Search NASA⌕ Search

SEARCH · Search NASA

Results for “sulfur radical”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

35 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS1980

Interstellar sulfur chemistry

The results of a chemical model of SO, CS, and OCS chemistry in dense clouds are summarized. The results are obtained from a theoretical study of sulfur chemistry in dense interstellar clouds using a large-scale time-dependent model of gas-phase chemistry. Among the results are the following: (1) owing to activation energy, the reaction of CS with O atoms is efficient as a loss mechanism of CS during the early phases of cloud evolution or in hot and oxygen-rich sources such as the KL nebula; (2) if sulfur is not abnormally depleted in dense clouds, then the observed abundances of SO, SO2, H2S, CS, OCS, H2CS, and SiS indicate that sulfur is mostly atomic in dense clouds; and (3) OCS is stable against reactions with neutral atoms and radicals in dense clouds.

Prasad, S. S.↗
NASA NTRS1983

Laser fluorescence studies of the chemical interactions of sodium species with sulfur bearing fuels

By using a large matrix of fuel rich and fuel lean H2/O2/N2 and fuel rich C2H2/O2/N2 flames, the behavior of sodium and its interactions with sulfur at high temperatures was extensively characterized. OH concentrations were measured for each flame using the previously validated laser induced fluorescence technique. Sodium atomic concentrations were obtained by the saturated laser fluorescence method. Measurements were made in the absence and presence of up to 2% sulfur. In oxygen rich systems sodium is depleted by NaO2 and NaOH formation. The relative amounts of each are controlled by the degree of nonequilibration of the flame radicals and by the temperature. The bond strength of NaO2 was established. For the first time, a complete understanding of the complex behavior of sodium in fuel lean H2/O2 flames has emerged and computer modeling has permitted various rate constants of Na, NaO2 and NaOH reactions to be approximately fixed.

Steinberg, M.↗
NASA NTRS1993

Chemical kinetic studies of atmospheric reactions using tunable diode laser spectroscopy

IR absorption using tunable diode laser spectroscopy provides a sensitive and quantitative detection method for laboratory kinetic studies of atmospheric trace gases. Improvements in multipass cell design, real time signal processing, and computer controlled data acquisition and analysis have extended the applicability of the technique. We have developed several optical systems using off-axis resonator mirror designs which maximize path length while minimizing both the sample volume and the interference fringes inherent in conventional 'White' cells. Computerized signal processing using rapid scan (300 kHz), sweep integration with 100 percent duty cycle allows substantial noise reduction while retaining the advantages of using direct absorption for absolute absorbance measurements and simultaneous detection of multiple species. Peak heights and areas are determined by curve fitting using nonlinear least square methods. We have applied these techniques to measurements of: (1) heterogeneous uptake chemistry of atmospheric trace gases (HCl, H2O2, and N2O5) on aqueous and sulfuric acid droplets; (2) vapor pressure measurements of nitric acid and water over prototypical stratospheric aerosol (nitric acid trihydrate) surfaces; and (3) discharge flow tube kinetic studies of the HO2 radical using isotopic labeling for product channel and mechanistic analysis. Results from each of these areas demonstrate the versatility of TDL absorption spectroscopy for atmospheric chemistry applications.

Worsnop, Douglas R.↗
NASA NTRS1986

Rate constant for the reaction SO + BrO yields SO2 + Br

The rate of the radical-radical reaction SO + BrO yields SO2 + Br has been determined at 298 K in a discharge flow system near 1 torr pressure with detection of SO and BrO via collision-free sampling mass spectrometry. The rate constant was determined using two different methods: measuring the decay of SO radicals in the presence of an excess of BrO and measuring the decay of BrO radicals in excess SO. The results from the two methods are in reasonable agreement and the simple mean of the two values gives the recommended rate constant at 298 K, k = (5.7 + or - 2.0) x 10 to the -11th cu cm/s. This represents the first determination of this rate constant and it is consistent with a previously derived lower limit based on SO2 formation. Comparison is made with other radical-radical reactions involving SO or BrO. The reaction SO + BrO yields SO2 + Br is of interest for models of the upper atmosphere of the earth and provides a potential coupling between atmospheric sulfur and bromine chemistry.

Brunning, J.↗
NASA NTRS1997

Halogen and Sulfur Reactions Relevant to Polar Chemistry

It is widely hypothesized that catalytic cycles involving BrO(x) species play an important role in the episodic destruction of ground-level ozone which is observed in the springtime Arctic boundary layer, although the exact mechanism for production of BrO(x) radicals remains an open question [Barrie et al., Bottenheim et al.; Finlayson-Pitts et al., McConnell et al.] The critical evidence linking ozone depletion with BrO(x) chemistry is an observed negative correlation between ozone and filterable bromine [Bottenheim et al., Kieser et al.] In a recent field study of springtime Arctic boundary layer chemistry [Kieser et al.] ozone concentrations and ethane concentrations were found to be correlated; this observation suggests chlorine atoms (which react rapidly with ethane) may also be an important catalyst for ozone destruction under springtime Arctic conditions.

Wine, Paul H.↗
NASA NTRS1973

The hydroperoxyl radical in atmospheric chemical dynamics - Reaction with carbon monoxide.

Discussion of laboratory measurements which indicate that the reaction of the thermalized HO(2) radical with CO is exceedingly slow and that this reaction should not, therefore, be of any significance in atmospheric chemistry. The large discrepancy between the new results and data obtained earlier by Westenberg and de Haas (1972) is explained in terms of the reacting hydroperoxyl radical being in a non-Boltzmann distribution in the former study. It appears that the most important reactions of thermalized HO(2) in the atmosphere are those involving the trace gases of NO and sulfur dioxide.

Davis, D. D.↗
NASA NTRS1986

Design and chemical synthesis of iodine-containing molecules for application to solar-pumped I* lasers

The design and chemical synthesis of new media for solar pumped iodine molecule lasers are explored. In an effort to prepare an iodo fluorocarbon compound absorbing strongly at 300 nm or above, the synthesis of perfluoro allylic iodides was investigated. These compounds furnish especially stable allylic radicals upon photodissociation. The desired red shift is anticipated in the absorption maximum could correlate with increasing radical stability. This expectation was based upon the analysis, previously reported, of the structures and absorption maxima of compounds studied earlier. A previously unknown substance was prepared, a prototypical target molecule, perfluoro-3-iodocyclopent-1-ene. It was obtained by reaction of perfluorocyclopentene with sulfur trioxide under the influence of antimony pentafluoride catalyst, followed by treatment of the resulting allylic fluorosulfonate with sodium iodide in sulfoland solvent. Preliminary data indicate that the absorption maximum for the iodo fluorocarbon is not shifted significantly to longer wavelength. It is not certain whether this result reflects an unexpected influence of the cyclic structure upon the position of the absorption maximum.

Shiner, C. S.↗
NASA NTRS2001

Heterogeneous Uptake and Conversion of HOBr on H2SO4 at Upper Tropospheric and Stratospheric Temperatures (255 - 210 K)

Halogen species are known to catalytically destroy ozone in several different regions of the atmosphere. In addition to directly destroying ozone, bromine compounds can indirectly enhance ozone loss through coupling to other radical families. Hypobromous acid (HOBr), a key species in the linkage of BrOx to ClOx and HOx, is produced by the hydrolysis of BrONO2 on sulfate aerosols, and thus the heterogeneous behavior of HOBr must be understood. We have measured the solubility of HOBr in 45 to 70 percent by weight sulfuric acid solutions. Over the temperature range 208 to 255 K, HOBr is very soluble in sulfuric acid, H(*) = 10(exp 4) to 10(exp 8) M/atm. The solubility is temperature dependent, and our results agree well with those of Waschewsky and Abbott for 60 percent by weight H2SO4. HOBr is nearly as soluble as HBr, indicating that equilibrium concentrations of HOBr could approach those of HBr in sulfuric acid aerosols. Despite the high solubility of HOBr, stratospheric aerosol volumes are not large enough to sequester a significant fraction of inorganic bromine from the gas phase. Uptake of HOBr was nearly always accompanied by reaction, producing Br2O and possibly Br2. The effect of this bromine conversion pathway on the HOx and ClOx families, particularly at temperatures as warm as 255 K, will be considered.

Iraci, Laura T.↗
NASA NTRS2021

Impact of Regional Northern Hemisphere Mid-latitude Anthropogenic Sulfur Dioxide Emissions on Local and Remote Tropospheric Oxidants

The unintended consequences of reductions in regional anthropogenic sulfur dioxide (SO2) emissions implemented to protect human health are poorly understood. SO2 decreases began in the 1970s in the US and Europe and are expected to continue into the future, while recent emissions decreases in China are also projected to continue. In addition to the well-documented climate effects (warming) from reducing aerosols, tropospheric oxidation is impacted via aerosol modification of photolysis rates and radical sinks. Impacts on the hydroxyl radical and other trace constituents directly affect climate and air quality metrics such as surface ozone levels. We use the Geophysical Fluid Dynamics Laboratory Atmospheric Model version 3 nudged towards National Centers for Environmental Prediction (NCEP) reanalysis wind velocities to estimate the impact of SO2 emissions from the US, Europe, and China by differencing a control simulation with an otherwise identical simulation in which 2015 anthropogenic SO2 emissions are set to zero over one of the regions. Springtime sulfate aerosol changes occur both locally to the emission region and also throughout the Northern Hemispheric troposphere, including remote oceanic regions and the Arctic. Hydroperoxy (HO2) radicals are directly removed via heterogeneous chemistry on aerosol surfaces, including sulfate, in the model, and we find that sulfate aerosol produced by SO2 emissions from the three individual northern mid-latitude regions strongly reduces both HO2 and hydroxyl (OH) by up to 10 % year-round throughout most of the troposphere north of 30∘ N latitude. Regional SO2 emissions significantly increase nitrogen oxides (NOx) by about 5 %–8 % throughout most of the free troposphere in the Northern Hemisphere by increasing the NOx lifetime as the heterogeneous sink of HO2 on sulfate aerosol declines. Despite the NOx increases, tropospheric ozone decreases at northern mid-latitudes by 1 %–4 % zonally averaged and by up to 5 ppbv in summertime surface air over China, where the decreases in HO2 and OH suppress O3 production. Since 2015 anthropogenic SO2 emissions in China exceed those in the US or Europe, the oxidative response is greatest for the China perturbation simulation. Chemical effects of aerosols on oxidation (reactive uptake) dominate over radiative effects (photolysis rates), the latter of which are only statistically significant locally for the large perturbation over China. We find that the SO2 emissions decrease in China, which has yet to be fully realized, will have the largest impact on oxidants and related species in the Northern Hemisphere free troposphere compared to future decreases in Europe or the US. Our results bolster previous calls for a multipollutant strategy for air pollution mitigation to avoid the unintended consequence of aerosol removal leading to surface ozone increases that offset or mask surface ozone gains achieved by regulation of other pollutants, especially in countries where current usage of high-sulfur emitting fuels may be phased out in the future.

anthropogenic sulfur dioxide emissions↗
NASA NTRS1990

Particle chemistry impactor experiment

Polar stratospheric cloud (PSC) particles are collected on impactors and studied with regard to physical and chemical properties to help explain the importance of heterogeneous chemical reactions for stratospheric ozone depletion. The nitric, hydrochloric, and sulfuric acid content of stratospheric aerosol particles collected at 18 km altitude was determined. It is suggested that nitric acid is a component of polar stratospheric clouds. This is important for two reasons: (1) it proves that chlorine activation takes place at the surface of PSC particles by converting chemically inert chlorine nitrate to chlorine radicals that can react with ozone; and (2) if the PSC particles are large enough to settle out from the stratosphere, the possibility of nitric acid removal can result in the denitrification of the stratosphere.

Pueschel, R. F.↗
NASA NTRS2019

Anthropogenic Control over Wintertime Oxidation of Atmospheric Pollutants

Anthropogenic air pollutants such as nitrogen oxides (NO(x) = NO + NO(2)), sulfur dioxide (SO(2)), and volatile organic compounds (VOC), among others, are emitted to the atmosphere throughout the year from energy production and use, transportation, and agriculture. These primary pollutants lead to the formation of secondary pollutants such as fine particulate matter (PM(2.5)) and ozone (O(3)) and perturbations to the abundance and lifetimes of short-lived greenhouse gases. Free radical oxidation reactions driven by solar radiation govern the atmospheric lifetimes and transformations of most primary pollutants and thus their spatial distributions. During winter in the mid and high latitudes, where a large fraction of atmospheric pollutants are emitted globally, such photochemical oxidation is significantly slower. Using observations from a highly instrumented aircraft, we show that multi-phase reactions between gas-phase NO(x) reservoirs and aerosol particles, as well as VOC emissions from anthropogenic activities, lead to a suite of atypical radical precursors dominating the oxidizing capacity in polluted winter air, and thus, the distribution and fate of primary pollutants on a regional to global scale.

Haskins, J. D.↗
NASA NTRS2004

Solubility of HOBr in Acidic Solution and Implications for Liberation of Halogens Via Aerosol Processing

Halogen species are known to catalytically destroy ozone in several regions of the atmosphere. In addition to direct catalytic losses, bromine compounds can indirectly enhance ozone loss through coupling to other radical families. Hypobromous acid (HOBr) is a key species in the linkage of BrOx to ClOx and HOx. The aqueous- phase coupling reaction HOBr + HCI (right arrow) BrCl + H2O may provide a pathway for chlorine activation on sulfate aerosols at temperatures warmer than those required for polar stratospheric cloud formation. We have measured t h e solubility of HOBr in 45 - 70 wt% sulfuric acid solutions. Over the temperature range 201 - 252 K, HOBr is quite soluble in sulfuric acid, H* = 10(exp 4) - 10(exp 7) mol dm(exp -3) atm(exp -1). The expected inverse dependence of H* on temperature was observed, but only a weak dependence on acidity was found. The solubility of HOBr is comparable to that of HBr, indicating that equilibrium concentrations of HOBr could equal or exceed those of HBr in upper tropospheric and lower stratospheric aerosols. Despite the high solubility of HOBr, aerosol volumes are not large enough to sequester a significant fraction of inorganic bromine from the gas phase. Our measurements of HOBr uptake in aqueous sulfuric acid in the presence of other brominated gases show the evolution of gaseous products including Br2O and Br2.

Iraci, Laura T.↗
NASA NTRS2005

Sulfur Oxidation and Contrail Precursor Chemistry

Sulfuric acid (H2SO4), formed in commercial aircraft operations via Fuel-S (right arrow) SO2 + SO3 (right arrow) H2SO4, plays an important role in affecting the global climate change through atmospheric chemical reactions and radiative forcing. Measurement of the sulfur oxidation rates is critical to the understanding of the contrail formation. The principle reaction pathway is SO2 + O + M (right arrow) SO3 + M. Although there are many measurements for the rates of this reaction, it has never been measured in the temperature and pressure regime available to aircraft operation. In this investigation, a series of experiments were performed behind the reflected shock waves in a shock tube. OH radicals were produced in lean, shock heated SO2/H2/O2/Ar mixtures. The reaction progress was followed using OH absorption spectroscopy at 310 nm. The data were analyzed with the aid of computer modeling/simulation. The mean value of the rate coefficients of R21 determined is k(sub 21,0)/[M]= 3.9 x 10(exp 15) cm(sup 6) per square mole per second at T = 960 - 1150 K and rho = 16-30 micromole per cubic centimeter with uncertainty limits of plus or minus 30%. A non-Arrhenius fit to our data together with all existing data gives k(sub 21,0)/[M] = 1.3 x 10(exp 24) T (exp -2.5) exp(-2350 K/T) cm(sup 6) per square mole per second at T = 300 - 2500 K with the same uncertainty limits given above. The calculated conversion of S(IV)(SO2) to S(VI) (SO3 + H2SO4) was about 2% in our experimental conditions.

DeWitt, Kenneth↗
NASA NTRS1987

Degradation mechanisms of sulfur and nitrogen containing compounds during thermal stability testing of model fuels

The degradation behavior of n-dodecane (singly or in combination with S- and N-containing dopants) was studied using a modified Jet Fuel Thermal Oxidation Tester facility between 200 and 400 C. The products were analyzed by gas chromatography and mass spectrometry. The soluble products consisted mainly of n-alkanes and 1-alkenes, aldehydes, tetrahydrofuran derivatives, dodecanol and dodecanone isomers, C21-C24 alkane isomers, and dodecylhydroperoxide (ROOH) decomposition products. The major products were always the same, with and without dopants, but their distributions varied considerably. The 3,4-dimercaptotoluene and dibutylsulfide dopants added individually to n-dodecane interferred with the hydrocarbon oxidation at the alkylperoxy radical and the alkylhydroperoxide link, respectively, while the 2,5-dimethylpyrrole dopant inhibited ROOH formation. Pyridine, pyrrole, and dibenzothiophene added individually showed few significant effects.

Reddy, K. T.↗
NASA NTRS1997

Sulfuric Acid and Soot Particles in Aircraft Exhaust

Aircraft have become the fastest, fairly convenient and, in most cases of long-distance travel, most economical mode of travel. This is reflected in the increase of commercial air traffic at a rate of 6% per year since 1978. Future annual growth rates of passenger miles of 4% for domestic and 6% for international routes are projected. A still larger annual increase of 8.5% is expected for the Asia/Pacific region. To meet that growth, Boeing predicts the addition of 15,900 new aircraft to the world's fleets, valued at more than $1.1 trillion, within the next 20 years. The largest concern of environmental consequences of aircraft emissions deals with ozone (O3), because: (1) the O3 layer protects the blaspheme from short-ultraviolet radiation that can cause damage to human, animal and plant life, and possibly affect agricultural production and the marine food chain; (2) O3 is important for the production of the hydroxyl radical (OH) which, in turn, is responsible for the destruction of other greenhouse gases, e.g., methane (CH4) and for the removal of other pollutants, and (3) O3 is a greenhouse gas. Additional information is contained in the original extended abstract.

Pueschel, Rudolf F.↗
NASA NTRS1986

The production of trace gases by photochemistry and lightning in the early atmosphere

Recent atmospheric calculation suggest that the prebiological atmosphere was most probably composed of nitrogen, carbon dioxide, and water vapor, resulting from volatile outgassing, as opposed to the older view of a strongly reducing early atmosphere composed of methane, ammonia, and hydrogen. Photochemical calculations indicate that methane would have been readily destroyed via reaction with the hydroxyl radical produced from water vapor and that ammonia would have been readily lost via photolysis and rainout. The rapid loss of methane and ammonia, coupled with the absence of a significant source of these gases, suggest that atmospheric methane and ammonia were very short lived, if they were present at all. An early atmosphere of N2, CO2, and H2O is stable and leads to the chemical production of a number of atmospheric species of biological significance, including oxygen, ozone, carbon monoxide, formaldehyde, and hydrogen cyanide. Using a photochemical model of the early atmosphere, the chemical productionof these species over a wide range of atmospheric parameters were investigated. These calculations indicate that early atmospheric levels of O3 were significantly below the levels needed to provide UV shielding. The fate of volcanically emitted sulfur species, e.g., sulfur dioxide and hydrogen sulfide, was investigated in the early atmosphere to assess their UV shielding properties. The photochemical calculations show that these species were of insufficient levels, due in part to their short photochemical lifetimes, to provide UV shielding.

Levine, J. S.↗
NASA NTRS2022

Trends in sulfur dioxide over the Indian subcontinent during 2003–2019

Sulfur dioxide (SO2) and its oxidation products profoundly impact the air quality and climate. In recent decades, contrasting SO2 trends have been observed over different regions of the globe due to urbanization, energy generation and control measures. In this study, we have investigated the SO2 trends over the rapidly developing Indian subcontinent using model reanalysis, satellite data, and emission inventories during 2003–2019 period. Copernicus Atmosphere Monitoring Service (CAMS) reanalysis shows rapid SO2 growth up to 0.4 ppbv/yr during 2003–2009, particularly significant over the Indo-Gangetic Plain (IGP) and eastern India. However, the growth becomes slower after 2010 and is followed by a stabilization or slight reduction. The CAMS results agree with the satellite-based observations, however, the model underestimates enhancements over eastern India. The analysis of inventory datasets also suggests slower growths in SO2 emissions and coal-fired electricity generation in recent years. Besides the changes in regional emissions, the enhancements in water vapor and OH radical coinciding with SO2 stabilization indicate strengthening of the sink processes. Model simulation (Modern-Era Retrospective analysis for Research and Applications version 2―MERRA-2) with constant emissions shows reduction in SO2 which confirms the stronger chemical losses. Overall, the SO2 trends over the Indian subcontinent are found to be a manifestation of the combined effects of the regional emission change and chemistry. Our findings highlight the need for studies to assess the impacts of changing SO2 trends in India on the regional and global climate.

Lakhima Chutia↗