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At least 379 records · Page 21

Kinetics and Thermochemistry of the Br((sup 2)P3/2) + NO2 Association Reaction

A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the Br((sup 2)P3/2) + NO2 association reaction as a function of temperature (259-432 K) pressure (12.5 - 700 Torr), and buffer gas identity (He, Ar, H2, N2, CO2, CF4, SF6). The reaction is found to be in the falloff regime between third and second order over the entire range of conditions investigated. At temperatures below 350 K, the association reaction is found to be irreversible on the time scale of the experiment (approximately 30 ms). At higher temperatures reversible addition is observed, allowing equilibrium constants for BrNO2 formation and dissociation to be determined. Second- and third-law analyses of the equilibrium data are in only fair agreement and lead to the following thermochemical parameters for the association reaction: Delta-H(298) = 19.6 +/- 1.7 kcal/mol, Delta-H(0) = -18.6 +/- 2.0 kcal/mol, Delta-S(298) = 29.3 +/- 4.2 cal/mol/K, Delta-H(sub f)(sub 298)(BrNO2) = 17.0 +/-1.8 kcal/mol(uncertainties are 2 sigma estimates of absolute accuracy). The value for Delta-H(0) determined in this study has been employed to calculate k(sub 0)(sup SC), the low-pressure third-order rate coefficient in the strong collision limit, by using the method of Troe; calculated values of k(sub 0)(sup SC) are inconsistent with experimental results unless Delta-H(0) is assigned a value near the lower limit derived from analysis of the high-temperature approach to equilibrium data, i.e. delta-H(0) approximately equals -16.6 kcal/mol. A potential source of systematic error in the calculation of both k(sub 0)(sup SC) and the absolute entropy of BrNO2 results from the complete lack of knowledge of the energies and degeneracies of the electronic states of BrNO3. The procedure developed by Troe and co-workers has been employed to extrapolate experimental falloff curves to the low- and high-pressure limits. Derived values for k(sub 0)(M,298K) in units of 10(exp -31) cm(exp 6)/sq molecule/s range from 2.75 for M = He to 6.54 for M = CO2; 2 sigma uncertainties are estimated to be +/- 20%. Values for k(sub 0)(N2,T) in units of 10(exp -31) cm(exp 6)/sq molecule/s are 5.73 at 259 K, 4.61 at 298 K, and 3.21 at 346 K; the observed temperature dependence for k(sub 0)(N2,T) is consistent with the theoretical temperature dependence for Beta(sub c)k(sub 0)(sup SC). Values for k(sub infinity)(T) in units of 10(exp -11) cu cm/molecule/s are 2.86 at 259 K, 3.22 at 298 K, and 3.73 at 346 K; 2 sigma uncertainties are estimated to be a factor of 2. Approximate falloff parameters in a convenient format for atmospheric modeling are also derived.

Kreutter, K. D.↗

O · , H · , and · OH radical etching probability of polystyrene obtained for a radio frequency driven atmospheric pressure plasma jet

Atmospheric pressure plasma jets have great potential for the surface modification of polymers. In this work, the authors report on polystyrene etching by a radio frequency driven atmospheric pressure plasma jet with a focus on the role of H · , O · , and · OH radicals in this process. The absolute flux of H · , O · , and · OH radicals reaching the surface of the polymer was determined by a COMSOL MULTIPHYSICS reacting fluid dynamics model incorporating detailed transport phenomena in the boundary layer near the substrate. The simulated results of H · and · OH densities in the jet effluent were experimentally verified by two-photon absorption laser induced fluorescence and laser induced fluorescence, respectively. The carbon atom removal flux from the polystyrene surface was taken from previously reported measurements using the same plasma source. The authors show that the boundary layer effects in the interfacial region above the substrate can have a significant impact on the calculated etching probabilities. The reaction probability (β) has a significant uncertainty although a variation of 2 orders of magnitude in β leads to uncertainties of approximately 1 order of magnitude variation in the determined etching probability. The etching probability of polystyrene by · OH radicals was confirmed to be at least an order of magnitude larger than the polystyrene etching probability by O · radicals. The authors also confirmed the weak polystyrene etching probability by H · radicals. The model suggests that the presence of a 30 ppm O 2 impurity can lead to the production of · OH radicals in the far effluent of the Ar + 1% H 2 plasma jet close to the substrate at sufficient densities to enable effective etching.

36 MATERIALS SCIENCE↗

Optical Mounts for Cryogenic Beam Splitters

Spring-loaded optical mounts maintain flatness and alinement of rigid, framed, or pellicle beam splitters over wide temperature range, despite differences in thermal expansion amoung materials. Mounts permit optical adjustments at ambient temperature even though optical system operated subsequently within few degrees of absolute zero. Mounts useful as holders for integrated-circuit master patterns, survey targets, vibrating membranes, noise- or pressure-sensing membranes, osmosis filters, and fuel-cell elements.

Rudman, A. A.↗

Rate constant for the reaction of O(3P) with diacetylene from 210 to 423 K

The absolute rate constant for the reaction of O(3P) with diacetylene (C4H2) has been measured as a function of pressure and temperature by the flash-photolysis/resonance-fluorescence method. At 298 K and below, no pressure dependence of the rate constant was observed, but at 423 K a moderate (factor-of-2) increase was detected in the range 3 to 75 torr Ar.Results at or near the high-pressure limit are represented by an Arrhenius expression over the temperature range 210 to 423 K. The results are compared with previous determinations, all of which employed the discharge-flow/mass-spectrometry technique. The mechanism of the reaction is considered, including both primary and secondary processes. The heats of formation of the reactants, adducts, and products for the O(3P) + C4H2 reaction are discussed and contrasted with those for O(3P) + C2H2.

Mitchell, M. B.↗

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.↗

A model-based diagnostic study of the rapid development phase of the Presidents' Day cyclone

A model simulation of the rapid development phaser of the Presidents' Day cyclone on February 19, 1979, is studied. Model trajectories and Eulerian analyses show that, during this phase, three airstreams converge into the cyclogenetic region. The evolution of the PJ-trough system and its associated tropopause fold is described, including the simulated surface low and the vertical profile of mass divergence which contributes to the decreasing sea-level pressure. The various terms of the vorticity equation are evaluated to identify the processes contributing to the increase in absolute vorticity. The nature and origin of airstreams entering the low-level circulation associated with rapid cyclogenesis are examined from a Lagrangian perspective.

Whitaker, Jeffrey S.↗

The trade-off characteristics of acoustic and pressure sensors for the NASP

Results of a trade study for the development of pressure and acoustic sensors for use on the National Aerospace Plane (NASP) are summarized. Pressure sensors are needed to operate to 100 psia; acoustic sensors are needed that can give meaningful information about a 200 dB sound pressure level (SPL) environment. Both sensors will have to operate from a high temperature of 2000 F down to absolute zero. The main conclusions of the study are the following: (1) Diaphragm materials limit minimum size and maximum frequency response attainable. (2) No transduction is available to meet all the NASP requirements with existing technology. (3) Capacitive sensors are large relative to the requirement, have limited resolution and frequency response due to noise, and cable length is limited to approximately 20 feet. (4) Eddy current sensors are large relative to the requirement and have limited cable lengths. (5) Fiber optic sensors provide the possibility for a small sensor, even though present developments do not exhibit that characteristic. The need to use sapphire at high temperature complicates the design. Present high temperature research sensors suffer from poor resolution. A significant development effort will be required to realize the potential of fiber optics. (6) Short-term development seems to favor eddy current techniques with the penalty of larger size and reduced dynamic range for acoustic sensors. (7) Long-term development may favor fiber optics with the penalties of cost, schedule, and uncertainty.

Winkler, Martin↗

Rockets using Liquid Oxygen

It is my task to discuss rocket propulsion using liquid oxygen and my treatment must be highly condensed for the ideas and experiments pertaining to this classic type of rocket are so numerous that one could occupy a whole morning with a detailed presentation. First, with regard to oxygen itself as compared with competing oxygen carriers, it is known that the liquid state of oxygen, in spite of the low boiling point, is more advantageous than the gaseous form of oxygen in pressure tanks, therefore only liquid oxygen need be compared with the oxygen carriers. The advantages of liquid oxygen are absolute purity and unlimited availability at relatively small cost in energy. The disadvantages are those arising from the impossibility of absolute isolation from heat; consequently, allowance must always be made for a certain degree of vaporization and only vented vessels can be used for storage and transportation. This necessity alone eliminates many fields of application, for example, at the front lines. In addition, liquid oxygen has a lower specific weight than other oxygen carriers, therefore many accessories become relatively larger and heavier in the case of an oxygen rocket, for example, the supply tanks and the pumps. The advantages thus become effective only in those cases where definitely scheduled operation and a large ground organization are possible and when the flight requires a great concentration of energy relative to weight. With the aim of brevity, a diagram of an oxygen rocket will be presented and the problem of various component parts that receive particularly thorough investigation in this classic case but which are also often applicable to other rocket types will be referred to.

Busemann, Adolf↗

Impact on a Compressible Fluid

Upon impact of a solid body on the plane surface of a fluid, there occurs on the vetted surface of the body an abrupt pressure rise which propagates into both media with the speed of sound. Below, we assume the case where the speed of propagation of sound in the body which falls on the surface of the fluid may be regarded as infinitely large in comparison with the speed of propagation of sound in the fluid; that is, we shall assume that the falling body is absolutely rigid. IN this case, the entire relative speed of the motion which takes place at the beginning of the impact is absorbed by the fluid. The hydrodynamic pressures arising thereby are propagated from the contact surface within the fluid with the speed of sound in the form of compression and expansion waves and are gradually damped. After this, they are dispersed like impact pressures, reach ever larger regions of the fluid remote fran the body and became equal to zero; in the fluid there remain hydrodynamic pressures corresponding to the motion of the body after the impact. Neglecting the forces of viscosity and taking into account, furthermore, that the motion of the fluid begins from a state of rest, according to Thomson's theorem, we may consider the motion of an ideal compressible fluid in the process of impact to be potential. We examine the case of impact upon the surface of a ccmpressible fluid of a flat plate of infinite extent or of a body, the immersed part of the surface of which may be called approximately flat. In this report we discuss the first phase of the impact pressure on the surface of a fluid, prior to the appearance of a cavity, since at this stage the hydrodynamic pressures reach their maximum values. Observations, after the fall of the bodies on the surface of the fluid, show that the free surface of the fluid at this stage is almost completely at rest if one does not take into account the small rise in the neighborhood of the boundaries of the impact surface.

Egorov, L. T.↗

Evaluation and optimization of flow boiling frictional pressure drop correlations using the data from traditional and next-generation refrigerants in a micro-fin tube

This study presents an experimental evaluation and optimization of flow boiling frictional pressure drop correlations for conventional and next-generation refrigerants in a horizontal micro-fin tube, with particular emphasis on the newly emerging refrigerant blends R-454C and R-455A, for which pressure-drop data in enhanced tubes remain limited. Experiments were conducted with R-410A, R-454C, R-455A, R-134a, R-1234yf, and R-1234ze(E) in a copper micro-fin tube with an inner diameter of 8.468 mm, over mass fluxes ranging from 100 to 300 kg/(m²·s) depending on the refrigerant, and evaporation temperatures of 7, 12, and 14 °C. Frictional pressure gradients were determined from measured total pressure drops after subtracting acceleration pressure drop, and the resulting database was used to assess four existing models: Kuo and Wang (1996), Cavallini et al. (1997), Goto et al. (2001), and Diani et al. (2014). The measured frictional pressure gradient increased with vapor quality and mass flux for all refrigerants and increased further at lower evaporation temperatures, with the overall trend strongly related to liquid viscosity. Among the four correlations, the Goto et al. (2001) model provided the best overall agreement with the measured data before optimization. To further improve prediction accuracy, the Kuo and Wang (1996) and Goto et al. (2001) models were optimized using the complete experimental database. After optimization, both models reduced the overall mean absolute deviation to below 15%, while the optimized Goto et al. (2001) model maintained the best and most consistent overall performance. The results provide new pressure-drop data for next-generation refrigerants and demonstrate that parameter optimization can significantly enhance the applicability of existing micro-fin-tube correlations.

Hu, Yifeng [ORNL] (ORCID:0000000242875185)↗

Compiled TBS data from Oliktok Point from ICARUS, AVPOP, and POPEYE

The dataset encompasses QA/QC TBS data, including TBS altitude, atmospheric pressure, dew point, POPs number concentrations and mean aerosol size, relative humidity, temperature, equivalent potential temperature, equivalent temperature, and date and time. These data are provided per day for at least one TBS flight. Supporting data from the AMF3 aligned with the timestamps of the TBS data include cloud base distance from TBS, if the time corresponds to cloud base transit of the TBS, surface-based pressure, surface-based precipitation rate, surface-based UHSAS data, ceilometer cloud base height, KAZR cloud top height, and MWR liquid water content. Both POPS and UHSAS aerosol number concentrations are provided as: (1) absolute (i.e. concentrations for each instrument's total size range) and (2) the overlapping size range (i.e. the same size bins for both instruments).

54 ENVIRONMENTAL SCIENCES↗

Absolute measurement of the photoionization cross section of atomic hydrogen with a shock tube for the extreme ultraviolet

The paper reports an experiment which is part of a program to measure the absolute values of the atomic photoionization cross sections of astrophysically abundant elements, particularly in stars and planetary atmospheres. An aerodynamic pressure-driven shock tube constructed from stainless steel with a quadratic cross section was used to measure the photoionization cross section of H I at 19 wavelength points from 910 to 609 A with experimental uncertainties between 7 and 20%. The shock tube was used to produce fully dissociated hydrogen and neon mixtures for the photoabsorption measurements.

Palenius, H. P.↗

An inverse inviscid method for the design of quasi-three dimensional rotating turbomachinery cascades

A new inverse inviscid method suitable for the design of rotating blade sections lying on an arbitrary axisymmetric stream-surface with varying streamtube width is presented. The geometry of the axisymmetric stream-surface and the streamtube width variation with meridional distance, the number of blades, the inlet flow conditions, the rotational speed and the suction and pressure side velocity distributions as functions of the normalized arc-length are given. The flow is considered irrotational in the absolute frame of reference and compressible. The output of the computation is the blade section that satisfies the above data. The method solves the flow equations on a (phi 1, psi) potential function-streamfunction plane for the velocity modulus, W and the flow angle beta; the blade section shape can then be obtained as part of the physical plane geometry by integrating the flow angle distribution along streamlines. The (phi 1, psi) plane is defined so that the monotonic behavior of the potential function is guaranteed, even in cases with high peripheral velocities. The method is validated on a rotating turbine case and used to design new blades. To obtain a closed blade, a set of closure conditions were developed and referred.

Bonataki, E.↗

Rate constant for the reaction of OH with CH3CCl2F (HCFC-141b) determined by relative rate measurements with CH4 and CH3CCl3

Determination of accurate rate constants for OH abstraction is of great importance for the calculation of lifetimes for HCFCs and their impact on the atmosphere. For HCFC-141b there has been some disagreement in the literature for absolute measurements of this rate constant. In the present work rate constant ratios for HCFC-141b were measured at atmospheric pressure in the temperature range of 298-358 K, with CH4 and CH3CCl3 as reference gases. Ozone was photolyzed at 254 nm in the presence of water vapor to produce OH radicals. Relative depletions of 141b and the reference gases were measured by FTIR. Arrhenius expressions for 141b were derived from each reference gas and found to be in good agreement with each other. The combined expression for HCFC-141b which we recommend is 1.4 x 10 exp -12 exp(-1630/T) with k at 298 K being 5.9 x 10 exp -15 cu cm/molec-s. This value is in excellent agreement with the JPL 92-20 recommendation.

Huder, Karin↗

Spectroscopic determination of electrical conductivity in an MHD duct from absolute intensity measurements

Measurements of the electrical conductivity in the NASA Lewis cesium seeded, H2-O2 MHD duct made by applying a voltage across the channel from one end electrode to the other, measuring the current, and using the inner electrodes as probes to monitor the voltage distribution along the channel were found to be in good agreement with theory except at low combustion pressures and/or high ratios of seed/oxygen mass flows. To corroborate these measurements and to analyze the possibility of nonuniform seed injection as a cause of the above deviations, a spectroscopic investigation of the plasma conductivity was undertaken. Radial profiles of emission coefficient were obtained from measured transverse profiles of the absolute integrated intensity by Abel inversion. Radial profiles of electrical conductivity were then obtained under two different assumptions. In the first the Cs seed fraction is assumed uniform and equal to the measured flow rate at the time when the temperature and conductivity were obtained. In the second method the local temperature and pressure are taken to be those given by a one-dimensional channel calculation including heat transfer and friction. The results of the two methods are compared to the previously measured conductivity.

Wang, S. Y.↗

Rate constant for the reaction of hydroxyl radical with formaldehyde over the temperature range 228-362 K

Absolute rate constants for the reaction OH + H2CO have been measured over the temperature range 228-362 K using the flash photolysis-resonance fluorescence technique. The results were independent of variations in forbidden H2CO, total pressure of forbidden Ar and flash intensity (i.e., initial forbidden OH). The rate constant was found to be invariant with temperature in this range, the best representation being k1 = (1.05 + or - 0.11) x 10 to the -11th cu cm/molecule sec where the error is two standard deviations. This result is compared with previous absolute and relative determinations of k1. The reaction is also discussed from a theoretical point of view.

Stief, L. J.↗

Spectroradiometric calibration techniques in the far ultraviolet - A stable emission source for the Lyman bands of molecular hydrogen

The problems associated with making accurate spectroradiometric measurements in the far UV region are sketched briefly. The equipment and methods that were developed for providing absolute sensitivity calibration of an Apollo 17 far UV spectrometer are described. The absolute reference standards were photoelectric diodes calibrated at the National Bureau of Standards. A complete vacuum optical facility, which included a premonochromator and stable UV light sources, was developed to calibrate the Apollo 17 instrument, and it has been used for a number of other tasks. Absolute radiometric calibrations between about 1200 and 1700 A were performed with an absolute accuracy of + or - 10%. The light source, which was designed to provide a very stable light output, is a low-pressure molecular hydrogen lamp in which the pressure is stabilized by thermal control of uranium hydride powder.-

Fastie, W. G.↗