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At least 199 records · Page 11

Chemical kinetic analysis of hydrogen-air ignition and reaction times

An anaytical study of hydrogen air kinetics was performed. Calculations were made over a range of pressure from 0.2 to 4.0 atm, temperatures from 850 to 2000 K, and mixture equivalence ratios from 0.2 to 2.0. The finite rate chemistry model included 60 reactions in 20 species of the H2-O2-N2 system. The calculations also included an assessment of how small amounts of the chemicals H2O, NOx, H2O2, and O3 in the initial mixture affect ignition and reaction times, and how the variation of the third body efficiency of H2O relative of N2 in certain key reactions may affect reaction time. The results indicate that for mixture equivalence ratios between 0.5 and 1.7, ignition times are nearly constant; however, the presence of H2O and NO can have significant effects on ignition times, depending on the mixture temperature. Reaction time is dominantly influenced by pressure but is nearly independent of initial temperature, equivalence ratio, and the addition of chemicals. Effects of kinetics on reaction at supersonic combustor conditions are discussed.

Rogers, R. C.↗

Tropospheric chemistry - A global perspective

Processes that affect the concentration of tropospheric OH are considered, taking into account linkages between the chemistry of OH and the chemistry of H, HO2, and H2O2. A review is presented of observational data of special relevance to OH, notably the distributions of CO, CH4, O3, H2O, HNO3, NO, and NO2. Most of the results presented in connection with the description of the model were obtained by solving time-dependent continuity equations. Rates for photolytic processes were allowed to vary diurnally with insolation. It is found that a well-calibrated and reliable model for OH places important constraints on global budgets for a variety of gases including CH4, H2, and CH3Cl in addition to CO. Accurate measurements of species such as CH3CCl3 can provide valuable checks on global models that must integrate over a variety of atmospheric conditions. However, emission rates for the relevant gases must be adequately quantified.

Logan, J. A.↗

Infrared absorption by OH containing compounds

The spectroscopy of the species H2O, H2O2, and HO2 are discussed. Their vibration rotation transitions are emphasized, but the pure rotational transitions in the vibrational ground state of H2O are also considered since they contribute to opacity in the middle infrared region.

Hillman, J. J.↗

Stratospheric eddy diffusion coefficients from tracer data

Global distributions of nitrous oxide, methane, ozone, and carbon 14 are used to estimate four sets of stratospheric eddy diffusion coefficients. A photochemical equilibrium model calculates O(3P), O(1D), H, HO2, OH, H2O2, NO, and NO2 densities, as a function of altitude, latitude, and time. The calculated O(1D), OH, and observed Cl densities are used to obtain the eddy profiles associated with the methane and nitrous oxide distributions, for altitudes between 10 and 40 km. Application of a constant flux condition to the seasonally averaged ozone data yields eddy values below 20 km. Time-dependent carbon 14 calculations produce eddy coefficients between 13 and 27 km. A composite profile is obtained by comparing the four sets of coefficients. Further, carbon 14 computations are used to test these profiles as well as those recommended in reports issued by the National Academy of Sciences in 1976 and 1979. The composite eddy profile produces the best agreement.

Massie, S. T.↗

A statistical analysis of simulated data from potential stratospheric satellite missions

A simplified one-dimensional model is used to analyze simulated data from typical proposed satellite measurements of trace species in the stratosphere. Uncertainties are introduced in simulated species concentration measurements and applied to the basic physical and chemical model data. The results of the calculations are then used to predict uncertainties in the species concentrations computed by the model. Candidate satellite missions can be evaluated for net information acquired by applying the error analysis. An abbreviated depiction of the computational procedure is given, and sample histograms based on an accumulation of 200 calculations are shown for H2O2 and ClNO3, demonstrating that emergent species distributions are roughly Gaussian in the logarithm of number density. Calculated vertical concentration profiles for these two species are presented.

Nealy, J. E.↗

Clouds and wet removal as causes of variability in the trace-gas composition of the marine troposphere

A modeling study of the effects of clouds and wet removal on the chemistry of the remote marine troposphere is described. Using a time-dependent model with parameterized vertical transport to calculate trace-gas concentrations, it is found that large variations in key species (e.g., HNO3, H2CO, and H2O2) result from simulations of sporadic rainfall, changes in cloud cover, and external inputs such as surface NO sources. Depending on the frequency and intensity of an event, the effects of these perturbations may persist for several days, thereby invalidating assumptions of photochemical equilibrium in the interpretation of measurements. Long-term integrations with fixed boundary conditions and regularly occurring cloud and rain episodes demonstrate a strong sensitivity of the mean concentration of longer-lived soluble gases to precipitation frequency but also confirm the validity of using properly chosen parameterizations of wet removal in steady state calculations.

Thompson, A. M.↗

Preliminary submillimeter spectroscopic measurements using a submillimeter heterodyne radiometer

A submillimeter heterodyne radiometer uses a submillimeter laser, pumped by a CO2 laser, as a local oscillator and a room temperature Schottky barrier diode as the first IF mixer. The radiometer can resolve spectral lines in the submillimeter region of the spectrum (arising from pure rotational molecular transitions) to within 0.3 MHz, using acousto-optic spectrum analyzer which measures the power spectrum by simultaneously sampling 0.3 MHz wide channels over a 100 MHz bandwidth spanning the line. Preliminary observations of eight spectral lines of H2O2, CO, NH3 and H2O, all lying in the 434-524 micrometer wavelength range are described. All eight lines were observed using two local oscillator frequencies obtained by operating the submillimeter laser with either methyl fluoride (CH3F) or formic acid (HCOOH) as the lasing gas. Sample calculations of line parameters from the observed data show good agreement with established values. One development goal is the size and weight reduction of the package to make it suitable for balloon or shuttle experiments to detect trace gases in the upper atmosphere.

Safren, H. G.↗

Model calculations of the molecular composition of interstellar grain mantles

A chemical reaction scheme comprising gas phase as well as grain surface reactions is used for the numerical calculation of the chemical composition of mantles accreting on interstellar grains. The composition of the growing grain mantle is determined on the basis of the relative accretion rates of the gas phase molecules and diffusion-controlled surface reactions. Results show that grain mantles generally consist of the molecules H2O, H2CO, N2, O2, CO, CO2, H2O2, and NH3. A detailed examination of the formation of H2 on grain surfaces leads to the conclusion that it proceeds through hydrogen abstraction from such molecules as H2CO, H2S, N2H2, and N2H4. The IR characteristics of the calculated grain mantles are discussed with emphasis on the observed ice band at the 3250/cm wavelength.

Tielens, A. G. G. M.↗

Oxidative peptide /and amide/ formation from Schiff base complexes

One hypothesis of the origin of pre-modern forms of life is that the original replicating molecules were specific polypeptides which acted as templates for the assembly of poly-Schiff bases complementary to the template, and that these polymers were then oxidized to peptide linkages, probably by photo-produced oxidants. A double cycle of such anti-parallel complementary replication would yield the original peptide polymer. If this model were valid, the Schiff base between an N-acyl alpha mino aldehyde and an amino acid should yield a dipeptide in aqueous solution in the presence of an appropriate oxidant. In the present study it is shown that the substituted dipeptide, N-acetyl-tyrosyl-tyrosine, is produced in high yield in aqueous solution at pH 9 through the action of H2O2 on the Schiff-base complex between N-acetyl-tyrosinal and tyrosine and that a great variety of N-acyl amino acids are formed from amino acids and aliphatic aldehydes under similar conditions.

Strehler, B. L.↗

Pulsed laser photolysis study of the reaction between O(3P) and HO2

It is pointed out that bimolecular reactions involving two free radicals are of great interest because both reactants have unpaired electrons and hence could interact at distances longer than those typical of radical-molecule encounters. A method based on laser photolysis is being developed to produce selectively free radicals in the homogeneous gas phase. This is to be done in such a way as to isolate the reaction of interest and subsequently follow the course of the reaction using spectroscopic techniques. The present investigation is concerned with a study in which the rate coefficient for the reaction of O(3P) with HO2, has been measured at N2 pressures ranging from 10 to 500 torr, taking into account the reaction O(3P)+HO2 yields OH-O2. In the described study, O(3P) and HO2 were produced by cophotolysis of O3 and H2O2 in N2 at 248.5 nm using a KrF excimer laser.

Ravishankara, A. R.↗

The composition of interstellar grain mantles

The molecular composition of interstellar grain mantles employing gas phase as well as grain surface reactions is studied. The calculated mixtures consist mainly of the molecules H2O, H2CO, N2, CO, O2, CO2, H2O2, NH3, and their deuterated counterparts in varying ratios. The exact compositions depend strongly on the physical conditions in the gas phase. The calculated mixtures are compared to the observations by using laboratory spectra of grain mantle analogs. The two are in reasonable agreement except for the strength of the 6.8-micrometers band. A possible solution for this discrepancy is discussed. Finally, future observations are suggested which may shed further light on the composition of interstellar grain mantles.

Tielens, Alexander G. G. M.↗

The composition of interstellar grain mantles

The molecular composition of interstellar grain mantles was calculated employing gas phase and grain surface reactions. The calculated mixtures consist mainly of H2O, H2CO, N2, CO, O2, CO2, H2O2, NH3, and their deuterated counterparts in varying ratios. The exact compositions depend strongly on the physical conditions in the gas phase. The calculated mixtures were compared to the observations by using laboratory spectra of grain mantle analogs. The two agree reasonably except for the strength of the 6.8 micron band.

Tielens, Alexander G. G. M.↗

Passive microwave remote sensing of the atmosphere from satellites

Present and future satellite atmospheric sounding is discussed. Although present systems sound principally the temperature profile and the water vapor and precipitation abundances over ocean, future systems will measure other constituents such as O3, H2O2, and ClO, and will provide improved spatial resolution, retrieval accuracy, and altitude coverage for temperature and humidity. Present systems with only a few channels will be replaced by systems with 20 or more, and larger antennas with more sensitive radiometers will permit horizontal resolutions of 15 to 50 km or less, even from geosynchronous orbit. The success of imaging microwave spectrometers in penetrating clouds and in yielding uniquely accurate measurements ensure a growing role in operational and research systems for these remote sensing techniques.

Staelin, D. H.↗

Electrode kinetics of oxygen reduction - A theoretical and experimental analysis of the rotating ring-disc electrode method

In order to calculate most of the rate constants for the intermediate formation of H2O2 in the electroreduction of O2 to H2O, the theoretical treatments of the rotating ring-disc electrode method by Damjanovic et al. (1966, 1967), Bagotskii et al. (1968, 1969), and Wroblowa et al. (1976) are modified. Rotating ring-disc electrode experimental data obtained for O2 reduction in Pt in 0.55 M H2SO4 are used to illustrate the calculations of rate constants according to the above theoretical treatments. A simple reaction model as proposed by the first author is consistent with the experimental data. The results indicate that O2 (97 percent) reduces to H2O in a direct four-electron transfer reaction. The adsorption of O2 is probably the rate-determining step in the potential region more negative than 0.5 V vs. reversible hydrogen electrode.

Hsueh, K.-L.↗

Surface analysis of grapite fiber reinforced polyimide composites. I

The results of experimental analyses of the effects of pretreatment on bonding between composite materials are reported. The materials comprised graphite fibers in a polyimide matrix. The surfaces were bonded as-received or subjected to grit blasting, bead blasting, hand sanding, washes with ethanolic KOH, NH2NH2-H2O or H2SO4 + 0.30 H2O2 or flashblasting. SEM and X-ray photoelectron spectroscopy revealed fluorine contents in the as-received samples. Contact angles were determined by means of five different liquids with various surface tensions. The flashblast technique removed all fluorine from the samples. Low critical surface tensions were found in the composite surfaces with high fluorine concentrations. The surface scanning techniques are concluded to be useful for studying factors influencing the strength and durability of adhesively bonded composites.

Messick, D. L.↗

Photodissociation rates of molecules by the interstellar radiation field

The photodissociation rates of CO, NO, H2O, HCN, NO2, SO2, CS2, OCS, NH3, CH4, H2O2, and C2H2 dissociated by the interstellar ultraviolet background in the solar neighborhood are calculated for the 106-200 nm wavelength region. The processes for photodissociation of various interstellar molecules into fragments are discussed.

Lee, L. C.↗

Assessment of Techniques for Measuring Tropospheric H Sub x O Sub y

In its continuing efforts to direct its applications programs towards relevant national needs, NASA is conducting the Tropospheric Chemistry Program, the long-range objective of which is to apply NASA's space technology to assess and predict human impact on the troposphere, particularly on the regional to global scale. One area of required research is instrumentation development, which is aimed at improving the capability to measure important trace gases and aerosols which are key species in the major atmospheric biogeochemical cycles. To focus on specific needs, the Instrumentation Worksphop for H(x)O(y) Tropospheric Species was conducted in August 1982. The workshop discussed current measurement needs and instrument capabilities for H(x)O(y) species, including OH, HO2, and H2O2. The workshop activities and conclusions are documented.

Hoell, J. M.↗

Effects of high CO2 levels on surface temperature and atmospheric oxidation state of the early earth

One-dimensional radiative and photochemical models are used to determine how much CO2 must have been present to maintain a temperate early climate and to examine the consequences that are implied for the controls on atmospheric oxidation state. It is shown that CO2 concentrations of the order of 1000 PAL are required to keep the average surface temperature close to the present value, if albedo changes and heating by reduced greenhouse gases were relatively unimportant. The oxidation state of such a high-CO2, prebiotic atmosphere should have been largely determined by the balance between the H2O2 rainout rate and the rate at which hydrogen escaped to space, with only a weak dependence on the volcanic outgassing rate or on other speculative sources of H2. The implied upper limit on the ground-level O2 mixing ratio is approximately 10 to the -11th and is subject to less uncertainty than the results of previous models.

Kasting, J. F.↗