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At least 37 records · Page 2

On reaction kinetics and atmospheric lifetimes of CF3CFHCF3 and CF3CH2Br

The rate constants for the reaction of the OH radical with CF3CFHCF3 and with CF3CH2Br have been measured as a function of temperature using the discharge flow technique with laser induced fluorescence detection of the OH radicals. The temperature dependent rate coefficients are well described by a simple Arrhenius expression, k(T) = A exp(E/(RT)). For the reaction of OH with CF3CFHCF3 we find A = 3.7 x 10 exp -13 cu cm/molecules/s and E/R = 1615 K; for the reaction of OH with CF3CH2Br we report A = 1.4 x 10 exp -12 cu cm/molecule/s and E/R = 1350 K. These Arrhenius parameters imply rate coefficients at 277 K of 1.09 x 10 exp -15 cu cm/molecule/s for CF3CFHCF3 and 1.06 x 10 exp -14 cu cm/molecule/s for CF3CH2Br. We find atmospheric lifetimes for CF3CFHCH3 and CF3CH2Br of 42 years and 4.1 years, respectively. We also estimate the steady state ozone depletion potential (ODP) of the brominated species relative to CFCl3 as about 0.84 using a semiempirical model.

Nelson, D. D., Jr.↗

Experimental studies on the reaction kinetics of 1,1-dimethylhydrazine and oxygen

Measurements behind shock waves in highly diluted 1,1 dimethylhydrazine-O2-Ar mixtures clearly showed a two-stage reaction. In the first stage, UDMH decomposes via a unimolecular step; in the second stage, clearly separated from the first one, the decay products react further with O2. Values for the rate constant of unimolecular decomposition were obtained.

Just, T.↗

Characterization of reaction kinetics in a porous electrode

A continuum-model approach, analogous to porous electrode theory, was applied to a thin-layer cell of rectangular and cylindrical geometry. A reversible redox couple is assumed, and the local reaction current density is related to the potential through the formula of Hubbard and Anson for a uniformily accessible thin-layer cell. The placement of the reference electrode is also accounted for in the analysis. Primary emphasis is placed on the effect of the solution-phase ohmic potential drop on the voltammogram characteristics. Correlation equations for the peak-potential displacement from E(sup 0 prime) and the peak current are presented in terms of two dimensionless parameters.

Fedkiw, Peter S.↗

Static-kinetic reactions of man under conditions of brief weightlessness

Physical characteristics of human responses to weightlessness simulation during parabolic flights establish body immobilization and visual illusions as the most manifest causes of sensory distrubances. Repeated brief weightlessness exposures gradually decreased expressions of static-kinetic disorders.

Kolosov, I. A.↗

Air oxidation of hydrazine. 1. Reaction kinetics on natural kaolinites, halloysites, and model substituent layers with varying iron and titanium oxide and O- center contents

Air oxidation of hydrazine was studied by using a group of kaolinites, halloysites, and substituent oxides as models for the tetrahedral and octahedral sheets. The rate was found to be linear with oxygen. The stoichiometry showed that oxygen was the primary oxidant and that dinitrogen was the only important nitrogen-containing product. The rates on kaolinites were strongly inhibited by water. Those on three-dimensional silica and gibbsite appeared not to be. That on a supposedly layered silica formed from a natural kaolinite by acid leaching showed transitional behavior--slowed relative to that expected from a second-order reaction relative to that on the gibbsite and silica but faster than those on the kaolinites. The most striking result of the reaction was the marked increase in the rate of reaction of a constant amount of hydrazine as the amount of clay was increased. The increase was apparent (in spite of the water inhibition at high conversions) over a 2 order of magnitude variation of the clay weight. The weight dependence was taken to indicate that the role of the clay is very important, that the number of reactive centers is very small, or that they may be deactivated over the course of the reaction. In contrast to the strong dependence on overall amount of clay, the variation of amounts of putative oxidizing centers, such as structural Fe(III), admixed TiO2 or Fe2O3, or O- centers, did not result in alteration of the rate commensurate with the degree of variation of the entity in question. Surface iron does play some role, however, as samples that were pretreated with a reducing agent were less active as catalysts than the parent material. These results were taken to indicate either that the various centers interact to such a degree that they cannot be considered independently or that the reaction might proceed by way of surface complexation, rather than single electron transfers.

NASA Discipline Number 52-20↗

An improved external recycle reactor for determining gas-solid reaction kinetics

These improvements in the recycle system effectively eliminate initial concentration variation by two modifications: (1) a vacuum line connection to the recycle loop which permits this loop to be evacuated and then filled with the test gas mixture to slightly above atmospheric pressure; and (2) a bypass line across the reactor which permits the reactor to be held under vacuum while the rest of the recycle loop is filled with test gas. A three-step procedure for bringing the feed gas mixture into contact with the catalyst at time zero is described.

Miller, Irvin M.↗

Reaction kinetics between fiber and matrix

Interdiffusion and interdiffusion controlled intermediate phase formation in metal matrix composites can be of interest for the prolonged application of these systems at high temperatures. Methods are discussed that address the kinetics of interdiffusion in systems that exhibit solid solution intermixing or the formation of a third intermediate phase at the fiber/matrix interface, or both. The tungsten fiber reinforced niobium and tungsten fiber reinforced superalloy systems are employed as model systems for experimentation and discussion. In an effort to impede interdiffusion, the concept of ion implanted diffusion barriers have been examined. Preliminary results on the feasibility and effectiveness of ion implanted diffusion barriers are presented.

Kopp, M. W.↗

Relation of Turbojet and Ramjet Combustion Efficiency to Second-Order Reaction Kinetics and Fundamental Flame Speed

Theoretical studies of the turbojet and ramjet combustion process are summarized and the resulting equations are applied to experimental data obtained from various combustor tests. The theoretical treatment assumes that one step in the over-all chain of processes which constitute jet-engine combustion is sufficiently slow to be the rate-controlling step that determines combustion efficiency.

Childs, J Howard↗

Assessment of Uncertainty in the Determination of Kinetic Reaction Parameters for Polymeric Materials

The use of thermogravimetric analysis to obtain data describing the thermal response of a polymeric resin with temperature. This data can then be used to obtain activation energy and pre-exponential factor used in an Arrhenius representation of material ablation. The methods which allow to assess the uncertainties associated with the experimental determination of activation energy and pre-exponential factor are employed.

Darby, Stephanie P.↗

Kinetics of the reaction of nitric oxide with hydrogen

Mixtures of NO and H2 diluted in argon or krypton were heated by incident shock waves, and the infrared emission from the fundamental vibration-rotation band of NO at 5.3 microns was used to monitor the time-varying NO concentration. The reaction kinetics were studied in the temperature range 2400-4500 K using a shock-tube technique. The decomposition of nitric oxide behind the shock was found to be modeled well by a fifteen-reaction system. A principle result of the study was the determination of the rate constant for the reaction H + NO yields N + OH, which may be the rate-limiting step for NO removal in some combustion systems. Experimental values of k sub 1 were obtained for each test through comparisons of measured and numerically predicted NO profiles.

Flower, W. L.↗

Kinetics of the reaction of OH with HCl

Measurements results are presented for the rate constant of the reaction OH + HCl yields H2O + Cl determined in a flow tube over the temperature range of 224 to 460 K using resonance fluorescence detection of OH. Stratospheric and reaction kinetic implications are briefly discussed.

Zahniser, M. S.↗