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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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All sourcesNASA NTRSDOE OSTI
NASA NTRS1996

On Kinetics Modeling of Vibrational Energy Transfer

Two models of vibrational energy exchange are compared at equilibrium to the elementary vibrational exchange reaction for a binary mixture. The first model, non-linear in the species vibrational energies, was derived by Schwartz, Slawsky, and Herzfeld (SSH) by considering the detailed kinetics of vibrational energy levels. This model recovers the result demanded at equilibrium by the elementary reaction. The second model is more recent, and is gaining use in certain areas of computational fluid dynamics. This model, linear in the species vibrational energies, is shown not to recover the required equilibrium result. Further, this more recent model is inconsistent with its suggested rate constants in that those rate constants were inferred from measurements by using the SSH model to reduce the data. The non-linear versus linear nature of these two models can lead to significant differences in vibrational energy coupling. Use of the contemporary model may lead to significant misconceptions, especially when integrated in computer codes considering multiple energy coupling mechanisms.

Gilmore, John O.↗
NASA NTRS2002

Slow Crack Growth of Brittle Materials With Exponential Crack-Velocity Formulation: Analysis - Part 1

Extensive slow-crack-growth (SCG) analysis was made using a primary exponential crack-velocity formulation under three widely used load configurations: constant stress rate, constant stress, and cyclic stress. Although the use of the exponential formulation in determining SCG parameters of a material requires somewhat inconvenient numerical procedures, the resulting solutions presented gave almost the same degree of simplicity in both data analysis and experiments as did the power-law formulation. However, the fact that the inert strength of a material should be known in advance to determine the corresponding SCG parameters was a major drawback of the exponential formulation as compared with the power-law formulation.

Choi, Sung R.↗
NASA NTRS1985

Photoconversion from the light-adapted to the dark-adapted state of bacteriorhodopsin

The dark and light adaptation of the bR(trans)570 (bacteriorhodopsin) and bR(cis)550 isomers is analyzed. The equilibrium between the two bR isomers in light-adapted purple membrane films is studied in terms of the wavelength of actinic light and hydration levels. Absorption spectra observed after light adaptations with red and yellow light reveal that red light is less efficient in converting bR(cis)550 to bR(trans)570 than yellow light and the amount of bR(cis)550 in a light-adapted sample increases with decreasing hydration. The rate constants of dark and light adaptation are evaluated; the rate constant of dark adaptation is independent of the hydration level and the rate constant of light adaptation increases with hydration. The acceleration of a dark adaptation by red light is investigated; the dependence of the accelerated dark adaptation on the light intensity is discussed. The action spectrum of light adaptation in a purple membrane suspension is compared with the absorption spectrum of bR(cis)550; correlation between the spectra reveals that cis-to-transconversion is due to excitation of bR(cis)550 and the mechanism of cis-to-trans conversion in film is not affected by humidity levels. It is noted that the light-driven trans-to-cis conversion is a single photon process. The branching at M410 from the all-trans into the 13-cis photocycle is examined.

Kouyama, T.↗
NASA NTRS1990

Limiting concentrations of activated mononucleotides necessary for poly(C)-directed elongation of oligoguanylates

Selected imidazolide-activated nucleotides have been subjected to hydrolysis under conditions similar to those that favor their template-directed oligomerization. Rate constants of hydrolysis of the P-N bond in guanosine 5'-monophosphate 2-methylimidazolide (2-MeImpG) and in guanosine 5'-monophosphate imidazolide (ImpG), kh, have been determined in the presence/absence of magnesium ion as a function of temperature and polycytidylate [poly(C)] concentration. Using the rate constant of hydrolysis of 2-MeImpG and the rate constant of elongation, i.e., the reaction of an oligoguanylate with 2-MeImpG in the presence of poly(C) acting as template, the limiting concentration of 2-MeImpG necessary for oligonucleotide elongation to compete with hydrolysis can be calculated. The limiting concentration is defined as the initial concentration of monomer that results in its equal consumption by hydrolysis and by elongation. These limiting concentrations of 2-MeImpG are found to be 1.7 mM at 37 degrees C and 0.36 mM at 1 degrees C. Boundary conditions in the form of limiting concentration of activated nucleotide may be used to evaluate a prebiotic model for chemical synthesis of biopolymers. For instance, the limiting concentration of monomer can be used as a basis of comparison among catalytic, but nonenzymatic, RNA-type systems. We also determined the rate constant of dimerization of 2-MeImpG, k2 = 0.45 +/- 0.06 M-1 h-1 in the absence of poly(C), and 0.45 +/- 0.06 less than or equal to k2 less than or equal to 0.97 +/- 0.13 M-1 h-1 in its presence at 37 degrees C and pH 7.95.(ABSTRACT TRUNCATED AT 250 WORDS).

NASA Discipline Number 52-20↗
NASA NTRS1978

Revised estimates for ozone reduction by shuttle operation

Previous calculations by five different modeling groups of the effect of space shuttle operations on the ozone layer yielded an estimate of 0.2 percent ozone reduction for the Northern Hemisphere at 60 launches per year. Since these calculations were made, the accepted rate constant for the reaction between hydroperoxyl and nitric oxide to yield hydroxyl and nitrogen dioxide, HO2 + NO yields OH + NO2, was revised upward by more than an order of magnitude, with a resultant increase in the predicted ozone reduction for chlorofluoromethanes by a factor of approximately 2. New calculations of the shuttle effect were made with use of the new rate constant data, again by five different modeling groups. The new value of the shuttle effect on the ozone layer was found to be 0.25 percent. The increase resulting from the revised rate constant is considerably less for space shuttle operations than for chlorofluoromethane production, because the new rate constant also increases the calculated rate of downward transport of shuttle exhaust products out of the stratosphere.

Potter, A. E.↗
NASA NTRS1988

Kinetics of the reaction OH + HO2 yields H2O + O2 from 254 to 382 K

The discharge-flow resonance fluorescence technique has been used to determine the absolute rate constant for the reaction OH + HO2 yields H2O + O2 from 254 to 382 K at a total pressure of 1 Torr. Pseudo-=first-order conditions were used with HO2 in large excess over OH. The rate constant was obtained directly from observed decays of OH and measured concentrations of HO2. Since the observed rate constant was found to be very sensitive to small background concentrations of O and H atoms, NO2 was used to remove both atom species from the system. With added NO2 the result at 299 K is (1.1 + or - 0.3) x 10 to the -10th cu cm/molecule where the error limits are one standard deviation and include an estimate of overall experimental uncertainty. The temperature dependence expressed in Arrhenius form is (4.8 + or - 0.8) x 10 to the -11th exp (250 + or - 50)/T. The results are independent of the type of reactor surface and the precursor used to produce OH and HO2. The present results agree well with earlier measurements near 1-atm total pressure and suggest that this rate constant exhibits little or no pressure dependence between 1 and 1000 Torr.

Keyser, Leon F.↗
NASA NTRS1977

Absolute rate of the reaction of Cl/2P/ with methane from 200-500 K

Rate constants for the reaction Cl + CH4 yields HCl + CH3 were measured in the range 200-500 K by the plot flash photolysis-resonance fluorescence technique. An Arrhenius plot of the mean rate constant observed at 14 equally spaced temperatures is best fit by the expression k = 5.44 times 10 to the minus 19th times T to the exponent 2.50 times exp(-608/T) cu cm per molecule per sec. Appropriate expressions are also given for the rate constant in the two ranges 200-299 K and 299-500 K. These results are compared with a number of other existing determinations of the rate constant by other methods and in different temperature ranges. Most discrepancies are attributed to the nonlinear Arrhenius behavior.

Whytock, D. A.↗
NASA NTRS1980

Temperature dependence of the reaction O/3P/ + OH/2 Pi/ yields O2 + H

Measurements of the absolute rate and temperature dependence of the rate constant for the reaction of ground state atomic oxygen with hydroxyl radicals to yield molecular oxygen and hydrogen atoms over the temperature range 211-499 K are presented. The reaction was monitored in a low-pressure discharge flow resonance fluorescence apparatus under pseudo-first-order conditions in which the oxygen concentration was greater than the hydroxyl concentration. An expression for the temperature dependence of the rate constant is derived from a least-squares fit to the observed bimolecular rate constants, which were found to range from 3.21 to 2.77 x 10 to the -11th cu cm/molecule per sec for temperatures from 211 to 499 K, indicative of a slight negative temperature dependence. Results are compared with those of previous workers, and the significance of the lower value of the rate constant obtained in the present study to models of HO(x) in the upper stratosphere is indicated.

Lewis, R. S.↗
NASA NTRS1974

Nonequilibrium boundary layer at a stagnation point for a hydrogen-helium stream over ablating graphite

The nonequilibrium axisymmetric stagnation point boundary layer over an ablating graphite surface is considered. The external stream is a high temperature mixture of hydrogen and helium. Variable thermodynamic and transport properties are assumed. Lennard-Jones potential model is used to calculate the transport coefficients of each species. Although the mixture rules for viscosity of the gas mixture are used, the weighting functions are more sophisticated than those commonly employed. For the conductivity of the mixture, generalized Wassiljewa coefficients are used. Seven species with 28 dissociation/recombination reactions are considered. Hansen's model for the dissociation rate constants is employed. The recombination rate constants are obtained by invoking detailed balance principles assisted by the JANAF thermodynamic data and the Hansen-Pearson thermodynamic data for C3.

Liu, T.-M.↗
NASA NTRS1980

Laser flash photolysis of ozone - O/1D/ quantum yields in the fall-off region 297-325 nm

The wavelength dependence of the quantum yield for O(1D) production from ozone photolysis has been determined between 297.5 nm and 325 nm in order to resolve serious discrepancies among previous studies. The results of this investigation are compared to earlier work by calculating atmospheric production rate constants for O(1D). It is found that for the purpose of calculating this rate constant, there is now good agreement among three studies at 298 K. Furthermore, it appears that previous data on the temperature dependence of the O(1D) quantum yield fall-off is adequate for determining the vertical profile of the O(1D) production rate constant. Several experimental difficulties associated with using NO2(asterisk) chemiluminescence to monitor O(1D) have been identified.

Brock, J. C.↗
NASA NTRS1979

Heterogeneous atmospheric reactions - Sulfuric acid aerosols as tropospheric sinks

The reaction probabilities of various atmospheric species incident on a bulk sulfuric acid surface are measured in order to determine the role of sulfuric acid aerosols as pollutant sinks. Reaction products and unreacted starting materials leaving a Knudsen cell flow reactor after collision at 300 K with a H2SO4 surface or a soot surface were detected by mass spectrometry. Significant collision reaction probabilities are observed on a H2SO4 surface for H2O2, HNO3, HO2NO2, ClONO2, N2O5, H2O and NH3, and on soot for NH3. Estimates of the contribution of heterogeneous reactions to pollutant removal under atmospheric conditions indicate that while aerosol removal in the stratosphere is insignificant (loss rate constants approximately 10 to the -10th/sec), heterogeneous reactions may be the dominant loss process for several tropospheric species (loss rate constant approximately 10 to the -5th/sec, comparable to photolysis rate constants).

Baldwin, A. C.↗
NASA NTRS1981

Analysis of the tensile stress-strain behavior of elastomers at constant strain rates. I - Criteria for separability of the time and strain effects

A theoretical analysis of the tensile stress-strain relation of elastomers at constant strain rate is presented which shows that the time and the stress effect are separable if the experimental time scale coincides with a segment of the relaxation modulus that can be described by a single power law. It is also shown that time-strain separability is valid if the strain function is linearly proportional to the Cauchy strain, and that when time-strain separability holds, two strain-dependent quantities can be obtained experimentally. In the case where time and strain effect are not separable, superposition can be achieved only by using temperature and strain-dependent shift factors.

Hong, S. D.↗
NASA NTRS1972

Transport phenomena of reactive fluid flow in heterogeneous combustion processes.

A previously developed computer program was used to model two transient hybrid combustion processes involving tubes of solid Plexiglas. In the first study, representing combustion of a hybrid rocket, the oxidizing gas was oxygen, and calculations were continued sufficiently long to obtain steady-state values. Systematic variations were made in reaction rate constant, mass flow rate, and pressure, alternatively using constant and temperature dependent regression rate models for the fuel surface. Consistent results were obtained, as is evidenced by the values for the mass function of the reaction product and the flame temperature, for which plots are supplied. In the second study, fire initiation in a duct was studied, with an air mixture as the oxidizing gas. It was demonstrated that a satisfactory flame spread mechanism could be reproduced on the computer. In both of the above applications, the general, transient, two-dimensional conservation equations were represented, together with chemical reactions, solid-fuel interface conditions, and heat conduction in the solid fuel.

Hung, W. S. Y.↗
NASA NTRS2002

Quantal Study of the Exchange Reaction for N + N2 using an ab initio Potential Energy Surface

The N + N2 exchange rate is calculated using a time-dependent quantum dynamics method on a newly determined ab initio potential energy surface (PES) for the ground A" state. This ab initio PES shows a double barrier feature in the interaction region with the barrier height at 47.2 kcal/mol, and a shallow well between these two barriers, with the minimum at 43.7 kcal/mol. A quantum dynamics wave packet calculation has been carried out using the fitted PES to compute the cumulative reaction probability for the exchange reaction of N + N2(J=O). The J - K shift method is then employed to obtain the rate constant for this reaction. The calculated rate constant is compared with experimental data and a recent quasi-classical calculation using a LEPS PES. Significant differences are found between the present and quasiclassical results. The present rate calculation is the first accurate 3D quantal dynamics study for N + N2 reaction system and the ab initio PES reported here is the first such surface for N3.

Wang, Dunyou↗
NASA NTRS2003

Estimation and Simulation of Slow Crack Growth Parameters from Constant Stress Rate Data

Closed form, approximate functions for estimating the variances and degrees-of-freedom associated with the slow crack growth parameters n, D, B, and A(sup *) as measured using constant stress rate ('dynamic fatigue') testing were derived by using propagation of errors. Estimates made with the resulting functions and slow crack growth data for a sapphire window were compared to the results of Monte Carlo simulations. The functions for estimation of the variances of the parameters were derived both with and without logarithmic transformation of the initial slow crack growth equations. The transformation was performed to make the functions both more linear and more normal. Comparison of the Monte Carlo results and the closed form expressions derived with propagation of errors indicated that linearization is not required for good estimates of the variances of parameters n and D by the propagation of errors method. However, good estimates variances of the parameters B and A(sup *) could only be made when the starting slow crack growth equation was transformed and the coefficients of variation of the input parameters were not too large. This was partially a result of the skewered distributions of B and A(sup *). Parametric variation of the input parameters was used to determine an acceptable range for using closed form approximate equations derived from propagation of errors.

Salem, Jonathan A.↗
NASA NTRS1982

Radiative lifetimes and quenching rate coefficients for directly excited rotational levels of OH/A 2Sigma +, v-prime = 0/

A narrow-bandwidth pulsed dye laser was used to excite OH X 2Pi i radicals to the A 2Sigma(+) state by pumping in the (0, 0) vibrational band around 308 nm. The radiative lifetimes of specific (K-prime, J-prime) rotational levels in v-prime = 0 were measured at low pressures (not greater than 1 mtorr), which yielded a mean lifetime of 0.71 + or - 0.009 microsec (2 sigma). Electronic quenching rate constants for N2, O2, H2O, and H2 were measured for a range of initially excited rotational levels. A strong dependence of this rate constant on the initially excited rotational level was found for N2, and less markedly for O2, with the rate constant tending to increase for the lowest rotational levels K-prime not greater than 3. The implications of these results for the laser-induced fluorescence detection of atmospheric OH are discussed.

Mcdermid, I. S.↗
NASA NTRS1983

Homogeneous processes of atmospheric interest

Upper atmospheric research programs in the department of chemical kinetics are reported. Topics discussed include: (1) third-order rate constants of atmospheric importance; (2) a computational study of the HO2 + HO2 and DO2 + DO2 reactions; (3) measurement and estimation of rate constants for modeling reactive systems; (4) kinetics and thermodynamics of ion-molecule association reactions; (5) entropy barriers in ion-molecule reactions; (6) reaction rate constant for OH + HOONO2 yields products over the temperature range 246 to 324 K; (7) very low-pressure photolysis of tert-bytyl nitrite at 248 nm; (8) summary of preliminary data for the photolysis of C1ONO2 and N2O5 at 285 nm; and (9) heterogeneous reaction of N2O5 and H2O.

Rossi, M. J.↗
NASA NTRS2002

Slow Crack Growth of Brittle Materials With Exponential Crack-Velocity Formulation: Constant Stress Rate Experiments - Part 2

The previously determined life prediction analysis based on an exponential crack-velocity formulation was examined using a variety of experimental data on glass and advanced structural ceramics in constant stress rate and preload testing at ambient and elevated temperatures. The data fit to the relation of strength versus the log of the stress rate was very reasonable for most of the materials. Also, the preloading technique was determined equally applicable to the case of slow-crack-growth (SCG) parameter n greater than 30 for both the power-law and exponential formulations. The major limitation in the exponential crack-velocity formulation, however, was that the inert strength of a material must be known a priori to evaluate the important SCG parameter n, a significant drawback as compared with the conventional power-law crack-velocity formulation.

Choi, Sung R.↗