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Golden, D. M.

Publications and source records attributed to Golden, D. M..

At least 19 records

Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies Evaluation Number 16. Supplement to Evaluation 15: Update of Key Reactions

This is the supplement to the fifteenth in a series of evaluated sets of rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation. The data are used primarily to model stratospheric and upper tropospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. Copies of this evaluation are available in electronic form and may be printed from the following Internet URL: http://jpldataeval.jpl.nasa.gov/.

atmospheric modeling↗

Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies Evaluation Number 15

This is the fifteenth in a series of evaluated sets of rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation. The data are used primarily to model stratospheric and upper tropospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. Copies of this evaluation are available in electronic form and may be printed from the following Internet URL: http://jpldataeval.jpl.nasa.gov/.

data evaluation↗

Chemical kinetics and photochemical data for use in Atmospheric Studies Evaluation Number 15

This is the fifteenth in a series of evaluated sets of rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation. The data are used primarily to model stratospheric and upper tropospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. Copies of this evaluation are available in electronic form and may be printed from the following Internet URL: http://jpldataeval.jpl.nasa.gov/

Orkin, V. L.↗

Methanol Uptake by Low Temperature Aqueous Sulfuric Acid Solutions

The global methanol budget is currently unbalanced, with source terms significantly larger than the sinks terms. To evaluate possible losses of gaseous methanol to sulfate aerosols, the solubility and reactivity of methanol in aqueous sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosols is under investigation. Methanol will partition into sulfate aerosols according to its Henry's law solubility. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H*, for cold (196 - 220 K) solutions ranging between 45 and 70 wt % H2SO4. We have found that methanol solubility ranges from approx. 10(exp 5) - 10(exp 7) M/atm for UT/LS conditions. Solubility increases with decreasing temperature and with increasing sulfuric acid content. Although methanol is slightly more soluble than are acetone and formaldehyde, current data indicate that uptake by clean aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These solubility measurements include uptake due to physical solvation and any rapid equilibria which are established in solution. Reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H is not significant over our experimental time scale for solutions below 80 wt % H2SO4. To confirm this directly, results obtained using a complementary equilibrium measurement technique will also be presented.

Iraci, L. T.↗

Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling

This is the twelfth in a series of evaluated sets of rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation. The primary application of the data is in the modeling of stratospheric processes, with special emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena.

DeMore, W. B.↗

Chemical kinetics and photochemical data for use in stratospheric modeling

As part of a series of evaluated sets, rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation are provided. The primary application of the data is in the modeling of stratospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. Copies of this evaluation are available from the Jet Propulsion Laboratory.

Demore, W. B.↗

Pressure and temperature dependence of reactions proceeding via a bound complex. II - Application to 2CH3 yielding C2H5 + H

The pressure and temperature dependence of a reaction between two methyl radicals proceeding via ethane intermediate was modeled. Single-channel RRKM calculations were performed, based upon a hindered Gorin model for the transition state; the hindrance parameters were chosen to reproduce the high-pressure limiting rate constant from 300-1400 K. It is shown that the reaction between two methyl radicals may be characterized over wide ranges of temperature and pressure, using three analytical expressions of the type introduced by Troe (1979) for single-channel unimolecular processes.

Stewart, P. H.↗

Chemical kinetics and photochemical data for use in stratospheric modeling evaluation Number 8

This is the eighth in a series of evaluated sets of rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation. The primary application of the data is in the modeling of stratospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. Copies of this evaluation are available from the Jet Propulsion Laboratory, Documentation Section, 111-116B, California Institute of Technology, Pasadena, California, 91109.

Demore, W. B.↗

Reaction of N2O5 with H2O on carbonaceous surfaces

The heterogeneous reaction of N2O5 with commercially available ground charcoal in the absence of H2O revealed a physisorption process (gamma = 0.003), together with a redox reaction generating mostly NO. Slow HNO3 formation was the result of the interaction of N2O5 with H2O that was still adsorbed after prolonged pumping at 0.0001 torr. In the presence of H2O, the same processes with gamma = 0.005 are observed. The redox reaction dominates in the early stages of the reaction, whereas the hydrolysis gains importance later at the expense of the redox reaction. The rate law for HNO3 generation was found to be d(HNO3)/dt = k(bi)(H2O)(N2O5) with k(bi), the effective bimolecular rate constants, for 10 mg of carbon being (1.6 + or - 0.3) x 10 to the -13th cu cm/s.

Brouwer, L.↗

Entropy bottlenecks in ion-molecule reactions

The significance of entropy bottlenecks in dissociation and recombination pathways in the prototype ionic system CH3 + CH3(+) has been investigated. Ion-molecule systems are shown to react through an entirely different dynamics than neutral systems, due to intrinsic differences in the shapes of the relevant potential surfaces. Consequences with regard to the interpretation of experimental rate parameters in the ion-molecule area are discussed.

Dodd, J. A.↗

Homogeneous processes of atmospheric interest

Upper atmospheric research programs in the department of chemical kinetics are reported. Topics discussed include: (1) third-order rate constants of atmospheric importance; (2) a computational study of the HO2 + HO2 and DO2 + DO2 reactions; (3) measurement and estimation of rate constants for modeling reactive systems; (4) kinetics and thermodynamics of ion-molecule association reactions; (5) entropy barriers in ion-molecule reactions; (6) reaction rate constant for OH + HOONO2 yields products over the temperature range 246 to 324 K; (7) very low-pressure photolysis of tert-bytyl nitrite at 248 nm; (8) summary of preliminary data for the photolysis of C1ONO2 and N2O5 at 285 nm; and (9) heterogeneous reaction of N2O5 and H2O.

Rossi, M. J.↗

Heterogeneous atmospheric reactions - Sulfuric acid aerosols as tropospheric sinks

The reaction probabilities of various atmospheric species incident on a bulk sulfuric acid surface are measured in order to determine the role of sulfuric acid aerosols as pollutant sinks. Reaction products and unreacted starting materials leaving a Knudsen cell flow reactor after collision at 300 K with a H2SO4 surface or a soot surface were detected by mass spectrometry. Significant collision reaction probabilities are observed on a H2SO4 surface for H2O2, HNO3, HO2NO2, ClONO2, N2O5, H2O and NH3, and on soot for NH3. Estimates of the contribution of heterogeneous reactions to pollutant removal under atmospheric conditions indicate that while aerosol removal in the stratosphere is insignificant (loss rate constants approximately 10 to the -10th/sec), heterogeneous reactions may be the dominant loss process for several tropospheric species (loss rate constant approximately 10 to the -5th/sec, comparable to photolysis rate constants).

Baldwin, A. C.↗

An explanation of the preferential formation of less stable isomers in three-body reactions - Cl + NO2 + M; ClO + NO2 + M

A realistic assessment of the potential depletion of stratospheric ozone due to manmade emissions requires a knowledge of the sources and sinks of the potential threat. The reactions ClO + NO2 + M yield products and Cl + NO2 + M yield products are of interest because they represent possible sink mechanism for both odd chlorine and odd nitrogen species. In this paper, the Troe method (1977) is used to calculate the low-pressure limit rate constants of the above three-body reactions. The result for the Cl + NO2 + M reaction is found to be in excellent agreement with the experimental finding of Niki et al. (1978), where both nitryl chloride and chlorine nitrate are products of the cited reaction. An explanation is proposed to account for apparent discrepancy between the measured rate constants for ClO + NO2 + M in the forward and reverse directions. Stratospheric implications are also discussed.

Chang, J. S.↗

Chemical kinetic and photochemical data for use in stratospheric modelling

An evaluated set of rate constants and photochemical cross sections were compiled for use in modelling stratospheric processes. The data are primarily relevant to the ozone layer, and its possible perturbation by anthropogenic activities. The evaluation is current to, approximately, January, 1979.

Demore, W. B.↗