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At least 19 records

Liquid-Vapor Equilibrium of Multicomponent Cryogenic Systems

Liquid-vapor and solid-vapor equilibria at low to moderate pressures and low temperatures are important in many solar system environments, including the surface and clouds of Titan, the clouds of Uranus and Neptune, and the surfaces of Mars and Triton. The familiar cases of ideal behavior are limiting cases of a general thermodynamic representation for the vapor pressure of each component in a homogeneous multicomponent system. The fundamental connections of laboratory measurements to thermodynamic models are through the Gibbs-Duhem relation and the Gibbs-Helmholtz relation. Using laboratory measurements of the total pressure, temperature, and compositions of the liquid and vapor phases at equilibrium, the values of these parameters can be determined. The resulting model for vapor-liquid equilibrium can then conveniently and accurately be used to calculate pressures, compositions, condensation altitudes, and their dependencies on changing climatic conditions. A specific system being investigated is CH4-C2H6-N2, at conditions relevant to Titan's surface and atmosphere. Discussed are: the modeling of existing data on CH4-N2, with applications to the composition of Titan's condensate clouds; some new measurements on the CH4-C2H6 binary, using a high-precision static/volumetric system, and on the C2H6-N2 binary, using the volumetric system and a sensitive cryogenic flow calorimeter; and describe a new cryogenic phase-equilibrium vessel with which we are beginning a detailed, systematic study of the three constituent binaries and the ternary CH4-C2H6-N2 system at temperatures ranging from 80 to 105 K and pressures from 0.1 to 7 bar.

Thompson, W. Reid↗

Vapor-liquid equilibrium thermodynamics of N2 + CH4 - Model and Titan applications

A thermodynamic model is presented for vapor-liquid equilibrium in the N2 + CH4 system, which is implicated in calculations of the Titan tropospheric clouds' vapor-liquid equilibrium thermodynamics. This model imposes constraints on the consistency of experimental equilibrium data, and embodies temperature effects by encompassing enthalpy data; it readily calculates the saturation criteria, condensate composition, and latent heat for a given pressure-temperature profile of the Titan atmosphere. The N2 content of condensate is about half of that computed from Raoult's law, and about 30 percent greater than that computed from Henry's law.

Thompson, W. R.↗

Study of the liquid vapor equilibrium in the bromine-hydrobromic acid-water system

A glass ebullioscope was built and at atmospheric pressure, liquid-vapor equilibria relative to the Br2-HBr-H2O system, in the concentration range of interest for evaluation of the Mark 13 cycle was studied. Measurements were performed for the brome-azeotrope (HBr-H2O) pseudo-binary system and for the ternary system at temperatures lower than 125 C and in the bromine concentration range up to 13% wt.

Benizri, R.↗

Crystal-liquid-vapor equilibrium experiments at high temperature (less than or equal to 1800 C) and low, controlled oxygen and hydrogen pressure (10(-1) to 10(-9) PA)

Evidence from carbonaceous chrondrites points to refractory oxides in the system CaO-MgO-Al2O3-TiO2-SiO2-Fe-O as being among the earliest phases to condense from the solar nebula. It is necessary to establish the equilibrium relationships between the relevant crystalline and amorphous phases before the chemical constraints can be meaningfully applied to models of solar system history. Preliminary experiments on earth show that such experiments are feasible. Earth-based experiments suffer from several unavoidable problems. These problems can be overcome by experimentation in the Space Station where the experiments can be conducted under near static pressure conditions and where total pressure equals the sum of controlled hydrogen and oxygen pressures and can be controlled for periods exceeding several hours.

Mysen, B. O.↗

Combustion of LOX with H2(sub g) under subcritical, critical, and supercritical conditions and experimental observation of dense spray and mixing of impinging jets

Progress made during the period of February 1 to October 15, 1992 is reported. The overall objective of Task 1 of the investigation is to achieve a better understanding of the combustion processes of liquid oxygen and gaseous hydrogen under subcritical, critical, and supercritical conditions. Specific objectives of the research program are: (1) to determine the evaporation- and burning-rate characteristics of LOX in hydrogen/helium environments under broad ranges of operating conditions; (2) to measure species concentration profile and surface temperature of LOX employing the gas chromatography and fine-wire thermocouples under non-reacting flow situations; (3) to perform a fugacity-based multicomponent thermodynamic phase equilibrium analysis for examining the high-pressure vapor-liquid equilibrium behavior at the liquid surface of LOX; (4) to formulate and solve a theoretical model for simulating the evaporation and combustion processes in a LOX/H2/He system; and (5) to validate the theoretical model with the measured experimental data. Task 2 of the investigation is described. Observation of a like-on-like injector element in the near-injector region performed in the previous phase of this project has identified the existence of a high Reynolds number regime in which the pre-impingement jets are fully turbulent and undergoing surface breakup. The new spray regime, which has not been observed by previous investigators, is characterized by the presence of many fine droplets and the disappearance of the well-defined liquid breakup wave pattern in the post-impingement region. It is speculated that a cavitating region may be present within the orifice so that it could induce strong turbulence, leading to an onset of atomization of the jets prior to impingement. To further investigate the dense spray behavior of the impinging jets in the high Reynolds number region, experiments were conducted using Plexiglas injector components for direct internal flow observation. The main objective is to determine under what conditions a cavitating region would form and whether or not the cavitation is reponsible for the development of the high Reynolds number spray regime. The procedure and major findings of the injector cavitation study are described.

Kuo, Kenneth K.↗

Three CLIPS-based expert systems for solving engineering problems

We have written three expert systems, using the CLIPS PC-based expert system shell. These three expert systems are rule based and are relatively small, with the largest containing slightly less than 200 rules. The first expert system is an expert assistant that was written to help users of the ASPEN computer code choose the proper thermodynamic package to use with their particular vapor-liquid equilibrium problem. The second expert system was designed to help petroleum engineers choose the proper enhanced oil recovery method to be used with a given reservoir. The effectiveness of each technique is highly dependent upon the reservoir conditions. The third expert system is a combination consultant and control system. This system was designed specifically for silicon carbide whisker growth. Silicon carbide whiskers are an extremely strong product used to make ceramic and metal composites. The manufacture of whiskers is a very complicated process. which to date. has defied a good mathematical model. The process was run by experts who had gained their expertise by trial and error. A system of rules was devised by these experts both for procedure setup and for the process control. In this paper we discuss the three problem areas of the design, development and evaluation of the CLIPS-based programs.

Parkinson, W. J.↗

Novel Aprotic Heterocyclic Anion-based Ionic Liquids for Carbon Dioxide Capture

Ionic liquids (ILs), or organic salts with melting points at or below room temperature are an incredibly versatile class of materials with many possible applications for NASA’s exploration needs. In particular, appropriately designed ILs can have a high affinity for absorbing carbon dioxide, making them excellent candidates for use as liquid sorbents in cabin air revitalization systems. Unfortunately, many of these ILs have high viscosity, which is only exacerbated by carbon dioxide uptake. High viscosity limits the rate of carbon dioxide uptake. A new class of IL sorbent containing aprotic heterocyclic anions (AHA) has been shown to offer excellent carbon dioxide uptake without a corresponding increase in viscosity. However, there is a paucity of sorption data for these AHA ILs at low partial pressures of carbon dioxide. This paper reports on the characterization of sorption behavior for AHA ILs previously reported in the literature at low concentrations of carbon dioxide and the synthesis and characterization of new, water miscible AHA ILs. Characterization of the new ILs includes measurement of density, viscosity, thermal stability, carbon dioxide capacity, carbon dioxide absorption kinetics, and water-IL vapor liquid equilibrium. Overall, these news ILs are promising alternatives to many of the commonly used IL sorbents.

Eric Townsend Fox↗

Isomerization reaction dynamics and equilibrium at the liquid-vapor interface of water. A molecular-dynamics study

The gauche-trans isomerization reaction of 1,2-dichloroethane at the liquid-vapor interface of water is studied using molecular-dynamics computer simulations. The solvent bulk and surface effects on the torsional potential of mean force and on barrier recrossing dynamics are computed. The isomerization reaction involves a large change in the electric dipole moment, and as a result the trans/gauche ratio is considerably affected by the transition from the bulk solvent to the surface. Reactive flux correlation function calculations of the reaction rate reveal that deviation from the transition-state theory due to barrier recrossing is greater at the surface than in the bulk water. This suggests that the system exhibits non-Rice-Ramsperger-Kassel-Marcus behavior due to the weak solvent-solute coupling at the water liquid-vapor interface.

Benjamin, Ilan↗

Liquid-vapor interface locations in a spheroidal container under low gravity

As a part of the general study of liquid behavior in low gravity environments, an experimental investigation was conducted to determine if there are equilibrium liquid-vapor interface configurations that can exist at more than one location in oblate spheroidal containers under reduced gravity conditions. Static contact angles of the test liquids on the spheroid surface were restricted to near 0 deg. The experiments were conducted in a low gravity environment. An oblate spheroidal tank was tested with an eccentricity of 0.68 and a semimajor axis of 2.0 cm. Both quantitative and qualitative data were obtained on the liquid-vapor interface configuration and position inside the container. The results of these data, and their impat on previous work in this area, are discussed. Of particular interest are those equilibrium interface configurations that can exist at multiple locations in the container.

Carney, M. J.↗

Combustion of liquid-fuel droplets in supercritical conditions

A comprehensive analysis of liquid-fuel droplet combustion in both subcritical and supercritical environments has been conducted. The formulation is based on the complete conservation equations for both gas and liquid phases, and accommodates variable thermophysical properties, finite-rate chemical kinetics, and a full treatment of liquid-vapor phase equilibrium at the drop surface. The governing equations and associated interfacial boundary conditions are solved numerically using a fully coupled, implicit scheme with the dual time-stepping integration technique. The model is capable of treating the entire droplet history, including the transition from the subcritical to supercritical state. As a specific example, the combustion of n-pentane fuel droplets in air is studied for pressures in the range of 5-140 atm. Results indicate that the ambient gas pressure exerts significant control of droplet gasification and burning processes through its influence on fluid transport, gas-liquid interfacial thermodynamics, and chemical reactions. The droplet gasification rate increases progressively with pressure. However, the data for the overall burnout time exhibit a considerable change in the combustion mechanism at the critical pressure, mainly as a result of reduced mass diffusivity and latent heat of vaporization with increased pressure.

Shuen, J. S.↗