todas as soluções estudadas apresentaram curvas com formato aproximadamente parabólico e valores positivos para entalpia molar em excesso em função da fração molar. Os resultados de entalpia molar em excesso aumentam com o aumento da temperatura e com o aumento da cadeia carbônica do álcool. Os modelos PFP e ERAS foram capazes de correlacionar satisfatoriamente os dados experimentais de entalpia molar em excesso. Utilizou-se alguns conceitos da teoria de forças intermoleculares na tentativa de analisar o comportamento dos dados experimentais e dos modelos matemáticos / Abstract: Abstract: This work is focused on the experimental study of the excess molar enthalpy as a functions of composition of binary liquid solutions containing 1-pentanol + acetonitrile and 1- hexanol + acetonitrile for 288,15, 298,15, 313,15 and 323,15K and atmospheric pressure. The excess molar enthalpy was calculated using colorimetric method. To accomplish this purpose the starting point was calculated using calorimetric method. To accomplish this purpose, the starting point was the experimental measure of the thermal effect that arises when a mixture of two pure components take place. This solution models PFP and ERAS were applied with the attempt of correlating the experimental data. All the studied system showed values of excess molar enthalpy increase with the temperature and with the number of carbons in the alkanol chain. Both models, ERAS and PFP, were able to describe the main features of the solutions and to correlate the experimental data of the excess molar enthalpy. Some concepts of molecular forces were applied as an attempt of analyzing the behaviour of the experimental data and the mathematical models / Mestrado / Sistemas de Processos Quimicos e Informatica / Mestre em Engenharia Química

Kimberlite hosts two populations of olivine that are distinguished on the basis of grain size and morphology; the populations are commonly described genetically as xenocrysts and phenocrysts. Recent studies of zoning patterns in kimberlitic olivine phenocrysts have cast doubt on the actual origins of the smaller olivine crystals. Here, we elucidate the nature and origins of the textural and chemical zonation that characterize both populations of olivine. Specifically, we show that both olivine-I and olivine-II feature chemically distinct overgrowths resulting from magmatic crystallization on pre-existing olivine xenocrysts. These results suggest that the total volume of olivine crystallized during transport is substantially lower (≤5%) than commonly assumed (e.g. ~25%), and that crystallization is dominantly heterogeneous. This reduces estimates of the Mg# in primitive kimberlite melt to more closely reconcile with measured phenocryst compositions. Several additional textures are observed in olivine, and include: sealed cracks, healed cracks, phases trapping in cracks, rounded grains, overgrowths and phase trapping in overgrowths. These features record processes that operate in kimberlite during ascent, and from these features we create a summary model for kimberlite ascent: • Olivine is incorporated into kimberlitic melts at great depths as peridotitic mantle xenoliths. • Shortly after the incorporation of these xenocrysts the tensile strength of the crystals within xenoliths is reached at a minimum of 20 km from its source. Disaggregation of mantle xenoliths producing xenocrysts is facilitated by expansion of the minerals within the xenoliths. • The void space produced by the failure of the crystals is filled with melt and crystals consisting of primary carbonate (high-Sr), chromite and spinel crystals. The carbonate later crystallizes to produce sealed fractures. • Subsequent decompression causes cracks that are smaller than the sealed cracks and are preserved as healed cracks that crosscut sealed cracks. • Mechanical rounding of the xenocrysts post-dates, and/or occurs contemporaneously with decompression events that cause cracking. • Saturation of olivine produces rounded overgrowths on large xenocrysts, euhedral overgrowths on smaller xenocrysts, and a volumetrically minor population of olivine phenocrysts. Olivine growth traps fluid, solid and melt inclusions. Calculations based on these relationships suggest that the melt saturates with olivine at a maximum depth of 20 km and a minimum depth of 7 km. / Science, Faculty of / Earth, Ocean and Atmospheric Sciences, Department of / Graduate

Release of uranium from Na-autunite, an artificial mineral created as a result of polyphosphate injection in the subsurface at the DOE Hanford Site, takes place during slow dissolution of the mineral structure. Stability information of the uranyl-phosphate phases is limited to conditions involving pH, temperature, and a few aqueous organic materials. The carbonate ion, which creates very strong complexes with uranium, is the predominant ion in the groundwater composition. The polyphosphate technology with the formation of autunite was identified as the most feasible remediation strategy to sequester uranium in contaminated groundwater and soil in situ. The objectives of the experimental work were (i) to quantify the effect of bicarbonate on the stability of synthetic sodium meta-autunite created as a result of uranium stabilization through polyphosphate injection, (ii) calculate the kinetic rate law parameters of the uranium release from Na-autunite during dissolution, and (iii) to compare the process parameters with those obtained for natural calcium meta-autunite. Experiments were conducted using SPTF apparatus, which consists of syringe pumps for controlling flow rate, Teflon reactors and a heating/cooling system. 0.25 grams of synthetic Na-autunite was placed in the reactor and buffer solutions with varying bicarbonate concentrations (0.0005 to 0.003 M) at different pH (6 - 11) were pumped through the reactors. Experiments were conducted at four different temperatures in the range of 5 - 60oC. It was concluded that the rate of release of uranium from synthetic Na-autunite is directly correlated to the bicarbonate concentration. The rate of release of uranium increased from 1.90 x 10-12 at pH 6 to 2.64 x 10-10 (mol m-2 s-1) at pH 11 at 23oC over the bicarbonate concentration range tested. The activation energy values were invariant with the change in the bicarbonate concentration; however, pH is shown to influence the activation energy values. Uranyl hydroxides and uranyl carbonates complexes helped accelerate the dissolution of autunite mineral.

In today’s society the energy usage for water, electricity and heat is closely monitored but ventilation is not. Why is that? Today the way ventilation is measured is either through airflow or the size of the room the air is distributed to. Lindab Innovation Hub wants to see if there is potential for a different solution to energy and air measurement within ventilation systems. This project has performed a concept and design for a new energy and air measurement technology. This technology was also compared to existing ones. Simulations of a real shopping mall containing four different shops were done in two different simulation programs. One which is designed for focus on heating, cooling, and ventilation inside of the ventilation system. And the second one which has a much broader perspective. After simulations, construction of a real ventilation system was also accomplished. The simulations were used to simulate theoretical values which then were used with the results from the experimental tests to see if the energy losses between the new and old solution could be neglected.The report presents important results between the two different kind of simulation programs as well as the difference in accuracy between the existing measuring technologies and a new enthalpy-based technology. The results also show that the energy that is not currently considered in the cost distribution is far from neglectable. With this project as a base, it is possible to create a correction factor for all kinds of facilities or rooms for a better economical and sustainable solution.

The ever-increasing focus of policy-makers on environmental issues are pushing the combustion community towards making combustion cleaner by optimizing the combustion equipment in order to reduce emissions, improve efficiency and satisfy the increasing energy demand. A major part of this involves advancing modelling capabilities of these complex combustion systems, which is a combination of computational fluid dynamics with detailed chemical kinetic models. A chemical kinetic model comprises of a series of elementary reactions with corresponding kinetic rate parameters and species thermodynamic and transport data. The predictive capability of these models depends on the accuracy to which individual chemical reaction rates, thermodynamic and transport parameters are known. A minor fraction of the rate constants and thermodynamic properties in the widely used kinetic mechanisms are experimentally derived or theoretically calculated. The remaining are approximated using rate rules and group additivity methods respectively for rate constants and thermodynamic properties. Recent works have highlighted the need for error checking when preparing such models using the approximations, but a useful community tool to perform such analysis is missing. In the initial part of this work, we developed a simple online tool to screen chemical kinetic mechanisms for bimolecular reactions exceeding collision limits. Furthermore, issues related to unphysically fast time scales can remain an issue even if all bimolecular reactions are within collision limits. Therefore, we also presented a procedure to screen ultra-fast reaction time scales using computational singular perturbation (CSP). The screening of kinetic models is a necessary condition, however, not a sufficient one. Therefore, exploring new approaches for the simulation of complex chemically reacting systems are needed. This work focuses on developing new methods for estimating thermodynamic data efficiently and accurately, thereby increasing the compliance of forth-mentioned screening. Machine Learning (ML) has been increasingly becoming a tool of choice for regression, replacing traditional function fittings. Group additivity incorporates simple functions and derive constants with a certain existing data and use these functions to estimate the unknown values. ML algorithms does the same without fixing a specific function there by letting algorithm to learn the non-linearity from the training data itself. With the new data coming in with time, ML algorithms learn better and improves over time, whereas this need not necessarily happen with traditional methods. In the first part of the study, data for standard enthalpy is collected from the literature sources and ML models are built on these databases. Two different models were built and studied for a straight-chain species and cyclic species dataset. Molecular descriptors are used as the datasets collected from literature are small for using any sparse representations as input. As expected, we observed a good improvement above group additivity method for these ML models. The improvement is observed to be more significant for cyclic species. With the motivation of ML models showing benefit over the group additivity method, a step further was taken. A homogenous and accurate dataset is necessary for building a ML model that can be used for generating the thermodynamic data for kinetic models. With this in mind, an accurate database for thermodynamic data is built from ab-intio calculations. The species in the dataset are taken from a detailed and well established mechanism to cover all the species in a typical kinetic mechanism. The calculations are performed at a high level of accuracy, in comparison to other similar datasets in literature. In the later part of this work, the dataset developed using ab-inito calculations is used for developing ML models. Unlike the ML models built from the literature datasets, this database consists of all the thermodynamic data required for kinetic models viz. standard enthalpy and standard entropy and heat capacity at 300 K and higher temperatures. To numerically mimic real gasoline fuel reactivity, surrogates are proposed to facilitate advanced engine design and predict emissions by chemical kinetic modelling. However, chemical kinetic models could not always accurately predict non-regular emissions, e.g. aldehydes, ketones and unsaturated hydrocarbons, which are important air pollutants. Therefore, we propose to use machine-learning algorithms directly to achieve better predictions, circumventing the kinetic models. Combustion chemistry of fuels constituting of 10 neat fuels, 6 primary reference fuels (PRF) and 6 FGX surrogates were tested in a jet stirred reactor. Experimental data were collected in the same setup to maintain data uniformity and consistency. Measured species profiles of methane, ethylene, propylene, hydrogen, carbon monoxide and carbon dioxide are used for machine-learning model development. The model considers both chemical effects and physical conditions. Chemical effects are described as different functional groups, viz. primary, secondary, tertiary, and quaternary carbons in molecular structures, and physical conditions as temperature. Both the Machine-learning models used in this study showed a good prediction accuracy. By expanding the experimental database, machine-learning models can be further applied to many other hydrocarbons in future work, for the direct predictions.

This study concerns the design, analysis, and initial testing of a novel skin friction gage for applications in three-dimensional, high-speed, high-enthalpy flows. Design conditions required favorable gage performance in the Arc-Heated Facilities at Arnold Engineering Development Center. Flow conditions are expected to be at Mach 3.4, with convective heat properties of h= 1,500 W/(m°·K) (264 Btu/(hr·ft°·°R)) and T_aw= 3,900 K (7,000 °R). The wall shear stress is expected to be as high as τ_w= 2,750 Pa (0.40 psi) with a correlating coefficient of skin friction value around C_f= 0.0035. Through finite element model and analytical analyses, a generic gage design is predicted to remain fully functional and within reasonable factors of safety for short duration tests. The deflection of the sensing head does not exceed 0.025 mm (0.0001 in). Surfaces exposed to the flow reach a maximum temperatures of 960 K (1,720 °R) and the region near the sensitive electronic components experience a negligible rise in temperature after a one second test run. The gage is a direct-measuring, non-nulling design in a cantilever beam arrangement. The sensing head is flush with the surrounding surface of the wall and is separated by a small gap, approximately 0.127 mm (0.005 in). A dual-axis, semi-conductor strain gage unit measures the strain in the beam resulting from the shear stress experienced by the head due to the flow. The gage design incorporates a unique bellows system as a shroud to contain the oil filling and protect the strain gages. Oil filling provides dynamic and thermal damping while eliminating uniform pressure loading. An active water-cooling system is routed externally around the housing in order to control the temperature of the gage system and electronic components. Each gage is wired in a full-bridge Wheatstone configuration and is calibrated for temperature compensation to minimize temperature effects. Design verification was conducted in the Virginia Tech Hypersonic Tunnel. The gage was tested in well-documented Mach 3.0, cold and hot flow environments. The tunnel provided stagnation temperatures and pressures of up to T₀= 655 K (1,180 °R) and P₀= 1,020 kPa (148 psi) respectively. The local wall temperatures ranged from T_w= 292 to 320 K (525 to 576 °R). The skin friction coefficient measurements were between 0.00118 and 0.00134 with an uncertainty of less than 5%. Results were shown to be repeatable and in good concurrence with analytical predictions. The design concept of the gage proved to be very sound in heated, supersonic flow. When it worked, it did so very effectively. Unfortunately, the implementation of the concept is still not robust enough for routine use. The strain gage units in general were often unstable and proved to be insufficiently reliable. The detailed gage design as built was subject to many potential sources of assembly misalignment and machining tolerances, and was susceptible to pre-loading. Further recommendations are provided for a better implementation of this design concept to make a fully functional gage test ready for Arnold Engineering Development Center. / Master of Science

Computational chemistry examination of the bond dissociation enthalpies of tungsten and main group elements. Includes quantification and calibration of theoretical methods to address the question of bond strengths including component σ and π molecular bonds.

Resumo: Quatro experimentos foram conduzidos para avaliar o efeito do sombreamento artificial e da pintura dos telhados na melhoria do conforto térmico de modelos reduzidos simulando galpões avícolas. Em todos os experimentos foram utilizadas coberturas com telha de fibrocimento, novas, sem cimento amianto, com 4,0mm de espessura. O Experimento 1 foi realizado na Universidade Estadual do Maranhão (UEMA), câmpus de São Luís, onde foram testados cinco tipos de coberturas: 1- sem tela, sem pintura (STSP - controle); 2- com tela a 0,05m de altura da telha, sem pintura (CT5SP); 3- com tela a 0,05m de altura da telha, com pintura (CT5CP); 4- com tela a 0,08m de altura da telha, sem pintura (CT8SP) e 5- com tela a 0,08m de altura da telha, com pintura (CT8CP). Foram determinados o Índice de Temperatura de Globo Negro e Umidade (ITGU), a Carga Térmica de Radiação (CTR) e a Entalpia Específica (H). As colheitas das variáveis meteorológicas (temperaturas de globo negro, de bulbo seco, de bulbo úmido e velocidade do vento) foram realizadas durante 12 dias experimentais (04 a 15 de nov. de 2009) às 10:00, 12:00, 14:00 e 16:00 horas. O tipo de cobertura CT5SP foi o que apresentou os melhores valores para ITGUcorr (79,81) e H (78,84 KJ.Kg-1 de ar seco). O melhor resultado para CTRcorr foi apresentado pelo tratamento CT5CP (480,12 W.m-2). O Experimento 2 foi realizado na Universidade Estadual Paulista (UNESP), câmpus de Jaboticabal, onde foram testados os mesmos tipos de coberturas do Experimento 1. As colheitas e registro das variáveis meteorológicas foram realizadas por 40 dias (13 de fev. a 24 de mar. de 2010), nos mesmos horários do Experimento 1. O tipo cobertura que proporcionou menor resultado para o ITGU (83,86) e H (86,41 KJ.Kg-1 de ar seco) foi o CT8CP. A menor CTR (549,52 W.m-2) foi verificada na cobertura CT5CP. O Experimento 3 objetivou verificar o efeito de dois tipos de telas... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Four experiments were conducted to assess the effect of shading and painting of roofs improving thermal comfort in reduced models of poultry houses. In all the experiments were used with roofing cement tile, new, no asbestos cement, with 4.0 mm thick. The first experiment was conducted at the Universidade Estadual do Maranhão (UEMA), campus of São Luís, where were tested five types of coverage: 1 - no shading, no paint (STSP - control), 2 - with shading 0.05 m in height tile, unpainted (CT5SP) 3 - with shading 0.05 m in height tile with painting (CT5CP) 4 - with shading 0.08 m in height tile, unpainted (CT8SP) and 5 - with shading 0.08 m height of the tile with painting (CT8CP). Were evaluated the index of black globe temperature and humidity (BGTHI), the Heat Load (HL) and the specific enthalpy (H). The readings of meteorological variables (black globe temperature, dry bulb, wet bulb temperatures and wind speed) were measured during 12 experimental days (from nov. 4th to 15th, 2009) at 10:00, 12:00, 14: 00 and 16:00 hours. The type of coverage CT5SP had the lowest values for BGTHI (79,81) and H (78,84 KJ.Kg-1 dry air). The best result for CTRcorr (480,12 W.m-2) was presented by treatment CT5CP. The second experiment was conducted at Universidade Estadual Paulista (UNESP), campus of Jaboticabal, where were tested the same types of coverages of Experiment 1. The collection and recording of meteorological variables were performed for 40 days (from feb. 13th to 24th, 2010), at the same times of Experiment 1. The type coverage that provided smaller results for the BGTHI (83,86) and H (86,41 KJ.Kg-1 dry air) was CT8CP. The lower HL (549,52 W.m-2) was verified with the coverage CT5CP. The third experiment aimed at assessing the effect of two types of shading screens (50 and 80%) on the thermal comfort... (Complete abstract click electronic access below) / Orientador: Renato Luís Furlan / Coorientador: Adhemar Pitelli Milani / Banca: Euclides Braga Malheiros / Banca: José Eduardo Pitelli Turco / Banca: Iran José Oliveira da Silva / Banca: Francisca Neide Costa / Doutor