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The rate coefficient for the reaction NO2 + NO3 yielding NO + NO2 + O2 from 273 to 313 K

The ratio of rate constants for the reaction NO3 + NO yielding 2 NO2 (k3) and the reaction NO2 + NO3 yielding NO + NO2 + O2 (k4) were determined by measuring of NO and NO2 concentrations of NO and NO2 in an N2O5/NO2/N2 mixture over the temperature range 273-313 K. The measured ratio was found to be expressed by the equation k3/k4 = 387 exp(-1375/T). The results are consistent with those of Hammer et al. (1986).

Cantrell, Chris A.↗

Absolute rate parameters for the reaction of ground state atomic oxygen with dimethyl sulfide and episulfide

It is pointed out that the investigated reaction of oxygen with dimethyl sulfide may play an important role in photochemical smog formation and in the chemical evolution of dense interstellar clouds. Kinetic data were obtained with the aid of the flash photolysis-resonance fluorescence method. The photodecomposition of molecular oxygen provided the oxygen atoms for the experiments. The decay of atomic oxygen was studied on the basis of resonance fluorescence observations. Both reactions investigated were found to be fast processes. A negative temperature dependence of the rate constants for reactions with dimethyl sulfide was observed.

Lee, J. H.↗

The rate constant for the reaction of oxygen /3P/ atoms with dichlorine monoxide

A fast flow discharge apparatus was used to measure the rate constant for the reaction of ground state oxygen atoms with dichlorine monoxide in the temperature range 236-295 K. The air afterflow technique (NO2 chemiluminescence) was used for detection of oxygen atoms. The Arrhenius expression for the rate constant was found to be 2.7 plus or minus 0.3 times 10 to the -11th power exp(-560 plus or minus 80/T) cu cm per molecule per sec. At 295 K the rate constant is 4.1 plus or minus 0.5 times 10 to the -12th power cu cm per molecule per sec.

Miziolek, A. W.↗

Computations and estimates of rate coefficients for hydrocarbon reactions of interest to the atmospheres of outer solar system

The rate coefficients, including Arrhenius parameters, have been computed for a number of chemical reactions involving hydrocarbon species for which experimental data are not available and which are important in planetary atmospheric models. The techniques used to calculate the kinetic parameters include the Troe and semiempirical bond energy-bond order (BEBO) or bond strength-bond length (BSBL) methods.

Laufer, A. H.↗

The rate coefficient for the O/+/ + N2 reaction in the ionosphere

The rate coefficient for the reaction O(+) + N2 yields NO(+) + N is determined as a function of temperature from the photochemistry of NO(+) for both day and night conditions by using a large sample of simultaneous measurements of ion and neutral concentrations and temperatures made by the Atmosphere Explorer C satellite. The results cover the ion temperature range from 500 to 1200 K. Using recent flow-drift-tube results, the rate coefficient is calculated as a function of ion temperature and mean ion drift velocity for ionospheric conditions. The satellite and laboratory determinations are found to be in good agreement. Using this temperature dependence, an earlier determination of the dissociative recombination coefficient of NO(+) with electrons is refined.

Torr, M. R.↗

Rate constant for the reaction NH2 + NO from 216 to 480 K

The absolute rate constant was measured by the technique of flash photolysis-laser induced fluorescence (FP-LIF). NH2 radicals were produced by the flash photolysis of ammonia and the fluorescent NH2 photons were measured by multiscaling techniques. At each temperature, the results were independent of variations in total pressure, and flash intensity. The results are compared with previous determinations using the techniques of mass spectrometry, absorption spectroscopy, laser absorption spectroscopy, and laser induced fluorescence. The implications of the results are discussed with regard to combustion, post combustion, and atmospheric chemistry. The results are also discussed theoretically.

Stief, L. J.↗

Rate constant for the reaction H + NO2 from 195 to 400 K with FP-RF and DF-RF techniques

Measurements are made of the rate constant for the reaction H + NO2 yielding OH + NO over significant temperature ranges with the flash photolysis-resonance fluorescence (FP-RF) technique and also with the discharge flow-resonance fluorescence (DF-RF) technique. Since it is important to study chemical reactions with more than one technique, the above reaction is investigated with the FP-RF technique over the temperature range 230-400 K. The results reported do not agree with earlier determinations. Accordingly, a separate set of measurements is made with the DF-RF technique over the temperature range 195-368 K; the results are also reported. The reaction is also considered theoretically, especially with regard to the question of temperature dependence and absolute magnitude of the rate constant.

Michael, J. V.↗

Pressure dependence of the absolute rate constant for the reaction Cl + C2H2 from 210-361 K

In recent years, considerable attention has been given to the role of chlorine compounds in the catalytic destruction of stratospheric ozone. However, while some reactions have been studied extensively, the kinetic data for the reaction of Cl with C2H2 is sparse with only three known determinations of the rate constant k3. The reactions involved are Cl + C2H2 yields reversibly ClC2H2(asterisk) (3a) and ClC2H2(asterisk) + M yields ClC2H2 + M (3b). In the present study, flash photolysis coupled with chlorine atomic resonance fluorescence have been employed to determine the pressure and temperature dependence of k3 with the third body M = Ar. Room temperature values are also reported for M = N2. The pressure dependence observed in the experiments confirms the expectation that the reaction involves addition of Cl to the unsaturated C2H2 molecule followed by collisional stabilization of the resulting adduct radical.

Brunning, J.↗

Reactions of ethynyl radicals - Rate constants with CH4, C2H6, and C2D6

An experiment to measure ethynyl radical reactivity with other simple molecules is described. Flash photolysis of CF3C2H, a C2H precursor, was kinetically and spectroscopically analyzed for C2H reactions with CH4, C2H6, and C2D6 and rate constants for the abstraction reaction at room temperature were determined. The experimental apparatus is described, and the acetylene feedstock purification procedures are outlined. Rate constants are provided, and additional examination of the effects of added helium showed no alterations over the pressure range 20-700 torr.

Laufer, A. H.↗

Laboratory Investigation of the Effect of Venusian Weathering on Mineral Spectra

Introduction: The recent selection of two missions to Venus has renewed the importance of deter-mining weathering reactions between minerals and the Venusian atmosphere, and the spectral signatures of minerals before, during, and after these reactions. The rate at which weathering reactions progress also constrain show long unstable minerals will be present on the surface (e.g., [1]), and enables the use of mineralogy as a constraint on surface age(e.g., [2-3]).In order to gain an understanding of how mineral compositions and spectra change with weathering, we have begun conducting experiments in a 1 atm experimental setup at Wesleyan University. This setup exposes minerals to the temperature and most abundant gases of the Venus atmosphere (CO2, SO2, N2).We conducted initial experiments using biotite, calcite, and montmorillonite in order to test our methodology with minerals that may be relevant to recording the history of water on Venus. Methods: Experiments were conducted in Thermo Fisher Scientific Lindberg/Blue M Mini-Mite horizontal tube furnaces at Wesleyan University. Experiments used natural mineral chips and powders, and were conducted at 1 atmosphere and 460 °C under pre-mixed gases provided by Air Gas(Table 1). The furnaces are set up in a flow through configuration so that solid samples are exposed to a fixed gas composition, and quartz glass process tubes were used in all experiments (1/4” diameter for experiment V4, ½” diameter for all others). These conditions were maintained for the du-rations listed in Table 1, at which point the furnace was turned off with gas flowing until the sample was cool enough to extract under N2and be placed in a desiccator for storage. Run products were carbon coated and examined using a Hitachi SU5000 Field Emission Gun Scanning Electron Microscope (SEM) equipped with an EDAX Octane Pro EDS detector located at Wesley-an University. Visible-Near Infrared Spectroscopy (VNIR) analysis was performed on powdered samples under a nitrogen atmosphere using an ASD Fieldspec Proover the 350-2500 nm range. Powdered mineral samples were milled to a particle size of < 45μm and were spiked with an internal standard (Al2O3, corundum) to obtain quantitative mineralogy. Samples were analyzed using a Panalytical X’Pert pro X-ray Diffractometer (XRD), with an X’Celerator high speed detector and Co Kα radiation, with data collected at a step size of 0.02 ̊/minute step counting rate from 2 to 80 degrees 2θ at 45 mA/40kV in the X-ray Diffraction Laboratory located at NASA Johnson Space Center. Materials Data Inc (MDI) software suite, JadeTMv9 was used for Rietveld refinement to determine phase abundances and mineral identification by comparing XRD patterns to International Center for Diffraction Data (ICDD) database patterns. Table 1: Experimental matrix. Experiment Name Duration (Days)Gas Com-position (trace gas)MineralsV487SO2/N2(1.4%)Montmorillonite, biotiteV519SO2/N2(1.4%)CalciteV619CO2/SO2/N2(1.4% SO2, 2.1% N2)Montmorillonite, biotiteV828SO2/N2(1.4%)Biotite, calcite Results: Calcite. In both experiments, calcite was exposed to the SO2/N2gas mixture, and in both experimental run products, XRD analysis detected anhydrite, which is consistent with EDS measurements conducted in the SEM. The XRD analyses show greater amounts of anhydrite present after 28 days than 19, suggesting the calcite reaction progressed further given longer duration. Grain surface morphology as seen in the SEM also shows secondary mineral growth (Fig. 1). VNIR spectra show no change, as expected since anhydrite lacks spectral features in this wavelength range. Montmorillonite. Montmorillonite was exposed to two different gas mixtures, the SO2/N2mix and CO2/SO2/N2mix over different durations (87 and 19 days, respectively). VNIR analyses of both run products show a reduction in the 1441and1910 nm water features as well as a shift of the 1411 and 2011 nm features to shorter wavelengths that may indicate re-structuring in the crystal lattice and the production of amorphous phases [4]. XRD results are consistent with this, showing a shift of the 001 peak from 15Åto 10Åin both run products. The amount of X-ray amorphous material in the montmorillonite run products was greater than that present in the unreacted clay, being the greatest in the 87 day V4 experiment. No other secondary phases were detected in the run products, however sulfur was present in EDS analyses of powder samples.

A R Santos↗

Diffusion in mixed solvents. II - The heat of mixing parameter

Correlation of second-order rate constants for many reactions involving electron transfer between organic molecules, solvated electron reactions, iodine diffusion coefficients, and triplet state electron transfer reactions has been made with the heat of mixing parameter (HMP) for the aqueous binary solvent systems. The aqueous binary solvents studied are those containing methanol or ethanol (type I solvent); 1-propanol or tert-butyl alcohol (type II solvent); or sucrose or glycerol (type III solvent). A plot of the HMP vs. the diffusion parameter for each reaction yields superimposable curves for these reactions in a particular solvent mixture over the entire solvent mixture range, irrespective of the value of the reaction's rate constant or diffusion coefficient in water.

Carapellucci, P. A.↗

The transport of photochemical pollutants to the background troposphere

The considered investigation is concerned with the phenomena occurring as a chemically reacting plume, with specific initial concentrations of NO, NO2, O3, and hydrocarbons, emerges from an urban area and is advected to the background troposphere. A better understanding of the global NOx and hydrocarbon budgets can be realized by determining the fractions of NOx and hydrocarbons that are transported to distances far enough to be considered background. The investigation makes use of a 56-step, lumped kinetic mechanism for photochemical smog, which includes current information on pertinent chemical reactions and rate constants for the reactions.

Bazzell, C. C.↗

The two-dimensional diagnostic model for tropospheric OH - An uncertainty analysis

Tropospheric OH is believed to play a major role in atmospheric photochemistry, and, via its chemical interactions OH ultimately may affect the climate, stratospheric ozone levels, and the pH of rain. A valuable tool for predicting the global OH abundance as a function of latitude and altitude is the two-dimensional diagnostic model for tropospheric OH. This model can also be applied to budget studies of species which interact with OH, such as CH4, CO, and O3. In addition to laboratory-obtained kinetic data, important variables include the rate constants for several reactions, the rate of heterogeneous removal of soluble species, and the global abundance and spatial variability in H2O, O3, CO, and NOx. The uncertainties in these parameters imply over a factor of 3 variability in the calculated global OH concentration as well as significant uncertainties in the latitudinal and vertical OH distribution.

Chameides, W. L.↗

Detailed reduction of reaction mechanisms for flame modeling

A method for reduction of detailed chemical reaction mechanisms, introduced earlier for ignition system, was extended to laminar premixed flames. The reduction is based on testing the reaction and reaction-enthalpy rates of the 'full' reaction mechanism using a zero-dimensional model with the flame temperature profile as a constraint. The technique is demonstrated with numerical tests performed on the mechanism of methane combustion.

Wang, Hai↗

Development of a Detailed Surface Chemistry Framework in DSMC

Many of the current direct simulation Monte Carlo (DSMC) codes still employ only simple surface catalysis models. These include only basic mechanisms such as dissociation, recombination, and exchange reactions, without any provision for adsorption and finite rate kinetics. Incorporating finite rate chemistry at the surface is increasingly becoming a necessity for various applications such as high speed re-entry flows over thermal protection systems (TPS), micro-electro-mechanical systems (MEMS), surface catalysis, etc. In the recent years, relatively few works have examined finite-rate surface reaction modeling using the DSMC method.In this work, a generalized finite-rate surface chemistry framework incorporating a comprehensive list of reaction mechanisms is developed and implemented into the DSMC solver SPARTA. The various mechanisms include adsorption, desorption, Langmuir-Hinshelwood (LH), Eley-Rideal (ER), Collision Induced (CI), condensation, sublimation, etc. The approach is to stochastically model the various competing reactions occurring on a set of active sites. Both gas-surface (e.g., ER, CI) and pure-surface (e.g., LH, desorption) reaction mechanisms are incorporated. The reaction mechanisms could also be catalytic or surface altering based on the participation of the bulk-phase species (e.g., bulk carbon atoms). Marschall and MacLean developed a general formulation in which multiple phases and surface sites are used and we adopt a similar convention in the current work. Microscopic parameters of reaction probabilities (for gas-surface reactions) and frequencies (for pure-surface reactions) that are require for DSMC are computed from the surface properties and macroscopic parameters such as rate constants, sticking coefficients, etc. The energy and angular distributions of the products are decided based on the reaction type and input parameters. Thus, the user has the capability to model various surface reactions via user-specified reaction rate constants, surface properties and parameters.

Gas↗

The molecular dynamics of atmospheric reaction

Detailed information about the chemistry of the upper atmosphere took the form of quantitative data concerning the rate of reaction into specified states of product vibration, rotation and translation for exothermic reaction, as well as concerning the rate of reaction from specified states of reagent vibration, rotation and translation for endothermic reaction. The techniques used were variants on the infrared chemiluminescence method. Emphasis was placed on reactions that formed, and that removed, vibrationally-excited hydroxyl radicals. Fundamental studies were also performed on exothermic reactions involving hydrogen halides.

Polanyi, J. C.↗