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At least 397 records · Page 22

Reactions of OH/+/ and H2O/+/ ions with some diatomic and simple polyatomic molecules

The rate constants and product distributions of the reactions of OH(+) and H2O(+) with some diatomic and simple polyatomic molecules were studied by ion cyclotron resonance (ICR) mass spectrometric techniques. Reaction rates with CO, NO, O2, N2, CO2, H2S, N2O, H2CO, CH4 and CD4 were measured. Charge transfer and proton transfer were generally observed in cases for which the reaction channel is exothermic, but processes involving rearrangement were not found.

Karpas, Z.↗

The impact of gas-surface reactions on mass spectrometric measurements of atomic nitrogen

The paper presents a simplified model of the ion source chemistry, explains several details of the data reduction method used in obtaining atomic-nitrogen (N) densities from OSS data, and discusses implications of gas-surface reactions for the design of future satellite-borne mass spectrometers. Because of various surface reactions, N appears in three different forms in the ion source, as N, NO, and NO2. Considering the rather small spin modulation of NO and NO2 in the semi-open ionization chamber used in the OSS instrument, it is not surprising that these reaction products have not been previously identified in closed source instruments as a measure of the presence of atomic nitrogen. Warmup and/or outgassing of the ion source are shown to drastically reduce the NO2 concentration, thereby making possible reliable measurement of ambient N densities.

Engebretson, M. J.↗

The reaction N/4S/ + O3 - An upper limit for the rate constant at 298 K

The reaction of N(4S) atoms with ozone was examined at 298 K using discharge flow and flash photolysis techniques, both coupled with resonance fluorescence detection of N(4S). No reaction was detected in either system, and an upper limit of 5 x 10 to the -16th cu cm/molecule/s was estimated for the rate constant. This is 1000 times lower than the presently accepted value of 5.7 x 10 to the -13th cu cm/molecule/s which is based on a discharge flow-mass spectrometric study of the reaction. Potential complications in the latter experiment are discussed.

Stief, L. J.↗

Reaction between nitric oxide and ozone in solid nitrogen

Nitrogen dioxide, NO2, is produced when nitric oxide, NO, and ozone, O3, are suspended in a nitrogen matrix at 11-20 K. The NO2 is formed with first-order kinetics, a 12 K rate constant of (1.4 + or - 0.2) x 0.00001/sec, and an apparent activation energy of 106 + or - 10 cal/mol. Isotopic labeling, variation of concentrations, and cold shield experiments show that the growth of NO2 is due to reaction between ozone molecules and NO monomers, and that the reaction is neither infrared-induced nor does it seem to be a heavy atom tunneling process. Reaction is attributed to nearest-neighbor NO.O3 pairs probably held in a specific orientational relationship that affects the kinetic behavior. When the temperature is raised, more such reactive pairs are generated, presumably by local diffusion. Possible mechanisms are discussed.

Lucas, D.↗

Nitrogen isotope fractionations in the Fischer-Tropsch synthesis and in the Miller-Urey reaction

Nitrogen isotope fractionations have been measured in Fischer-Tropsch and Miller-Urey reactions in order to determine whether these processes can account for the large N-15/N-14 ratios found in organic matter in carbonaceous chondrites. Polymeric material formed in the Fischer-Tropsch reaction was enriched in N-15 by only 3 per mil relative to the starting material (NH3). The N-15 enrichment in polymers from the Miller-Urey reaction was 10-12 per mil. Both of these fractionations are small compared to the 80-90 per mil differences observed between enstatite chondrites and carbonaceous chondrites. These large differences are apparently due to temporal or spatial variations in the isotopic composition of nitrogen in the solar nebula, rather than to fractionation during the production of organic compounds.

King, C.-C.↗

Heterogeneous phase reactions of Martian volatiles with putative regolith minerals

The chemical reactivity of several minerals thought to be present in Martian fines is tested with respect to gases known in the Martian atmosphere. In these experiments, liquid water is excluded from the system, environmental temperatures are maintained below 0 C, and the solar illumination spectrum is stimulated in the visible and UV using a xenon arc lamp. Reactions are detected by mass spectrometric analysis of the gas phase over solid samples. No reactions were detected for Mars nominal gas over sulfates, nitrates, chloride, nontronite clay, or magnetite. Oxidation was not observed for basaltic glass, nontronite, and magnetite. However, experiments incorporating SO2 gas an expected product of volcanism and intrusive volatile release - gave positive results. Displacement of CO2 by SO2 occurred in all four carbonates tested. These reactions are catalyzed by irradiation with the solar simulator. A calcium nitrate hydrate released NO2 in the presence of SO2. These results have implications for the cycling of atmospheric CO2, H2O, and N2 through the regolith.

Clark, B. C.↗

Charge transfer coefficients for the O+/2D/ + N2 and O+/2D/ + O2 excited ion reactions at thermal energy

An investigation of the reactions of metastable O(+) ions and O2 using drift tube-mass spectrometer techniques is presented. It was shown that ordinary charge transfer is the dominant reaction branch in both cases; it occurs with large rate coefficients, k(N2) = (8 + or - 2) x 10 to the -10th cu cm/s and k(O2) = (7 + or - 2) x 10 to the -10th cu cm/s, at an effective ion temperature of about 550 K. The reaction He(+) + O2 is used as a source of metastable O(+) ions, and evidence is presented that the O(+) ions so produced are in the 2D state rather than the 2P state. The results are compared with previous measurements, and inferences drawn from ionospheric observations.

Johnsen, R.↗

Burning-to-violent-reaction transitions in explosions

In a program to study fragment initiation of cased propellants and explosives, it was found that one area of extreme importance is that of the cased reactive-material burning reactions triggered by the perforation of the case by an impacting fragment. Once the reaction is started, the importance of the impactor decreases, and the sequence of events is controlled by the burning properties of the reactive material, its physical condition, and the nature of the confinement. A brief history of the results obtained by previous investigators is presented along with a discussion of variations in experimental results caused by geometrical changes in the test configurations. Changes in interpretations of the results are discussed. Results of recent confined-burn tests with Composition B, PBXC-116, PBXC-117, and Destex are presented, including results of metallurgical examination of the confined fragments. These examinations indicate a transition to a violent reaction which is not a detonation, although it produces many effects that resemble a detonation.

Graham, K. J.↗

Sympathetic reaction tests and analyses

The critical separation distances for explosive reactions of a solid rocket propellant were measured. Explosive reactions included low order explosion, low order detonation, and high order detonation. The effects of sample size, shape, damage and temperature on sympathetic reaction were determined experimentally. The sympathetic detonation of small cubes of solid rocket propellant was modelled numerically, using the Eulerian reactive hydrodynamic code 2DE with Forest Fire burn rates. The model was applied to cubes of 2.54 - 7.62 cm (1 - 3 in.), with agreement between calculated and experimental results.

Ricardson, D. E.↗

A comprehensive model to determine the effects of temperature and species fluctuations on reactions in turbulent reacting flows

The joint probability distribution function (pdf), which is a modification of the bivariate Gaussian pdf, is discussed and results are presented for a global reaction model using the joint pdf. An alternative joint pdf is discussed. A criterion which permits the selection of temperature pdf's in different regions of turbulent, reacting flow fields is developed. Two principal approaches to the determination of reaction rates in computer programs containing detailed chemical kinetics are outlined. These models represent a practical solution to the modeling of species reaction rates in turbulent, reacting flows.

Antaki, P. J.↗

Laboratory studies of some of the major ion-molecule reactions occurring in cometary comae

Laboratory results have been obtained for some of the key ion-molecule reactions which should occur in the inner coma of comets. A complete listing is given of laboratory data presently available for ion-molecule reactions occurring in a mixture of H2O, CO2, CO, CH4, N2, and NH3 cometary volatiles. From these data, the most important reactions occurring in the coma of a water-dominated comet are extracted for use in models of the physics and chemistry of cometary comae.

Huntress, W. T., Jr.↗

An ICR study of ion-molecule reactions in the C2H2/HCN system

Using the ICR technique, rate constants are obtained for the reaction of C2H2(+) with HCN and of HCN(+) with C2H2. They are, respectively, 3.6 x 10 to the -10 cu cm/molecule-s and 6.9 x 10 to the -10 cu cm/molecule-s. Discrepancies between these results and other measurements of the first reaction are discussed. The relevance of this reaction to the formation of HC3N in interstellar clouds is considered.

Mcewan, M. J.↗

An ICR study of an association reaction at low pressure

The reactions of the gaseous ion CH3+ with HCN are investigated, using the ion cyclotron resonance technique. The pressure range of the experiment was 1 x 10 to the -6 to 3 x 10 to the -4 Torr with a rate coefficient of 2 x 10 to the -10 cu cm/sec. Good agreement was found between rate coefficients determined in the trapping mode at the low end of the pressure range and the drift mode at the high end of the pressure range. It is shown that the association reaction of CH3 with HCN follows second order kinetics throughout the entire pressure range of the experiment. The reaction is interpreted in terms of both a saturated three-body and a radiative association mechanism. Some explanations for the disagreement of the rate coefficient with that reported previously are also given.

Mcewan, M. J.↗

A kinetics study of the reaction of SO2 with CH3O2

The reaction of CH3O2 with SO2 has been studied using the flash photolysis/ultraviolet absorption technique. In contrast to previous measurements, no reaction could be detected over the temperature range 298-423 K. An upper limit of 5 x 10 to the -17th cu cm/molecule/sec has been determined for the reaction rate constant.

Sander, S. P.↗

Oxygen atom reaction with shuttle materials at orbital altitudes

Surfaces of materials used in the space shuttle orbiter payload bay and exposed during STS-1 through STS-3 were examined after flight. Paints and polymers, in particular Kapton used on the television camera thermal blanket, showed significant change. Generally, the change was a loss of surface gloss on the polymer with apparent aging on the paint surfaces. The Kapton surfaces showed the greatest change, and postflight analyses showed mass loss of 4.8 percent on STS-2 and 35 percent on STS-3 for most heavily affected surfaces. Strong shadow patterns were evident. The greatest mass loss was measured on surfaces which were exposed to solar radiation in conjunction with exposure in the vehicle velocity vector. A mechanism which involves the interaction of atomic oxygen with organic polymer surfaces is proposed. Atomic oxygen is the major ambient species at low orbital altitudes and presents a flux of 8 x 10 to the 14th power atoms/cu cm sec for reaction. Correlation of the expected mass loss based on ground-based oxygen atom/polymer reaction rates shows lower mass loss of the Kapton than measured. Consideration of solar heating effects on reaction rates as well as the high oxygen atom energy due to the orbiter's orbital velocity brings the predicted and measured mass loss in surprisingly good agreement. Flight sample surface morphology comparison with ground based Kapton/oxygen atom exposures provides additional support for the oxygen interaction mechanism.

Leger, L. J.↗

A photochemical study of the kinetics of the reactions of NH2 with phosphine, ethylene, and acetylene using flash photolysis-laser induced fluorescence

The photochemistry of the reactions of NH2 was investigated in an attempt to explain the existence of an abundance of ammonia in the Jovian atmosphere. The production of ammonia reservoirs from the coupling of ammonia with other atmospheric constituents was considered. The rate constants for the reactions of NH2 radicals with phosphine, acetylene, and ethylene were measured. Flash photolysis was used for the production of NH2 radicals and laser induced fluorescence was employed for radical detection. It was determined that the rates of the reactions were too slow to be significant as a source of ammonia reservoirs in the Jovian atmosphere.

Bosco, S. R.↗

A laser flash photolysis kinetics study of the reaction OH + H2O2 yields HO2 + H2O

Absolute rate constants for the reaction are reported as a function of temperature over the range 273-410 K. OH radicals are produced by 266 nm laser photolysis of H2O2 and detected by resonance fluorescence. H2O2 concentrations are determined in situ in the slow flow system by UV photometry. The results confirm the findings of two recent discharge flow-resonance fluorescence studies that the title reaction is considerably faster, particularly at temperatures below 300 K, than all earlier studies had indicated. A table giving kinetic data from the reaction is included.

Wine, P. H.↗

The temperature dependence of the rate constant for the reaction of hydroxyl radicals with nitric acid

The rate constant for the reaction of hydroxyl radicals with nitric acid in the 225-443 K temperature range has been measured by means of the flash photolysis resonance fluorescence technique. Above 300 K, the rate constant levels off in a way that can only be explained by the occurrence of two reaction channels, of which one, operative at low temperatures, proceeds through the formation of an adduct intermediate. The implications of these rate constant values for stratospheric reaction constants is discussed.

Kurylo, M. J.↗