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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 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
NASA NTRS1974

Vibrationally excited nitrogen in stable auroral red arcs and its effect on ionospheric recombination

The time-dependent continuity equations, including diffusion, were solved for the first six energy levels of molecular nitrogen for conditions in the thermosphere corresponding to stable auroral red (SAR) arcs. The results show that molecular nitrogen is excited vibrationally to the degree that the rate constant for the ionospheric loss process, O(+) + N2 yields NO(+) + N, is increased by as much as a factor of 7.6 at F2 region altitudes. It was found that deviations from the energetically equivalent Boltzmann distribution were large, causing the rate constant to be as much as 1.6 times the rate constant calculated for the Boltzmann distribution. These results indicate that SAR arc intensities as small as 58 R can produce noticeable increases in the ionosphere ion-atom interchange reaction rate and hence in the rate of loss of ionospheric electrons. It is suggested that the observed decrease of electron density in the F2 region in SAR arcs can probably be explained by enhanced reaction rates for ion-atom interchange between O(+) and N2 caused by vibrational excitation of molecular nitrogen by electron impact.

Newton, G. P.↗
NASA NTRS1985

Measurements of HO2 chemical kinetics with a new detection method

In this research program, HO2 was detected by the OH(A-X) photofragment from dissociative excitation of HO2 at 147 nm. This detection method was applied to measure the reaction rate constant of HO2 + O3. This reaction rate constant is needed for the understanding of stratospheric chemistry. Since C12 was used in the flow system, photoexcitation of C12 may produce fluorescence to interfere with the measurements. Thus, the photoexcitation process of C12 in the vacuum ultraviolet region was also examined in this research period using synchrotron radiation as a light source. The research results are summarized.

Lee, L. C.↗
NASA NTRS1977

Kinetics of the reactions of ClO with O and with NO

The rate constants k1, k2, and k3 for the reactions Cl + O3 yields ClO + O2 (1), ClO + O yields Cl + O2 (2), and ClO + NO yields Cl + NO2 (3), respectively, were measured by the discharge-flow technique, in which chlorine atoms are added to a flow of O3 and either O or NO in a helium carrier gas. The conditions of the experiment were such that the steady-state concentration ratios of Cl to ClO are simply interpretable in terms of the rate constant ratios k2/k3 or k3/k1. These rate constant ratios were measured over the range 220 to 298 K and combined with the directly determined k1 value to yield k2 and k3. The results are: k1 = 2.12 x 10 to the -11th exp(-157/T); k2 = 3.38 x 10 to -11th exp(75 plus or minus 40/T); and k3 = 1.13 x 10 to the -11th exp(200 plus or minus 30/T) cu cm/sec.

Zahniser, M. S.↗
NASA NTRS1986

A kinetics study of the homogeneous and heterogeneous components of the HCl + ClONO2 reaction

The kinetics of the reaction HCl + ClONO2 to Cl2 + HNO3 were investigated at 298 K using a flow reactor with FTIR analysis to assess the importance of this reaction for stratospheric chemistry. The observed reaction was characteristic of a heterogeneous process; an upper limit of 5 x 10 to the -18th cu cm/molecule per s was obtained for the homogeneous gas phase rate constant. From calculations of the first order wall rate constant, estimates were made of the reaction rate on stratospheric aerosols. Because both HCl and ClONO2 need to be adsorbed on the particle surface, the reaction will be of negligible importance under most stratospheric conditions.

Friedl, Randall R.↗
NASA NTRS1986

Kinetics and mechanism of the IO + IO reaction

The flash photolysis-absorption technique has been used to measure the rate constant for the reaction IO + IO over the temperature range 250-373 K and pressure range 20-700 torr of N2. The rate constant for the overall reaction was found to be independent of pressure and equal to 1.73 x 10 to the -12th exp (1020 + or - 200)/T cu cm/molecule s. Branching ratios for the reaction channels forming 2I + O2, I2 + O2, and I2O2, were found to be pressure dependent, with the I2 channel accounting for less than 5 percent of the total reaction over the observed pressure range. A stable reaction product was observed between 230 and 300 nm which was formed on a long time scale compared to IO disappearance. The rate constant for the reaction I + O3 + yields to IO + O2 was measured at 298 K and found to be (9.5 + or - 1.5) x 10 to the -13th cu cm/molecule s.

Sander, S. P.↗
NASA NTRS1975

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.↗
NASA NTRS1993

Rates of hydroxyl radical reactions with some HFCs

Relative rate constants for OH reactions with some HFCs have been determined at 298 K by a technique which measures the loss of HFC greater than OH. The following ratios were determine: k(152a)/k(CH4) = 5.2 +/- 0.5, k(CH4)/k(125) = 3.9 +/- 0.5, k(CH4)/k(134a) = 2.1 +/- 0.2, k(134a)/k(125) = 2.0 +/- 0.2, and k(C2H6)/k(152a) = 6.2 +/- 1.0. These results are in good agreement with literature values for the absolute rate constants except for HFC 134a, where a slower rate constant is indicated.

Demore, William B.↗
NASA NTRS1989

Airfoil stall penetration at constant pitch rate and high Reynolds number

The model wing consists of a set of fiberglass panels mounted on a steel spar that spans the 8 ft test section of the UTRC Large Subsonic Wind Tunnel. The first use of this system was to measure surface pressures and flow conditions for a series of constant pitch rate ramps and sinusoidal oscillations a Mach number range, a Reynolds number range, and a pitch angle range. It is concluded that an increased pitch rate causes stall events to be delayed, strengthening of the stall vortex, increase in vortex propagation, and increase in unsteady airloads. The Mach number range causes a supersonic zone near the leading edge, stall vortex to be weaker, and a reduction of unsteady airloads.

Lorber, Peter F.↗
NASA NTRS1999

The Influence of Airmass Histories on Radical Species during POLARIS

The Goddard trajectory chemistry model was used with ER-2 aircraft data to test our current knowledge of radical photochemistry during the POLARIS (Polar Ozone Loss in the Arctic Region In Summer) campaign. The results of the trajectory chemistry model with and without trajectories are used to identify cases where steady state does not accurately describe the measurements. Over the entire mission, using trajectory chemistry reduces the variability in the modeled NO(x) comparisons to data by 25% with respect to the same model simulating steady state. Although the variability is reduced, NO(x)/NO(y) trajectory model results were found to be systematically low relative to the observations by 20-30% as seen in previous studies. Using new rate constants for reactions important in NO(y) partitioning improves the agreement of NO(x)/NO(y) with the observations but a 5-10% bias still exists. OH and HO2 individually are underpredicted by 15% of the standard steady state model and worsen with the new rate constants. Trajectory chemistry model results of OH/HO2 were systematically low by 10-20% but improve using the new rates constants because of the explicit dependence on NO. This suggests that our understanding of NO(x) is accurate to the 20% level and HO(x) chemistry is accurate to the 30% level in the lower stratosphere or better for the POLARIS regime. The behavior of the NO(x) and HO(x) comparisons to data using steady state versus trajectory chemistry and with updated rate coefficients is discussed in ten-ns of known chemical mechanisms and lifetimes.

Pierson, J. M.↗
NASA NTRS1984

Kinetics of the reaction Cl + NO2 + M

Using atomic chlorine resonance fluorescence at 140 nm to detect the decay of atomic chlorine in the presence of an excess of NO2, the rate constant for the reaction Cl + NO2 + M, where M is the total gas concentration, is measured over the temperature range 264 to 417 K and at a pressure 1 to 7 torr in a discharge flow system. The rate constants for M= He and M= N2 are measured and the results are summarized in a table. The systematic error of the rate constants is estimated to be about 15 percent. A static photolysis system coupled with an FTIR spectrophotometer is used to determine the branching ratio for the formation of two possible isomers. The ratio is concluded to be ClONO (greater than or equal 75 percent) and ClNO2 (less than or equal 25 percent) which is in agreement with the results of Niki et al. (1978).

Leu, M.-T.↗
NASA NTRS1981

Rate of reaction of OH with HNO3

Measurements of the kinetics of the reaction of OH with HNO3, and mechanisms of HNO3 removal from the stratosphere, are reported. Bimolecular rate constants were determined at temperatures between 224 and 366 K by monitoring the concentrations of OH radicals produced by HNO3 photolysis and HNO3 according to their resonance fluorescence and 184.9-nm absorption, respectively. The rate constant measured at 298 K is found to be somewhat faster than previously accepted values, with a negative temperature dependence. Calculations of a one-dimensional transport-kinetic atmospheric model on the basis of the new rate constant indicate reductions in O3 depletion due to chlorofluoromethane release and NOx injection, of magnitudes dependent on the nature of the reaction products.

Wine, P. H.↗
NASA NTRS1992

The relative abundance of ethane to acetylene in the Jovian stratosphere

The inclusion of the results of laboratory kinetics studies on the reaction of C2H3 and H2 to yield C2H4, which is suggestive of an efficient chemical mechanism for the hydrogenation of C2H2 to C2H6, can be included in a comprehensive model of the Jupiter atmosphere hydrocarbon photochemistry to explain the observed altitude variation of the C2H6/C2H2 ratio. The sensitivity of these results to uncertainties in key low-temperature rate constants is demonstrated. These key reaction-rate constants decrease with falling temperature.

Allen, Mark↗
NASA NTRS1999

Combustion of Interacting Droplet Arrays in a Microgravity Environment

Investigations into droplet interactions date back to Rex et al. Recently, Annamalai and Ryan and Annamalai published extensive reviews of droplet array and cloud combustion studies. The authors studied the change in the burning rate constant, k, (relative to that of the single droplet) that results from interactions. Under certain conditions, there exists a separation distance where the droplet lifetime reaches a minimum, or average burning rate constant is a maximum . Additionally, since inter-droplet separation distance, L, increases relative to the droplet size, D, as the burning proceeds, the burning rate is not constant throughout the burn, but changes continuously with time. Only Law and co-workers and Mikami et al. studied interactions under conditions where buoyant forces were negligible. Comparing their results with existing theory, Law and co-workers found that theory over predicted the persistency and intensity of droplet interactions. The droplet interactions also depended on the initial array configuration as well as the instantaneous array configuration. They also concluded that droplet heating was retarded due to interactions and that the burning process did not follow the "D-squared" law. Mikami et al. studied the combustion of a two-droplet array of heptane burning in air at one atm pressure in microgravity. They showed that the instantaneous burning rate constant increases throughout the droplet lifetime, even for a single droplet. Also, the burn time of the array reached a minimum at a critical inter-droplet spacing. In this article, we examine droplet interactions in normal and microgravity environments. The microgravity experiments were in the NASA GRC 2.2 and 5.2 second drop towers, and the JAMIC (Japan Microgravity Center) 10 second drop tower. Special emphasis is directed to combustion under conditions that yield finite extinction diameters, and to determine how droplet interactions affect the extinction process.

Dietrich, D. L.↗
NASA NTRS1982

Modeling of polymer photodegradation for solar cell modules

It was shown that many of the experimental observations in the photooxidation of hydrocarbon polymers can be accounted for with a computer simulation using an elementary mechanistic model with corresponding rate constants for each reaction. For outdoor applications, however, such as in photovoltaics, the variation of temperature must have important effects on the useful lifetimes of such materials. The data bank necessary to replace the isothermal rate constant values with Arrhenius activation parameters: A (the pre-exponential factor) and E (the activation energy) was searched. The best collection of data assembled to data is summarized. Note, however, that the problem is now considerably enlarged since from a theoretical point of view, with 51 of the input variables replaced with 102 parameters. The sensitivity of the overall scheme is such that even after many computer simulations, a successful photooxidation simulation with the expanded variable set was not completed. Many of the species in the complex process undergo a number of competitive pathways, the relative importance of each being often sensitive to small changes in the calculated rate constant values.

Somersall, A. C.↗
NASA NTRS1994

Effect of vibrationally excited oxygen on ozone production in the stratosphere

Photolysis of vibrationally excited oxygen produced by ultraviolet photolysis of ozone in the upper stratosphere is incorporated into the Lawrence Livermore National Laboratory two-dimensional zonally averaged chemical-radiative-transport model of the troposphere and stratosphere. The importance of this potential contributor of odd oxygen to the concentration of ozone is evaluated based on recent information on vibrational distributions of excited oxygen and on preliminary studies of energy transfer from the excited oxygen. When energy transfer rate constants similar to those of Toumi et al. (1991) are assumed, increases in model ozone concentrations of up to 4.0% in the upper stratosphere are found, and the model ozone concentrations are found to agree slightly better with measurements, including recent data from the Upper Atmosphere Research Satellite. However, the ozone increase is only 0.3% when the larger energy transfer rate constants indicated by recent experimental work are applied to the model. An ozone increase of 1% at 50 km requires energy transfer rate constants one-twentieth those of the preliminary observations. As a result, vibrationally excited oxygen processes probably do not contribute enough ozone to be significant in models of the upper stratosphere.

Patten, K. O., Jr.↗
NASA NTRS1992

Theoretical study of thermodynamic properties and reaction rates of importance in the high-speed research program

One of the primary goals of NASA's high-speed research program is to determine the feasibility of designing an environmentally safe commercial supersonic transport airplane. The largest environmental concern is focused on the amount of ozone destroying nitrogen oxides (NO(x)) that would be injected into the lower stratosphere during the cruise portion of the flight. The limitations placed on NO(x) emission require more than an order of magnitude reduction over current engine designs. To develop strategies to meet this goal requires first gaining a fundamental understanding of the combustion chemistry. To accurately model the combustor requires a computational fluid dynamics approach that includes both turbulence and chemistry. Since many of the important chemical processes in this regime involve highly reactive radicals, an experimental determination of the required thermodynamic data and rate constants is often very difficult. Unlike experimental approaches, theoretical methods are as applicable to highly reactive species as stable ones. Also our approximation of treating the dynamics classically becomes more accurate with increasing temperature. In this article we review recent progress in generating thermodynamic properties and rate constants that are required to understand NO(x) formation in the combustion process. We also describe our one-dimensional modeling efforts to validate an NH3 combustion reaction mechanism. We have been working in collaboration with researchers at LeRC, to ensure that our theoretical work is focused on the most important thermodynamic quantities and rate constants required in the chemical data base.

Langhoff, Stephen↗
NASA NTRS1997

Rate Coefficients for Reactions of Ethynyl Radical (C2H) With HCN and CH3CN: Implications for the Formation of Comples Nitriles on Titan

Rate coefficients for the reactions of C2H + HCN yields products and C2H + CH3CN yields products have been measured over the temperature range 262-360 K. These experiments represent an ongoing effort to accurately measure reaction rate coefficients of the ethynyl radical, C2H, relevant to planetary atmospheres such as those of Jupiter and Saturn and its satellite Titan. Laser photolysis of C2H2 is used to produce C2H, and transient infrared laser absorption is employed to measure the decay of C2H to obtain the subsequent reaction rates in a transverse flow cell. Rate constants for the reaction C2H + HCN yields products are found to increase significantly with increasing temperature and are measured to be (3.9-6.2) x 10(exp 13) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 297-360 K. The rate constants for the reaction C2H + CH3CN yields products are also found to increase substantially with increasing temperature and are measured to be (1.0-2.1) x 10(exp -12) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 262-360 K. For the reaction C2H + HCN yields products, ab initio calculations of transition state structures are used to infer that the major products form via an addition/elimination pathway. The measured rate constants for the reaction of C2H + HCN yields products are significantly smaller than values currently employed in photochemical models of Titan, which will affect the HC3N distribution.

Hoobler, Ray J.↗
NASA NTRS1986

Pressure and temperature dependences of the reaction of OH with nitric acid

Rate constants for the reaction of OH with HNO3 have been measured by using a laser flash photolysis resonance absorption technique at 298 and 248 K in the presence of 10-730 Torr of He, N2, and SF6. A dependence on total pressure was observed with rate constant values increasing at 298 K from 1.11 x 10 to the -13th cu cm/molecule/s at 10 Torr to 1.45 x 10 to the -13th cu cm/molecule/s at 730 Torr, and at 248 K from 1.87 x 10 to the -13th cu cm/molecule/s at 10 Torr to 3.07 x 10 to the -13th cu cm/molecule/s at 730 Torr with helium as the diluent gas. Falloff behavior occurred at lower pressures with SF6 or N2 as the diluent gas. Extrapolated zero pressure rate constants were determined and correspond to an Arrhenius activation energy of E/R = -710 K.

Stachnik, R. A.↗