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Sander, Stanley P.

Publications and source records attributed to Sander, Stanley P..

52 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS1990

Spatial variation of ozone depletion rates in the springtime Antarctic polar vortex

An area-mapping technique, designed to filter out synoptic perturbations of the Antarctic polar vortex such as distortion or displacement away from the pole, was applied to the Nimbus-7 TOMS (Total Ozone Mapping Spectrometer) data. This procedure reveals the detailed morphology of the temporal evolution of column O3. The results for the austral spring of 1987 suggest the existence of a relatively stable collar region enclosing an interior that is undergoing large variations. A simplified photochemical model of O3 loss and the temporal evolution of the area-mapped polar O3 are used to constrain the chlorine monoxide (ClO) concentrations in the springtime Antarctic vortex. The O3 loss rates could be larger than deduced here because of underestimates of total O3 by TOMS near the terminator.

Yung, Yuk L.↗
NASA NTRS1990

Tunable diode laser IR spectrometer for in situ measurements of the gas phase composition and particle size distribution of Titan's atmosphere

A new instrument, the Probe Infrared Laser Spectrometer (PIRLS), is described for in situ sensing of the gas composition and particle size distribution of Titan's atmosphere on the NASA/ESA Cassini mission. For gas composition measurements, several narrow-band (0.0001/cm) tunable lead-salt diode lasers operating near 80 K at selected mid-IR wavelengths are directed over a path length defined by a small reflector extending over the edge of the probe spacecraft platform; volume mixing ratios of 10 to the -9th should be measurable for several species of interest. A cloud-particle-size spectrometer using a diode laser source at 780 nm shares the optical path and deployed reflector; a combination of imaging and light scattering techniques is used to determine sizes of haze and cloud particles and their number density as a function of altitude.

Webster, Christopher R.↗
NASA NTRS1990

Evaluated rate constants for selected HCFC's and HFC's with OH and O((sup)1D)

The chemistry of HCFC's and HFC's in the troposphere is controlled by reactions with OH in which a hydrogen atom is abstracted from the halocarbon to form water and a halo-alkyl radical. The halo-alkyl radical subsequently reacts with molecular oxygen to form a peroxy radical. The reactions of HCFC's and HFC's with O(exp1D) atoms are unimportant in the troposphere, but may be important in producing active chlorine of OH in the stratosphere. Here, the rate constants for the reactions of OH and O(exp1D) with many HFC's and HCFC's are evaluated. Recommendations are given for the five HCFC's and three HFC's specified by AFEAS as primary alternatives as well as for all other isomers of C1 and C2 HCFC's and HFC's where rate data exist. In addition, recommendations are included for CH3CCl3, CH2Cl2, and CH4.

Hampson, Robert F.↗
NASA NTRS1989

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↗
NASA NTRS1989

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.↗
NASA NTRS1989

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.↗
NASA NTRS1989

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.↗
NASA NTRS1988

Kinetics and product studies of the BrO + ClO reaction - Implications for Antarctic chemistry

Discharge flow-mass spectrometry and flash photolysis-UV spectrometry were used to investigate the reaction of ClO with BrO over the temperature range of 220-400 K and the pressure range of 1-760 Torr. Rate constants were determined for: (1) Br + ClOO, (2) Br + OClO, and (3) BrCl + O2. It is found that the rate constants for the overall reaction and each reaction branch are inversely dependent on temperature and independent of pressure. For temperatures found in the Antarctic stratosphere, the rate coefficients for the channels yielding ClOO and OClO are a factor of 2-3 larger than previously estimated.

Sander, Stanley P.↗
NASA NTRS1988

Studies of ClO and BrO reactions important in the polar stratosphere: Kinetics and mechanism of the ClO+BrO and ClO+ClO reactions

The reactions, BrO + ClO yields Br + ClOO (1a) yields Br + OClO (1b) yields BrCl + O2 (1c) and ClO + ClO yields Cl + CiOO (2a) yields Cl + OClO (2b) yields Cl2 + O2 (2c) yields (ClO)2 (2d) have assumed new importance in explaining the unusual springtime depletion of ozone observed in the Antarctic stratosphere. The mechanisms of these reactions involve the formation of metastable intermediates which subsequently decompose through several energetically allowed products providing the motivation to study these reactions using both the discharge flow-mass spectrometric and flash photolysis - ultraviolet absorption techniques. These methods have also been used to explore aspects of the kinetics and spectroscopy of the ClO dimer.

Friedl, Randall R.↗
NASA NTRS1988

High resolution FTIR spectroscopy of the ClO radical

The chlorine monoxide radical, ClO, plays a significant role in the catalytic destruction of ozone in the Earth's stratosphere. Because of its atmospheric importance, ClO has been the subject of numerous observational attempts. In order to deduce ClO concentrations from stratospheric infrared measurements, the infrared spectroscopy of ClO must be well characterized. Approximately 830 individual lines were measured form ClO imfrared spectra with the ClO concentration between 1 x 10 to the 13th power and 6 x 10 to the 13th power molecules per cu cu. The lines were then averaged and fit to a function of m (where m = O, -J or J+1 for the Q,P and R branches respectively) to obtain the band strength, S sub v and the first Herman-Wallis coefficient, alpha. The total S sub v for the two main isotopmers was 13.11 plus or minus 1 cm(-2) atm(-1) while alpha was 0.00412 plus or minus .00062.

Lang, Valerie↗
NASA NTRS1988

Multiple-Diode-Laser Gas-Detection Spectrometer

Small concentrations of selected gases measured automatically. Proposed multiple-laser-diode spectrometer part of system for measuring automatically concentrations of selected gases at part-per-billion level. Array of laser/photodetector pairs measure infrared absorption spectrum of atmosphere along probing laser beams. Adaptable to terrestrial uses as monitoring pollution or control of industrial processes.

Webster, Christopher R.↗
NASA NTRS1988

Absolute infrared band strength measurement of the ClO radical by Fourier transform infrared spectroscopy

High-resolution (0.005/cm) FTIR spectra of the X2Pi(i)-X2Pi(i) (1-0) rovibrational bands of (C-35)(O-16) and (Cl-37)(O-16) were obtained in 1 torr of helium carrier gas. After measuring the strengths of approximately 830 individual IR lines from several spectra, a total band strength of 13.1 + or - 1.1/sq cm atm and a first Herman-Wallis coefficient of (4.12 + or - 0.62) x 10 to the -3rd were determined.

Lang, Valerie I.↗
NASA NTRS1986

A kinetics study of the homogeneous and heterogeneous components of the HCl + ClONO2 reaction

The kinetics of the reaction HCl + ClONO2 to Cl2 + HNO3 were investigated at 298 K using a flow reactor with FTIR analysis to assess the importance of this reaction for stratospheric chemistry. The observed reaction was characteristic of a heterogeneous process; an upper limit of 5 x 10 to the -18th cu cm/molecule per s was obtained for the homogeneous gas phase rate constant. From calculations of the first order wall rate constant, estimates were made of the reaction rate on stratospheric aerosols. Because both HCl and ClONO2 need to be adsorbed on the particle surface, the reaction will be of negligible importance under most stratospheric conditions.

Friedl, Randall R.↗
NASA NTRS1986

Temperature dependence of the NO3 absorption spectrum

The absorption spectrum of the gas-phase NO3 radical has been studied between 220 and 700 nm by using both flash photolysis and discharge flow reactors for the production of NO3. In the flash photolysis method, cross sections at the peak of the (0,0) band at 661.9 nm were measured relative to the cross section of ClONO2 at several different wavelengths. From the best current measurements of the ClONO2 spectrum, the NO3 cross section at 661.9 nm was determined to be (2.28 + or 0.34) x 10 to the -17th sq cm/molecule at 298 K. Measurements at 230 K indicated that the cross section increases by a factor of 1.18 at the peak of the (0,0) band. The discharge flow method was used both to obtain absolute cross sections at 661.9 nm and to obtain relative absorption spectra between 300 and 700 nm at 298 and 230 K. A value of (1.83 + or - 0.27) x 10 to the -17th sq cm/molecule was obtained for sigma NO3 at 661.9 nm at 298 K. Upper limits to the NO3 cross sections were also measured between 220 and 260 nm with the discharge flow method.

Sander, Stanley P.↗
NASA NTRS1965

Production of NO2 from Photolysis of Peroxyacetyl Nitrate

Peroxyacetyl nitrate (PAN) vapor was photolyzed at 248 nm, and the NO2 photoproduct was detected by laser-induced fluorescence. The quantum yield for the production of NO2 from PAN photolysis was determined by comparison to HNO3 photolysis data taken under identical experimental conditions. The average of data collected over a range of total pressures, precursor concentrations, and buffer gases was 0.83 +/- 0.09 for the NO2 quantum yield, where the statistical uncertainty is 2 standard deviations.

Mazely, Troy L.↗