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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.

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At least 343 records · Page 19

Rate constant for formation of chlorine nitrate by the reaction ClO + NO2 + M

The pseudo-first-order decay of ClO in a large excess of NO2 was monitored in a discharge flow/mass-spectrometer apparatus in order to measure the rate constant of the reaction ClO + NO2 + M yields ClONO2 + M for M = He, Ar, and N2 over the temperature range from 248 to 417 K. Numerical results are given for He at 248, 299, 360, and 417 K (1 to 9 torr); for Ar at 298 K (1 to 4 torr); and for N2 at 299, 360, and 417 K (1 to 6 torr). Systematic errors are estimated, and identification of the reaction product is discussed. The results obtained are shown to be in excellent agreement with other recent measurements of the same rate constant.

Leu, M. T.↗

Rate constant for the reaction of atomic chlorine with methane

The rate constant and temperature dependence of the Cl + CH4 reaction have been investigated by the techniques of competitive chlorination of CH4/C2H6 mixtures and by discharge-flow/mass spectroscopy. The objectives were to determine an accurate value for the rate constant for use in stratospheric modeling, and to clarify discrepancies in results previously obtained by different techniques. The results deduced from the competitive chlorination study are in good agreement with the absolute values measured by the mass spectrometric method, and at temperatures above 300 K are in good agreement with measurements by other techniques based on resonance fluorescence detection of atomic chlorine. However, in the 220-300 K region, the competitive experiments indicate lower rate constants than those obtained by resonance fluorescence methods, and do not reproduce the curved Arrhenius plots seen in some of those studies.

Lin, C. L.↗

Rate constant for the reaction ClO + NO yields Cl + NO2

The rate constant for the reaction ClO + NO yields Cl + NO2 has been determined over the temperature range 226.7-415.4 K in a discharge flow system using a mass spectrometer as a detector. The results, expressed in the Arrhenius form, are compared with previous measurements.

Leu, M. T.↗

Rate constants for the reactions of OH with ClO, Cl2, and Cl2O at 298K

Recent concern about the depletion of stratospheric ozone by chlorine species from the decomposition of chlorofluoromethanes has emphasized the need for laboratory studies of the first reaction steps involved, especially those which control the concentration of the OH and ClO radicals in the stratosphere. Rate constants for the reactions of OH with ClO, Cl2, and Cl2O at 298 K have been determined in a discharge flow system using resonance fluoresence detection. The results are (9.1 + or - 1.3) x 10 to the -12th, (5.5 + or - 0.3) x 10 to the -14th, and (6.5 + or - 0.5) x 10 to the -12th (all in units of cu cm/sec), respectively.

Leu, M. T.↗

Product distribution for the reaction of HO2 with ClO

The paper reports the direct measurement of the reaction product HOCl from the reaction of H2O with ClO, and sets an upper limit for the possible product O3, using a discharge flow/mass spectrometry/resonance fluorescence apparatus. The upper limits of the reaction channel producing HCl + O3 are 1.5% at 298 K and 3.0% at 248 K. It is seen that the HCl production rate from the HO2 + ClO reaction could be as large as that from the Cl + CH4 reaction in the lower and middle stratosphere. Thus, this reaction may possibly increase the HCl production rate appreciably and thereby reduce the calculated O3 destruction by chlorofluoromethanes.

Leu, M.-T.↗

Upper limits for the rate constant for the reaction Br + H2O2 yields HB2 + HO2

Upper limits for the rate constant for the reaction Br + H2O2 yields HBr + HO2 have been measured over the temperature range 298 to 417 K in a discharge flow system using a mass spectrometer as a detector. Results are k sub 1 less than 1.5 x 10 to the -15th power cu cm/s at 298 K and k sub 1 less than 3.0 x 10 to the -15th power cu cm/s at 417 K, respectively. The implication to stratospheric chemistry is discussed.

Leu, M.-T.↗

Kinetics of the gas-phase reaction between hydroxyl and carbonyl sulfide over the temperature range 300-517 K

By use of a discharge-flow resonance-fluorescence method the rate constant for the title reaction has been measured at five temperatures in the range 300-520 K. The Arrhenius expression is k(OH + OCS) = (1.3 + or - 0.3) x 10 to the -12th exp/-(2300 + or - 100)/T/ cu cm/s. Mass spectrometry has been used to detect the product HS and to collect some information about its reactivity. This study has carefully avoided the pitfalls associated with possible photolysis of reactants and complications due to H2S impurity in carbonyl sulfide that may have marred previous studies. This study has confirmed that the rate constant for this reaction is so much lower than the value originally used in computer modeling of the upper and lower atmosphere that conclusions about the relative importance of photolysis of OCS and of the reaction OH + OCS in the stratosphere must now be reassessed. The reaction OH + OCS has little significance for atmospheric chemistry.

Leu, M.-T.↗

Rate constant for the reaction between OH and CS2 at 298 and 520 K

In an attempt to resolve discrepancies between published values of the rate constant for the reaction between the hydroxyl radical and carbon disulfide, the reaction has been studied in a discharge flow system by using resonance fluorescence for kinetic measurements and mass spectrometry for product analysis. On the basis of the measured rate constant for disappearance of OH, and measurements of the amount of carbonyl sulfide formed, it was estimated that for the reaction HO + CS2 yields HS + OCS, rate constant values are not greater than 3 x 10 to the -15th/cu cm per sec at 520 K and not greater than 7 x 10 to the -15th/cu cm per sec at 298 K, upper limits are specified because of the inability to isolate exclusively this reaction channel, and because of possible involvement of wall reactions. These results confirm the low values found for this rate constant in two very recent studies.

Leu, M.-T.↗

Kinetics of the reaction O + ClO yields Cl + O2

The bimolecular rate constant for the reaction O + ClO yields Cl + O2 has been measured over the temperature range 236-422 K in a discharge flow system using atomic oxygen resonance fluorescence at 130 nm to monitor the decay of O in an excess of ClO. The results are found to be independent of the method used to produce the ClO radical. At 296 K, the rate constant is given by (3.6 + or - 0.7) x 10 to the -11th cu cm/sec and the temperature dependence expressed in Arrhenius form by k2 = (5.0 + or - 1.0) x 10 to the -11th exp-(96 + or - 20)/T cu cm/sec. The results are compared with earlier values, and the implications for stratospheric chemistry are discussed briefly.

Leu, M.-T.↗

Kinetics of the reaction Cl + NO2 + M

Using atomic chlorine resonance fluorescence at 140 nm to detect the decay of atomic chlorine in the presence of an excess of NO2, the rate constant for the reaction Cl + NO2 + M, where M is the total gas concentration, is measured over the temperature range 264 to 417 K and at a pressure 1 to 7 torr in a discharge flow system. The rate constants for M= He and M= N2 are measured and the results are summarized in a table. The systematic error of the rate constants is estimated to be about 15 percent. A static photolysis system coupled with an FTIR spectrophotometer is used to determine the branching ratio for the formation of two possible isomers. The ratio is concluded to be ClONO (greater than or equal 75 percent) and ClNO2 (less than or equal 25 percent) which is in agreement with the results of Niki et al. (1978).

Leu, M.-T.↗