Search NASA⌕ Search

Engineering topics

Friedl, Randall R.

Publications and source records attributed to Friedl, Randall R..

At least 19 records

Atmospheric Effects of Subsonic Aircraft: Interim Assessment Report of the Advanced Subsonic Technology Program

This first interim assessment of the subsonic assessment (SASS) project attempts to summarize concisely the status of our knowledge concerning the impacts of present and future subsonic aircraft fleets. It also highlights the major areas of scientific uncertainty, through review of existing data bases and model-based sensitivity studies. In view of the need for substantial improvements in both model formulations and experimental databases, this interim assessment cannot provide confident numerical predictions of aviation impacts. However, a number of quantitative estimates are presented, which provide some guidance to policy makers.

Friedl, Randall R.↗

The Quantum Yield of NO3 from Peroxyacetyl Nitrate Photolysis

Peroxyacetyl nitrate (PAN) vapor was photolyzed at 248nm and the NO3 photoproduct was detected by laser induced fluorescence. The excited state flourescence contributions were investigated and a data analysis methodology was established to minimize their effects.

Peroxyacetyl Nitrate Photolysis↗

Atmospheric Effects of Aviation: First Report of the Subsonic Assessment Project

This document is the first report from the Office of Aeronautics Advanced Subsonic Technology (AST) Program's Subsonic Assessment (SASS) Project. This effort, initiated in late 1993, has as its objective the assessment of the atmospheric effects of the current and predicted future aviation fleet. The two areas of impact are ozone (stratospheric and tropospheric) and radiative forcing. These are driven, respectively, by possible perturbations from aircraft emissions of NOX and soot and/or sulfur-containing particles. The report presents the major questions to which project assessments will be directed (Introduction) and the status of six programmatic elements: Emissions Scenarios, Exhaust Characterization, Near-Field Interactions, Kinetics and Laboratory Studies, Global Modeling, and Atmospheric Observations (field studies).

Thompson, Anne M.↗

Interaction of Peroxynitric Acid with Solid H2O Ice

The uptake of peroxynitric acid (PNA), HO2NO2 or HNO4, on solid H2O ice at 193 K (-80 C) was studied using a fast flow-mass spectrometric technique. An uptake coefficient of 0.15 +/- 0.10 was measured, where the quoted uncertainty denotes 2 standard deviations. The uptake process did not result in the production of gas phase products. The composition of the condensed phase was investigated using programmed heating (3 K/min) of the substrate coupled with mass spectrometric detection of desorbed species. Significant quantities of HNO, and HNO3 desorbed from the substrates at temperatures above 225 K and 246 K, respectively. The desorbed HNO3, which was less than 9% of the desorbed HNO, and remained unchanged upon incubation of the substrate, was likely due to impurities in the HNO4 samples rather than reaction of HNO, on the substrate. The onset temperatures for HNO4 desorption increased with increasing H2O to HNO4 ratios, indicating that HNO4, like HNO3, tends to be hydrated in the presence of water. These observations suggest possible mechanisms for removal of HNO4 or repartitioning of total odd nitrogen species in the Earth's upper troposphere and stratosphere.

Li, Zhuangjie↗

Pressure-Dependent Yields and Product Branching Ratios in the Broadband Photolysis of Chlorine Nitrate

The photolysis of chlorine nitrate was studied using broadband flash photolysis coupled with long-path ultraviolet-visible absorption spectroscopy. Branching ratios for the Cl + NO3 and ClO + NO2 product channels were determined from time-dependent measurements of ClO and NO3 concentrations. Yields of the ClO and NO3 products displayed a dependence on the bath gas density and the spectral distribution of the photolysis pulse. Product yields decreased with increasing bath gas density regardless of the spectral distribution of the photolysis pulse; however, the decrease in product yield was much more pronounced when photolysis was limited to longer wavelengths. For photolysis in a quartz cell (lambda > 200 nm) the yield decreased by a factor of 2 over the pressure 10-100 Torr. In a Pyrex cell (lambda > 300 nm), the yield decreased by a factor of 50 over the same pressure range. When photolysis was limited to lambda > 350 nm, the yield decreased by a factor of 250. Branching ratios for the photolysis channels [ClONO2 + h.nu yields ClO + NO2 (1a) and ClONO2 + h.nu yields Cl + NO3 (lb)] were determined from the relative ClO and NO3 product yields at various pressures. Although the absolute product yield displayed a pressure dependence, the branching between the two channels was independent of pressure. The relative branching ratios (assuming negligible contributions from other channels) are 0.61 +/- 0.20 for channel 1a and 0.39 +/- 0.20 for channel lb for photolysis with lambda > 200 nm and 0.44 +/- 0.08 for channel 1a and 0.56 +/- 0.08 for channel 1b for photolysis with lambda > 300 nm. The implications of these results for the chemistry of the lower stratosphere are discussed.

Nickolaisen, Scott L.↗

The 1995 scientific assessment of the atmospheric effects of stratospheric aircraft

This report provides a scientific assessment of our knowledge concerning the impact of proposed high-speed civil transport (HSCT) aircraft on the atmosphere. It comes at the end of Phase 1 of the Atmospheric Effects of Stratospheric Aircraft element of the NASA High-Speed Research Program. The fundamental problem with stratospheric flight is that pollutant residence times are long because the stratosphere is a region of permanent temperature inversion with stable stratification. Using improved two-dimensional assessment models and detailed fleet emissions scenarios, the assessment examines the possible impact of the range of effluents from aircraft. Emphasis is placed on the effects of NO(x) and H2O on the atmospheric ozone content. Measurements in the plume of an in-flight Concorde supersonic transport indicated a large number of small particles. These measurements, coupled with model sensitivity studies, point out the importance of obtaining a more detailed understanding of the fate of sulfur in the HSCT exhaust. Uncertainties in the current understanding of the processes important for determining the overall effects of HSCT's on the atmosphere are discussed and partially quantified. Research directions are identified to improve the quantification of uncertainties and to reduce their magnitude.

Stolarski, Richard S.↗

The nu(sub 6), nu(sub 7), nu(sub 8), and nu(sub 10) Bands of HO2NO2

Two new fundamental vibration-rotation bands have been observed for HO2NO2 and assigned. They are nu(sub 7) at 648 1/cm and nu(sub 8) at 466 1/cm. On the basis of these assignments the previously observed bands at 722, 801.5, and 919 1/cm are assigned to nu(sub 10), nu(sub 7) + nu(sub 12), and 2 nu(sub 8), respectively. A partial rotational analysis of the atmospherically relevant nu(sub 6) band has been carried out, and the effects of tunneling, Coriolis interactions, and hot bands on the rotational structure have been characterized.The band origin derived from this analvsisis 8O2.54(sub 3) 1/cm.

Friedl, Randall R.↗

Experimental and Theoretical Studies of Atmosphereic Inorganic Chlorine Chemistry

Over the last five years substantial progress has been made in defining the realm of new chlorine chemistry in the polar stratosphere. Application of existing experimental techniques to potentially important chlorine-containing compounds has yielded quantitative kinetic and spectroscopic data as well as qualitative mechanistic insights into the relevant reactions.

Atmosphere Chlorine Chemistry↗

Kinetics and Mechanism of the CIO + CIO Reaction: Pressure and Temperature Dependences of the Bimolecular and Termolecular Channels andThermal Decomposition of Chlorine Peroxide, CIOOCI

The kinetics and mechanism of the CIO + CIO reaction and the thermal decomposition of CIOOCI were studied using the flash photolysis/long path ultraviolet absorption technique. Pressure and temperature dependences were determined for the rate coefficients for the bimolecular and termolecular reaction channels, and for the thermal decompositon of CIOOCI.

Kinetics Thermal Decomposition Biomolecul↗

A compact, high resolution Michelson interferometer for atmospheric spectroscopy in the near ultraviolet

A new, compact Fourier Transform Michelson interferometer (FTUV) with an apodized resolving power greater than 300,000 at 300 nm, high throughput and wide spectral coverage has been developed. The objectives include atmospheric spectroscopy (direct solar absorption and solar scattering) and laboratory spectroscopy of transient species. In this paper, we will briefly describe the prototype FTUV instrument and the results of preliminary laboratory investigations of OH and ClO spectra in emission and absorption.

Sander, Stanley P.↗

Chloryl nitrate - A novel product of the OClO + NO3 + M recombination

The products of the reaction of OClO with NO3 were investigated between 220 and 298 K using a flow reactor and infrared, visible, and ultraviolet analysis. At temperatures below 250 K new infrared and ultraviolet absorption features were observed and assigned to the novel compound chloryl nitrate (O2ClONO2). Additionally, ClO and NO2 were observed as reaction products, indicating the existence of a second reaction channel. O2ClONO2 formation predominates at temperatures below 230 K. The reaction rate constant at 220 K is estimated to be on the order of 10 exp -14 cu cm/molecule s in 1-5 Torr of helium. These observations suggest that O2ClONO2 may exist in the terrestrial stratosphere.

Friedl, Randall R.↗

The rotational spectrum and structure of chlorine peroxide

The dimerization products of the ClO + ClO reaction were investigated in a flowing chemical reactor using submillimeter wave spectroscopy. The major products were identified as the chlorine peroxide (Cl2O2) and chlorine dioxide (OClO). The rotational constants as well as a complete set of quartic centrifugal distortion constants were determined. The identification of the chlorine peroxide supports the earlier proposed ClO-dimer mechanisms, which partly explain the ozone hole formation during the Antarctic springtime.

Birk, Manfred↗

Rate of formation of the ClO dimer in the polar stratosphere - Implications for ozone loss

The gas-phase recombination of chlorine monoxide (ClO) has been investigated under the conditions of pressure and temperature that prevail in the Antarctic stratosphere during the period of maximum ozone (O3) disappearance. Measured rate constants are less than one-half as great as the previously accepted values. One-dimensional model calculations based on the new rate data indicate that currently accepted chemical mechanisms can quantitatively account for the observed O3 losses in late spring (17 September to 7 October). A qualitative assessment indicates that the existing mechanisms can only account for at most one-half of the measured O3 depletion in the early spring (28 August to 17 September), indicating that there may be additional catalytic cycles, besides those currently recognized, that destroy O3.

Sander, Stanley P.↗

Kinetics and product studies of the reaction ClO + BrO using flash photolysis-ultraviolet absorption

The reaction between BrO and ClO was studied over the pressure range 50-700 torr and temperature range 220-400 K, using the flash photolysis-ultraviolet absorption method described by Watson et al. (1979). In order to investigate the mechanism of the BrO + ClO reaction, the product branch reactions Br + Cl2O yielding ClO + BrCl and Cl2O + h(nu) yielding products were examined. The rate constant for the overall reaction and the Arrhenius expression for the Br + Cl2O reaction are given, as well as the quantum yield for the production of atomic oxygen from the Cl2O photolysis.

Sander, Stanley P.↗

Kinetics and product studies of the reaction ClO + BrO using discharge-flow mass spectrometry

The kinetics and product branching ratios of the reaction between ClO and BrO were studied at 1 torr pressure over the temperature range 220-400 K, using the method of discharge-flow mass spectrometry. Three product channels were identified and quantified: Br + ClOO, Br + OClO, and BrCl + O2, indicating that the reaction mechanism of ClO + BrO involves metastable intermediates. The overall reaction rate coefficient and the rate coefficients for the three channel reactions are given.

Friedl, Randall R.↗