Propellant vaporization as a criterion for rocket engine design : calculations of chamber length to vaporize a single n-heptane drop
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This work describes the ongoing development of an instrument package for the in-situ detection and isotopic analysis of water (from ice, icy soils, and hydrated minerals) on future lunar, asteroid, or martian exploration missions. This instrument is intended to be mounted on a robotic arm and be brought to the sample, rather than necessitating expensive and complicated sample handling to bring the sample to the instrument.
Washington River Protections Solutions, LLC (WRPS) is the prime contractor for the Department of Energy (DOE) Tank Farm Operations at the Hanford Site, and is responsible for the management and retrieval of millions of gallons of radioactive and chemical wastes, stored in 177 underground tanks; a legacy of decades of production activities at the Site. The potential for workforce exposure to the chemical vapors from the tanks has long been a concern for the workforce and for DOE and its tank contractors; concerns about tank vapors is an issue that pre-dates WRPS's incumbency as the Tank Operations Contractor. In response to an increase in the number of tank vapor events reported by workers at the Hanford Site in 2014, WRPS commissioned the Savannah River National Laboratory with establishing and overseeing a panel of external, independent experts (Tank Vapor Assessment Team (TVAT)) to examine chemical vapor management and related worker-protection measures at the Hanford Tank Farms. The TVAT released the Hanford Tank Vapor Assessment Report (SRNL-RP-2014-00791) in late 2014, which included several recommendations to reduce the potential for chemical vapor exposures. From 2015- 2018, governmental and external groups conducted additional assessments to review the progress made in implementing the TVAT recommendations, and the overall Industrial Hygiene (IH) program. All of these assessments specifically recommended WRPS take action to improve communications with the workforce around the subject of tank vapors. Some further recommended assessing the effectiveness of vapors-related communications. In fiscal year 2016, WRPS and DOE Office of River Protection (DOE-ORP) formed an Integrated Project Team (IPT) to: (1) develop the strategy for addressing chemical vapors and (2) define the future chemical vapor protection actions at the Tank Farms. The actions are designed to address the recommendations from the external assessments as part of the overall effort to mitigate vapors-related exposure incidences, and to ensure workers are safe and feel safe while working in and around the Hanford Tank Farms. A comprehensive vapor management communication plan, engagement processes, and effectiveness measurements were established as essential components of the IPT effort. The Chemical Protection Program Office (CPPO) was formed, in part, to deliver on these IPT initiatives, monitor performance, and drive improvements to WRPS's vapors-related communications and engagement efforts at the Hanford Tank Farms. The CPPO was created as a temporary program office tailored to address these unique challenges by augmenting traditional company performance monitoring and communications (i.e. all employee e-mails, posters, and formal briefings). Modeled in broad concept after the successful program office WRPS created to support the American Recovery and Reinvestment Act, CPPO has also proven successful in its mission. Because concerns about chemical vapors in the workplace were expressed by the workforce, they are a key stakeholder. As such, the CPPO has concentrated its information sharing efforts toward the WRPS workforce. With a focus on empathetic engagement, continuous improvement, and transparent information sharing, the CPPO has developed and implemented a strategy for improving worker trust in vapors-related communications and increasing the workforce knowledge of responses taken to address chemical vapors. Effective implementation of this strategy is demonstrated by the results of workforce surveys, which indicate measured and important improvement in the effectiveness of vapors-communications and the knowledge level workers report about vapor issues compared to the previous year. This paper discusses the utilization of a temporary program office and the unique approach that the CPPO implemented to achieve success, including: strategic application of the technical and communications staff skill mix of the organization (including talent development opportunities such as stretch assignments for WRPS's Strategic Talent Development program members and support from WRPS college interns), teaming with other WRPS' organizations such as IH, Engineering and Communications and Public Relations (C and PR), the development of new types of information sharing to support the effort, and the methods by which the effectiveness of the communications efforts are measured to drive continuous improvement. (authors)
Knowing accurate saturated vapor pressures of explosives at ambient conditions is imperative to provide realistic boundaries on available vapor for ultra-trace detection. In quantifying vapor content emanating from low-volatility explosives, we observed discrepancies between the quantity of explosive expected based on literature vapor pressure values and the amount detected near ambient temperatures. Most vapor pressure measurements for low-volatility explosives, such as RDX (1,3,5-trinitro-1,3,5-triazinane) and HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane), have been made at temperatures far exceeding 25 °C and linear extrapolation of these higher temperature trends appears to underestimate vapor pressures near room temperature. Our goal was to measure vapor pressures as a function of temperature closer to ambient conditions. We used saturated RDX and HMX vapor sources at controlled temperatures to produce vapors that were then collected and analyzed via atmospheric flow tube-mass spectrometry (AFT-MS). The parts-per-quadrillion (ppqv) sensitivity of AFT-MS enabled measurement of RDX vapor pressures at temperatures as low as 7 °C and HMX vapor pressures at temperatures as low as 40 °C for the first time. Furthermore, these vapor pressures were corroborated with analysis of vapor generated by nebulizing low concentration solutions of RDX and HMX. We report updated vapor pressure values for both RDX and HMX. Based on our measurements, the vapor pressure of RDX at 25 °C is 3 ± 1 x 10-11 atm (i.e. 30 parts per trillion by volume, pptv), the vapor pressure of HMX is 1.0 ± 0.6 x 10-14 atm (10 ppqv) at 40 °C and, with extrapolation, HMX has a vapor pressure of 1.0 ± 0.6 x 10-15 atm (1.0 ppqv) at 25 °C.
DOE contractor CH2M Hill Plateau Remediation Company is currently responsible for conducting groundwater contamination monitoring at several RCRA treatment, storage, and disposal units located on the Hanford Site in Richland, Washington State. The Nonradioactive Dangerous Waste Landfill treatment, storage, and disposal unit presents a distinct groundwater monitoring problem because of a large multi-contaminant soil vapor plume beneath it that is a likely source of low-level volatile organic compound groundwater contamination. Adjacent to Nonradioactive Dangerous Waste Landfill is the Solid Waste Landfill. Volatile organic compounds are inventory components of both the Nonradioactive Dangerous Waste Landfill and the Solid Waste Landfill. Therefore, it is possible that both sites could be contributing to the soil vapor plume. For regulatory purposes, it is important to differentiate which site is the primary contributor of volatile organic compounds to the plume. An approach was developed to identify the primary volatile organic compound source of the soil vapor plume beneath Nonradioactive Dangerous Waste Landfill and Solid Waste Landfill. The site conceptual model hypothesis of vapor-phase volatile organic compound transport to the dissolved phase in groundwater was tested by a simple mathematical model of vapor/liquid equilibrium concentrations at the groundwater/air interface. Once it was shown that vapor-phase volatile organic compound transport to groundwater was a valid conceptual model for Nonradioactive Dangerous Waste Landfill and Solid Waste Landfill, spatial and statistical methods were used to determine the primary site contributing to the majority of volatile organic compounds to the soil vapor plume. Average groundwater chloroform, tetrachloroethene, and trichloroethene concentrations from Nonradioactive Dangerous Waste Landfill and Solid Waste Landfill monitoring network wells were plotted on maps of the facilities and immediate vicinities and compared to soil vapor sampling probe locations. Principal component analysis and mixing ratios were used to identify source contributions of each treatment, storage, and disposal unit to the plume. Results of the vapor/liquid equilibrium concentrations mathematical model showed that transport phenomena outweigh steady-state equilibria. Estimated vapor/liquid equilibrium concentrations were considerably lower than soil vapor measurements. The results indicate that dynamic vadose zone and groundwater factors such as decreased vapor concentrations with depth, vapor dilution from dispersion in the vadose zone, and advective and diffusional volatile organic compound dilution in groundwater result in groundwater volatile organic compound concentrations much less than would be measured under steady-state equilibrium conditions. Site source contribution differentiation by principal component analysis and mixing ratios was inconclusive using actual soil gas data because of the similarity in concentration values in both datasets for Nonradioactive Dangerous Waste Landfill and Solid Waste Landfill. Similar data populations suggest mixing of the vapor contributions from both sites by dispersion through the soil matrix pore spaces. However, when groundwater volatile organic compound data were compared between the Nonradioactive Dangerous Waste Landfill and Solid Waste Landfill monitoring networks, Solid Waste Landfill mean concentrations were higher, suggesting more vapor-phase volatile organic compound transport to groundwater at those locations. Simulated volatile organic compound soil vapor and groundwater datasets created to test the methods developed for this study show that the method can be successful in source differentiation when significantly different datasets are compared. This paper will describe a method of testing a conceptual model for vapor-phase contaminant transport to groundwater and for differentiating site sources of contaminants comprising a mixed-constituent soil vapor plume. (authors)
Previous work by Savannah River National Laboratory (SRNL) indicated that the actual Next Generation Solvent vapor pressure would be higher than the Original Caustic Side Solvent Extraction (CSSX) solvent vapor pressure, but below a bounding vapor pressure using Raoult’s Law. Since solvent vapor pressure has a significant impact on Composite Lower Flammability Limits (CLFL) and attendant accident analyses, obtaining an additional margin from the bounding NGS vapor pressure would be valuable. In order to quantify how much margin might be gained from the NGS bounding solvent, SRNL researchers were requested to perform vapor pressure testing with the Next Generation Solvent (NGS) by Savannah River Mission Completion (SRMC). The vapor pressure curve for the NGS formulation set to be deployed at the Salt Waste Processing Facility (SWPF) has been determined by SRNL up to 55°C (131°F) using headspace Gas Chromatography (GC). It was expected that NGS would have a higher vapor pressure than the Original CSSX solvent; however, experimental results indicate a lower vapor pressure. At this time, it is uncertain if this difference is due to the 7x increase in concentration of the large calixarene in the solvent (0.007M BOBCalix in Original CSSX solvent vs. 0.05M MaxCalix in NGS) or to minor batch-to-batch variations in Isopar-L constituents. The NGS and the Original CSSX solvent vapor pressure data were fitted to the Antoine Equation. The Antoine equation gives a more accurate representation of the expected vapor pressure of the solvents outside of the temperature range tested. The Antoine equation fitting for NGS is given below: $P=10^{6.364⁻\frac{1788.4}{T+219.3}}$. Where, p is the vapor pressure (partial pressure) of NGS in mmHg and T is the temperature in °C. It is recommended that SRMC either continue using the more conservative Isopar-L vapor pressure calculations at SWPF with the equation developed for the Original CSSX solvent, or the equation presented above for the NGS solvent. Additionally, it is recommended to study the variability in Isopar-L vapor pressure between lots.
Design assumptions during the vacuum refill phase of the Pulsed Jet Mixers (PJMs) in the Hanford Waste Treatment and Immobilization Plant (WTP) equate the vapor pressure of all process streams to that of water when calculating the temperature at which the vacuum refill is reduced or eliminated. WTP design authority asked the authors to assess this assumption by performing calculations on proposed feed slurries to calculate the vapor pressure as a function of temperature. The vapor pressure was estimated for each WTP waste group. The vapor pressure suppression caused by dissolved solids is much greater than the increase caused by organic components such that the vapor pressure for all of the waste group compositions is less than that of pure water. The vapor pressure for each group at 145°F ranges from 81% to 98% of the vapor pressure of water. If desired, the PJM could be operated at higher temperatures for waste groups with high dissolved solids that suppress vapor pressure. The SO4 group with the highest vapor pressure suppression could be operated up to 153°F before reaching the same vapor pressure of water at 145°F. However, most groups would reach equivalent vapor pressure at 147 to 148°F. If any of these waste streams are diluted, the vapor pressure can exceed the vapor pressure of water at mass dilution ratios greater than 10, but the overall effect is less than 0.5%.
Much of the experimental work on vapor phase lubrication has employed certain organo phosphorous compounds as the vapor phase lubricant. Graham and Klaus, for instance, used tricresyl phosphate (TCP) and tributyl phosphate to vapor phase lubricate a four-ball wear tester using M50 steel balls at 370 C. Makki and Graham were able to vapor phase lubricate a reciprocating pin on plate tribometer using 1018 steel at 280 C with TCP vapor. Although a few organo phosphorous compounds, such as TCP, have been successfully used as vapor phase lubricants in many laboratory experiments, many problems remain unsolved. Two areas of concern relate to the 'durability' of phosphate deposited films and to the ability of the lubricating system to "self-recover" when vapor phase lubricated with an organo phosphorous compound. Durability refers to the ability of the deposited film to provide effective lubrication, for a period of time, after the vapor flow to the lubricating surfaces has been interrupted. Vapor phase lubrication tests, conducted at Cleveland State University with their high temperature tribometer, revealed that when TCP vapor flow to the lubricating surfaces was interrupted the frictional coefficient of the system rapidly increased from a value less than 0.1 to a value of 0.3 which was selected as our failure point. Self-recovery means the ability of the vapor phase lubricant to reduce the frictional coefficient of the lubricating system back down to value less than 0.1 after startup of the interrupted vapor flow. Lubrication tests conducted at Cleveland State University revealed that the high temperature tribometer could not self-recover after startup of the interrupted TCP vapor flow.
The method disclosed herein may be practiced by passing the vapors to be sampled along a path with halogen vapor, preferably chlorine vapor, heating the mixed vapors to halogenate those of the sampled vapors subject to halogenation, removing unreacted halogen vapor, and then sensing the vapors for organic halogenated compounds. The apparatus disclosed herein comprises means for flowing the vapors, both sample and halogen vapors, into a common path, means for heating the mixed vapors to effect the halogenation reaction, means for removing unreacted halogen vapor, and a sensing device for sensing halogenated compounds. By such a method and means, the vapors of low molecular weight hydrocarbons, ketones and alcohols, when present, such as methane, ethane, acetone, ethanol, and the like are converted, at least in part, to halogenated compounds, then the excess halogen removed or trapped, and the resultant vapors of the halogenated compounds sensed or detected. The system is highly sensitive. For example, acetone in a concentration of 30 parts per billion (volume) is readily detected.
Metal carbonyls are of great importance in chemical vapor deposition (CVD), composite materials fabrication, and other near-net shape technologies. Carbonyl CVD is used for deposition of high-purity metallic and alloy coatings for which vapor pressure data is essential. In this study, we report vapor pressures of solid Ir 4 (CO) 12 and Re 2 (CO) 10 carbonyls measured by using the Knudsen Cell methodology using a torsion effusion thermogravimetric system. The vapor pressure of the Ir 4 (CO) 12 exhibited incongruent vaporization, as the molecular weight (MW) of the effusing species was determined as 128 g/mol as compared to the theoretical MW of 1105 g/mol. It is proposed that the Ir 4 (CO) 12 (s) partially decomposed (~66%) to Ir 4 (CO) 12 (g), Ir(s), and CO(g). The Re 2 (CO) 10 on the other hand, showed congruent behavior with Re 2 (CO) 10 (s) vaporizing to Re 2 (CO) 10 (g) in the measured temperature range. The raw data for vapor pressures was measured using two sets of Knudsen cells with different orifice sizes, and the equilibrium vapor pressures were calculated using Whitman-Motzfeldt methodology. The equilibrium vapor pressures of these carbonyls, partial pressures of gaseous species in case of decomposition, average molecular weights of the effusing gasses were determined. The vapor pressures and Gibbs energies of vaporization reactions of the two above mentioned carbonyls, as well as comparison of vaporization thermodynamics these two carbonyls with other carbonyls from Group VIB to VIIIB are presented in this work.
Water vapor in the atmosphere plays an important role in radiative transfer and the process of radiative balance so critical for understanding global change. It is the principal ingredient in cloud formation, one of the most difficult atmospheric processes to model, and the most variable component of the Earth-atmosphere albedo. And as a free molecule, it is the most active infrared absorber and emitter, thus, the most important greenhouse gas. The radiative impact of water vapor is important at all levels of the atmosphere. Even though moisture decreases by several orders-of-magnitude from the Earth's surface to the tropopause, recent research has shown that, from a radiative standpoint, a small percentage change in water vapor at any level is nearly equivalent. Therefore accurate and precise measurements of this important atmospheric constituent are needed at all levels to evaluate the full radiative impact. The need for improved measurements in the upper troposphere is particularly important because of the generally hostile (very dry and cold) conditions encountered. Because of the importance of water vapor to the understanding of radiative transfer, the Department of Energy's Atmospheric Radiation Measurements (ARM) program initiated a series of measurement campaigns at the Cloud And Radiation Testbed (CART) site in Oklahoma, especially focused on atmospheric water vapor. Three water vapor intensive observation period (water vapor IOP) campaigns were planned. Two of the water vapor IOP campaigns have been completed: the first IOP was held during the fall of 1996 with a focus on boundary layer water vapor measurements, and the second was conducted during the fall of 1997 with a focus on both boundary layer moisture e and moisture in the upper troposphere. This paper presents a review of the intercomparisons of water vapor measurements in the upper troposphere aquired during the second water vapor IOP. Data to be presented include water vapor measurements ements from: two Raman Lidars, the NASA Goddard Scanning Raman Lidar (SRL) and the CART Raman Lidar (CARL), a number of Vaisala radiosondes launched during the IOP campaign, and a dew point hygrometer flown on the University of North Dakota Cessna Citation Aircraft.
A method for continuously removing water vapor from a carrier gas is disclosed. This method includes, first, causing direct contact of the carrier gas with a liquid mixture in a separation chamber, the carrier gas condensing at a lower temperature than the water vapor. A combination of chemical effects cause the water vapor to condense, complex, or both condense and complex with the liquid mixture. The liquid mixture is chosen from the group consisting of: first, a combination of components that can be maintained in a liquid phase at a temperature below the water vapor's condensation point, whereby the water vapor condenses into the liquid mixture; second, a combination of components where at least one component forms a chemical complex with the water vapor and thereby extracts at least a portion of the water vapor from the carrier gas; and third, a combination of components that can both be maintained in a liquid phase at a temperature below the water vapor's condensation point, and wherein at least one component forms a chemical complex with the water vapor and thereby extracts at least a portion of the water vapor from the carrier gas. The liquid mixture is then reconstituted after passing through the separation chamber by a chemical separation process chosen to remove an equivalent amount of the water vapor from the liquid mixture as was removed from the carrier gas. The reconstituted liquid mixture is restored to temperature and pressure through heat exchange, compression, and expansion, as necessary, in preparation for recycling back to the separation chamber. The liquid mixture is then returned to the separation chamber. In this manner, the carrier gas leaving the exchanger has between 1% and 100% of the water vapor removed.
Increasing atmospheric humidity and convective precipitation over land provide evidence of intensification of the hydrologic cycle – an expected response to surface warming. The extent to which terrestrial ecosystems modulate these hydrologic factors is important to understand feedbacks in the climate system. We measured the oxygen and hydrogen isotope composition of water vapor at a very tall tower (185 m) in the upper Midwest, United States, to diagnose the sources, transport, and fractionation of water vapor in the planetary boundary layer (PBL) over a 3-year period (2010 to 2012). These measurements represent the first set of annual water vapor isotope observations for this region. Several simple isotope models and cross-wavelet analyses were used to assess the importance of the Rayleigh distillation process, evaporation, and PBL entrainment processes on the isotope composition of water vapor. The vapor isotope composition at this tall tower site showed a large seasonal amplitude (mean monthly δ 18 O v ranged from –40.2 to –15.9 ‰ and δ 2 H v ranged from –278.7 to –113.0 ‰) and followed the familiar Rayleigh distillation relation with water vapor mixing ratio when considering the entire hourly data set. However, this relation was strongly modulated by evaporation and PBL entrainment processes at timescales ranging from hours to several days. The wavelet coherence spectra indicate that the oxygen isotope ratio and the deuterium excess ( d v ) of water vapor are sensitive to synoptic and PBL processes. According to the phase of the coherence analyses, we show that evaporation often leads changes in d v , confirming that it is a potential tracer of regional evaporation. Isotope mixing models indicate that on average about 31 % of the growing season PBL water vapor is derived from regional evaporation. However, isoforcing calculations and mixing model analyses for high PBL water vapor mixing ratio events ( > 25 mmol mol –1 ) indicate that regional evaporation can account for 40 to 60 % of the PBL water vapor. These estimates are in relatively good agreement with that derived from numerical weather model simulations. This relatively large fraction of evaporation-derived water vapor implies that evaporation has an important impact on the precipitation recycling ratio within the region. In conclusion, based on multiple constraints, we estimate that the summer season recycling fraction is about 30 %, indicating a potentially important link with convective precipitation.
Remote sensing of troposheric water vapor profiles from current geostationary weather satellites is made using a few broadband infrared (IR) channels in the 6-13 micron region. Uncertainties greater than 20% exist in derived water vapor values just above the surface from the IR emission measurements. In this paper, we propose three near-IR channels, one within the 0.94-micron water vapor band absorption region, and the other two in nearby atmospheric windows, for remote sensing of precipitable water vapor over land areas, excluding lakes and rivers, during daytime from future geostationary satellite platforms. The physical principles are as follows. The reflectance of most surface targets varies approximately linearly with wavelength near 1 micron. The solar radiation on the sun-surface-sensor ray path is attenuated by atmospheric water vapor. The ratio of the radiance from the absorption channel with the radiances from the two window channels removes the surface reflectance effects and yields approximately the mean atmospheric water vapor transmittance of the absorption channel. The integrated water vapor amount from ground to space can be obtained with a precision of better than 5% from the mean transmittance. Because surface reflectances vary slowly with time, temporal variation of precipitable water vapor can be determined reliably. High spatial resolution, precipitable water vapor images are derived from spectral data collected by the Airborne Visable-Infrared Imaging Spectrometer, which measures solar radiation reflected by the surface in the 0.4-2.5 micron region in 10-nm channels and has a ground instantaneous field of view of 20 m from its platform on an ER-2 aircraft at 20 km. The proposed near-IR reflectance technique would complement the IR emission techniques for remote sensing of water vapor profiles from geostationary satellite platforms, especially in the boundary layer where most of the water vapor is located.
The Airborne Visible-Infrared Imaging Spectrometer (AVIRIS) measures the total upwelling spectral radiance from 400 to 2500 nm sampled at 10 nm intervals. The instrument acquires spectral data at an altitude of 20 km above sea level, as images of 11 by up to 100 km at 17x17 meter spatial sampling. We have developed a nonlinear spectral fitting algorithm coupled with a radiative transfer code to derive the total path water vapor from the spectrum, measured for each spatial element in an AVIRIS image. The algorithm compensates for variation in the surface spectral reflectance and atmospheric aerosols. It uses water vapor absorption bands centered at 940 nm, 1040 nm, and 1380 nm. We analyze data sets with water vapor abundances ranging from 1 to 40 perceptible millimeters. In one data set, the total path water vapor varies from 7 to 21 mm over a distance of less than 10 km. We have analyzed a time series of five images acquired at 12 minute intervals; these show spatially heterogeneous changes of advocated water vapor of 25 percent over 1 hour. The algorithm determines water vapor for images with a range of ground covers, including bare rock and soil, sparse to dense vegetation, snow and ice, open water, and clouds. The precision of the water vapor determination approaches one percent. However, the precision is sensitive to the absolute abundance and the absorption strength of the atmospheric water vapor band analyzed. We have evaluated the accuracy of the algorithm by comparing several surface-based determinations of water vapor at the time of the AVIRIS data acquisition. The agreement between the AVIRIS measured water vapor and the in situ surface radiometer and surface interferometer measured water vapor is 5 to 10 percent.