Search NASA⌕ Search

SEARCH · Search NASA

Results for “hydroxyl radicals”

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.

At least 253 records · Page 14

Oxidation of CS2 and COS - sources for atmospheric SO2

The oxidation of COS and CS2 by reaction with hydroxyl radicals is investigated as a possible source of atmospheric SO2 in remote marine regions. Calculations of the vertical profiles of SO2 were performed based on a one-dimensional photochemical model of the formation and destruction of SO2 by various processes for observed O3, CO, CH4 and H2O profiles at 15 deg S. Variations in the rate of SO2 destruction, the chosen deposition velocity and the loss due to aerosols are shown to lead to similar SO2 profiles, which indicate higher mixing ratios at high altitude, while the oxidation of dimethyl sulfide or hydrogen sulfide can not account for the profiles observed. Possible diffuse sources of CS2 and COS are indicated, and it is concluded that the oxidation of COS and possibly CS2 may provide an explanation for the existence of a uniform background level of SO2.

Logan, J. A.↗

Influence of gravity wave activity on lower thermospheric photochemistry and composition

The wind and temperature oscillations of internal gravity waves can cause horizontal variations of a factor of two in minor gas number densities in the lower thermosphere over length scales of several hundred kilometers. The variations are due both to vertical transport of constituents whose lifetimes are long compared to the wave period and to chemical activity driven by temperature dependent reaction rate coefficients. The nightglow emission of the hydroxyl radical provides a remote sensor of wave activity between 80 and 90 km. Theoretical calculations show that the horizontal variations in the atomic hydrogen distribution are the largest single contributor to wave structure in the nightglow followed by the effects of temperature fluctuations on the rate coefficient of the reaction H + O3 yields O2 + OH (nu prime is greater than 0).

Frederick, J. E.↗

Absolute rate constant of the reaction OH + H2O2 yields HO2 + H2O from 245 to 423 K

The absolute rate constant of the reaction between the hydroxyl radical and hydrogen peroxide was measured by using the discharge-flow resonance fluorescence technique at total pressure between 1 and 4 torr. At 298 K the result is (1.64 + or - 0.32) x 10 to the -12th cu cm/molecule s. The observed rate constant is independent of pressure, surface-to-volume ratio, the addition of vibrational quenchers, and the source of OH. The temperature dependence has also been determined between 245 and 423 K; the resulting Arrhenius expression is k cu cm/molecule s is equal to (2.51 + or - 0.6) x 10 to the -12th exp(-126 + or - 76/T).

Keyser, L. F.↗

A model of CO-CH4 global transport/chemistry. I - Chemistry model

A simplified chemistry model was developed to incorporate the CO-CH4 chemistry into the global transport model of these compounds. CO is important because of its effects on atmospheric chemistry and is partly responsible for controlling the hydroxyl radical (OH) concentration in the troposphere. The model includes the photodissociation rate coefficients expressed as functions of solar zenith angle and altitude, and it was applied to determine the sensitivity of the OH concentration to trace gaseous species, such as NOx, O3, and H2O. Also, the concentrations and diurnal variations of OH and HO2, and the contribution of individual reactions to OH generation and consumption were calculated.

Peters, L. K.↗

Solar extinction radiometry

Work on the spectral line parameters of hydroxyl radical band was completed. The UV-visible data obtained during 1977 balloon flights were used for zone quantification. The region between from 3100 A to 3500 A appears to be the best region to use for determining ozone columns with the three wavelength method. Ozone volume mixing ratios determined for the 1977 data were compared with standard middle latitude ozone profiles. Numerous high and low Sun scans were obtained during ascent and from float altitude (1981 balloon flight) at 0.003 A resolution in the 3068 A to 3089 A region. The spectra are being studied for OH identification and quantification.

Goldman, A.↗

QH observations

A model of the dissociative lifetime of the hydroxyl radical is computed where the H2O and OH velocities are vectorially added. A lifetime of approximately 3 x 100,000 seconds is determined.

Festou, M.↗

A wavelength scannable XeCl oscillator-ring amplifier laser system

A holographic grating at grazing angle of incidence was used to achieve tunable, narrow bandwidth (0.005 nm) operation of a XeCl oscillator for injection locking of a ring amplifier. The amplifier's narrow bandwidth output energy was constant and equal to the untuned, broadband output (approximately 15 mJ) in regions where injection locking was achieved. Scanning was provided by use of a stepping motor-driven differential micrometer on the tuning mirror. This system was used to produce a laser excitation spectrum of hydroxyl radicals (OH) in a flame.

Pacala, T. J.↗

Rate constant for the reaction between OH and CS2 at 298 and 520 K

In an attempt to resolve discrepancies between published values of the rate constant for the reaction between the hydroxyl radical and carbon disulfide, the reaction has been studied in a discharge flow system by using resonance fluorescence for kinetic measurements and mass spectrometry for product analysis. On the basis of the measured rate constant for disappearance of OH, and measurements of the amount of carbonyl sulfide formed, it was estimated that for the reaction HO + CS2 yields HS + OCS, rate constant values are not greater than 3 x 10 to the -15th/cu cm per sec at 520 K and not greater than 7 x 10 to the -15th/cu cm per sec at 298 K, upper limits are specified because of the inability to isolate exclusively this reaction channel, and because of possible involvement of wall reactions. These results confirm the low values found for this rate constant in two very recent studies.

Leu, M.-T.↗

Remote sensing of OH in the atmosphere using the technique of laser-induced fluorescence

The use of a laser-induced fluorescence technique for the sensitive measurement of the atmospheric hydroxyl radical is discussed. Results of laboratory studies of the fluorescence and other spectroscopic properties of OH which allow the calculation of OH concentrations from the returned signals for various altitudes, water vapor contents and temperatures are presented. The experimental setup used for airborne OH measurements is then described, with particular attention given to the use of a telescope for excitation and light collection in a coaxial configuration and the periodic tuning of the exciting radiation necessary to obtain an OH signal in the presence of strong solar and nonresonant fluorescence backgrounds. The best detection limit obtained to date with the system is noted to be about 700,000 OH/cu cm, and it is expected that, with planned improvements in detection and tuning schemes, limits in the neighborhood of 1,000,000 OH/cu cm will be achieved routinely.

Wang, C. C.↗

Carbon monoxide in the earth's atmosphere - Increasing trend

The results of an analysis of more than 60,000 atmospheric measurements of carbon monoxide taken over 3-1/2 years at Cape Meares, Oregon (45 deg N, 125 deg W), indicate that the background concentration of this gas is increasing. The rate of increase, although uncertain, is about 6 percent per year on average. Human activities are the likely cause of a substantial portion of this observed increase; however, because of the short atmospheric lifetime of carbon monoxide and the relatively few years of observations, fluctuations of sources and sinks related to the natural variability of climate may have affected the observed trend. Increased carbon monoxide may deplete tropospheric hydroxyl radicals, slowing down the removal of dozens of man-made and anthropogenic trace gases and thus indirectly affecting the earth's climate and possibly the stratospheric ozone layer.

Khalil, M. A. K.↗

Hydrogen atom abstraction from aldehydes - OH + H2CO and O + H2CO

The essential features of the potential energy surfaces governing hydrogen abstraction from formaldehyde by oxygen atom and hydroxyl radical have been characterized with ab inito multiconfiguration Hartree-Fock (MCHF) and configuration interaction (CI) wave functions. The results are consistent with a very small activation energy for the OH + H2CO reaction, and an activation energy of a few kcal/mol for the O + H2CO reaction. In the transition state structure of both systems, the attacking oxygen atom is nearly collinear with the attacked CH bond.

Dupuis, M.↗

Tropospheric methane in the mid-latitudes of the Southern Hemisphere

More than 800 methane concentration measurements have been obtained for the Southern Hemisphere's troposphere over the September 1980-March 1983 period. Concentrations are noted to increase throughout the troposphere during the study period, adding further support to the view that CH4 concentrations are currently increasing on a global scale. In the surface methane data, a seasonal cycle with a peak-to-peak amplitude of 28 ppbv is found. Maxima and minima are on September-October and March, respectively. The phase and amplitude of the cycle are qualitatively consistent with the concept that the major sink for methane is oxidation by hydroxyl radicals. Evidence is found for a positive vertical gradient in methane content.

Fraser, P. J.↗

Water and the photochemistry of the troposphere

A discussion is presented concerning the role of water in its liquid and gaseous states in the chemistry and photochemistry of the earth's troposphere, with attention to the formation of the hydroxyl radical, oxidation chains involving the gases methane, carbon monoxide and ammonia, the atmospheric chemistry of the sulfur, hydrogen, halogen and nitrogen species, and the function of lightning as a source of tropospheric species. The phenomena of 'rainout', 'washout', and the aqueous chemistry of cloud an rain droplets and of water-covered aerosols, are noted. A section is devoted to the past and anticipated impact of anthropogenic activities on the chemistry and composition of the earth's atmosphere.

Levine, J. S.↗

An intercomparison of carbon monoxide, nitric oxide, and hydroxyl measurement techniques - Overview of results

Results from an intercomparison of methods to measure carbon monoxide (CO), nitric oxide (NO), and the hydroxyl radical (OH) are discussed. The intercomparison was conducted at Wallops Island, Virginia, in July 1983 and included a laser differential absorption and three grab sample/gas chromatograph methods for CO, a laser-induced fluorescence (LIF) and two chemiluminescence methods for NO, and two LIF methods and a radiocarbon tracer method for OH. The intercomparison was conducted as a field measurement program involving ambient measurements of CO (150-300 ppbv) and NO (10-180 pptv) from a common manifold with controlled injection of CO in incremental steps from 20 to 500 ppbv and NO in steps from 10 to 220 pptv. Only ambient measurements of OH were made. The agreement between the techniques was on the order of 14 percent for CO and 17 percent for NO. Hardware difficulties during the OH tests resulted in a data base with insufficient data and uncertanties too large to permit a meaningful intercomposition.

Hoell, J. M.↗

The atmospheric lifetime of methylchloroform (CH3CCl3)

The lifetime of atmospheric methylchloroform (CH3CCl3) is estimated to be about 6 (+ or - 1.5) years based on extensive measurements taken over the past seven years at remote locations of the world, ranging from inside the Arctic Circle to the South Pole. The average level of tropospheric hydroxyl radicals (OH) deduced from the lifetime of CH3CCl3 is about 8 x 10 to the 5th molecules/cu cm, but this value is uncertain by up to + or - 75 percent.

Khalil, M. A. K.↗

Photodissociation rates of OH, OD, and CN by the interstellar radiation field

The photoabsorption cross sections for OH, OD, and CN in the vacuum ultraviolet region are measured. The cross sections for the hydroxyl radicals are of the order of 10 to the -17th sq cm, but the photoabsorption for CN is so low that only an upper limit of 2 x 10 to the -18th sq cm is obtained. The molecular photodissociative processes are discussed. The photodissociation cross sections are inferred from the photoabsorption cross sections. On the basis of the measured data, the photodissociation rates by the interstellar radiation field are computed and discussed.

Nee, J. B.↗

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.↗