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At least 847 records · Page 47
All sourcesNASA NTRSDOE OSTI
NASA NTRS1979

Rate constants for the reactions of OH with ClO, Cl2, and Cl2O at 298K

Recent concern about the depletion of stratospheric ozone by chlorine species from the decomposition of chlorofluoromethanes has emphasized the need for laboratory studies of the first reaction steps involved, especially those which control the concentration of the OH and ClO radicals in the stratosphere. Rate constants for the reactions of OH with ClO, Cl2, and Cl2O at 298 K have been determined in a discharge flow system using resonance fluoresence detection. The results are (9.1 + or - 1.3) x 10 to the -12th, (5.5 + or - 0.3) x 10 to the -14th, and (6.5 + or - 0.5) x 10 to the -12th (all in units of cu cm/sec), respectively.

Leu, M. T.↗
NASA NTRS1977

The rate constant for the reaction of O/3P/ atoms with ClONO2

Experiments were conducted in a conventional fast flow apparatus to study the rate constant and the activation energy for the reaction O(3P) + ClONO2. The air-afterglow technique was used for the detection of oxygen atoms under pseudo first order conditions. A value of (3.4 plus or minus 0.6) x 10 to the -12th exp/(-840 plus or minus 60)T/cu cm/molecule/s was obtained for the rate constant. The observed rate is sufficiently slow so that oxygen atom attack is of minor importance in the stratosphere compared to photolysis.

Molina, L. T.↗
NASA NTRS2004

The Rate Constant for the Reaction H + C2H5 at T = 295 - 150K

The reaction between the hydrogen atom and the ethyl (C2H3) radical is predicted by photochemical modeling to be the most important loss process for C2H5 radicals in the atmospheres of Jupiter and Saturn. This reaction is also one of the major sources for the methyl radicals in these atmospheres. These two simplest hydrocarbon radicals are the initial species for the synthesis of larger hydrocarbons. Previous measurements of the rate constant for the H + C2H5 reaction varied by a factor of five at room temperature, and some studies showed a dependence upon temperature while others showed no such dependence. In addition, the previous studies were at higher temperatures and generally higher pressures than that needed for use in planetary atmospheric models. The rate constant for the reaction H + C2H5 has been measured directly at T = 150, 202 and 295 K and at P = 1.0 Torr He for all temperatures and additionally at P = 0.5 and 2.0 Torr He at T = 202 K. The measurements were performed in a discharge - fast flow system. The decay of the C2H5 radical in the presence of excess hydrogen was monitored by low-energy electron impact mass spectrometry under pseudo-first order conditions. H atoms and C2H5 radicals were generated rapidly and simultaneously by the reaction of fluorine atoms with H2 and C2H6, respectively. The total rate constant was found to be temperature and pressure independent. The measured total rate constant at each temperature are: k(sub 1)(295K) = (1.02+/-0.24)x10(exp -10), k(sub 1)(202K) = (1.02+/-0.22)x10(exp -10) and k(sub 1)(150K) = (0.93+/-0.21)x10(exp -10), all in units of cu cm/molecule/s. The total rate constant derived from all the combined measurements is k(sub 1) = (l.03+/-0.17)x10(exp -10) cu cm/molecule/s. At room temperature our results are about a factor of two higher than the recommended rate constant and a factor of three lower than the most recently published study.

Pimentel, Andre S.↗
NASA NTRS1995

Rate constants and temperature dependences for the reactions of hydroxyl radical with several halogenated methanes, ethanes, and propanes by relative rate measurements

Rate constants of 15 OH reactions with halogen-substituted alkanes, C1 to C3, were studied using a relative rate technique in the temperature range 283-403 K. Compounds studied were CHF2Cl (22), CHF2Br (22B), CH3F (41), CH2F2 (32), CHF3 (23), CHClFCCl2F (122a), CHCl2CF3 (123), CHClFCF3 (124), CH3CF3 (143a), CH3CH2F (161), CF3CHFCF3 (227ea), CF3CH2CF3 (236fa), CF3CHFCHF2 (236ea), and CHF2CF2CH2F (245ca). Using CH4, CH3CCl3, CF3CF2H, and C2H6 as primary reference standards (JPL 92-20 rate constants), absolute rate constants are derived. Results are in good agreement with previous experimental results for six of the compounds studied, including CHF2Cl, CHF2Br, CH2F2, CH3CF3, CHFClCFCl2, and CF3CHFCF3. For the remainder the relative rate constants are lower than those derived from experiments in which OH loss was used to measure the reaction rate. Comparisons of the derived Arrhenius A factors with previous literature transition-state calculations show order of magnitude agreement in most cases. However, the experimental A factors show a much closer proportionality to the number of H atoms in the molecule than is evident from the transition state calculations. For most of the compounds studied, an A factor of (8 +/- 3)E-13 cm(exp 3)/(molecule s) per C-H bond is observed. A new measurement of the ratio k(CH3CCl3)/k(CH4) is reported that is in good agreement with previous data.

Hsu, K.-J.↗
NASA NTRS1984

The reactions of cobalt, iron and nickel in SO-2 atmospheres: Similarities and differences

The reactions of cobalt, iron and nickel in SO2 atmospheres are reviewed and compared. A mixed oxide-sulfide product layer is observed in all cases. Cobalt and nickel exhibits similar behavior. The observed rates are near the sulfidation rates, and the reaction rate is strongly influenced by the outward diffusion of metal through an interconnected sulfide network. A continuous interconnected sulfide is not observed in the oxide-sulfide scales formed on iron, and the reaction rates are more difficult to summarize. The differences and similarities among the three metals are explained in terms of the absence of scale-gas equilibrium and the ratio of the metal diffusivity in the corresponding oxide and sulfide.

Jacobson, N. S.↗
NASA NTRS1985

The reactions of cobalt, iron and nickel in SO2 atmospheres Similarities and differences

The reactions of cobalt, iron and nickel in SO2 atmospheres are reviewed and compared. A mixed oxide-sulfide product layer is observed in all cases. Cobalt and nickel exhibit similar behavior. The observed rates are near the sulfidation rates, and the reaction rate is strongly influenced by the outward diffusion of metal through an interconnected sulfide network. A continuous interconnected sulfide is not observed in the oxide-sulfide scales formed on iron, and the reaction rates are more difficult to summarize. The differences and similarities among the three metals are explained in terms of the absence of scale-gas equilibrium and the ratio of the metal diffusivity in the corresponding oxide and sulfide.

Jacobson, N. S.↗
NASA NTRS1993

Rate constants for the reactions of OH with HFC-134a (CF3CH2F) and HFC-134 (CHF2CHF2)

Measurements of rate constants for HFC-134 (CF2HCF2H) relative to CH3CCl3, HFC-125, and HFC-134a are reported. The measurements were made in a slow-flow, temperature controlled photochemical reactor, and were based on relative rates of disappearance of the parent compounds as measured by FTIR spectroscopy. Hydroxyl radicals were generated by 254-nm photolysis of O3 in the presence of water vapor. NASA/JPL rate constants for the reference compounds are used to derive temperature-dependent rate constants of both compounds. Rate constants obtained from the different reference compounds are in excellent agreement. The presently recommended rate constant for HFC-134a is about 25 percent too high.

Demore, W. B.↗
NASA NTRS1972

The Bosch process.

Many previous studies have been carried out to elucidate certain aspects of the Bosch process wherein CO2 is reacted over an iron catalyst to form carbon and water at temperatures around 1100 F. These results are assembled, and with the aid of new experimental data, are used to analyze the various reactions involved. It is shown that CO2 and H2 will not usually react to deposit carbon unless water is removed in a recycle loop. The critical importance of large catalyst areas is stressed relative to catalyst pretreatment processes. It is shown that in most operating Bosch reactions, mass transfer controls the rate of reaction, and it is suggested that the carbon filaments found are the expected result of such a rate limiting process. Typical recycle gas mixtures are considered, and maximum water yields are determined from various cases. A few suggestions are made to improve Bosch reaction performance, and a number of unresolved problems are noted.

Meissner, H. P.↗
NASA NTRS1987

Clustering reactions of H2CN(+) ions with HCN

The rate coefficients for the first and second steps in the clustering sequence of H2CN(+) ions with HCN, H2CN(+) + HCN + M - H2CN(+) (HCN) + M and H2CN(+) (HCN) + HCN + M - H2CN(+) (HCN)2 + M, have been measured at temperatures from 189 to 296 K for M = He. The three-body association rate coefficients for both reactions are least-squares fitted for a power dependence on gas temperature. The temperature dependences of the three-body association reaction rate coefficients fitted in the range 200 to 300 K are given. The absolute values and temperature dependences are rather similar.

Chatterjee, B. K.↗
NASA NTRS1991

Calculations on the rate of the ion-molecule reaction between NH3(+) and H2

The rate coefficient for the ion-molecule reaction NH3(+) + H2 yields NH4(+) + H has been calculated as a function of temperature with the use of the statistical phase space approach. The potential surface and reaction complex and transition state parameters used in the calculation have been taken from ab initio quantum chemical calculations. The calculated rate coefficient has been found to mimic the unusual temperature dependence measured in the laboratory, in which the rate coefficient decreases with decreasing temperature until 50-100 K and then increases at still lower temperatures. Quantitative agreement between experimental and theoretical rate coefficients is satisfactory given the uncertainties in the ab initio results and in the dynamics calculations. The rate coefficient for the unusual three-body process NH3(+) + H2 + He yields NH4(+) + H + He has also been calculated as a function of temperature and the result found to agree well with a previous laboratory determination.

Herbst, Eric↗
NASA NTRS1992

Radiation safety in aircraft operations

Data from a 7-yr flight experiment program to measure the significant biological components (tissue ionization rates, neutron flux, and nuclear reaction star rates) as a function of solar cycle, altitude, latitude and longitude from which biological risk from radiation is estimated are used to evaluate radiation dose and dose equivalents along specific flight trajectories. The data base used and the corresponding time-dependent global model are described. Ionization rates in air measured by argon filled chambers at solar minimum and maximum, and radiation measurements of the Brookhaven National Laboratory instrument compared to the present model are illustrated in tabular form. The global pressure distribution for solstice conditions at 14 km is shown.

Wilson, J. W.↗
NASA NTRS1996

Investigation of shock-induced combustion past blunt projectiles

A numerical study is conducted to simulate shock-induced combustion in premixed hydrogen-air mixtures at various free-stream conditions and parameters. Two-dimensional axisymmetric, reacting viscous flow over blunt projectiles is computed to study shock-induced combustion at Mach 5.11 and Mach 6.46 in hydrogen-air mixture. A seven-species, seven reactions finite rate hydrogen-air chemical reaction mechanism is used combined with a finite-difference, shock-fitting method to solve the complete set of Navier-Stokes and species conservation equations. The study has allowed an improved understanding of the physics of shock-induced combustion over blunt projectiles and the numerical results can now be explained more readily with one-dimensional wave-interaction model.

Ahuja, J. K.↗
NASA NTRS1978

Upper bound and probable value of the rate constant of the reaction OH + HO2 yields H2O + O2

Discharge-flow experiments at 295 K of the OH + HO2 reaction are described in which excess O3 is added to OH through a movable injector; OH concentration is measured downstream by resonance fluorescence with and without addition of excess NO just upstream of the detector so that both OH concentration and OH concentration + HO2 concentration are determined independently. The data are compared with a computer model involving 12 reaction steps. A simple sensitivity analysis is carried out to establish how errors in the other 'known' rate constants affect the data fit. Best agreement is obtained between computer calculations and experiments when k1 for the OH + HO2 reaction is in the range 2-3 x 10 to the -11th cu cm/s. Values above about 5 x 10 to the -11th are very unlikely whereas those below about 1 x 10 to the -11th are less strongly excluded.

Chang, J. S.↗
NASA NTRS1997

Isolation of novel ribozymes that ligate AMP-activated RNA substrates

BACKGROUND: The protein enzymes RNA ligase and DNA ligase catalyze the ligation of nucleic acids via an adenosine-5'-5'-pyrophosphate 'capped' RNA or DNA intermediate. The activation of nucleic acid substrates by adenosine 5'-monophosphate (AMP) may be a vestige of 'RNA world' catalysis. AMP-activated ligation seems ideally suited for catalysis by ribozymes (RNA enzymes), because an RNA motif capable of tightly and specifically binding AMP has previously been isolated. RESULTS: We used in vitro selection and directed evolution to explore the ability of ribozymes to catalyze the template-directed ligation of AMP-activated RNAs. We subjected a pool of 10(15) RNA molecules, each consisting of long random sequences flanking a mutagenized adenosine triphosphate (ATP) aptamer, to ten rounds of in vitro selection, including three rounds involving mutagenic polymerase chain reaction. Selection was for the ligation of an oligonucleotide to the 5'-capped active pool RNA species. Many different ligase ribozymes were isolated; these ribozymes had rates of reaction up to 0.4 ligations per hour, corresponding to rate accelerations of approximately 5 x10(5) over the templated, but otherwise uncatalyzed, background reaction rate. Three characterized ribozymes catalyzed the formation of 3'-5'-phosphodiester bonds and were highly specific for activation by AMP at the ligation site. CONCLUSIONS: The existence of a new class of ligase ribozymes is consistent with the hypothesis that the unusual mechanism of the biological ligases resulted from a conservation of mechanism during an evolutionary replacement of a primordial ribozyme ligase by a more modern protein enzyme. The newly isolated ligase ribozymes may also provide a starting point for the isolation of ribozymes that catalyze the polymerization of AMP-activated oligonucleotides or mononucleotides, which might have been the prebiotic analogs of nucleoside triphosphates.

NASA Discipline Exobiology↗
NASA NTRS1973

Rate constants for the reactions of hydroxyl and hydroperoxyl radicals with ozone.

Chain decomposition of ozone by hydroxyl and hydroperoxyl radicals has been observed. The rate constant at 300 K for OH + O3 yielding HO2 + O2 is eight times ten to the -14th power cubic centimeters per second. The rate constant for HO2 + O3 yielding OH + 2O2 is three times ten to the -15th power cubic centimeters per second. These results have implications concerning stratospheric ozone.

Demore, W. B.↗
NASA NTRS1987

Analysis of non-premixed turbulent reacting flows

Studies of chemical reactions occurring in turbulent flows are important in the understanding of combustion and other applications. Current numerical methods are limited in their applications due to the numerical resolution required to completely capture all length scales, but, despite the fact that realistic combustion cannot be solved completely, numerical simulations can be used to give insight into the interaction between the processes of turbulence and chemical reaction. The objective was to investigate the effects of turbulent motion on the effects of chemical reaction to gain some insight on the interaction of turbulence, molecular diffusion, and chemical reaction to support modeling efforts. A direct turbulence simulation spectral code was modified to include the effects of chemical reaction and applied to an initial value problem of chemical reaction between non-premixed species. The influence of hydrodynamics on the instantaneous structure of the reaction was investigated. The local scalar dissipation rates and the local reaction rates were examined to determine the influence of vorticity or rate of strain on the reaction and the structure of the scalar field.

Leonard, Andy D.↗