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At least 253 records · Page 14

Rate constant for the fraction of atomic chlorine with formaldehyde from 200 to 500K

A flash photolysis - resonance fluorescence technique was used to measure rate constant. The results were independent of substantial variations in H2CO, total pressure (Ar), and flash intensity (i.e., initial Cl). The rate constant was shown to be invariant with temperature, the best representation for this temperature range being K = (7.48 + or - 0.50) x 10 to the minus 11 power cu cm molecule-1 s-1 where the error is one standard deviation. The rate constant is theoretically discussed and the potential importance of the reaction in stratospheric chemistry is considered.

Michael, J. V.↗

Characterization of the adsorption of water vapor and chlorine on microcrystalline silica

The characterization of water adsorption on silica is necessary to an understanding of how hydrogen chloride interacts with silica. The adsorption as a function of outgas temperatures of silica and as a function of the isotherm temperature was studied. Characterization of the silica structure by infrared analysis, X-ray diffraction and differential scanning calorimetry, surface area determinations, characterization of the sample surface by electron spectroscopy for chemical analysis (ESCA), and determinations of the heat of immersion in water of silica were investigated. The silica with a scanning electron microscope was examined.

Skiles, J. A.↗

Rate constant measurements for the reaction Cl + CH2O yields HCl + CHO Implications regarding the removal of stratospheric chlorine

The flash photolysis resonance fluorescence technique was employed to investigate the rate constant for the reaction Cl + CH2O yields HCl + CHO from 223 to 323 K. An Arrhenius fit of the data gives a rate constant equal to (1.09 + or - 0.40) x 10 to the -10th exp/-(131 + or - 98)/T/ in units of cu cm/molecule per sec. The results are compared to two very recent kinetic studies and are assessed in view of the reaction's role in disrupting the Cl-ClO stratospheric ozone depletion chain.

Anderson, P. C.↗

Effect of sodium, potassium, magnesium, calcium, and chlorine on the high temperature corrosion of IN-100, U-700, IN-792, and Mar M-509

The effects of potential impurities such as Na, K, Mg, Ca, and Cl, in coal-derived liquid fuels on accelerated corrosion of IN-100, U-700, IN-792, and Mar M-509 were investigated using a Mach 0.3 burner rig for times to 200 hours in one hour cycles. These impurities were injected in combination as aqueous solutions into the combustor. Other variables were time, temperature, and fuel-to-air ratio. The experimental matrix was a central composite fractional fractorial design divided into blocks to allow modification of the design as data was gathered. The extent of corrosion was determined by metal consumption. The time exponent was near 1.0 for the least corrosion resistant alloys, U-700 and IN-100; near 0.8 for the moderately resistant IN-792; and close to Mar M-509, the most corrosion resistant alloy. As anticipated, corrosion rapidly increased with increasing temperature as well as Na and K concentrations, while corrosion decreased somewhat as the Ca concentration increased for all alloys. Mg was beneficial for the Ni-base alloys but had little effect on the Co-base alloy. Surprisingly, the effect of increasing Cl was to decrease the corrosion of all alloys. Little interaction among the dopants was noted.

Lowell, C. E.↗

Stratospheric free chlorine measured by balloon-borne in situ resonance fluorescence

Eight balloon-borne in situ measurements of ClO in the stratosphere are analyzed and are compared with recent model calculations. While the use of in situ stratospheric studies of free radicals to test models by comparing observed and predicted concentration profiles is essential for a prognosis of changes in stratospheric ozone, resulting from future changes in stratospheric ozone, such studies provide only limited insight into the nature of stratospheric photochemistry, because natural variability and the large number of fast reactions which compete in the coupling among the key radicals frustrate a detailed comparison between a mean distribution provided by the models and an instantaneous distribution provided by a single observation.

Anderson, J. G.↗

Is there any chlorine monoxide in the stratosphere?

A ground based search for the 856.50137/cm R(9.5) and for the 859.76765 R(12.5) transitions of stratospheric (Cl-35)O was made in the solar absorption mode using an infrared heterodyne spectrometer. Lines due to stratospheric HNO3 and tropospheric OCS were detected, at about 0.3% absorption levels. The expected lines of ClO in this same region were not detected, even though the optical depth of the ClO lines should be on the order of 0.2% using currently accepted ClO abundances. These infrared measurements suggest that stratospheric ClO is at least a factor of 7 less abundant than is indicated by indirect in situ fluorescence measurements, and the upper limit of 2.4x10 to the 13th power molecules/sq cm to the integrated column density of ClO is a factor of over 4 less than is indicted by microwave measurements. Results imply that the release of fluorocarbon precursors of ClO may be significantly less important for the destruction of stratospheric ozone than was previously thought.

Rogers, J. D.↗

Is there any chlorine monoxide in the stratosphere?

A ground-based search for stratospheric 35-ClO was carried out using an infrared heterodyne spectrometer in the solar absorption mode. Lines due to stratospheric HNO3 and tropospheric OCS were detected at about 0.2% absorptance levels, but the expected 0.1% lines of ClO in this same region were not seen. We find that stratospheric ClO is at least a factor of seven less abundant than is indicated by in situ measurements, and we set an upper limit of 2.3x10 to the 13th molecules/sq cm at the 95% confidence level for the integrated vertical column density of ClO. Our results imply that the release of chlorofluorocarbons may be significantly less important for the destruction of stratospheric ozone (O3) than is currently thought.

Mumma, M. J.↗

Chlorine nitrate - The sole product of the ClO + NO2 + M recombination

A laser operating at 266 nm is used to photolyze the product of the ClO + NO2 + M reaction, and the yield of Cl atoms, measured by resonance fluorescence, is found to be identical with that from equivalent concentrations of ClONO2. This is interpreted as a strong indication that no other isomers are formed in the recombination reaction. Evidence for isomers is surveyed, and the apparent forward-and-reverse-rate constant discrepancy is explained as a probable uncertainty in the thermochemistry.

Margitan, J. J.↗

Is there any chlorine monoxide in the stratosphere?

A ground-based search for stratospheric 35-ClO was carried out using an infrared heterodyne spectrometer in the solar absorption mode. Lines due to stratospheric HNO3 and tropospheric OCS were detected at about 0.2 percent absorptance levels, but the expected 0.1 percent lines of ClO in this same region were not seen. We find that stratospheric ClO is at least a factor of seven less abundant than is indicated by in situ measurements, and we set an upper limit of 2.3 x 10 to the 13th molecules/sq cm at the 95 percent confidence level for the integrated vertical column density of ClO. Our results imply that the release of chlorofluorocarbons may be significantly less important for the destruction of stratospheric ozone (O3) than is currently thought. Previously announced in STAR as N83-27518

Mumma, M. J.↗