Rate Constants for the Reaction of OH with Halocarbons
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Halocarbons Hydroxyl Radical Ethyl Cloride↗
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Rate Constants For The Reactions of OH With HFC-134a(CF(sub 3)CH(sub 2)F) and HFC-134 (CHF(sub 2)CHF(sub 2))
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atmospheric lifetimes of compounds↗
Rates for neutron-capture reactions on tungsten isotopes in iron meteorites
High-precision W isotopic analyses by Harper and Jacobsen indicate the W-182/W-183 ratio in the Toluca iron meteorite is shifted by -(3.0 +/- 0.9) x 10(exp -4) relative to a terrestrial standard. Possible causes of this shift are neutron-capture reactions on W during Toluca's approximately 600-Ma exposure to cosmic ray particles or radiogenic growth of W-182 from 9-Ma Hf-182 in the silicate portion of the Earth after removal of W to the Earth's core. Calculations for the rates of neutron-capture reactions on W isotopes were done to study the first possibility. The LAHET Code System (LCS) which consists of the Los Alamos High Energy Transport (LAHET) code and the Monte Carlo N-Particle(MCNP) transport code was used to numerically simulate the irradiation of the Toluca iron meteorite by galactic-cosmic-ray (GCR) particles and to calculate the rates of W(n, gamma) reactions. Toluca was modeled as a 3.9-m-radius sphere with the composition of a typical IA iron meteorite. The incident GCR protons and their interactions were modeled with LAHET, which also handled the interactions of neutrons with energies above 20 MeV. The rates for the capture of neutrons by W-182, W-183, and W-186 were calculated using the detailed library of (n, gamma) cross sections in MCNP. For this study of the possible effect of W(n, gamma) reactions on W isotope systematics, we consider the peak rates. The calculated maximum change in the normalized W-182/W-183 ratio due to neutron-capture reactions cannot account for more than 25% of the mass 182 deficit observed in Toluca W.
Masarik, J.↗
The reaction NH2 + PH3 yields NH3 + PH2 - Absolute rate constant measurement and implication for NH3 and PH3 photochemistry in the atmosphere of Jupiter
The rate constant is measured over the temperature interval 218-456 K using the technique of flash photolysis-laser-induced fluorescence. NH2 radicals are produced by the flash photolysis of ammonia highly diluted in argon, and the decay of fluorescent NH2 photons is measured by multiscaling techniques. For each of the five temperatures employed in the study, the results are shown to be indepenent of variations in PH3 concentration, total pressure (argon), and flash intensity. It is found that the rate constant results are best represented for T between 218 and 456 K by the expression k = (1.52 + or - 0.16) x 10 to the -12th exp(-928 + or - 56/T) cu cm per molecule per sec; the error quoted is 1 standard deviation. This is the first determination of the rate constant for the reaction NH2 + PH3. The data are compared with an estimate made in order to explain results of the radiolysis of NH3-PH3 mixtures. The Arrhenius parameters determined here for NH2 + PH3 are then contrasted with those for the corresponding reactions of H and OH with PH3.
Bosco, S. R.↗
The reaction NH2 + PH3 yields NH3 + PH2: Absolute rate constant measurement and implication for NH3 and PH3 photochemistry in the atmosphere of Jupiter
The rate constant is measured over the temperature interval 218-456 K using the technique of flash photolysis-laser-induced fluorescence. NH2 radicals are produced by the flash photolysis of ammonia highly diluted in argon, and the decay of fluorescent NH2 photons is measured by multiscaling techniques. For each of the five temperatures employed in the study, the results are shown to be independent of variations in PH3 concentration, total pressure (argon), and flash intensity. It is found that the rate constant results are best represented for T between 218 and 456 K by the expression k = (1.52 + or - 0.16) x 10 to the -12th exp(-928 + or - 56/T) cu cm per molecule per sec; the error quoted is 1 standard deviation. This is the first determination of the rate constant for the reaction NH2 + PH3. The data are compared with an estimate made in order to explain results of the radiolysis of NH3-PH3 mixtures. The Arrhenius parameters determined here for NH2 + PH3 are then constrasted with those for the corresponding reactions of H and OH with PH3.
Bosco, S. R.↗
Performance of Cassini Reaction Wheel Friction Compensation Scheme During Spin Rate Zero-Crossing and Drag Spikes
Cassini uses reaction wheels to achieve the spacecraft pointing stability that is needed during imaging operations of several science instruments. The Cassini flight software makes inflight estimates of reaction wheel bearing drag torque and the reaction wheel controller uses these estimates to achieve a high level of spacecraft pointing stability. However, the Cassini drag torque estimator was designed to accurately track the bearing drag torque only in the steady state. When the physical drag torque changes abruptly (for example, during a reaction wheel spin rate reversal or when wheel bearings experienced drag spikes), the drag estimator will not be able to track the physical drag closely. This will lead to a degradation in the spacecraft pointing stability performance. For Cassini, this was not a problem because of the significant performance margin in pointing stability. However, for missions that have very challenging pointing stability requirements and that must perform well in the presence of frequent wheel rate reversals, alternative drag-compensating control schemes must be considered. To this end, alternative drag torque compensating control schemes (such as the adaptive model reference control scheme) are briefly reviewed in this paper. Selected design features used in these friction compensation schemes may be incorporated in reaction wheel controller design to improve the robustness of spacecraft pointing stability performance with regard to a wide range of reaction wheel drag torque anomalous behavior.
Lee, Allan Y↗
A model for the pyrolysis of unfilled and filled polymers and comparisons with NBS smoke-density chamber data
This paper considers a model for the pyrolysis of polymers for use in mass loss and smoke density predictions in a fire situation. It is based on the fundamental postulate that the overall rate-limiting reactions are in the relatively low temperature condensed phase; the rate limiting step is the polymer degradation to a vaporizable state. The state of the polymer (chain length) at the surface is specified by the vapor pressure equilibrium criterion. For the case of polymers with inert fillers, like alumina trihydrate, the further assumption is made that the linear regression rate of the material is identical to the unfilled material's at the same surface temperature. The fraction of polymer mass loss converted to smoke is inferred from the literature. The smoke density in the NBS-smoke density chamber is predicted for a polyester and the same polyester with two different loads of alumina trihydrate filler. Diffusional effects in the smoke spreading are considered in an elementary manner. The comparisons with experimental data are encouraging. The overall fire characteristics are predicted using only the fundamental physicochemical property values of ingredients.
Kumar, R. N.↗
An assessment of the potential impact of solid-fueled rocket engines in the stratosphere
The effects of shuttle-emitted HCl on stratospheric ozone are reported. A one-dimensional model of the distribution of trace constituents in the stratosphere and mesosphere is described, and chemical reactions and photodissociation rates in the chlorine chemistry are listed. Analysis of mathematical models is presented, and the results show ozone depletion when emissions are considered to be spread uniformly in the horizontal over a hemisphere and an increase in ozone when emissions are considered in a zone 1000 km wide centered at Cape Kennedy. Sensitivity studies to determine the effects of some assumptions in the model and comparisons with nitric oxide reactions are described. The importance of a two-dimensional model for a proper long term study is noted. Lists of reaction rate coefficients and photodissociation rates for the O-H-N system are included.
Whitten, R. C.↗
Carbon Nanotube Synthesis in a Flame with Independently Prepared Laser-Ablated Catalyst Particles
Laser ablation has been used ex situ to create metal nanoparticles for introduction into a reactive pyrolysis flame. By prior synthesis of the metal nanoparticles, the effects of the reactive gases can be clearly separated from the pyrolysis chemistry of a solvent carrier, as when nebulized solutions are used. Moreover, varying reactivity issues associated with particle growth and size are bypassed. Our results show that Fe selectively reacts with CO to produce nanotubes, whereas Ni selectively reacts with C2H2 to produce nanofibers. These observations are interpreted through the donation and withdrawal of electron density between the adsorbate's molecular orbitals and surface atoms of the metal nanoparticle. The rate of reaction of Ni with only C2H2 is found to be greater than the rate with C2H2 and CO. This suggests that CO inhibits the Ni-catalyzed reaction.
Nanotubes, Carbon/chemistry/ultrastructure↗
The reaction of atomic hydrogen with germane - Temperature dependence of the rate constant and implications for germane photochemistry in the atmospheres of Jupiter and Saturn
Studies of the formation and loss processes for GeH4 are required in order to provide data to help determine the major chemical form in which germanium exists in the atmospheres of Jupiter and Saturn. The reaction of hydrogen atoms with germane is one of the most important of these reactions. The absolute rate constant for this reaction as a function of temperature and pressure is studied. Flash photolysis of dilute mixtures of GeH4 in argon, combined with time-resolved detection of H atoms via Lyman alpha resonance fluorescence, is employed to measure the reaction rate. The reaction is shown to be moderately rapid, independent of total pressure, but possessing a positive temperature dependence.
Nava, David F.↗
Expansion of Additive Manufacturing Capabilities Into in Situ Alloying of Dispersion Strengthened, High Temperature Cu Alloys
New alloys and materials are potentially possible through additive manufacturing’s unique thermal history. Current literature explores the fabrication of eutectic and solid solution strengthened alloys through in-situ alloying, to take advantage of AM’s unique thermal history. The resulting lessons learned by in-situ alloying currently available materials will likely lead to the development of novel materials solely possible through in-situ alloying. This work will expand the application of in-situ alloying via additive manufacturing to NASA’s GRCop-42 (Cu-4at% Cr-2at% Nb), a high temperature copper alloy which has shown success in additively manufactured combustion chambers from pre-alloyed powders. GRCop-42 is unique to literature because a reaction to form the Cr2Nb dispersoids is required during the in-situ alloying. Both reaction completion rate and how input energy from the AM process influences the reaction progress will be evaluated. Ultimately, expansion of in-situ alloying capabilities provides further insight to develop novel materials using AM.
David Steven Scannapieco↗
Estimation of Gravitation Parameters of Saturnian Moons Using Cassini Attitude Control Flight Data
A major science objective of the Cassini mission is to study Saturnian satellites. The gravitational properties of each Saturnian moon is of interest not only to scientists but also to attitude control engineers. When the Cassini spacecraft flies close to a moon, a gravity gradient torque is exerted on the spacecraft due to the mass of the moon. The gravity gradient torque will alter the spin rates of the reaction wheels (RWA). The change of each reaction wheel's spin rate might lead to overspeed issues or operating the wheel bearings in an undesirable boundary lubrication condition. Hence, it is imperative to understand how the gravity gradient torque caused by a moon will affect the reaction wheels in order to protect the health of the hardware. The attitude control telemetry from low-altitude flybys of Saturn's moons can be used to estimate the gravitational parameter of the moon or the distance between the centers of mass of Cassini and the moon. Flight data from several low altitude flybys of three Saturnian moons, Dione, Rhea, and Enceladus, were used to estimate the gravitational parameters of these moons. Results are compared with values given in the literature.
angular momentum↗
Kinetics of the reaction OH + H2O2 yields HO2 + H2O
The paper describes an experimental study of the title reaction that uses the discharge-flow technique, laser-induced-fluorescence detection of OH and simultaneous monitoring of O and H atoms in the 250-459 K range. The reaction is normal and free from surface effect interference in Teflon or halocarbon wax-coated tube, but not in clean Pyrex. OH radicals are generated in three ways and at low concentrations to eliminate side reactions. The rate constants were determined at 298 K and over the 250-459 K range, with a factor of two higher at 298 K and factors of 3 to 5 higher at 10 to 30 km altitude in the terrestrial atmosphere than previous studies have indicated. The effect of the higher rate constant on atmospheric processes and on recent laboratory measurements of other reactions is also discussed.
Sridharan, U. C.↗
Reactive iron in marine sediments
The influence of reactive iron oxides on sediment pore-water chemistry is considered in detail. A carefully calibrated extraction scheme is used to determine the depth distributions of reactive iron phases at two very different localities: the relatively iron-rich Mississippi Delta and the relatively iron-poor FOAM site in Long Island Sound. Closed system incubations are used to characterize the rates of reaction between sulfide and both naturally occurring and pure iron mineral phases. Rates of iron liberation to pore solution are measured in the presence and absence of sulfate reduction, and the origin of dissolved iron in organic-rich sediments is speculated upon.
Canfield, Donald E.↗
Model free simulations of a high speed reacting mixing layer
The effects of compressibility, chemical reaction exothermicity and non-equilibrium chemical modeling in a combusting plane mixing layer were investigated by means of two-dimensional model free numerical simulations. It was shown that increased compressibility generally had a stabilizing effect, resulting in reduced mixing and chemical reaction conversion rate. The appearance of 'eddy shocklets' in the flow was observed at high convective Mach numbers. Reaction exothermicity was found to enhance mixing at the initial stages of the layer's growth, but had a stabilizing effect at later times. Calculations were performed for a constant rate chemical rate kinetics model and an Arrhenius type kinetics prototype. The Arrhenius model was found to cause a greater temperature increase due to reaction than the constant kinetics model. This had the same stabilizing effect as increasing the exothermicity of the reaction. Localized flame quenching was also observed when the Zeldovich number was relatively large.
Steinberger, Craig J.↗
Oxidative vaporization kinetics of chromium (III) oxide in oxygen from 1270 to 1570 K
Rates of oxidative vaporization of Cr2O3 on preoxidized resistively heated chromium were determined in flowing oxygen at 0.115 torr for temperatures from 1270 to 1570 K. Reaction controlled rates were obtained from experimental rates by a gold calibration technique. These rates were shown to agree with those predicted by thermochemical analysis. The activation energy obtained for the oxidative vaporation reaction corresponded numerically with the thermochemical enthalpy of the reaction. A theoretical equation is given for calculating the rate from thermodynamic data by using boundary layer theory.
Stearns, C. A.↗
Oxidation Study of an Ultra High Temperature Ceramic Coatings Based on HfSICN
High temperature fiber-reinforced ceramic matrix composites (CMCs) are important for aerospace applications because of their low density, high strength, and significantly higher-temperature capabilities compared to conventional metallic systems. The use of the SiC(sub f)/SiC and C(sub f)/SiC CMCs allows the design of lighter-weight, more fuel efficient aircraft engines and also more advanced spacecraft airframe thermal protection systems. However, CMCs have to be protected with advanced environmental barrier coatings when they are incorporated into components for the harsh environments such as in aircraft engine or spacecraft applications. In this study, high temperature oxidation kinetics of an advanced HfSiCN coating on C(sub f)/SiC CMC substrates were investigated at 1300 C, 1400 C, and 1500 C by using thermogravimetric analysis (TGA). The coating oxidation reaction parabolic rate constant and activation energy were estimated from the experimental results. The oxidation reaction studies showed that the coatings formed the most stable, predominant HfSiO4-HfO2 scales at 1400 C. A peroxidation test at 1400 C then followed by subsequent oxidation tests at various temperatures also showed more adherent scales and slower scale growth because of reduced the initial transient oxidation stage and increased HfSiO4-HfO2 content in the scales formed on the HfSiCN coatings.
environmental barrier coatings (EBCs)↗
An improved flux-split algorithm applied to hypersonic flows in chemical equilibrium
An explicit, finite-difference, shock-capturing numerical algorithm is presented and applied to hypersonic flows assumed to be in thermochemical equilibrium. Real-gas chemistry is either loosely coupled to the gasdynamics by way of a Gibbs free energy minimization package or fully coupled using species mass conservation equations with finite-rate chemical reactions. A scheme is developed that maintains stability in the explicit, finite-rate formulation while allowing relatively high time steps. The codes use flux vector splitting to difference the inviscid fluxes and employ real-gas corrections to viscosity and thermal conductivity. Numerical results are compared against existing ballistic range and flight data. Flows about complex geometries are also computed.
Palmer, Grant↗