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Direct observation of ClO from chlorine nitrate photolysis

Chlorine nitrate photolysis has been investigated with the use of a molecular beam technique. Excitation at both 248 and 193 nanometers led to photodissociation by two pathways, ClONO2 yields ClO + NO2 and ClONO2 yields Cl + NO3, with comparable yields. This experiment provides a direct measurement of the ClO product channel and consequently raises the possibility of an analogous channel in ClO dimer photolysis. Photodissociation of the ClO dimer is a critical step in the catalytic cycle that is presumed to dominate polar stratospheric ozone destruction. A substantial yield of ClO would reduce the efficiency of this cycle.

Minton, Timothy K.↗

MLS observations of lower stratospheric ClO and O3 in the 1992 Southern Hemisphere winter

UARS MLS measurements of ClO in the 1992 Southern Hemisphere winter are described. Lower stratospheric ClO abundances greater than 1 ppbv were observed in the vortex beginning 1 June. The enhanced ClO reached largest areal extent in mid-August, then retreated poleward. ClO abundances at 22 hPa decreased in early September while those at 46 hPa remained high. O3 decrease within the vortex was observed by mid-August, and was coincident with the enhanced ClO.

Waters, J. W.↗

The evolution of ClO and NO along air parcel trajectories

Back trajectory analysis of Arctic and Antarctic aircraft data reveals that high ClO concentrations are associated with predicted polar stratospheric cloud (PSCs) encounters. The ClO concentrations within the Arctic and Antarctic polar vortices vary widely but appear to be inversely related to parcel solar exposure since the last PSC interaction. These results imply that production of NO(x) from HNO3 photolysis and reaction with OH is the mechanism for the loss of chlorine radicals through the reformation of chlorine nitrate. Highly denitrified air parcels show no change in ClO with solar exposure. The recovery process is quantitatively duplicated using a model of chemistry along trajectories. Although PSC processing is the primary mechanism for producing elevated ClO amounts, back trajectories apparently unperturbed by PSC's also show slightly elevated ClO levels in 1992 compared to Arctic 1989 and Antarctic 1987 measurements presumably due to the presence of Pinatubo aerosol.

Schoeberl, M. R.↗

Validation of UARS Microwave Limb Sounder ClO Measurements

Validation of stratospheric ClO measurements by the Microwave Limb Sounder (MLS) on the Upper Atmosphere Research Satellite (UARS) is described. Credibility of the measurements is established by (1) the consistency of the measured ClO spectral emission line with the retrieved ClO profiles and (2) comparisons of ClO from MLS with that from correlative measurements by balloon-based, ground-based, and aircraft-based instruments. Values of "noise" (random), "scaling" (multiplicative), and "bias" (additive) uncertainties are determined for the Version 3 data, in the first version public release of the known artifacts in these data are identified. Comparisons with correlative measurements indicate agreement to within the combined uncertainties expected for MLS and the other measurements being compared. It is concluded that MLS Version 3 ClO data, with proper consideration of the uncertainties and "quality" parameters produced with these data, can be used for scientific analyses at retrieval surfaces between 46 and 1 hPa (approximately 20-50 km in height). Future work is planned to correct known problems in the data and improve their quality.

Waters, J. W.↗

The Response of ClO Radical Concentrations to Variations in NO2 Radical Concentrations in the Lower Stratosphere

The response of ClO concentrations to changes in NO2 concentrations has been inferred from simultaneous observations of [ClO], [NO], [NO2] and [O3] in the mid-latitude lower stratosphere. This analysis demonstrates that [ClO] is inversely correlated with [NO2], consistent with formation and photolysis of [ClONO2]. A factor of ten range in the concentration of NO2 was sampled (0.1 to 1 x 10(exp 9) mol/cc), with a comparable range in the ratio of [ClO] to total available inorganic chlorine (1% <= [ClO]/[Cl(sub y)] <= 5%). This analysis leads to an estimate of [ClONO2]/[Cl(sub y)] = 0.12 (x/divided by 2), in the mid-latitude, lower-stratospheric air masses sampled.

Stimpfle, R. M.↗

Ground-Based Microwave Measurements of ClO and O3 Over Scott Base, Antarctica

We present measurements from a new microwave instrument that has been deployed at Scott Base, Antarctica, primarily to measure ClO. The new instrument allows for the extension of the time series of lower stratospheric ClO measurements begun in 1996 at this site, while some of the technical improvements offer the possibility of making additional measurements. We show measurements of ClO and O 3 in both the upper and lower stratosphere near both the fall and spring equinox and document the diurnal variations of these measurements throughout the season. The ground-based measurements are compared with Aura Microwave Limb Sounder (MLS) measurements, which are available twice per day, and with a NASA Goddard 2D model (GSFC2D) simulation. We show that, in agreement with the GSFC2D model diurnal variations, upper stratospheric ClO mixing ratios gradually increase throughout the daylight hours, while in the lower stratospheric austral spring, when heterogeneous chemistry associated with polar stratospheric clouds occurs, daily maximum ClO mixing ratios of near 2 ppbv occur near noon. We also show measurements of stratospheric O 3 , primarily in the upper stratosphere, which, while exhibiting a low bias of ∼15%–20% relative to Aura MLS, show temporal variations in good agreement with MLS.

stratospheric ozone↗

Quantum magnetism in the frustrated square lattice oxyhalides YbBi 2 IO 4 and YbBi 2 ClO 4

Square-lattice systems offer a direct route for realizing two-dimensional (2D) quantum magnetism with frustration induced by competing interactions. In this work, the square lattice materials YbBi 2 IO 4 and YbBi 2 ClO 4 were investigated using a combination of magnetization and specific-heat measurements on polycrystalline samples. Specific-heat measurements provide evidence for long-range magnetic order below $T$ N = 0.21 K (0.25 K) for YbBi 2 IO 4 (YbBi 2 ClO 4 ). On the other hand, a rather broad maximum is found in the temperature-dependent magnetic susceptibility, located at $T$ max = 0.33 K (0.38 K) in YbBi 2 IO 4 (YbBi 2 ClO 4 ), consistent with the quasi-2D magnetism expected for the large separation between the magnetic layers. Estimation of the magnetic entropy supports the expected Kramers' doublet ground state for Yb 3+ and the observed paramagnetic behavior is consistent with a well-isolated doublet. Roughly two-thirds of the entropy is consumed above $T$ N , due to a combination of the quasi-2D behavior and magnetic frustration. The impact of frustration is examined from the viewpoint of a simplified $J$ 1 -$J$ 2 square lattice model, which is frustrated for antiferromagnetic interactions. Specifically, a high-temperature series expansion analysis of the temperature-dependent specific-heat and magnetization data yields $J$ 2 /$J$ 1 = 0.30 (=0.23) for YbBi 2 IO 4 (YbBi 2 ClO 4 ). In conclusion, this simplified analysis suggests strong frustration that should promote significant quantum fluctuations in these compounds, and thus motivates future work on the static and dynamic magnetic properties of these materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Measurement of the fundamental vibration-rotation spectrum of ClO

The ClO fundamental absorption band near 850/cm is observed, with a tunable PbSnTe diode laser used as a source of monochromatic radiation. The chlorine monoxide concentration in the absorption tube was measured indirectly via a UV transmission technique. Frequencies and assignments for the ClO lines, and band centers and rotational constants for the ClO fundamental vibration, are tabulated. Diatomic vibration-rotation transitions within and between electronic substates are discussed. The tunable diode laser is valuable for studying the hyperfine structure. The IR spectroscopic technique is developed in order to monitor chlorine monoxide concentration in the stratosphere, since the short-lived ClO is a crucial intermediate participant in reactions involving destruction of stratospheric ozone.

Menzies, R. T.↗

Kinetics of the reactions of ClO with O and with NO

The rate constants k1, k2, and k3 for the reactions Cl + O3 yields ClO + O2 (1), ClO + O yields Cl + O2 (2), and ClO + NO yields Cl + NO2 (3), respectively, were measured by the discharge-flow technique, in which chlorine atoms are added to a flow of O3 and either O or NO in a helium carrier gas. The conditions of the experiment were such that the steady-state concentration ratios of Cl to ClO are simply interpretable in terms of the rate constant ratios k2/k3 or k3/k1. These rate constant ratios were measured over the range 220 to 298 K and combined with the directly determined k1 value to yield k2 and k3. The results are: k1 = 2.12 x 10 to the -11th exp(-157/T); k2 = 3.38 x 10 to -11th exp(75 plus or minus 40/T); and k3 = 1.13 x 10 to the -11th exp(200 plus or minus 30/T) cu cm/sec.

Zahniser, M. S.↗

Aircraft search for millimeter-wavelength emission by stratospheric ClO

Three millimeter-wavelength transitions of ClO were searched for in the stratospheric emission spectrum during May-August 1977 using aircraft-based instruments. The measurements indicate that if stratospheric ClO has a vertical distribution of the form predicted by present photochemical models, then the ClO volume mixing ratio at the profile peak did not exceed 10 to the -9th at the time and place of the measurements. The observed spectra suggest the presence of ClO in the stratosphere but do not provide a definitive detection.

Waters, J. W.↗

Ground-based detection of stratospheric ClO and average column density measurement over 17 days of observation

A very sensitive mm-wave heterodyne receiver of a type originally developed for radio astronomy is used in combination with a broadband filter bank spectrometer to detect and measure the 204-GHz rotational transition of stratospheric ClO. Data is acquired in the form of a dimensionless ratio and is converted to units expressing signal intensity. Computed line shapes are matched against the data for a comparison with theoretical stratospheric models and previous measurements. The ClO distribution in the stratosphere measured at 42 deg N latitude in early spring is significantly different from that expected based on existing theoretical models. There is much less ClO at latitudes below about 36 km than predicted, and average ClO column density found for 42 deg N is 20-30% less than that from existing balloon flight measurements at 32 deg N.

Dezafra, R.↗

A re-evaluation of laser heterodyne radiometer ClO measurements

Previously reported measurements of stratospheric ClO using a balloon-borne laser heterodyne radiometer, launched from Palestine, Texas, are re-evaluated as a result of recent spectroscopic data. A spectral feature which was observed during September, 1978 and November, 1979 flights was incorrectly identified as a ClO absorption line, while a second feature observed during the latter flight with somewhat limited sensitivity is now believed to be due to ClO. This new interpretation results in a measured ClO profile which falls off more rapidly with decreasing altitude than the previous results indicated.

Menzies, R. T.↗

Daytime ClO over McMurdo in September 1987: Altitude profile retrieval accuracy

During the 1987 National Ozone Expedition, mm-wave emission line spectra of the 278.6 GHz rotational stratospheric ClO were observed at McMurdo Station, Antarctica. The results confirm the 1986 discovery of a lower stratospheric layer with approximately 100 times the normal amount of ClO; the 1987 observations, made with a spectrometer bandwidth twice that used in 1986, make possible a more accurate retrieval of the altitude profile of the low altitude component of stratospheric ClO from the pressure broadened line shape, down to approximately 16 km. The accuracy of the altitude profile retrievals is discussed, using the daytime (09:30 to 19:30, local time) data from 20 to 24 September, 1987 as an example. The signal strength averaged over this daytime period is approx. 85 percent of the midday peak value. The rate of ozone depletion implied by the observed ClO densities is also discussed.

Barrett, J.↗

In situ observations of ClO in the wintertime Northern Hemisphere: ER-2 aircraft results from 21 N to 61 N latitude

Measurements of lower stratospheric ClO taken during a NASA ER-2 flight between Moffett Field, CA (37 N, 122 W) and Great Slave Lake, Canada (61 N, 116 W) on 13 February 1988 are reported. Northbound, the aircraft was flown at about 20 km altitude from 39 N to 56 N, at 18 km from there to 58 N, in a descent to 15 km at 60 N, and in a rise and turn at the northernmost point. The southbound leg was flown in a gradual climb from 20 km to 21.5 km. On this day, the central position of the Arctic polar vortex, as determined by an NMC analysis of heights and temperatures at the 50 mb and 70 mb levels, was approximately 79 N, 100 W. Because the vortex was located on the North American side of the pole, the aircraft was able to reach a point slightly inside the maximum horizontal wind region where wind speeds were 80 to 90 knots. The general pattern for the observed ClO is that it increased with both latitude and altitude, and attained a maximum of about 55 pptv at 61 N latitude and 20.5 km altitude. This value is about 20 times smaller than the maxima observed over Antarctica, but is comparable to those seen just outside the chemical containment vessel located inside the Antarctic Polar vortex. On the other hand, in a comparison with northern midlatitude data taken on this and three other February flights, ClO mixing ratios observed north of 55 N latitude are 2 to 5 times larger at all flight altitudes (15 to 20 km). Possible reasons are discussed for this enhancement over midlatitude and the evidence is considered for whether or not the instruments sampled Arctic polar vortex air. A second feature of the data is the strong positive correlation between ClO and O3 during the entire flight.

Brune, W. H.↗

In situ northern mid-latitude observations of ClO, O3, and BrO in the wintertime lower stratosphere

In order to test photochemical theories linking chlorofluorocarbon derivatives to O3 depletion at high latitudes in the springtime, several related atmospheric species, including O3, ClO, and BrO were measured in the lower stratosphere. The flight path extended to the center of the polar jet associated with but outside of the Arctic vortex, in which the abundance of O3 was twice its midlatitude value, whereas BrO levels were five parts per trillion (pptv) by volume between 18 and 21 km, and 2.4 pptv below that altitude. The ClO mixing ratio was as much as 65 pptv at 60 N latitude at an altitude of 20 km, and was enhanced over midlatitude values by a factor of three to five at altitudes above 18 km and by as much as a factor of 40 at altitudes below 17 km. Levels of ClO and O3 were highly correlated on all measured distance scales, and both showed an abrupt change in character at 54 N latitude. The ClO abundance north of 54 N was probably caused by low NO2 levels in the flight path.

Brune, W. H.↗

New observations of a large concentration of ClO in the springtime lower stratosphere over Antarctica and its implications for ozone-depleting chemistry

New measurements of stratospheric chlorine monoxide (ClO) were made at McMurdo Station, Antarctica, during the austral spring of 1987. Rotational emission line spectroscopy, employing a ground-based detector, was used to determine mixing ratio profiles over the range about 17-45 km. A spectral band pass double that was used for similar measurements in 1986 allowed an improvement to be made in the definition of the anomalous low-altitude stratospheric ClO layer associated with springtime ozone depletion. A peak mixing ratio of 1.6 + or - 0.4 parts per billion by volume (ppbv) (95 percent confidence level) was found at 19.5 + or - 1 km at midday during the period September 20-24, 1987. The observed peak mixing ratio and diurnal behavior are discussed in relation to chemical depletion theories. Calculations indicate that the large observed ClO concentration provides an efficient closure for a catalytic Cl cycle through the ClO dimer mechanism, yielding good agreement with various observed features of O3 depletion.

De Zafra, R. L.↗

Search for infrared absorption lines of atmospheric chlorine monoxide (ClO)

A search for features of the ClO (1-0) vibration-rotation band has been conducted based on a 5000 signal-to-rms noise ratio IR spectrum derived by coadding 39 high-quality 0.0053/cm resolution solar spectra recorded with the McMath Fourier transform spectrometer on Kitt Peak. Evidence for absorption has been found at the locations of several of the stronger ClO P-branch lines with minimal interference. Detailed results are presented for the P(8.5) and P(7.5) 2Pi3/2-2Pi3/2 lines of Cl-35O at 833.2974 and 834.6249/cm, respectively. If ClO is present in the stratosphere at the concentrations indicated by other methods, our analysis indicates that modest improvements in signal-to-noise ratio and spectral resolution would permit a definitive detection of ClO in IR ground-based spectra.

Rinsland, Curtis P.↗

Induced ClO vacuum ultraviolet fluorescence

Some vibronic transitions of ClO such as G(v-prime = 11 )-X(v-double prime = 10), G(v-prime = 5)-X(v-double prime = 3) and H(v-prime = 4)-X(v-double prime = 2), which promote overtones of X(2pi3/2) to bound Rydberg states, are nearly resonant with the 130.6 nm O-atom emission line and possess sizable Franck-Condon factors. On this basis broadband detection of 'O atom' fluorescence in experiments involving vibrationally excited ClO(X) is ascribed to the radiative decay of ClO(G, H) rather than to the formation of O atoms; these observations raise the probability of monitoring ClO(X; v = 0) by VUV-induced fluorescence.

Colussi, A. J.↗