Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “N2O5”

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 55 records · Page 3

Wintertime Overnight NOx Removal in a Southeastern United States Coal-Fired Power Plant Plume: A Model for Understanding Winter NOx Processing and Its Implications

Nitric oxide (NO) is emitted in large quantities from coal-burning power plants. During the day, the plumes from these sources are efficiently mixed into the boundary layer, while at night, they may remain concentrated due to limited vertical mixing during which they undergo horizontal fanning. At night, the degree to which NO is converted to HNO3 and therefore unable to participate in next-day ozone (O3) formation depends on the mixing rate of the plume, the composition of power plant emissions, and the composition of the background atmosphere. In this study, we use observed plume intercepts from the Wintertime INvestigation of Transport, Emissions and Reactivity (WINTER) campaign to test sensitivity of overnight NOx removal to the N2O5 loss rate constant, plume mixing rate, background O3, and background levels of volatile organic compounds using a 2-D box model of power plant plume transport and chemistry. The factor that exerted the greatest control over NOx removal was the loss rate constant of N2O5. At the lowest observed N2O5 loss rate constant, no other combination of conditions converts more than 10 percent of the initial NOx to HNO3. The other factors did not influence NOx removal to the same degree.

air quality↗

Homogeneous processes of atmospheric interest

Upper atmospheric research programs in the department of chemical kinetics are reported. Topics discussed include: (1) third-order rate constants of atmospheric importance; (2) a computational study of the HO2 + HO2 and DO2 + DO2 reactions; (3) measurement and estimation of rate constants for modeling reactive systems; (4) kinetics and thermodynamics of ion-molecule association reactions; (5) entropy barriers in ion-molecule reactions; (6) reaction rate constant for OH + HOONO2 yields products over the temperature range 246 to 324 K; (7) very low-pressure photolysis of tert-bytyl nitrite at 248 nm; (8) summary of preliminary data for the photolysis of C1ONO2 and N2O5 at 285 nm; and (9) heterogeneous reaction of N2O5 and H2O.

Rossi, M. J.↗

LIMS data - Inferred stratospheric distribution of NOx and HOx trace constituents and the calculated odd nitrogen budget

LIMS, SAMS, SBUV and in-situ data have been used to infer species not measured but which are of photochemical interest, e.g., O(3P), O(1D), NO, N2O5, OH, HO2, ClO and HCl. (LIMS = limb infrared monitor of the stratosphere; SAMS = stratospheric and mesospheric sounder; and SBUV = solar backscattered ultraviolet instrument.) Production and loss of odd nitrogen have been calculated and estimates have been made of the odd nitrogen transport due to adiabatically driven circulation derived from LIMS data. Data used from LIMS include O3, NO2, HNO3, H2O and T. CH4 and N2O were taken from SAMS and the UV solar flux from the SBUV instrument. Species were inferred for periods in October, December, March and May. Results for December are discussed. Results indicate: (1) maximum stratospheric odd nitrogen levels of 25 ppbv; (2) evidence of odd nitrogen transport from the mesosphere appearing at 25 km in the wintertime polar latitudes; (3) the polar night build-up of high levels of N2O5 beginning after the autumnal equinox; and (4) the possibility of large downward fluxes of odd nitrogen into the troposphere during the winter at latitudes poleward of 60 degrees.

Callis, L. B.↗

Heterogeneous chemistry on Antarctic polar stratospheric clouds - A microphysical estimate of the extent of chemical processing

A detailed model of polar stratospheric clouds (PSCs), which includes nucleation, condensational growth. and sedimentation processes, has been applied to the study of heterogeneous chemical reactions. For the first time, the extent of chemical processing during a polar winter has been estimated for an idealized air parcel in the Antarctic vortex by calculating in detail the rates of heterogeneous reactions on PSC particles. The resulting active chlorine and NO(x) concentrations at first sunrise are analyzed with respect to their influence upon the Antarctic ozone hole using a photochemical model. It is found that the species present at sunrise are primarily influenced by the relative values of the heterogeneous reaction rate constants and the initial gas concentrations. However, the extent of chlorine activation is also influenced by whether N2O5 is removed by reaction with HCl or H2O. The reaction of N2O5 with HCl, which occurs rapidly on type 1 PSCs, activates the chlorine contained in the reservoir species HCl. Hence the presence and surface area of type 1 PSCs early in the winter are crucial in determining ozone depletion.

Drdla, K.↗

A model for heterogeneous chemical processes on the surfaces of ice and nitric acid trihydrate particles

The study presents a model that incorporates the physics and physical chemistry of ice surfaces relevant to polar stratospheric clouds. Surface concentrations of H2O, HCl, HOCl, ClONO2, and N2O5 on ice and nitric acid trihydrate (NAT) crystals are computed, and surface reaction rates and reaction probabilities (sticking coefficients) are determined. For gas pressures of about 10 exp -7 torr and temperatures in the range of 180-200 K, HCl completely coats ice and water-rich NAT surfaces, while HOCl, ClOHO2, and N2O5 may cover 0.01-1 percent of these surfaces. The energy parameters are used to calculate surface temperatures such as adsorption and desorption constants, surface coverages, reaction rate coefficients, surface diffusion coefficients, and reaction probabilities for various species and chemical interactions on ice and NAT surfaces. Implications for chemical processing on polar stratospheric clouds are discussed.

Tabazadeh, Azadeh↗

Modulations of stratospheric ozone by volcanic eruptions

We have used a time series of aerosol surface based on the measurements of Hofmann to investigate the modulation of total column ozone caused by the perturbation to gas phase chemistry by the reaction N2O5(gas) + H2O(aero) yields 2HNO3(gas) on the surface of stratospheric aerosols. We have tested a range of values for its reaction probability, gamma = 0.02, 0.13, and 0.26 which we compared to unperturbed homogeneous chemistry. Our analysis spans a period from Jan. 1974 to Oct. 1994. The results suggest that if lower values of gamma are the norm then we would expect larger ozone losses for highly enhanced aerosol content that for larger values of gamma. The ozone layer is more sensitive to the magnitude of the reaction probability under background conditions than during volcanically active periods. For most conditions, the conversion of NO2 to HNO3 is saturated for reaction probability in the range of laboratory measurements, but is only absolutely saturated following major volcanic eruptions when the heterogeneous loss dominates the losses of N2O5. The ozone loss due to this heterogeneous reaction increases with the increasing chlorine load. Total ozone losses calculated are comparable to ozone losses reported from TOMS and Dobson data.

Blanchette, Christian↗

The MIPAS balloon borne trace constitutent experiment

A novel cryogenic Fourier transform spectrometer (FTS) has been developed for limb emission measurements in the mid IR-region from balloon-borne platforms. The FTS is a rapid scanning interferometer using a modified Michelson arrangement which allows a spectral resolution of 0.04 cm(exp -1) to be achieved. Solid carbon-dioxide cooling of the spectrometer and liquid-helium cooling of the detectors provide adequate sensitivity. The line of sight can be stabilized in terms of azimuth and elevation. A three-mirror off-axis telescope provides good vertical resolution and straylight rejection. Calibration is performed by high elevation and internal blackbody measurements. Four balloon flights were performed, two of them during spring turn-around 1989 and 1990 over mid-latitudes (Aire sur L'Adour, France, 44 deg N) and two near the northern polar circle in winter 1992 (Esrange, Sweden, 68 deg N). Limb emission spectra were collected from 32 km to 39 km floating altitudes covering tangent heights between the lower troposphere and the floating altitude. The trace gases CO2, H2O, O3, CH4, N2O, HNO3, N2O5, ClONO2, CF2Cl2, CFCl3, CHF2Cl, CCl4, and C2H6 have been identified in the measured spectra. The 1989 data have been analyzed to retrieve profiles of O3, HNO3, CFCl3 and CF2Cl2. The flights over Kiruna have provided the first ever reported profile measurements of the key reservoir species ClONO2 and N2O5 inside the polar vortex.

Oelhaf, H.↗

Two-dimensional simulation of Pinatubo aerosol and its effect on stratospheric ozone

This paper presents time-dependent simulations of the response of the stratosphere to the injection into the atmosphere of massive amounts of sulfur during the eruption of Mt. Pinatubo (The Philippines) in June 1991. The study is based on a coupled two-dimensional chemical-dynamical-radiative model to which a microphysical model for sulfate aerosol formation and fate has been added. The study suggests that, during the first year (July 1991 to June 1992) following the volcanic eruption, the observed changes in the ozone amount integrated between 65 deg S and 65 deg N were caused primarily by changes in the meridional circulation (associated with heating by the volcanic cloud in the tropics) and in the photolysis rate of molecules such as ozone (associated with backscattering of light by the cloud). During the second year after the eruption, as the aerosol was dispersed at all latitudes and, in particular, reached the polar region, the largest contribution to ozone reduction resulted from the heterogeneous chemical conversion of N2O5 and ClONO2 on the surface of the aerosol particles. The conversion of the latter compound, and hence the magnitude of the calculated ozone depletion, is highly dependent on the temperature in the lower stratosphere. Despite the fact that the surface area provided by aerosol particles decreased during the second year following the eruption, the calculated ozone depletion remained significant because the conversion of N2O5 is insensitive to the aerosol surface area density for values larger than 1-10 sq microns/cu cm (depending on latitude). The predicted reduction in ozone at 20 km in March during the third year (July 1993 to June 1994) of the model integration is smaller by a factor of 2 than it was during the second year.

Tie, Xuexi↗

A Comparison of Observations and Model Simulations of NO(x)/NO(y) in the Lower Stratosphere

Extensive airborne measurements of the reactive nitrogen reservoir (NOY) and its component nitric oxide (NO) have been made in the lower stratosphere. Box model. simulations that are constrained by observations of radical and longlived species and which include heterogeneous chemistry systematically underpredict the NO(x) (= NO + NO2) to NOY ratio. The model agreement is substantially improved if newly measured rate coefficients for the OH + NO2 and OH + HNO3 reactions are used. When included in 2-D models, the new rate coefficients significantly increase the calculated ozone loss due to NO(x) and modestly change the calculated ozone abundances in the lower stratosphere. Ozone changes associated with the emissions of a fleet of supersonic aircraft are also altered. phase chemistry linking NO(x) and nitric acid (HNO3), which is generally the most abundant NOY species. Because the continuous daylight present at summer high latitudes limits the heterogeneous production of HNO3 by N2O5 hydrolysis, gas-phase reactions primarily control the balance between NO(x) and NO(y). Outside summer polar regions, the N2O5 hydrolysis reaction occurring on stratospheric sulfate aerosols is a more important sink of NO(x), particularly in the lower stratosphere during winter when heterogeneous pathways account for most of the HNO3 production.

Gao, R. S.↗

The photolysis of ozone

Ozone was photolyzed at 25 C with steady illumination at several wavelengths from 2288 to 2850 A, at O3 pressures from 0.1 to 2.7 torr, and at absorbed intensities from 0.15 to 65 microns/min. Experiments were done in pure dry O3, and in the presence of He, CO2, N2, H2O, H2, N2O, He-CO2, He-H2O, CO2-H2O, O2-N2O, CO2-O2, and N2O5-O2-CO2 mixtures. The results show that in the absence of added gases or in the presence of He, the quantum yield of O3 consumption is 5.5 independent of conditions, except at pressures below 0.4 torr. In the presence of CO2 or N2, ozone consumption falls toward 4.0. The primary photolytic act produces O(1 D) and siglet O2, presumably O2(1 delta), at all wavelengths below 3000 A. Relative quenching constants O(1 D) removal by various gases were measured at 2288, 2537, and 2800 A. For O3, CO2, and N2, the relative rates are 1.0/0.4 to 0.5/0.08 to 0.11 at all wavelengths. For H2O the constant at 2537 A is 1.5 relative to that for O3. With N2O, a noticeable wavelength effect is observed and the relative rate constants are 1.5, 2 to 3, 4.0 for O3 compared to N2O at 2800, 2537, and 2288 A, respectively.

Lissi, E.↗

Photochemistry of nitrogen in the Martian atmosphere

Models are developed for the photochemistry of a CO2-H2O-N2 atmosphere on Mars. Estimates are given for the concentrations of N, NO, NO2, NO3, N2O5, HNO2, HNO3, and N2O as a function of altitude. Nitric oxide is the most abundant form of odd nitrogen, present with a mixing ratio relative to CO2 of the order of 1 hundred-millionth. Deposition rates for nitrite and nitrate minerals could be as large as 300,000 N equivalent atoms per sq cm/sec under present conditions and may have been higher in the past.

Yung, Y. L.↗

Inorganic chemistry: Direct syntheses from pure liquid SO3 and from trivalent and pentavalent nitrogen derivatives

From pure liquid SO3 direct synthesis reactions were carried out with N2O5, NO2Cl, NOCl which yielded N2O54SO3, 3SO3, 2SO3-NO2Cl2SO3-NOCl2SO3 and NOCl2SO3, the latter being obtained for the first time in the pure state. In all cases the crystallized product was obtained by separating the constituents of the mixture and then going through a single viscous liquid phase.

Vandorpe, B.↗

An experiment concept to measure stratospheric trace constituents by laser heterodyne spectroscopy

Laser heterodyne spectroscopy (LHS) techniques were used to measure radical gases from Spacelab. Major emphasis was placed on the measurement of ClO, ClOnO2, HO2, H2O2, N2O5, and HOCl in solar occultation with vertical resolution less than or equal to 2-km and vertical range from 1O to 70-km. Sensitivity analyses were performed on ClO and O3 to determine design criteria for the LHS instrument. Results indicate that O3 and ClO vertical profiles can be measured with an accuracy more than or equal to 95% and more than or equal to 80%, respectively, over the total profile.

Allario, F.↗

The problem of nighttime stratospheric NO3

Detailed calculations of the behavior of the NO3 column content as a function of time after sunset show that it takes nearly 2 hours to increase from daytime values of approximately 10 to the 11th/sq cm to nighttime values of 10 to the 14th/sq cm. These results appear to be in conflict with the measured NO3-concentration rise time of 40 min after sunset obtained from the 662-nm absorption data of Noxon et al. (1978). Changes in the rate constants affecting the NO, NO2, NO3, N2O5 system, the atmospheric temperature, and the amount of NO2 are not able to bring the calculated rise time for the NO3 column content into agreement with observations.

Herman, J. R.↗

Heterogeneous atmospheric reactions - Sulfuric acid aerosols as tropospheric sinks

The reaction probabilities of various atmospheric species incident on a bulk sulfuric acid surface are measured in order to determine the role of sulfuric acid aerosols as pollutant sinks. Reaction products and unreacted starting materials leaving a Knudsen cell flow reactor after collision at 300 K with a H2SO4 surface or a soot surface were detected by mass spectrometry. Significant collision reaction probabilities are observed on a H2SO4 surface for H2O2, HNO3, HO2NO2, ClONO2, N2O5, H2O and NH3, and on soot for NH3. Estimates of the contribution of heterogeneous reactions to pollutant removal under atmospheric conditions indicate that while aerosol removal in the stratosphere is insignificant (loss rate constants approximately 10 to the -10th/sec), heterogeneous reactions may be the dominant loss process for several tropospheric species (loss rate constant approximately 10 to the -5th/sec, comparable to photolysis rate constants).

Baldwin, A. C.↗

Integrated band intensities of gaseous N/2/O/5/

Values for mid-IR integrated band intensities of gaseous N2O5 were determined at room temperature. The absorptions studied were at 1720, 1246, 743, and 557/cm. The integrated intensities were 2204, 581, 685, and 699/atm cm, respectively. Implications of these results for the stratospheric detection of N(2)O(5) are discussed.

Lovejoy, R. W.↗

An experiment concept to measure stratospheric trace constituents by Laser Heterodyne Spectroscopy

The concept and techniques of a Laser Heterodyne Spectrometer experiment for measuring the vertical profiles of several stratospheric trace gases are discussed. The goal of the experiment is to develop a laser heterodyne receiver capable of measuring 2-4 gases simultaneously from Spacelab and, ultimately, from free-flying platforms. Sensitivity analyses are currently being performed for tenuous molecules such as ClO, ClONO2, NOCl, HO2, H2O2, and N2O5, although the capability exists for measuring more abundant gases, such as O3, HNO3, N2O, NO2, and CH4. Results indicate that O3 and ClO vertical profiles can be measured with an accuracy equal to or better than 95% and 80%, respectively, over the total profile. Laboratory measurements of the performance characteristics of the local oscillator and heterodyne detector are discussed with reference to 'excess-noise' and Doppler-shift effects.

Allario, F.↗

Precision of NO2 photolysis rate measurements

Gas-phase kinetic calculations indicate that actinometric measurements of the rate of solar photolysis of NO2 in nitrogen can be in error by +5 to -15% or more, unless odd oxygen N2O5 chemistry, and trace oxygen content are considered. A field experiment confirms that the effect of the quartz tube on the measured photolysis rate is less than 1.7%.

Dickerson, R. R.↗