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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 829 records · Page 46
All sourcesNASA NTRSDOE OSTI
NASA NTRS1995

Temperature-Dependent Rate Constants and Substituent Effects for the Reactions of Hydroxyl Radicals With Three Partially Fluorinated Ethers

Rate constants and temperature dependencies for the reactions of OH with CF3OCH3 (HFOC-143a), CF2HOCF2H (HFOC-134), and CF3OCF2H (HFOC-125) were studied using a relative rate technique in the temperature range 298-393 K. The following absolute rate constants were derived: HFOC-143a, 1.9E-12 exp(-1555/T); HFOC-134, 1.9E-12 exp(-2006/T); HFOC-125, 4.7E-13 exp(-2095/T). Units are cm(exp 3)molecule(exp -1) s(exp -1). Substituent effects on OH abstraction rate constants are discussed, and it is shown that the CF3O group has an effect on the OH rate constants similar to that of a fluorine atom. The effects are related to changes in the C-H bond energies of the reactants (and thereby the activation energies) rather than changes in the preexponential factors. On the basis of a correlation of rate constants with bond energies, the respective D(C-H) bond strengths in the three ethers are found to be 102, 104, and 106 kcal/mol, with an uncertainty of about 1 kcal/mol.

Hsu, K.-J.↗
NASA NTRS1997

Construction of a Visible Diode Laser Source for Free Radical Photochemistry and Spectroscopy Experiments

Tunable diode lasers are reliable sources of narrow-band light and comparatively cheap. Optical feedback simplifies frequency tuning of the laser diodes. We are building an inexpensive diode laser system incorporating optical feedback from a diffraction grating. The external optical cavity can be used with lasers that emit between 2 and 100 mW, and will also work if they are pulsed, although this will significantly degrade the bandwidth. The diode laser output power and bandwidth are comparable to CW dye lasers used in kinetics and dynamics experiments. However, their cost and maintenance will be much less as will alignment time. We intend to use the diode lasers to investigate CN and C2 kinetics as well as to study dissociation dynamics of atmospherically important molecules.

Newman, Bronjelyn↗
NASA NTRS1997

Kinetics and Mechanism of the Reaction of Hydoxyl Radicals with Acetonitrile under Atmospheric Conditions

The pulsed laser photolysis-pulsed laser induced fluorescence technique has been employed to determine absolute rate coefficients for the reaction OH + CH3CN (1) and its isotopic variants, OH + CD3CN (2), OD + CH3CN (3), and OD + CD3CN (4). Reactions 1 and 2 were studied as a function of pressure and temperature in N2, N2/O2, and He buffer gases. In the absence of O2 all four reactions displayed well-behaved kinetics with exponential OH decays and pseudo-first rate constants which were proportional to substrate concentration. Data obtained in N2 over the range 50-700 Torr at 298 K are consistent with k(sub 1), showing a small pressure dependence. The Arrhenius expression obtained by averaging data at all pressures in k(sub 1)(T) = (1.1(sup +0.5)/(sub -0.3)) x 10(exp -12) exp[(-1130 +/- 90)/T] cu cm /(molecule s). The kinetics of reaction 2 are found to be pressure dependent with k(sub 2) (298 K) increasing from (1.21 +/- 0.12) x 10(exp -14) to (2.16 +/- 0.11) x 10(exp -14) cm(exp 3)/ (molecule s) over the pressure range 50-700 Torr of N2 at 298 K. Data at pressures greater than 600 Torr give k(sub 2)(T) = (9.4((sup +13.4)(sub -5.0))) x 10(exp -13) exp[(-1180 +/- 250)/T] cu cm/(molecule s). The rates of reactions 3 and 4 are found to be independent of pressure over the range 50-700 Torr of N2 with 298 K rate coefficient given by k(sub 3) =(3.18 +/- 0.40) x 10(exp -14) cu cm/(molecule s) and k(sub 4) = (2.25 +/-0.28) x 10(exp -14) cu cm/(molecule s). In the presence of O2 each reaction shows complex (non-pseudo-first-order) kinetic behavior and/or an apparent decrease in the observed rate constant with increasing [O2], indicating the presence of significant OH or OD regeneration. Observation of regeneration of OH in (2) and OD in (3) is indicative of a reaction channel which proceeds via addition followed by reaction of the adduct, or one of its decomposition products, with O2. The observed OH and OD decay profiles have been modeled by using a simple mechanistic scheme to extract kinetic information about the adduct reations with O2 and branching ratios for OH regeneration. A plausible mechanism for OH regeneration in (2) involves OH addition to the nitrogen atom followed by O2 addition to the cyano carbon atom, isomeriazation and decomposition to D2CO + DOCN + OH. Our results suggest that the OH + CH3CN reaction occurs via a complex mechanism involving both bimolecular and termolecular pathways, analogous to the mechanisms for the the important atmospheric reactions of OH with CO and HNO3.

Hynes, A. J.↗
NASA NTRS1996

Experimental and Estimated Rate Constants for the Reactions of Hydroxyl Radicals with Several Halocarbons

Relative rate experiments are used to measure rate constants and temperature dependencies of the reactions of OH with CH3F (41), CH2FCl (31), CH2BrCl (30B1), CH2Br2 (3OB2), CHBr3 (2OB3), CF2BrCHFCl (123aBl(alpha)), and CF2ClCHCl2 (122). Rate constants for additional compounds of these types are estimated using an empirical rate constant estimation method which is based on measured rate constants for a wide range of halocarbons. The experimental data are combined with the estimated and previously reported rate constants to illustrate the effects of F, Cl, and Br substitution on OH rate constants for a series of 19 halomethanes and 25 haloethanes. Application of the estimation technique is further illustrated for some higher hydrofluorocarbons (HFCs), including CHF2CF2CF2CF2H (338pcc), CF3CHFCHFCF2CF3 (43-10mee), CF3CH2CH2CF3 (356ffa), CF3CH2CF2CH2CF3 (458mfcf), CF3CH2CHF2 (245fa), and CF3CH2CF2CH3 (365mfc). The predictions are compared with literature data for these compounds.

DeMore, W.B.↗
NASA NTRS2001

Free Radicals and Reactive Intermediates for the SAGE III Ozone Loss and Validation Experiment (SOLVE) Mission

This grant provided partial support for participation in the SAGE III Ozone Loss and Validation Experiment. The NASA-sponsored SOLVE mission was conducted Jointly with the European Commission-sponsored Third European Stratospheric Experiment on Ozone (THESEO 2000). Researchers examined processes that control ozone amounts at mid to high latitudes during the arctic winter and acquired correlative data needed to validate the Stratospheric Aerosol and Gas Experiment (SAGE) III satellite measurements that are used to quantitatively assess high-latitude ozone loss. The campaign began in September 1999 with intercomparison flights out of NASA Dryden Flight Research Center in Edwards. CA. and continued through March 2000. with midwinter deployments out of Kiruna. Sweden. SOLVE was co-sponsored by the Upper Atmosphere Research Program (UARP). Atmospheric Effects of Aviation Project (AEAP). Atmospheric Chemistry Modeling and Analysis Program (ACMAP). and Earth Observing System (EOS) of NASA's Earth Science Enterprise (ESE) as part of the validation program for the SAGE III instrument.

Anderson, James G.↗
NASA NTRS2004

Radical is Temporary

I suspect that even if Ken had stayed on, we would have evolved to the state we're in right now. In terms of the nature of the work that we're doing, we've gone from development to maintenance, and so the project team needed to evolve to reflect that change. The analogy I use to describe Hubble is a data factory, and we provide the factory controller. The telescope takes in light and produces pictures, and we're the ones sending all of the control signals and monitoring the temperature, power, and voltages in the factory to make sure the production line is doing its job and that it's not reaching some sort of a stress point. That's basically it. We maintain the Hubble command and control system. I think we're still putting out a good quality product. We still meet our schedule and cost milestones. Every time we make a change to the ground system, we run a suite of tests to make sure that the system still runs as expected, and that it correctly controls the spacecraft. Other than that, provided the interfaces are controlled, everything is okay.

Barrett, Larry↗
NASA NTRS2004

Right on Time, Radically

Back in the early 1990s, reengineering was all the rage. All of the corporations and their CEOs got excited about the prospect of having to streamline and reorganize, reengineering their organizations in an effort to improve the bottom line. NASA Goddard Space Flight Center was no exception to that rule. Some folks in upper management wanted to take advantage of this new paradigm and they turned their attention to the Hubble Space Telescope ground system. The objective was to reduce the operating cost of the system by at least 50 percent. This was a noble objective, as Hubble would likely be around for another ten to fifteen years at least.

Lehtonen, Ken↗
NASA NTRS2004

Radicals and Reservoirs in the GMI Chemistry and Transport Model: Comparison to Measurements

The most important use of atmospheric chemistry and transport models is to predict the future composition of the atmosphere. The amounts of gases like chlorofluorcarbons, methyl bromide, nitrous oxide and methane are changing and the stratospheric ozone layer will change because these gases are changing. Methyl bromide, nitrous oxide and methane all have natural sources, and also change because of human activity. Chlorofluorcarbons are man-made gases; these are known to decrease stratospheric ozone and future production is banned. They are long-lived gases, and many decades will pass before they are insignificant in the atmosphere. The models are used to predict changes in ozone and other gases; this is a straightforward application. The models must be also tested using observations for the present day atmosphere. This is a challenging task, because the model contains more than 50 species and more than 150 chemical reactions. Data from satellites, ground stations, aircraft and balloons are used to evaluate the model. Different models that are used in international assessments produce different results; in the most recent assessment some predict that ozone will return to 1980 levels by 2025 and others predict that this will not happen until 2050. Since all the parts of the models are conceptually the same, there must be differences in implementation that produce these differences, This work takes a single model, two different sets of winds and temperatures, and repeats the same prediction for the future. Here we compare the results for these two simulations with many observations. The purpose is to identify differences in the model results for the present atmosphere that will lead to different predictions. This sort of controlled comparison will reduce uncertainty in the predictions for stratospheric ozone.

Douglas, Anne R.↗
NASA NTRS2000

An all-woman crew to Mars: a radical proposal

It is logical to propose that if a human mission is flown to Mars, it should be composed of an entirely female crew. On the average, women have lower mass and take less volume than males, and use proportionately less consumables. In addition, sociological research indicates that a female crew may have a preferable interpersonal dynamic, and be likely to choose non-confrontational approaches to solve interpersonal problems.

Space Flight/organization & administration↗
NASA NTRS2017

Non-Classical Stress Concentration Behavior in a Radically Stretched Hyperelastic Sheet Containing a Circular Hole

Non-classical stress concentration behavior in a stretched circular hyperelastic sheet (outer radius b = 10 in., thickness t = 0.0625 in.) containing a central hole (radius a = 0.5 in.) was analyzed. The hyperelastic sheet was subjected to different levels of remote radial stretchings. Nastran large-strain large-deformation analysis and the Blatz-Ko large deformation theory were used to calculate the equal-biaxial stress concentration factors K. The results show that the values of K calculated from the Blatz-Ko theory and Nastran are extremely close. Unlike the classical linear elasticity theory, which gives the constant K = 2 for the equal-biaxial stress field, the hyperelastic K values were found to increase with increased stretching and can exceed the value K = 6 at a remote radial extension ratio of 2.35. The present K-values compare fairly well with the K-values obtained by previous works. The effect of the hole-size on K-values was investigated. The values of K start to decrease from a hole radius a = 0.125 in. down to K = 1 (no stress concentration) as a shrinks to a = 0 in. (no hole). Also, the newly introduced stretch and strain magnification factors {K(sub λ),K(sub ε) } are also material- and deformation-dependent, and can increase from linear levels of {1.0, 4.0} and reaching {3.07, 4.61}, respectively at a remote radial extension ratio of 2.35.

stress concentration↗