Competitive reaction of O/3P/ with ozone and carbonyl sulfide
Competitive reaction of O/3P/ atoms with ozone and carbonyl sulfide in temperature range 197 K - 299 K
Krezenski, D. C.↗
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The competitive reaction of O/D-1/ with ozone and nitrous oxide
Reaction kinetics of excited oxygen deuterium atoms with ozone and nitrous oxide in upper atmosphere
Goldman, C. S.↗
Calorimetry of 25 Ah lithium/thionyl chloride cells
Heat flow measurements of 25-Ah lithium thionyl chloride cells provided a method to calculate an effective thermal potential, E(TP) of 3.907 V. The calculation is useful to determine specific heat generation of this cell chemistry and design. The E(TP) value includes heat generation by electrochemical cell reactions, competitive chemical reactions, and resistance heating at the tabs, connectors, and leads. Heat flow was measured while applying electrical loads to the cell in an isothermal calorimeter set at 0, 20, and 60 C.
Johnson, C. J.↗
Shock tube study of the fuel structure effects on the chemical kinetic mechanisms responsible for soot formation
Soot formation in toluene-, benzene-, and acetylene-oxygen-argon mixtures was investigated to study soot formation in a combustion environment. High concentrations of oxygen completely suppress soot formation. The addition of oxygen at relatively low concentrations uniformly suppresses soot formation at high pressures, while at relatively lower pressures it suppresses soot formation at higher temperatures while promoting soot production at lower temperatures. The observed behavior indicates that oxidation reactions compete with ring fragmentation. The main conclusion to be drawn from the results is that the soot formation mechanism is probably the same for the pyrolysis and oxidation of hydrocarbons. That is, the addition of oxygen does not alter the soot route but rather promotes or inhibits this route by means of competitive reactions. An approach to empirical modeling of soot formation during pyrolysis of aromatic hydrocarbons is also presented.
Frenklach, M.↗
Analysis of Pyrolysis Products from Ablative Thermal Protection Systems
NASA’s state-of-the-art ablative materials are composed of a three-dimensional network of carbon fibers impregnated with polymers that dissipate thermal energy through pyrolysis. A fundamental understanding of the decomposition mechanisms and pyrolysis product distributions of various classes of polymers is instrumental in the design of new ablative materials. Furthermore, innovative experiments are essential to the continuous modernization of material response models by providing high-fidelity data. Thus, an apparatus has been designed to measure pyrolysis products from polymers and composite materials by implementing in-situ mass spectrometric techniques. Initial results from experiments performed on siloxane resins and a common phenolic resin will be discussed. Both classes of polymers exhibit heating-rate-dependent decomposition mechanisms. At the onset of heating, phenolic polymers decompose through competitive reactions to form gaseous products and a carbonaceous char. Gas phase products of phenolic resins are typically composed of molecular hydrogen, water, and aromatic hydrocarbons. Pyrolysis products from siloxane polymers include molecular hydrogen, small molecules, and cyclic oligomers from the polymer backbone.
Pyrolysis↗
Analysis of Pyrolysis Products from Ablative TPS
NASA’s state-of-the-art ablative materials are composed of a three-dimensional network of carbon fibers impregnated with polymers that dissipate thermal energy through pyrolysis. A fundamental understanding of the decomposition mechanisms and pyrolysis product distributions of various classes of polymers is instrumental in the design of new ablative materials. Furthermore, innovative experiments are essential to the continuous modernization of material response models by providing high-fidelity data. Thus, an apparatus has been designed to measure pyrolysis products from polymers and composite materials by implementing in-situ mass spectrometric techniques. Initial results from experiments performed on siloxane resins and a common phenolic resin will be discussed. Both classes of polymers exhibit heating-rate-dependent decomposition mechanisms. At the onset of heating, phenolic polymers decompose through competitive reactions to form gaseous products and a carbonaceous char. Gas phase products of phenolic resins are typically composed of molecular hydrogen, water, and aromatic hydrocarbons. Pyrolysis products from siloxane polymers include molecular hydrogen, small molecules, and cyclic oligomers from the polymer.
Pyrolysis↗
Calculations on the competition between association and reaction for C3H(+) + H2
The ab initio results presently obtained for the potential energy surface of competing associative and reactive ion-molecule processes of the reactants H2 and C3H(+) show that the linear ion is able to directly access the deep potential well of the propargyl ion H2CCCH(+). Using the minimum energy potential pathway and properties of the stationary point structures determined via the ab initio methods, calculation results are obtained for both the association-rate coefficient for C3H3(+) production as a function of density, and the branching ratio between the propargyl and cyclic structures of the ion.
Maluendes, Sergio A.↗
Competition between charge exchange and chemical reaction - The D2/+/ + H system
Study of the special features of molecular charge exchange and its competition with chemical reaction in the case of the D2(+) + H system. The trajectory surface hopping (TSH) model proposed by Tully and Preston (1971) is used to study this competition for a number of reactions involving the above system. The diatomics-in-molecules zero-overlap approximation is used to calculate the three adiabatic surfaces - one triplet and two singlet - which are needed to describe this system. One of the significant results of this study is that the chemical reaction and charge exchange are strongly coupled. It is also found that the number of trajectories passing into the chemical regions of the three surfaces depends very strongly on the surface crossings.-
Preston, R. K.↗
Heterogeneous Reactions of ClONO2, HCl, and HOCl on Liquid Sulfuric Acid Surfaces
The heterogeneous reactions of ClONO2 + H2O yields HNO3 + HOCl (1), ClONO2 + HCl yields C12 + HNO3 (2), and HOCl + HCl yields Cl2 + H2O (3) on liquid sulfuric acid surfaces have been studied using a fast flow reactor coupled to a quadrupole mass spectrometer. The main objectives of the study are to investigate: (a) the temperature dependence of these reactions at a fixed H2O partial pressure typical of the lower stratosphere (that is, by changing temperature at a constant water partial pressure, the H2SO4 content of the surfaces is also changed), (b) the relative importance or competition between reactions 1 and 2, and (c) the effect of HNO3 on the reaction probabilities due to the formation of a H2SO4/HNO3/H2O ternary system. The measurements show that all the reactions depend markedly on temperature at a fixed H2O partial pressure: they proceed efficiently at temperatures near 200 K and much slower at temperatures near 220 K. The reaction probability (gamma(sub 1)) for ClONO2 hydrolysis approaches 0.01 at temperatures below 200 K, whereas the values for gamma(sub 2) and gamma(sub 3) are on the order of a few tenths at 200 K. Although detailed mechanisms for these reactions are still unknown, the present data indicate that the competition between ClONO2 hydrolysis and ClONO2 reaction with HCl may depend on temperature (or H2SO4 Wt %): in the presence of gaseous HCl at stratospheric concentrations, reaction 2 is dominant at lower temperatures (less than 200 K), but reaction 1 becomes important at temperatures above 210 K. Furthermore, reaction probability measurements performed on the H2SO4/HNO3/ H2O ternary solutions do not exhibit noticeable deviation from those performed on the H2SO4/H2O binary system, suggesting little effect of HNO3 in sulfate aerosols on the ClONO2 and HOCl reactions with HCl. The results reveal that significant reductions in the chlorine-containing reservoir species (such as ClONO2 and HCl) can take place on stratospheric sulfate aerosols at high latitudes in winter and early spring, even at temperatures too warm for Polar Stratospheric Clouds (PSCs) to form or in regions where nucleation of PSCs is sparse. This is particularly true under elevated sulfuric acid loading, such as that after the eruption of Mt. Pinatubo. Comparisons between our results and those presently available have also been made.
Zhang, Renyi↗
A Competitive Kinetics Study of the Reaction of Cl with CS2 in Air at 298 K
The relative rate technique has been used to investigate the kinetics of the reaction of Cl atoms with carbon disulfide, CS2, at 700 Torr total pressure of air at 298 K. The decay rate of CS2 was measured relative to CH4, CH3Cl and CHF2CL. For experiments using CH4 and CH3Cl references, the decay rate of CS2 was dependent on the ratio of the concentration of the reference to that of CS2. We ascribe this behavior to the generation of OH radicals in the system leading to complicated secondary chemistry. From experiments using CHF2Cl we are able to assign an upper limit of 4 x 10(exp -15) cu cm/(molecule s) for the overall reaction, Cl + CS2 yields products.
Wallington, Timothy J.↗
Competitive Oxidation and Hydration During Aqueous Alteration of Asteroids
Introduction: Studies of chondrites show that incorporation of H2O ice during formation of asteroids followed by radioactive heating caused partial oxidation and hydration of primary reduced and anhydrous rocks. Oxidation of kamacite, phosphides, troilite and organic polymers occurred through consumption of water s oxygen and release of H2. Hydration caused formation of serpentine, saponite, chlorite, talc and hydrated salts. Since H2O was the major reactant in oxidation and hydration, these processes could have been competitive. Redox reactions in asteroids should have been closely connected to hydration (dehydration) during aqueous alteration and thermal metamorphism. For example, dehydration and reduction release H2O that can be consumed in oxidation and hydration, respectively. We model asteroidal processes in order to quantify the fate of H2O and water s oxygen in major redox and hydration/dehydration reactions. Model: Equilibrium compositions in the gas-solid-liquid
Zolotov, M. Y.↗
Experimental Observations of the Effect of Gravity Changes on Smoldering Combustion
The effects of gravity changes on the natural convection smolder characteristics of flexible polyurethane foam were determined in order to provide information on the potential onset of a smolder-initiated fire in a space-based facility. Experiments were conducted in an aircraft following parabolic trajectories providing up to 25 seconds of low gravity. Temperature histories of polyurethane foam were measured at several locations along the fuel sample interior. Results are presented and discussed for both upward and downward smoldering. Results indicate that gravity significantly effects the competition between supply of oxidizer to, and the transfer of heat to and from the reaction zone. This competition determines the characteristics of the smolder reaction. Within the reaction zone the reduction in oxygen supply in low gravity is dominant and the reaction weakens. Away from the reaction zone the reduction in convective cooling at low gravity tends to increase the material temperature. The opposite was observed at high gravity.
Torero, J. L.↗
Unimolecular decomposition reactions at low-pressure: A comparison of competitive methods
The lack of a simple rate coefficient expression to describe the pressure and temperature dependence hampers chemical modeling of flame systems. Recently developed simplified models to describe unimolecular processes include the calculation of rate constants for thermal unimolecular reactions and recombinations at the low pressure limit, at the high pressure limit and in the intermediate fall-off region. Comparison between two different applications of Troe's simplified model and a comparison between the simplified model and the classic RRKM theory are described.
Adams, G. F.↗
Skeletal unloading inhibits the in vitro proliferation and differentiation of rat osteoprogenitor cells
Loss of weight bearing in the growing rat decreases bone formation, osteoblast numbers, and bone maturation in unloaded bones. These responses suggest an impairment of osteoblast proliferation and differentiation. To test this assumption, we assessed the effects of skeletal unloading using an in vitro model of osteoprogenitor cell differentiation. Rats were hindlimb elevated for 0 (control), 2, or 5 days, after which their tibial bone marrow stromal cells (BMSCs) were harvested and cultured. Five days of hindlimb elevation led to significant decreases in proliferation, alkaline phosphatase (AP) enzyme activity, and mineralization of BMSC cultures. Differentiation of BMSCs was analyzed by quantitative competitive polymerase chain reaction of cDNA after 10, 15, 20, and 28 days of culture. cDNA pools were analyzed for the expression of c-fos (an index of proliferation), AP (an index of early osteoblast differentiation), and osteocalcin (a marker of late differentiation). BMSCs from 5-day unloaded rats expressed 50% less c-fos, 61% more AP, and 35% less osteocalcin mRNA compared with controls. These data demonstrate that cultured osteoprogenitor cells retain a memory of their in vivo loading history and indicate that skeletal unloading inhibits proliferation and differentiation of osteoprogenitor cells in vitro.
NASA Discipline Musculoskeletal↗
Summary of Research/Publications
Summary of research/publications include:(1) Comment on broadening of water microwave lines by collisions with helium atoms; (2) Calculations of ion-molecule deuterium fractionation reactions involving HD; (3) Ab initio predictions on the rotational spectra of carbon-chain carbene molecules; (4) Theoretical IR spectra of ionized naphthalene; (5) Improved collisional excitation rates for interstellar water; (6) Calculations on the competition between association and reaction for C3H+ + H2; (7) Theoretical infrared spectra of some model polycyclic aromatic hydrocarbons: effect of ionization; (8) Calculations concerning interstellar isomeric abundance ratios for C3H and C3H2; (9) New calculations on the ion-molecule processes C2H2+ + H2 C2H3+ + H and C2H2+ + H2 C2H4+; (10) Anisotropic rigid rotor potential energy function for H2O-H2; (11) A correlated ab initio study of linear carbon-chain radicals CnH (n=2-7); (12) Ab initio characterization of MgCCH, MgCCH+, and MgC2 and pathways to their formation in the interstellar medium; (13) Why HOC+ is detectable in interstellar clouds: The rate of the reaction between HOC+ and H2; (14) A correlated ab initio study of the X 2A 1 and A 2E states of MgCH3; (15) On the stability of interstellar carbon clusters: The rate of the reaction between C3 and O; and (16) The rate of the reaction between CN and C2H2 at interstellar temperatures.
Source record↗
Industry Consolidation and Future Airline Network Structures in Europe
In the current downturn in demand for air travel, major airlines are revising and rationalizing their networks in an attempt to improve financial performance and strengthen their defences against both new entrants and traditional rivals. Expansion of commercial agreements or alliances with other airlines has become a key reaction to the increasingly competitive marketplace. In the absence, for regulatory reasons, of cross-border mergers these are the principal means by which the industry can consolidate internationally. This paper analyzes the developments which have been taking place and attempts to itentify the implications for airline network structures and the function of different hub airports. The range of services available to passengers in long-haul markets to/from Europe is evaluated before and after recent industry reorganization. Hubs are crucial to interlink the route networks of parmers in an alliance. However, duplication between nearby hub airports that find themselves within the same airline alliance can lead to loss of service at the weaker locations. The extent to which the alliance hubs in Europe duplicate or complement each other in terms of network coverage is assessed and this methodology also enables the optimal partnerships for "unattached" airlines to be identified. The future role of the various European hubs is considered under different scenarios of global alliance development. The paper concludes by considering possible longer-term developments. In an environment where the low-cost carriers will provide a major element of customer choice, it is suggested that the traditional airlines will retrench around their hubs, surrendering many secondary cities to the low-cost sector. Further reduction in the number of alliances could threaten more of the European hubs. For both regulatory and commercial reasons, the end result may be just one airline alliance - so recreating in the deregulated market the historic rule of IATA.
Dennis, Nigel↗
Study of the techniques feasible for food synthesis aboard a spacecraft
Synthesis of sugars by Ca(OH)2 catalyzed formaldehyde condensation (the formose reaction) has produced branched carbohydrates that do not occur in nature. The kinetics and mechanisms of the homogeneously catalyzed autocatalytic condensation were studied and analogies between homogeneous and heterogeneous rate laws have been found. Aldol condensations proceed simultaneously with Cannizzaro and crossed-Cannizzaro reactions and Lobry de Bruyn-Van Eckenstein rearrangements. The separate steps as well as the interactions of this highly complex reaction system were elucidated. The system exhibits instabilities, competitive catalytic, mass action, and equilibrium phenomena, complexing, and parallel and consecutive reactions. Specific finding that have been made on the problem will be of interest for synthesizing sugars, both for sustained space flight and for large scale food manufacture. A contribution to methodology for studying complex catalyzed reactions and to understanding control of reaction selectivity was a broad goal of the project.
Weiss, A. H.↗
Effect of pollutant gases on ozone production by simulated solar radiation
The present investigation provides some information related to the problem of ozone destruction by nitric oxide emission from high flying vehicles. It is found that CO and H2O can counteract NO destruction of O3 in laboratory simulations. The addition of CO and H2O to aircraft exhausts could be a practical means of reducing the damage of the UV-filtering ozone layer. It is also discovered that NO is not regenerated as it destroys ozone, except at low stratospheric pressures. It is believed that the presence of H2O and CO gives rise to a series of reactions which provide a kinetically competitive pathway for the NO, causing it to go into NO2 production via these substrates rather than via O3.
Wong, E. L.↗