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At least 379 records · Page 21

The reaction of NH2 with NO2

Ammonia (NH3) was photolyzed at 213.9 nm in the presence of NO2 at 25 C in order to study the reactions of NH2 with NO2. The products included NO, with a quantum yield of 1.0. The other measured products of the reaction were N2 and N2O with respective quantum yields of 0.94 plus or minus 0.10 and 0.3 in the presence of small amounts of He and 0.65 plus or minus 0.15 and 0.13 in the presence of a large excess of He. The quantum yield for NO2 consumption was 6.0 plus or minus 2.0 in the absence of He. These results are explained in terms of various reactions.

Jayanty, R. K. M.↗

Visual reaction times during prolonged angular acceleration parallel the subjective perception of rotation

The effect of prolonged angular acceleration on choice reaction time to an accelerating visual stimulus was investigated, with 10 commercial airline pilots serving as subjects. The pattern of reaction times during and following acceleration was compared with the pattern of velocity estimates reported during identical trials. Both reaction times and velocity estimates increased at the onset of acceleration, declined prior to the termination of acceleration, and showed an aftereffect. These results are inconsistent with the torsion-pendulum theory of semicircular canal function and suggest that the vestibular adaptation is of central origin.

Mattson, D. L.↗

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.↗

Periodic solutions to systems of reaction-diffusion equations

Necessary and sufficient conditions are derived for the existence of temporally periodic 'dissipative structure' solutions in weak diffusion with the reaction rate terms dominant in a generic system of reaction-diffusion differential equations. The enumerator index i of the equations denotes the density or concentration of the ith participating molecular or biological species, and D sub i is the diffusivity constant for the ith species while Q sub i (c), an algebraic function of the n-tuple c, expresses the local rate of production of the ith species due to chemical reactions or biological interactions.

Rosen, G.↗

Proton transfer reactions from H3/+/ ions to N2, O2, and CO molecules

The rate constants for proton transfer from H3(+) ions to N2, O2, and CO have been measured as function of hydrogen-buffer-gas partial pressure. The rate constant for proton transfer from H3(+) to N2 shows a very large pressure dependence, increasing from 1.0 by 10 to the -9th power cu cm/s at low H2 partial pressures to 1.7 by 10 to the -9th power cu cm/s at high H2 partial pressures. The rate constants for proton transfer from H3(+) to O2 and CO are constant with partial pressure of H2. The roles of excess vibrational energy in H3(+) ions and of equilibrium between forward and back reactions are discussed. Back reaction is observed only for the reaction of H3(+) ions with O2, and an equilibrium constant of 2.0 (plus or minus 0.4) at 298 K has been determined. From these data, the proton affinity of O2 is deduced to be 0.47 (plus or minus 0.11) kcal/mole higher than that of H2.

Kim, J. K.↗

Absolute rate of the reaction of O/3-P/ with hydrogen sulfide over the temperature range 263 to 495 K

The technique of flash photolysis coupled with time resolved detection of O via resonance fluorescence has been used to obtain rate constants for the reaction of O(3-P) with H2S at temperatures from 263 to 495 K and at pressures in the range 10-400 torr. Under conditions where secondary reactions are avoided, the measured rate constants for the primary step obey the Arrhenius equation k = (7.24 plus or minus 1.07) x 10 to the -12th exp(-3300 plus or minus 100/1.987 T) cu cm/molecules/s. Experiments with D2S show that the reaction exhibits a primary isotope effect, in support of a hydrogen abstraction mechanism.

Whytock, D. A.↗

Absolute rate of the reaction of Cl(p-2) with molecular hydrogen from 200 - 500 K

Rate constants for the reaction of atomic chlorine with hydrogen are measured from 200 - 500 K using the flash photolysis-resonance fluorescence technique. The results are compared with previous work and are discussed with particular reference to the equilibrium constant for the reaction and to relative rate data for chlorine atom reactions. Theoretical calculations, using the BEBO method with tunneling, give excellent agreement with experiment.

Whytock, D. A.↗

Reactions between NO/+/ and metal atoms using magnetically confined afterglows

A new method of studying thermal energy ion-neutral collision processes involving nongaseous neutral atoms is described. A long magnetic field produced by a solenoid in a vacuum chamber confines a thermal-energy plasma generated by photoionization of gas at very low pressure. As the plasma moves toward the end of the field, it is crossed by a metal atom beam. Ionic products of ion-atom reactions are trapped by the field and both the reactant and product ions move to the end of the magnetic field where they are detected by a quadrupole mass filter. The cross sections for charge transfer between NO(+) and Na, Mg, Ca, and Sr and that for rearrangement between NO(+) and Ca have been obtained. The charge-transfer reaction is found strongly dominant over the rearrangement reaction that forms metallic oxide ions.

Lo, H. H.↗

Upper limits of the rate constants for the reactions of CFCl3/F-11/, CF2Cl2/F-12/, and N2O with OH - Estimates of corresponding lower limits to their tropospheric lifetimes

A discharge-flow system with resonance fluorescence detection of OH is used to study the reactions of CFCl3, CF2Cl2, and N2O with OH at temperatures up to 480 K. Little, if any reaction was found, with upper limits of 5, 6, and 4 x 10 to the -16th cu cm/s reported at 480 K for the three rate constants. A very simple model is used to calculate removal times exceeding 10,000 years for reaction with tropospheric OH.

Chang, J. S.↗

Thermochemical hydrogen production via a cycle using barium and sulfur - Reaction between barium sulfide and water

The reaction between barium sulfide and water, a reaction found in several sulfur based thermochemical cycles, was investigated kinetically at 653-866 C. Gaseous products were hydrogen and hydrogen sulfide. The rate determining step for hydrogen formation was a surface reaction between barium sulfide and water. An expression was derived for the rate of hydrogen formation.

Ota, K.↗

Space shuttle orbiter reaction control system interactions with the vehicle flow field

Test data on the effect of the interaction between the space shuttle orbiter rear-mounted reaction control system jets and the flow over the vehicle in the atmosphere are analyzed with particular attention to yaw angle effects. Masted tank-plus-orbiter jet interactions resulting from combinations of forward and rear-mounted reaction control jets being fired prior to external tank staging are also documented. The primary correlating parameter used for the mated data is a single-jet momentum ratioed to free-stream momentum. An analytic model for computing reaction control system interactions for all control combinations used for mated vehicle coast is included.

Rausch, J. R.↗

On the possibility of negative activation energies in bimolecular reactions

The temperature dependence of the rate constants for model reacting systems was studied to understand some recent experimental measurements which imply the existence of negative activation energies. A collision theory model and classical trajectory calculations are used to demonstrate that the reaction probability can vary inversely with collision energy for bimolecular reactions occurring on attractive potential energy surfaces. However, this is not a sufficient condition to ensure that the rate constant has a negative temperature dependence. On the basis of these calculations, it seems unlikely that a true bimolecular reaction between neutral molecules will have a negative activation energy.

Jaffe, R. L.↗

Product distributions for some thermal energy charge transfer reactions of rare gas ions

Ion cyclotron resonance methods were used to measure the product distributions for thermal-energy charge-transfer reactions of He(+), Ne(+), and Ar(+) ions with N2, O2, CO, NO, CO2, and N2O. Except for the He(+)-N2 reaction, no molecular ions were formed by thermal-energy charge transfer from He(+) and Ne(+) with these target molecules. The propensity for dissociative ionization channels in these highly exothermic charge-transfer reactions at thermal energies contrasts with the propensity for formation of parent molecular ions observed in photoionization experiments and in high-energy charge-transfer processes. This difference is explained in terms of more stringent requirements for energy resonance and favorable Franck-Condon factors at thermal ion velocities.

Anicich, V. G.↗

Flash photolysis resonance fluorescence investigation of the reaction of O /P-3/ atoms with ClONO2

The rate constant for the reaction of O (P-3) atoms with ClONO2 at 10 torr total pressure is assessed over the temperature range 225-273 K by the flash photolysis resonance fluorescence technique. The data, taken together with results given by Molina et al. (1977), have been used to formulate an Arrhenius expression suitable for stratospheric modeling applications. Comparison of the rate of ClONO2 destruction via the oxygen atom reaction with the solar photolysis rate shows that chemical reaction accounts for less than 15% of the CLONO2 removal at altitudes between 20 and 30 km.

Kurylo, M. J.↗

Upper bound and probable value of the rate constant of the reaction OH + HO2 yields H2O + O2

Discharge-flow experiments at 295 K of the OH + HO2 reaction are described in which excess O3 is added to OH through a movable injector; OH concentration is measured downstream by resonance fluorescence with and without addition of excess NO just upstream of the detector so that both OH concentration and OH concentration + HO2 concentration are determined independently. The data are compared with a computer model involving 12 reaction steps. A simple sensitivity analysis is carried out to establish how errors in the other 'known' rate constants affect the data fit. Best agreement is obtained between computer calculations and experiments when k1 for the OH + HO2 reaction is in the range 2-3 x 10 to the -11th cu cm/s. Values above about 5 x 10 to the -11th are very unlikely whereas those below about 1 x 10 to the -11th are less strongly excluded.

Chang, J. S.↗

Review of rate coefficients of ionic reactions determined from measurements made by the atmosphere explorer satellites

The large data base of aeronomic parameters measured by the Atmosphere Explorer C, D, and E satellites since December 1973 has been used to determine a number of reaction rate coefficients highly relevant to our understanding of thermospheric chemistry. In this paper the results are reviewed for ionic rate coefficients for recombination of NO(+), O2(+), for reactions of O(+) + N2, N2(+) + O, and O(++) + O, and for various reactions involving O(+)(2D) and O(+)(2P) ions with O and N2.

Torr, D. G.↗

Interface reaction and characterization in B/Al composites

Interfacial reactions, strength degradation, and fracture morphology have been characterized in B/Al(1100) and B/Al(6061) composite systems at a volume fraction of 0.55. Reaction was promoted by isothermal exposure at 350 C or 500 C for times up to 860,000 s. Tetragonal AlB12 was identified as the reaction product in the 6061 matrix and hexagonal AlB2 in the 1100 matrix. Interface development is analyzed based on a moving boundary model modified by the addition of ternary elements. While strength decreases in both systems, the time dependence of elevated-temperature exposure is different in the two matrix materials. In the 45 deg fiber orientation, failure occurs primarily by matrix shear, whereas in the 90 deg fiber orientation, fracture morphology is characterized by a mixture of fiber splitting, ductile matrix fracture, and failure at fiber-matrix interfaces.

Kim, W. H.↗

Variations in pore structure of reaction-bonded silicon nitride /RBSN/

A discussion is presented relating the observed pore structures (sizes) to the reaction mechanisms in reaction-bonded silicon nitride (alpha- and beta-Si3N4) on the basis of information available from the literature. While the techniques for reducing the residual macroporosity are quite well-developed for reaction-bonded Si3N4 (RBSN), it is important to be aware of three other orders of magnitude for porosity present in RBSN as a result of the nitriding process itself, and how these types of nitridation-induced porosity can be controlled. For ease of description, these types of nitridation-induced porosity are called micropores, nanopores, and picopores in order of their decreasing size. A scanning electron micrograph is presented, showing nanopores isolated in the unreacted Si and picopores in the alpha-matte Si3N4. The assumption that an alpha-matte growth mechanism is active explains the occurrence of nanopores and their partial filling with alpha-Si3N4, leaving behind very fine-grained alpha-matte and picopores.

Danforth, S. C.↗