High temperature properties of sodium, potassium, and cesium progress report no. 14, 1 jan. - 31 mar. 1964
Thermophysical properties of sodium and potassium and their vapors
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Thermophysical properties of sodium and potassium and their vapors
Thermodynamic and mass transport calculations, and laboratory experiments elucidating the behavior of sodium chloride in combustion environments, in the deposition process, and in reactions with certain oxides on the surfaces of superalloys are summarized. It was found that some of the ingested salt is separated out of the air stream by the compressor. However, sodium chloride does pass from the compressor to the combustor where numerous chemical reactions take place. Here some of the salt is vaporized to yield gaseous sodium chloride molecules. Hydrogen and oxygen atoms present in the combustion products react with some sodium chloride to yield other gaseous species such as sodium, and a fraction of the salt remains as particulates. Both the gas phase and condensed sodium chloride can lead to sodium sulfate formation by various routes, all of which involve reaction with sulfur oxides and oxygen. In addition to contributing to the formation of sodium sulfate, the sodium chloride can contribute to corrosion directly.
Amount of sodium chloride in individual aerosol particles measured in real time by analyzer that includes mass spectrometer. Analyzer used to determine mass distributions of active agents in therapeutic or diagnostic aerosols derived from saline solutions and in analyzing ocean spray. Aerosol particles composed of sodium chloride introduced into oven, where individually vaporized on hot wall. Vapor molecules thermally dissociated, and some of resulting sodium atoms ionized on wall. Ions leave oven in burst and analyzed by spectrometer, which is set to monitor sodium-ion intensity.
Previous work reported from JPL has included characterization of electrode kinetics and alkali atom transport from electrodes including Mo, W, WRh(sub x), WPt(sub x)(Mn), in sodium AMTEC cells and vapor exposure cells, and Mo in potassium vapor exposure cells. These studies were generally performed in cells with small area electrodes (about 1 to 5 cm(sup 2)), and device geometry had little effect on transport. Alkali diffusion coefficients through these electrodes have been characterized, and approximate surface diffusion coefficients derived in cases of activated transport. A basic model of electrode kinetic at the alkali metal vapor/porous metal electrode/alkali beta'-alumina solid electrolyte three phase boundary has been proposed which accounts for electrochemical reaction rates with a collision frequency near the three phase boundary and tunneling from the porous electrode partially covered with adsorbed alkali metal atoms. The small electrode effect in AMTEC cells has been discussed in several papers, but quantitative investigations have described only the overall effect and the important contribution of electrolyte resistance. The quantitative characterization of transport losses in cells with large area electrodes has been limited to simulations of large area electrode effects, or characterization of transport losses from large area electrodes with significant longitudinal temperature gradients. This paper describes new investigations of electrochemical kinetics and transport, particularily with WPt(sub 3.5) electrodes, including the influence of electrode size on the mass transport loss in the AMTEC cell. These electrodes possess excellent sodium transport properties making verification of device limitations on transport much more readily attained.
Previous work reported from JPL has included characterization of electrode kinetics and alkali atom transport from electrodes including Mo, W, WRh x (Mn), in sodium AMTEC cells and vapor exposure cells; and Mo in potassium vapor exposure cells. These studies were generally performed in cells with small area electrodes (about 1 to 5 cm 2 ), and device geometry had little effect on transport. Alkali metal diffusion coefficients through these electrodes have been characterized, and approximate surface diffusion coefficients were derived in cases of activated transport. A basic model of electrode kinetics and transport at the alkali metal vapor/pourous metal electrode/alkali beta"-alumina solid electrolyte (BASE) three phase boundary has been proposed which accounts for electrochemical reaction rates with a collision frequency near the three phase boundary and tunneling from the porous electrode partially covered with adsorbed alkali metal atoms. The small electrode effect in AMTEC cells has been discussed in several papers, but quantitative investigations have described only the overall effect and the important contribution of electrolyte resistance. The quantitative characterization of transport losses in cells with large area electrodes has been limited to simulations of large area electrode effects, or characterization of transport losses from large area electrodes with significant longitudinal temperature gradients. This paper describes new investigations of electrochemical kinetics and transport, with four 14.4 cm 2 WPt 3.5 electrodes, including the influence of electrode size on the mass transport loss in the AMTEC cell. These electrodes exhibit very slow sintering, as well as excellent sodium transport properties, making them attractive candidates for AMTEC power conversion use. However, the facile sodium transport in WPt 3.5 electrodes makes characterization of the transport process difficult.
Na-β''-alumina (Na 2 O.~6Al 2 O 3 ) is known to be an excellent sodium ion conductor in battery and sensor applications. In this study we report fabrication of Na- β''-alumina + YSZ dual phase composite to mitigate moisture and CO 2 corrosion that otherwise can lead to degradation in pure Na-β''-alumina conductor. Subsequently, we heat-treated the samples in molten AgNO 3 and LiNO3 to respectively form Ag-β''-alumina + YSZ and Li-β''-alumina + YSZ to investigate their potential applications in silver- and lithium-ion solid state batteries. Ion exchange fronts were captured via SEM and EDS techniques. Their ionic conductivities were measured using electrochemical impedance spectroscopy. Both ion exchange rates and ionic conductivities of these composite ionic conductors were firstly reported here and measured as a function of ion exchange time and temperature.
Measurements of coefficient of diffusion in the upper atmosphere
Thermophysical properties of sodium, potassium, and cesium at high temperatures - density of liquid potassium and vapor pressure of cesium
Phase change (solid/liquid or liquid/vapor) is a process that enables a large heat transfer capacity for a broad range of engineering applications, such as steam generators, condensers, thermal energy storage, thermosyphons, and heat pipes. Water has been the most usable phase-change cooling medium. Advanced applications are proposing alkali metals (e.g., sodium, potassium, lithium) to increase the total heat transfer rate for moderate and high-temperature applications. Sodium and potassium have the advantage of relatively low melting temperatures (98 and 64°C, respectively) make them suitable for high-temperature applications (700–1100 K). At too high of temperatures (above 1200 K), lithium is an excellent choice as a working fluid because of its high latent heat vaporization and high-surface tension. The low vapor pressure of alkali metals makes them candidates for closed spaces applications, such as thermosyphons and heat pipes. Lithium has the lowest vapor pressure than potassium and sodium, which can work at a much higher temperature without over-pressurizing the container.
The transient operation of the liquid phase of a high temperature heat pipe is studied. The study was conducted in support of advanced heat pipe applications that require reliable transport of high temperature drops and significant distances under a broad spectrum of operating conditions. The heat pipe configuration studied consists of a sealed cylindrical enclosure containing a capillary wick structure and sodium working fluid. The wick is an annular flow channel configuration formed between the enclosure interior wall and a concentric cylindrical tube of fine pore screen. The study approach is analytical through the solution of the governing equations. The energy equation is solved over the pipe wall and liquid region using the finite difference Peaceman-Rachford alternating direction implicit numerical method. The continuity and momentum equations are solved over the liquid region by the integral method. The energy equation and liquid dynamics equation are tightly coupled due to the phase change process at the liquid-vapor interface. A kinetic theory model is used to define the phase change process in terms of the temperature jump between the liquid-vapor surface and the bulk vapor. Extensive auxiliary relations, including sodium properties as functions of temperature, are used to close the analytical system. The solution procedure is implemented in a FORTRAN algorithm with some optimization features to take advantage of the IBM System/370 Model 3090 vectorization facility. The code was intended for coupling to a vapor phase algorithm so that the entire heat pipe problem could be solved. As a test of code capabilities, the vapor phase was approximated in a simple manner.
The design and construction of a prototype vaporization generator for highly dispersed sodium chloride aerosols is described. The aerosol generating system is to be used in the Science Simulator of the Cloud Physics Laboratory Project and as part of the Cloud Physics Laboratory payload to be flown on the shuttle/spacelab.
Scaled-charge models have been recently introduced for molecular simulations of electrolyte solutions and molten salts to attempt to implicitly represent polarizability. Although these models have been found to accurately predict electrolyte solution dynamic properties, they have not been tested for coexistence properties, such as the vapor pressure of the melt. In this work, we evaluate the vapor pressure of a scaled-charge sodium chloride (NaCl) force field and compare the results against experiments and a non-polarizable full-charge force field. The scaled-charge force field predicts a higher vapor pressure than found in experiments, due to its overprediction of the liquid-phase chemical potential. Reanalyzing the trajectories generated from the scaled-charge model with full charges improves the estimation of the liquid-phase chemical potential but not the vapor pressure.
The paper examines the rapidly expanding use of lasers for spectroscopic studies of alkali metal vapors. Since the alkali metals (lithium, sodium, potassium, rubidium and cesium) are theoretically simple ('visible hydrogen'), readily ionized, and strongly interacting with laser light, they represent ideal systems for quantitative understanding of microscopic interconversion mechanisms between photon (e.g., solar or laser), chemical, electrical and thermal energy. The possible implications of such understanding for a wide variety of practical applications (sodium lamps, thermionic converters, magnetohydrodynamic devices, new lasers, 'lithium waterfall' inertial confinement fusion reactors, etc.) are also discussed.
The overall operating temperature and efficiency of solar-powered Stirling engines can be improved by adding a heat transport system to more uniformly supply heat to the heater head tubes. One heat transport system with favorable characteristics is an alkali metal pool boiler. An alkali metal pool boiler heat transport system was designed for a 25-kW advanced Stirling conversion system (ASCS). Solar energy concentrated on the absorber dome boils a eutectic mixture of sodium and potassium. The alkali metal vapors condense on the heater head tubes, supplying the Stirling engine with a uniform heat flux at a constant temperature. Boiling stability is achieved with the use of an enhanced boiling surface and noncondensible gas.
Refueling systems for fast reactors are designed to handle fresh and used core assemblies (fuel, reflector, and shield core assemblies) within the reactor vessel in an opaque coolant environment without visual reference. These refueling machines are designed to work in a sodium (or other fast reactor coolant) and argon vapor space environment and are engineered with the rotatable plug system to allow for the movement of fresh and spent fuel into and out of the reactor core. The refueling machines are a critical component in any reactor and thus need to undergo extensive testing in a prototypic environment to ensure that they will meet all of the system functions and requirements. Argonne has developed an innovative compact refueling system design for the Advanced Fast Reactor-100 that is based upon some mechanisms used in previous reactor designs, such as the U.K.’s Prototype Fast Reactor (PFR) and some mechanisms that have not been used in sodium. This compact refueling machine supports the reduction in size of the AFR-100’s reactor vessel, and if fully developed, would support and inform the development of the in-vessel refueling machines for such commercial reactors as the GEH PRISM reactor plant, the ARC Clean Energy’s ARC-100 reactor, and the Natrium reactor, among others. This refueling system is a vital component of a fast reactor that supports reducing the cost of the reactor and increasing its reliability. During the development of the compact fuel handling machine conceptual design for the AFR-100, a lack of testing data for many mechanical components in sodium under typical in-reactor loads and conditions was discovered. The reduction in lifetime of the various mechanical components in the liquid sodium environment needs to be quantified versus the calculated component lifetimes under normal conditions in the testing while they are subjected to typical loading profiles experienced in the past. The Gripper Test Assembly discussed here includes a full-size gripper device with appropriate mechanical features that will be tested in sodium to provide this testing data. The Gripper Test Assembly is used to test various mechanical fuel handling components submerged in high temperature liquid sodium. These mechanisms are gears, bearings, gripper jaws and head, universal joints and shafts, ball screws, among others. These components will be tested under the typical sodium environmental conditions experienced during refueling operations with appropriate loading conditions that simulate the removal and insertion of core assemblies into a fast reactor grid plate structure. This Gripper Test Assembly is the second in a series of refueling system mechanisms developed for testing in sodium. The first test assembly is the Gear Test Assembly (GTA) which was used to test the performance of gears and bearings operating in sodium. Because of the successful testing conducted with the GTA, it was decided to continue with the development of the Gripper Test Assembly which uses the same gears and bearings tested in GTA. Using the data collected during operation of this gripper test assembly, lifetime reduction factors of the various mechanical components can be calculated for the material combinations selected. These lifetime reduction factors can be used in the design of future mechanical systems which operate in these environments to accurately predict component end of life. In addition, an understanding of the ability of these components and mechanisms to operate under-sodium with the chosen materials will be accomplished. Again, this Gripper Test Assembly is the follow-on test article to the Gear Test Assembly which was testing the ability of gears and bearings operating in a sodium environment. Once fabricated and qualified, it will be tested in the Mechanism Engineering Test Loop (METL) facility located in Building 308 at Argonne National Laboratory.
We present a Monte Carlo model of the distribution of neutral sodium in Mercury's exosphere and tail using data from the Mercury Atmospheric and Surface Composition Spectrometer (MASCS) on the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft during the first two flybys of the planet in January and September 2008. We show that the dominant source mechanism for ejecting sodium from the surface is photon-stimulated desorption (PSD) and that the desorption rate is limited by the diffusion rate of sodium from the interior of grains in the regolith to the topmost few monolayers where PSD is effective. In the absence of ion precipitation, we find that the sodium source rate is limited to approximately 10(exp 6) - 10(exp 7) per square centimeter per second, depending on the sticking efficiency of exospheric sodium that returns to the surface. The diffusion rate must be at least a factor of 5 higher in regions of ion precipitation to explain the MASCS observations during the second MESSENGER f1yby. We estimate that impact vaporization of micrometeoroids may provide up to 15% of the total sodium source rate in the regions observed. Although sputtering by precipitating ions was found not to be a significant source of sodium during the MESSENGER flybys, ion precipitation is responsible for increasing the source rate at high latitudes through ion-enhanced diffusion.
Recent results on meteor ablation are used as input to a model in which ablation (or evaporation) is the source and deposition on dust particles is the sink. The dust comes from recondensation of the rest of the meteor vapor. An excellent match is found to the observed characteristics of the sodium layer. It is argued that the high-latitude winter maximum of abundance (and layer height) is due to the much lower rate of ionization there and over the polar cap. The computations show the required factor of 4-5 and also match the height variation. To keep the ion density from being too large, downward electrodynamic transport at about 50 cm/sec must be invoked. The different behavior and low abundance of potassium require an additional sink. The one proposed is Penning ionization by metastable excited O2. Inherent in the model is that sodium and its compounds reside almost entirely on dust particles below 80 km. Large abundances in the free form at stratospheric heights are very unlikely and are not a good explanation of observed ambient ions.
The atmosphere of the Moon and Mercury will be studied by means of high resolution spectroscopy of sodium and potassium resonance line emissions. The variation of metal vapor abundances with time, and with location will be measured with a view to understanding the origin and evolution of these elements in the atmospheres of the Moon and Mercury. Infrared spectroscopic measurements will be made of Mercury to determine the surface mineralogy, predicated on the availability of the Kuiper Airborne Observatory and infrared charge coupled device (CCD). During the past year, an excellent series of measurements were completed of the spatial distribution of sodium on Mercury. Sodium was found to be concentrated at the polar regions, and to be displaced towards the terminator by solar radiation pressure. Sodium and potassium were discovered in the atmosphere of the Moon. The ratio of sodium to potassium approximates that of the lunar regolith. Thermal infrared measurements of Mercury showed that the Christiansen peak was located shortwards of 8 micrometer, which indicates an acidic mineralogy.