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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
NASA NTRS2024

The Relationship Between Volatile Element Abundances and Iron Carrying Capacity in Lunar Volcanic and Impact Vapors

The highly volatile elements (e.g. H, C, S, Cl) released during lunar volcanism provide important insights into the bulk volatile composition of the Moon. Once erupted, some fraction of the species containing these elements may have migrated to the poles where they could have become sequestered in shadowed cold traps such as those found near the lunar South pole. The volatiles trapped in the lunar South pole are of great interest to the upcoming Artemis missions, which will be operating nearby and could sample some of those materials. Volcanic vapor deposits in the polar regions might also be supplemented by volatiles from other sources both exogenous (i.e. comets) and endogenous (i.e. remobilization of lunar volatiles by impact). Characterizing these endogenous sources is challenging because the highly volatile elements often leave little trace behind in the rocks themselves, which are inherently refractory by nature. Minerals are found on vug, vesicle, or fracture surfaces that have characteristics consistent with phases formed via direct deposition of a vapor, as opposed to crystallization from a liquid or via solid state decomposition. One common vapor-deposited species is metallic Fe, typically observed as subhedral to euhedral crystals found on vug or vesicle walls in mare basalts and on select breccia clast surfaces in regolith soil samples returned from the Moon. A particularly striking example is seen below in Fig. 1, where numerous Fe crystals are deposited onto the wall of a vug in Apollo 17 basalt sample 71036. Euhedral Fe crystals are not very common in Apollo breccia samples, though this may be from the limited number of systematic searches that have been performed. However, when Fe crystals are found, they can occur in extremely high abundance(e.g., sample 15402 which was specifically selected because of its numerous Fe crystals, was found to have a clast with 477 euhedral Fe crystals in a 570 x 570 μm area). What struck us as interesting about this was not only that it takes a large amount of Fe to make these crystal-rich deposits, but also that these crystal-rich deposits are not ubiquitous, and therefore they must be controlled by some aspect of their depositional conditions that varies. Since those conditions are inherently difficult to investigate and are critically interesting, we used thermochemical modeling as a tool to investigate the relationship between vapor-deposited Fe and various intensive and extensive parameters. We assumed that a high abundance of Fe in the vapor is required to form these crystals, thus the mass of Fe in the vapor was used to determine the plausibility of the vapor-deposited, euhedral Fe crystals observed in Apollo samples.

thermodynamics↗
NASA NTRSDate not supplied

Validation of a Multiphase Computational Fluid Dynamics Model for Vapor Pull-Through in Normal and Low Gravity

On-orbit fluid transfer such as refueling of propellant tanks and life-support systems can enable long-duration space missions. For safe and efficient liquid transfer operations, prior knowledge of liquid positioning and liquid-vapor interface behavior while draining in a low-gravity environment is required. Numerical models capable of predicting vapor ingestion (or vapor pull-through) can be used to design liquid transfer operations while reducing liquid residuals, mission risk and settling thrust required to prevent vapor ingestion. An experimental program conducted in the 2.2 Second Drop Tower facility at NASA Glenn Research Center investigated the vapor ingestion phenomenon for a range of outflow rates and tank sizes providing a database for validation. This study presents a Computational Fluid Dynamics model capable of accurately predicting the vapor ingestion using the Volume-of-Fluid multiphase solver in commercial code STAR-CCM+. A description of the experimental setup and general trends from similar studies are presented. Comparisons of the numerical prediction and test data in normal and low gravity show good agreement and give confidence in pursuing design of full-scale propellant transfer systems.

Computational Fluid Dynamics↗
NASA NTRSDate not supplied

Validation of a Multiphase Computational Fluid Dynamics Model for Vapor Pull-Through in Normal and Low Gravity

On-orbit fluid transfer such as refueling of propellant tanks and life-support systems can enable long-duration space missions. For safe and efficient liquid transfer operations, prior knowledge of liquid positioning and liquid-vapor interface behavior while draining in a reduced-gravity environment is required. Numerical models capable of predicting vapor ingestion (or vapor pull-through) can be used to design liquid transfer operations while reducing liquid residuals, mission risk and settling thrust required to prevent vapor ingestion. An experimental program conducted in the 2.2 Second Drop Tower facility at NASA Lewis Research Center in 1969 investigated the vapor ingestion phenomenon for a range of outflow rates and tank sizes providing a database for validation. This study presents a Computational Fluid Dynamics model capable of accurately predicting the vapor ingestion using the Volume-of-Fluid multiphase solver in commercial code STAR-CCM+. A description of the experimental setup and general trends from similar studies are presented. Comparisons of the numerical prediction and test data in normal and low gravity show good agreement and give confidence in pursuing design of full-scale propellant transfer systems.

Computational Fluid Dynamics↗
NASA NTRSDate not supplied

Validation of A Multiphase Computational Fluid Dynamics Model for Vapor Pull-Through in Normal and Low Gravity

On-orbit fluid transfer such as refueling of propellant tanks and life-support systems can enable long-duration space missions. For safe and efficient liquid transfer operations, prior knowledge of liquid positioning and liquid-vapor interface behavior while draining in a reduced-gravity environment is required. Numerical models capable of predicting vapor ingestion (or vapor pull-through) can be used to design liquid transfer operations while reducing liquid residuals, mission risk and settling thrust required to prevent vapor ingestion. An experimental program conducted in the 2.2 Second Drop Tower facility at NASA Lewis Research Center in 1969 investigated the vapor ingestion phenomenon for a range of outflow rates and tank sizes providing a database for validation. This study presents a Computational Fluid Dynamics model capable of accurately predicting the vapor ingestion using the Volume-of-Fluid multiphase solver in commercial code STAR-CCM+. A description of the experimental setup and general trends from similar studies are presented. Comparisons of the numerical prediction and test data in normal and low gravity show good agreement and give confidence in pursuing design of full-scale propellant transfer systems.

Propellant Transfer↗
DOE OSTI2022

At-Line Sampling and Characterization of Pyrolytic Vapors from Biomass Feedstock Blends Using SPME-GC/MS-PCA: Influence of Char on Fast Pyrolysis

Solid-phase microextraction (SPME) coupled with GC-MS analysis was used for at-line sampling of pyrolytic vapors produced during fast pyrolysis of biomass. The pure and binary blends of switchgrass (SWG) and pine harvest residues (PT6) were used as feedstock. Sequential SPME sampling allowed for monitoring of changes in the pyrolysis vapors as char accumulated in the fluid bed. The concentration and composition of the vapors desorbed from the SPME fibers were investigated using GC-MS, and the data sets were then analyzed using principal component analysis (PCA) to compare the composition of the pyrolysis vapors over the course of the pyrolysis run. The chemical composition of both carbohydrate and lignin fragments varied as the char builds up in the reactor bed. Fragments derived from cellulose and xylan included anhydrosugars, furans and light oxygenated compounds. Lignin fragments included methoxyphenols, phenolic ketones and aldehydes, low molecular weight aromatics. The composition of the carbohydrate fragments changed more than the lignin fragments as the char build-up in the fluid bed. This combination of SPME-GC/MS-PCA were a novel, easy and effective method for measuring the composition and changes in the composition of pyrolysis vapors during the fast pyrolysis process. Here, this work also highlighted the effect of char build-up on the composition of the overall pyrolysis vapors.

09 BIOMASS FUELS↗
DOE OSTI2021

Vapor–liquid equilibrium of water with the MB-pol many-body potential

Among the many existing molecular models of water, the MB-pol many-body potential has emerged as a remarkably accurate model, capable of reproducing thermodynamic, structural, and dynamic properties across water's solid, liquid, and vapor phases. In this work, we assessed the performance of MB-pol with respect to an important set of properties related to vapor-liquid coexistence and interfacial behavior. Through direct coexistence classical molecular dynamics simulations at temperatures of 400 K < T < 600 K, we calculated properties such as equilibrium coexistence densities, vapor-liquid interfacial tension, vapor pressure, and enthalpy of vaporization and compared the MB-pol results to experimental data. We also compared rigid vs fully flexible variants of the MB-pol model and evaluated system size effects for the properties studied. We found that the MB-pol model predictions are in good agreement with experimental data, even for temperatures approaching the vapor-liquid critical point; this agreement was largely insensitive to system sizes or the rigid vs flexible treatment of the intramolecular degrees of freedom. Furthermore, these results attest to the chemical accuracy of MB-pol and its high degree of transferability, thus enabling MB-pol's application across a large swath of water's phase diagram.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

A Deep Potential model for liquid–vapor equilibrium and cavitation rates of water

Computational studies of liquid water and its phase transition into vapor have traditionally been performed using classical water models. Here, we utilize the Deep Potential methodology—a machine learning approach—to study this ubiquitous phase transition, starting from the phase diagram in the liquid–vapor coexistence regime. The machine learning model is trained on ab initio energies and forces based on the SCAN density functional, which has been previously shown to reproduce solid phases and other properties of water. Here, we compute the surface tension, saturation pressure, and enthalpy of vaporization for a range of temperatures spanning from 300 to 600 K and evaluate the Deep Potential model performance against experimental results and the semiempirical TIP4P/2005 classical model. Moreover, by employing the seeding technique, we evaluate the free energy barrier and nucleation rate at negative pressures for the isotherm of 296.4 K. Further, we find that the nucleation rates obtained from the Deep Potential model deviate from those computed for the TIP4P/2005 water model due to an underestimation in the surface tension from the Deep Potential model. From analysis of the seeding simulations, we also evaluate the Tolman length for the Deep Potential water model, which is (0.091 ± 0.008) nm at 296.4 K. Finally, we identify that water molecules display a preferential orientation in the liquid–vapor interface, in which H atoms tend to point toward the vapor phase to maximize the enthalpic gain of interfacial molecules. We find that this behavior is more pronounced for planar interfaces than for the curved interfaces in bubbles. This work represents the first application of Deep Potential models to the study of liquid–vapor coexistence and water cavitation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Application of templated vapor-liquid-solid growth to heteroepitaxy of InP on Si

Direct growth of III–V semiconductors on Si promises to combine the superior optoelectronic properties of III–Vs with the existing large-scale fabrication capabilities for Si. Vapor-liquid-solid-based growth techniques have previously been used to grow optoelectronic-quality III–Vs in polycrystalline films and various photolithography-defined features. We show that templated vapor-liquid-solid growth can produce epitaxial material when performed on crystalline substrates. In templated vapor-liquid-solid growth, the metal group-III precursor is evaporated along with a capping SiO 2 layer on the crystalline substrate, then melted and converted with exposure to a vapor-phase group-V precursor. We demonstrate homoepitaxial growth of InP on InP wafers using two forms of the SiO x capping layer to confine the liquid metal: evaporated SiO 2 and solgel SiO x , the latter of which is necessary for growth on Si. We then demonstrate heteroepitaxial growth of InP islands on Si substrates from both evaporated and electroplated In metals. The templated vapor-liquid-solid process provides better material utilization and growth rates than common vapor-phase techniques, with similar control and convenience, providing a path toward the large-scale fabrication of integrated optoelectronic components.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS2013

Assessing the Temperature Dependence of Narrow-Band Raman Water Vapor Lidar Measurements: A Practical Approach

Narrow-band detection of the Raman water vapor spectrum using the lidar technique introduces a concern over the temperature dependence of the Raman spectrum. Various groups have addressed this issue either by trying to minimize the temperature dependence to the point where it can be ignored or by correcting for whatever degree of temperature dependence exists. The traditional technique for performing either of these entails accurately measuring both the laser output wavelength and the water vapor spectral passband with combined uncertainty of approximately 0.01 nm. However, uncertainty in interference filter center wavelengths and laser output wavelengths can be this large or larger. These combined uncertainties translate into uncertainties in the magnitude of the temperature dependence of the Raman lidar water vapor measurement of 3% or more. We present here an alternate approach for accurately determining the temperature dependence of the Raman lidar water vapor measurement. This alternate approach entails acquiring sequential atmospheric profiles using the lidar while scanning the channel passband across portions of the Raman water vapor Q-branch. This scanning is accomplished either by tilt-tuning an interference filter or by scanning the output of a spectrometer. Through this process a peak in the transmitted intensity can be discerned in a manner that defines the spectral location of the channel passband with respect to the laser output wavelength to much higher accuracy than that achieved with standard laboratory techniques. Given the peak of the water vapor signal intensity curve, determined using the techniques described here, and an approximate knowledge of atmospheric temperature, the temperature dependence of a given Raman lidar profile can be determined with accuracy of 0.5% or better. A Mathematica notebook that demonstrates the calculations used here is available from the lead author.

Raman lidar↗
DOE OSTI2020

Respirator Cartridge Performance on Mixed Vapors from Hanford Tank Headspaces and Exhausters - 20427

Between 2016 and 2018, the Hanford Tank Operations Contractor - Washington River Protection Solutions (WRPS) - conducted a series of tests of air-purifying respirator (APR) chemical cartridges commonly used at Hanford tank farms to determine the period of time for which the cartridges would provide adequate performance when used in APRs and powered-air-purifying respirators (PAPRs) to protect workers when exposed to a mixture of vapors exiting tank headspaces. Although cartridge manufacturers provide service life estimating tools for individual chemical compounds, the projected performance of these cartridges on complex vapor mixtures is not available, and the adequacy of APRs for tank farm applications represents an important workforce concern. The Occupational Safety and Health Administration identifies cartridge testing as a valid approach for establishing cartridge service life. The primary function of the WRPS Cartridge Test Program was to obtain objective data to determine service lives for the APR and PAPR cartridges used at Hanford tank farms. WRPS contracted with Pacific Northwest National Laboratory to analyze the test data and offer an independent analysis of and recommendations based on respirator cartridge performance. A total of 28 APR and 10 PAPR cartridge tests were conducted between 2016 and 2018 on 12 different tank headspaces and tank farm exhauster slipstreams. Two APR cartridges from SCOTT (now 3M) and two PAPR cartridges from MSA Safety, Inc. and 3M were evaluated using a cartridge testing system specifically designed to measure and monitor test conditions and sample cartridge inlet and outlet vapor streams for important chemical compounds. Testing focused on analysis of approximately 61 tank vapor chemicals of potential concern (COPCs) that have been previously detected in tank vapors at levels above 10% of their occupational exposure limits (OELs). Each test was conducted over 16 hours of run time. Evidence of chemical breakthrough was assessed by comparing inlet and outlet COPC concentrations over the duration of each test. The breakthrough threshold was normally defined as exceeding 10% of the compounds OEL at the cartridge outlet. Ammonia breakthrough was observed in a majority of the cartridge tests and occurred earlier than breakthrough of any other chemical compound. Several other COPCs did exhibit breakthrough behavior, including mercury, 1,3-butadiene, furan, 2,5 dihydrofuran, and N-nitrosodimethylamine (NDMA), but only in a very limited number of cartridge tests and only after ammonia breakthrough had occurred. In addition, tests results suggest that breakthrough of some of these COPCs may have been affected by competition with and breakthrough of other non-COPC organics, such as ethanol and acetone, with substantially lower toxicological hazard. Comparison of cartridge manufacturers' service life estimates with the experimentally derived breakthrough times indicates that manufacturers' estimates are generally conservative, even in the presence of the complex mixed vapor streams experienced in these tests. With consideration of appropriate safety margins, these results provide valuable insights on cartridge performance to inform industrial hygiene professionals in establishing appropriate cartridge change-out schedules for APR and PAPR use in the Hanford tank farms. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Aerosol Indirect Effects on Water Vapor in the UTLS of Typhoon Saomai (2006)

The evolution of landfalling Typhoon Saomai (2006) is simulated using the Weather Research and Forecasting model with spectral bin microphysics scheme, showing tropical cyclone (TC) could vertically transport water vapor from troposphere to upper troposphere and lower stratosphere (UTLS). Three aerosol sensitivity experiments are conducted to explore the indirect effects of aerosol served as cloud condensation nuclei (CCN) on overshooting convection (OTC) and water vapor content in UTLS, namely MAR (maritime), MIX (semi‐continental) and CON (continental). Results revealed that CON simulation with high initial aerosol concentration showing invigorated convection at the periphery of the TC, which interfered with the reformation of TC eyewall, leading to TC weakening finally. In addition, CON simulated the least water content in UTLS through suppressing the number of convection overshooting the tropopause level. Most overshooting events take place during TC developing stage in the eyewall region before landfall. Higher levels of CCN concentration could lead to decreased number of OTC in TC, consistently reduced the water vapor content in UTLS. CON and MIX experiments simulated respectively 21.9% (16.2%) and 9.96% (1.5%) less OTC (water vapor content in UTLS) than MAR simulation. Further, water vapor content in UTLS is affected by the interaction of OTC and ice‐phase microphysics. The interesting point is that the CCN sensitivity experiments show that water vapor content in UTLS of a TC is sensitive to the CCN concentration in the boundary layer.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Sensitivity of magnetohydrodynamic simulations of Joule-heated conductors to the vaporization curve in equations of state

Magnetohydrodynamic (MHD) simulations of electrically exploded aluminum and copper rods demonstrate a technique to validate equations of state (EOS) for rapidly Joule-heated conductors. The balance of internal and magnetic forces at the conductor-insulator interface drives the metal there along the vaporization phase boundary. Variations between critical points and vaporization curves in existing models predict differing densities and temperatures in MHD simulations for these models. Here, the inclusion of Maxwell constructs in the liquid-vapor biphase region of the EOS caused the rod surface to vaporize earlier in time than unmodified tables with van der Waals loops. Velocimetry of recent experiments is used to validate the location of the vaporization curve in existing EOS models and differentiate between the vapor dome treatments. Dielectric coatings applied to the metal surface restricted the conductor’s expansion and diverted the metal into the warm dense matter regime.

36 MATERIALS SCIENCE↗
DOE OSTI2020

The Incredible Lightness of Water Vapor

The molar mass of water vapor is much less than that of dry air. This makes a moist parcel lighter than a dry parcel of the same temperature and pressure. This effect is referred to as the vapor buoyancy effect and has often been overlooked in climate studies. We propose that the vapor buoyancy effect increases Earth’s outgoing longwave radiation (OLR) and that this negative radiative effect increases with warming, stabilizing Earth’s climate. We illustrate this mechanism in an idealized tropical atmosphere, where there is no horizontal buoyancy gradient in the free troposphere. Temperature increases toward dry atmosphere columns to compensate the reduced vapor buoyancy, increasing OLR by O(1 W m −2 ) at the reference climate. In warmer climates, the temperature difference between moist and dry columns would increase as a result of increasing atmospheric water vapor, leading to enhanced radiative effect and thereby stabilizing Earth’s climate. We estimate that this feedback strength is about O(0.2 W m −2 K −1 ) in the idealized atmosphere, which compares to cloud feedback and surface albedo feedback in the current climate. We further show evidence from observations and real-gas radiative transfer calculations for a significant radiative effect of vapor buoyancy in the tropical atmosphere.

Yang, Da↗
DOE OSTI2022

Development of electrostatic precipitator (ESP) technology to remove elemental mercury vapor, HG(0)

The presence of mercury vapor or other forms of mercury presents issues with worker safety, decommissioning facilities, and environmental impacts. As such, it is desired to develop a strategy to either remove or reduce mercury levels in Oak Ridge’s Y-12 Complex facilities. A testing methodology was developed to evaluate electrostatic precipitator technology for removal of mercury vapor. This methodology involved supplying mercury vapor-containing air to the ESP device by flowing air through a column containing alternating layers of sand and liquid mercury droplets. Initial attempts at quantifying the efficacy of the ESP device in removing mercury vapor were plagued with difficulties in controlling the flow of mercury into the ESP device due to poor performance of the generator column and the contamination of these experiments with mercury from an unknown source. These issues were resolved by creating a new generator column with slower air velocity and higher surface area of liquid mercury, along with moving the air intake for the ESP device to outside of the chemical hood in which testing took place. This resulted in a steady, quantified flow of mercury vapor from the generator column and no observation of unintended mercury sources. A final test of the ESP device under these controlled conditions showed that for a certain amount of time (on the order of 20-30 minutes) mercury concentrations were reduced by approximately 33 - 67% of the inlet concentration. However, episodic releases or pulses of mercury observed only at the outlet indicated that the mercury accumulated in the ESP device is periodically expelled. As a result, it was not deemed to be an efficient strategy for the removal of elemental mercury vapor.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Permeation Properties of Disordered Metal-Organic Framework Membranes Made by Vapor Phase Ligand Treatment

Zeolitic imidazolate frameworks (ZIFs) are nanoporous molecular sieves offering exciting opportunities for membrane- and adsorption-based gas separations. The Tsapatsis group developed an all-vapor-phase ligand induced permselectivation (LIPS) method for the fabrication of ZIF nanocomposite membranes. The LIPS method consists of a combination of atomic layer deposition of a dense oxide inside the mesopores of a porous support followed by transformation of the dense oxide deposit to nanoporous ZIF by exposure to sublimated vapors of an imidazolate ligand. It enables the formation of thin nanocomposite films consisting of ZIF deposited inside pores with diameters smaller than 10 nm. Vapor-phase conversion of the impermeable ZnO to ZIF increases flux of certain gases more than others. Vapor phase linker/ligand treatment (VPLT) can further modify the properties of LIPS and other membranes. The combination of LIPS with VPLT provides an all-vapor methodology for making and modifying ZIF membranes with the ability to control the ZIF deposit composition and the level of confinement in a variety of mesoporous supports. The propylene/propane separation performance of LIPS/VPLT ZIF membranes confined (entirely or partially) inside mesopores is remarkably superior to that of most conventional ZIF membranes consisting of unconfined (deposited on the external surface of porous supports) polycrystalline films. The accomplishments of this award are: (i) understanding of the LIPS process using mathematical models of atomic layer deposition (ALD), (ii) development of surface modification methods (vapor, e-beam, plasma, and X-ray treatments) to tune permeation properties, (iii) microstructural control of ZIF-8 films using ALD (support modification, direct ALD, and by use of in situ permeability monitoring), (iv) molecular simulations, and (v) thin film characterization and adsorption measurements using spectroscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1975

Dynamic sampling of laser-induced vapor plumes by mass spectrometry

Mass spectrometric techniques and instrumentation for the dynamic sampling of laser-induced vapor clouds during their submillisecond expansion periods are discussed. Illustrations are drawn primarily from the results of pulsed-laser heating of some oxides and graphites; these include comparisons of incident laser beam pulses with the resultant pulses of positive ions and selected neutral species. Observed characteristics of vapor pulses from graphite are shown to correlate with calculated surface temperature response. Dynamic velocity measurements of individual vapor species are described and, from these velocities, vaporization temperatures are derived and compared using four gas dynamic models for vapor expansion into vacuum. Additional measurements indicate that the laser beam may interact directly with the neutral vapors to produce ions.

Lincoln, K. A.↗
NASA NTRS1979

Mass spectrometric investigation of the vaporization of sodium and potassium chromates: Preliminary results

Knudsen cell mass spectrometry was used to study the vaporization of sodium and potassium chromates. For both salts, the vaporization proceeds predominately by the reactions M2CrO4(c)=2M(g)+5/4O2(g)+1/2 Cr203(s) and M2CrO4(c)=M2CrO4(g) where M = Na or K. The distribution of the ions M(+), O2(+) and M2CrO4(+) in the measured mass spectrum was found to depend on the material used for the Knudsen cell, even for materials such as platinum and gold. In the case of sodium chromate, the decomposition reaction appears to be less important than the molecular vaporization reaction. A preliminary value of 72 kcal/mole at 1141 K was measured for the heat of the molecular vaporization reaction for sodium chromate. In the case of potassium chromate, it has not been possible to conclude which mode of vaporization dominates. For potassium chromate a value of 101 kcal/mole at 1173 K was obtained for the heat of the molecular vaporization reaction.

Stearns, C. A.↗
NASA NTRS1982

Vaporization thermodynamics of K2S and K2SO3

The vaporization reactions, vapor pressures, and thermodynamics of potassium sulfide and potassium sulfite were studied for purposes of providing fundamental data for the seed cycle in magnetohydrodynamic electric power generation. Rate of effusion studies, supported by tube furnace experiments, X-ray powder diffraction, mass spectrometry and appropriate chemical analyses and tests, revealed that potassium sulfite disproportionates at high temperatures to form potassium sulfide and potassium sulfate. Potassium sulfide was observed to vaporize incongruently, the initial vapors beng predominantly potassium atoms, with minor species being S2 and various K-S molecules. The ratio of K/S2 in the vapor is very large initially and decreases steadily with prolonged heating. Several materials were evaluated for purposes of containing K2S/K2SO3 at temperatures or = 800 C: Pt, Mo, W, quartz, machinable glass, BN, high density graphite, pyrolytic coated graphite, and alumina. Of these, only alumina was observed to be chemically inert to both K2S but reacted with K2SO3. The other materials were not suitable for either substance. Thermodynamic calculations based on measured vapor pressures and approximate free energy functions are described. Results from isothermal total mass loss experiments and from thermogravimetric experiments are also included.

Bennet, J. E.↗