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At least 757 records · Page 42

Airborne observations in support of a satellite observation-based OH product

This presentation outlines work to date analyzing airborne observations to improve a satellite observation-based hydroxyl radical (OH) column product by interrogating model chemistry processes. Anderson et al., 2023, established a machine learning method to combine satellite observations of O3, CO, NO2, HCHO, H2O, and aerosol optical depth, along with analyzed sea surface temperatures, for the prediction of tropospheric column OH (TCOH). Since the TCOH machine learning model was trained on output from the MERRA-2 GMI model simulation, we seek to identify if any model deficiencies may yield errors in the TCOH prediction. By evaluating F0AM box model simulations and neural networks trained to reproduce in situ OH concentrations, together with output reaction rates and interpretability metrics, respectively, we validate the Anderson et al. TCOH model and assess the largest contributors to uncertainties.

Hydroxyl, oxidizing capacity, troposphere, airborn↗

Simplified Structure Models for Premixed n-Alkane Cool Flames

The chemical kinetics of cool flames in mixtures of normal alkanes, oxygen, and nitrogen recently have been reduced to obtain simplified asymptotic flame-structure models that can be used to compare theoretical predictions with experimental measurements. A key step that affects flame structures strongly, namely the abstraction of a hydrogen atom from the alkyl radical by an oxygen molecule, had not been taken into account in those models. This deficiency has now been remedied for diffusion flames. The present contribution reports the corresponding remedy for premixed-flame analyses. In the new model, non-zero chemical reaction rates are restricted to narrow regions in the vicinity of the maximum temperature, whereas previously they extended throughout the preheat zone. Comparisons of the new predictions with experimental burning-velocity measurements seem favorable.

premixed cool flames↗

Will MSR Samples Cached on the Martian Surface Experience Significantly Greater Thermal Degradation than Samples Retained in the Rover?

Since the first Mars Sample Return (MSR)-related report published by the Jet Propulsion Laboratory (JPL) in 1974, a series of panels, reports, and white papers have recognized the importance of sample temperature in meeting mission goals and defined a sample maximum temperature (henceforth SMT) limit. The Mars Sample Handling and Requirements Panel (MSHARP, 1999) flatly stated that “[t]he main issue in sample preservation is temperature”. The Mars Exploration Program Analysis Group (MEPAG)’s “Science Priorities for Mars Sample Return” report (2008), declared that “[s]ignificant loss, particularly to biological studies, occurs if samples reach +50°C for three hours ” whereby “scientific objectives related to life goals could be seriously compromised”. Overall, a total of seven panels, white papers, and conference reports adopted a SMT of -40±17°C to preserve samples sufficiently to confidently achieve success in studies of past or present Martian life (see more detail in [5]). In contrast, the Mars 2020 rover (M2020) mission adopted a SMT of +60°C for samples stored on the Martian surface and +50°C for samples retained inside the rover, as stated in a conference poster presented by Beaty et al., 2016. M2020 is currently collecting samples for MSR in tubes. Half of those tubes will be retained within the M2020 rover body (hereafter rover samples, or RS) and half will be deposited on the Martian surface (cached samples or CS), with a currently undetermined number of each collected up to ten years later for return to Earth. CS samples can be expected to experience significantly higher temperatures than RS samples based on their exposed location in sunlight. This work will explore differences in deleterious chemical reaction rates due to thermal environment of both tube types. The findings here should be debated openly and considered when deciding which samples to return to Earth.

M Fries↗

Two-Phase Flow in Filters and Orifices: In preparation for Measurements on ISS Packed Bed Reactor Experiment-Water Recovery Series (PBRE-WRS)

Understanding the hydrodynamics of adiabatic two-phase flows in packed bed reactors offers numerous benefits. It enables the optimization of chemical reactions rates and products, crucial for pharmaceuticals and energy production industries. Additionally, this understanding aids in designing more efficient and compact reactors, reducing space and resource requirements. Insights gained from studying such flows in microgravity contribute to advancements of space technologies and the enhancement of our capabilities for undertaking future long duration safe, and sustainable space exploration missions. The Packed Bed Reactor Experiment-Water Recovery Series (PBRE-WRS) is a flight experiment planned for operation on the Microgravity Science Glove box (MSG) facility of the International Space Station (ISS). The objective of the experiment is to validate hydrodynamic models at a range of gas and liquid flow rates. The microgravity environment allows for measurement and observation of aspects of fluid dynamics that are unique when compared to observations made in full or partial gravity environments. The experiment consists of testing two-phase flow hydrodynamics in three different filters, four (4) orifices and one check valve test articles. The experiment utilizes the hardware of the previously flown PBRE and PBRE-2 with packed beds of different packings materials and sizes. The fluid system of the PBRE-WRS consists of a nitrogen gas delivery and water delivery subsystems. The gas delivery subsystem can accommodate two ranges of gas flow rates, just as for the water delivery system. The nitrogen gas loop is open whereas the water loop is closed. Gas is separated from the water using a gas-liquid phase separator which is located in the water delivery module. Preliminary results from ground testing show the pressure drop increasing at different rates with the liquid and gas flow rates in the Brine filter. In this work, a detailed system description is presented along with a summary of results from ground performance testing of different test sections in an end-to-end preflight testing campaign.

Packed Bed Reactor Experiment↗

Two-Phase Flow in Filters and Orifices: ISS Packed Bed Reactor Experiment Water Recovery Series (PBRE-WRS)

Understanding the hydrodynamics of adiabatic two-phase flows in packed bed reactors offers numerous benefits. It enables the optimization of chemical reactions rates and products which results in more efficient and compact reactors, thus reducing space and resource requirements, crucial for long duration space missions. The Packed Bed Reactor Experiment-Water Recovery Series (PBRE-WRS) is a flight experiment planned for operation on the Microgravity Science Glove box (MSG) facility of the International Space Station (ISS). The objective of the experiment is to validate hydrodynamic models at a range of gas and liquid flow rates, where these models are used in the design of processes for life support systems in microgravity. The microgravity environment allows for measurement and observation of aspects of fluid dynamics that are unique when compared to observations made in full or partial gravity environments. The experiment consists of testing two-phase flow hydrodynamics in three different filters, four (4) orifices and one check valve test articles. The experiment utilizes the hardware of the previously flown PBRE and PBRE-2 with packed beds of different packings materials and sizes. The fluid system of the PBRE-WRS consists of a nitrogen gas delivery and water delivery subsystems. The gas delivery subsystem can accommodate two ranges of gas flow rates, just as for the water delivery system. The nitrogen gas loop is open whereas the water loop is closed. Gas is separated from the water using a gas-liquid phase separator which is located in the water delivery module. Preliminary results from ground testing show the pressure drop across the filters increasing at different rates with the liquid and gas flow rates. In this work, a detailed system description is presented along with a summary of results from ground performance testing of different test sections in an end-to-end preflight testing campaign.

ISS↗

Two-Phase Flow in Packed Beds, Filters and Orifices: Summary of Findings of the Packed Bed Reactor Experiment Onboard of the International Space Station

Understanding the hydrodynamics of adiabatic two-phase flows in packed bed reactors enables the optimization of chemical reaction rates and products that crucial in pharmaceuticals and energy production industries. Additionally, this understanding aids in designing more efficient and compact reactors and reducing space and resource requirements. Insights gained from studying and understanding such flows in microgravity contribute to advancements of space technologies and the enhancement of our capabilities for undertaking future long duration safe, and sustainable space exploration missions. The objective of the Packed Bed Reactor Experiment series (PBRE and PBRE-2) was to develop a fundamental understanding of the hydrodynamics of adiabatic two-phase flows through porous media in microgravity. This work provides a description of the PBRE fluid system and presents the highlights of the PBRE and PBRE-2 previously flown with different packings and operated onboard of the International Space Station Microgravity Science Glovebox (ISS-MSG). These highlights include flow patterns and two-phase pressure drop, and the impact of capillary effects on pressure drop at various gas and liquid flow rates. This work also presents preliminary results from the Packed Bed Reactor Experiment-Water Recovery Series (PBRE-WRS) recently flown with filters and orifices, which was also operated on the ISS-MSG. The objective of the experiment is to validate hydrodynamic models at a range of gas and liquid flow rates pertinent to the operation of these test articles. The microgravity environment allows for measurement and observation of aspects of fluid dynamics that are unique when compared to observations made in full or partial gravity environments.

ISS↗

The Trajectory of Recent Solid State Fusion Results

Both NASA and Google have explored and funded Low Energy Nuclear Reaction (LENR) aka Solid-State Fusion or Lattice Confinement Fusion (LCF) research. NASA has funded efforts since 1989, and Google Research began in 2014. Google, and researchers initially-funded by Google, published significant scientific papers in Nature, Nature Communications and the Journal of Applied Physics. NASA began a significant set of LENR-triggering programs in 2012 resulting in papers in Physical Review C, the Journal of Electroanalytical Chemistry and the Journal of Condensed Matter Nuclear Science. Both NASA and Google engaged researchers across fields of nuclear physics, chemistry, electrochemistry, material science and more. NASA built upon early novel gas pumping experiments then followed the patented work of the US Navy SPAWAR (US8,419,919, “System and Method to Generate Particles”) and experiments with the Naval Surface Warfare Centers. Google supported researchers at Lawrence Berkeley National Laboratory (LBNL), the University of British Columbia (UBC), MIT and others. This resulted in patent applications and two granted patents (US10264661B2, “Target structure for enhanced electron screening” and US10566094B2 “Enhanced electron screening through plasmon oscillations”). These separate efforts, unknown to the researchers at the time, provided the impetus for the DoE ARPA-E LENR program followed by the DARPA DSO “Mechanisms for Amplification of Fusion Reaction Rates in Solids” (MARRS) program. This document briefly describes the overlapping NASA and Google Research efforts in plasma loading and electron screening emphasizing the results of the latest paper in Nature Communications. The papers and patents cited are listed.

electron screening↗

Significance of vapor phase chemical reactions on CVD rates predicted by chemically frozen and local thermochemical equilibrium boundary layer theories

This paper investigates the role played by vapor-phase chemical reactions on CVD rates by comparing the results of two extreme theories developed to predict CVD mass transport rates in the absence of interfacial kinetic barrier: one based on chemically frozen boundary layer and the other based on local thermochemical equilibrium. Both theories consider laminar convective-diffusion boundary layers at high Reynolds numbers and include thermal (Soret) diffusion and variable property effects. As an example, Na2SO4 deposition was studied. It was found that gas phase reactions have no important role on Na2SO4 deposition rates and on the predictions of the theories. The implications of the predictions of the two theories to other CVD systems are discussed.

Gokoglu, Suleyman A.↗

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2) and (for CH2Cl2) HFC-161 (CH3CH2F). Using absolute rate constants for HFC-152a and HFC-161, which we have determined relative to those for CH4, CH3CCl3, and C2H6, temperature dependent rate constants of both compounds were derived. The derived rate constant for CH3Br is in good agreement with recent absolute measurements. However, for the chloromethanes all the rate constants are lower at atmospheric temperatures than previously reported, especially for CH2Cl2 where the present rate constant is about a factor of 1.6 below the JPL 92-20 value. The new rate constant appears to resolve a discrepancy between the observed atmospheric concentrations and those calculated from the previous rate constant and estimated release rates.

Hsu, K.-J.↗

Absolute rate of the reaction of O/3-P/ with hydrogen sulfide over the temperature range 263 to 495 K

The technique of flash photolysis coupled with time resolved detection of O via resonance fluorescence has been used to obtain rate constants for the reaction of O(3-P) with H2S at temperatures from 263 to 495 K and at pressures in the range 10-400 torr. Under conditions where secondary reactions are avoided, the measured rate constants for the primary step obey the Arrhenius equation k = (7.24 plus or minus 1.07) x 10 to the -12th exp(-3300 plus or minus 100/1.987 T) cu cm/molecules/s. Experiments with D2S show that the reaction exhibits a primary isotope effect, in support of a hydrogen abstraction mechanism.

Whytock, D. A.↗

Rates of hydroxyl radical reactions with some HFCs

Relative rate constants for OH reactions with some HFCs have been determined at 298 K by a technique which measures the loss of HFC greater than OH. The following ratios were determine: k(152a)/k(CH4) = 5.2 +/- 0.5, k(CH4)/k(125) = 3.9 +/- 0.5, k(CH4)/k(134a) = 2.1 +/- 0.2, k(134a)/k(125) = 2.0 +/- 0.2, and k(C2H6)/k(152a) = 6.2 +/- 1.0. These results are in good agreement with literature values for the absolute rate constants except for HFC 134a, where a slower rate constant is indicated.

Demore, William B.↗

Absolute rate of the reaction of atomic hydrogen with ethylene from 198 to 320 K at high pressure

The rate constant for the H+C2H4 reaction has been measured as a function of temperature. Experiments were performed with high pressures of Ar heat bath gas at seven temperatures from 198 to 320 K with the flash photolysis-resonance fluorescence (FP-RF) technique. Pressures were chosen so as to isolate the addition rate constant k1. The results are well represented by an Arrhenius expression. The results are compared with other studies and are theoretically discussed.

Lee, J. H.↗

Photochemistry of the Martian atmosphere

A critical analysis is carried out for models which may be fine tuned to give agreement with observational constraints for O2, CO, and O3 in the Martian lower atmosphere and which are in accord also with upper atmospheric data for O and CO. The models have a number of features in common: dynamic mixing must be exceedingly rapid at heights above 90 km; if heterogeneous processes are not assumed to play a major role in the removal of atmospheric CO and O2, mixing must be rapid at heights between 30 and 40 km. The value implied for the diffusion coefficient in this region depends on the assumptions made regarding the rates for reaction of OH with HO2 to form H2O and the rate of reaction of HO2 with itself to form H2O2. If these reaction rates are taken to have values similar to those used in current models of the earth's stratosphere, the eddy diffusion coefficient at 40 km above the Martian surface should be about 5 by 10 to the seventh power sq cm/sec.

Kong, T. Y.↗

The rate of the reaction of OH with HCl

Using the techniques of laser/flash photolysis-resonance fluorescence, the absolute rate constant for the OH + HCl reaction is measured from 240 to 295 K. Ultraviolet and infrared spectrophotometry are used to continuously monitor the HCl concentrations. It is shown that the rate constant values obtained in the study are 20-30 percent larger than those recommended by Smith and Zellner (1974) and Ravishankara et al. (1977) for modeling of stratospheric chemistry.

Molina, M. J.↗

Rate constant for the reaction Cl + HO2NO2 yielding products

The rates for the reaction of Cl atoms iwth HO2NO2 were calculated from data obtained by the use of the discharge flow/resonance fluorescence (DF/RF) and the discharge flow/mass spectrometric (DF/MS) techniques. The total rate constant, k1, for the overall reaction: 1a (Cl + HO2NO2 yielding HCl + NO2 +O2), 1b (yielding HO2 + ClNO2), and the two possible additional channels was found to be less than 1.0 x 10 to the -13th cu cm/s at 296 K. The value of (k1a + k1b) was found to be 3.4 + or - 1.4) x 10 to the -14th cu cm/s. Thus, the reaction of Cl with peroxynitric acid is too slow, by a factor of 100, to contribute significantly to the hydrogen abstraction by Cl in the stratosphere.

Simonaitis, R.↗

Why HOC+ is detectable in interstellar clouds: the rate of the reaction between HOC+ and H2

The recent confirmation by Ziurys and Apponi of the detection of HOC+ toward Sgr B2 (OH), and their identification of the ion in Orion-KL and several other sources show that HOC+ is far more abundant than predicted by previous ion-molecule models. In these models, the reaction HOC(+) + H2 --> HCO(+) + H2 is assumed to rapidly destroy HOC+, based on the results of a prior calculation. We have recalculated the rate of this reaction as a function of temperature using a new ab initio potential surface and a phase space approach to the dynamics which includes tunneling. The newly calculated rate is small (< or = 1 x 10(-10) cm3 s-1) at temperatures under 100 K.

Non-NASA Center↗

Rate constants for reactions of ClO/x/ of atmospheric interest

Chemical kinetics measurements on 82 gas phase reactions of chlorine containing species are reviewed. Recommended rate constants are given. The principal species of interest are Cl, Cl2, ClO, Cl2O, ClOO, OClO, CINO, HCl and halo derivatives of methane and ethane. Absorption spectra are given for 21 species. In addition the chemical kinetics methods used to obtain these data are discussed with regard to their applicability and reliability.

Watson, R. T.↗