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The reaction HCl + ClONO2 yields Cl2 + HNO3 has been studied by Fourier transform infrared spectroscopy and by a static wall-less UV absorption technique. An upper limit to the homogeneous bimolecular rate constant of 10 to the -19th cu cm/molecule per sec was established, making the reaction unimportant in the stratosphere.
X-ray photoelectron spectroscopy investigations of the reaction of several monolayer-thick films of aluminum with glassy carbon substrates are presented. The influence of molecular oxygen and water vapor on the rate of reaction is examined. It is concluded that water vapor catalyzed the formation of aluminum carbide from aluminum and carbon by forming active sites which weakened carbon-carbon bonds at the glassy carbon surface, thus assisting their cleavage. The rate of carbide formation for undosed and molecular oxygen-dosed examples was less as neither metallic aluminum nor oxygen-formed alumina could bond to the carbon atom with sufficient strength to dissociate it quickly.
The stability of a two-dimensional compressible supersonic flow in the wake of a flat plate is discussed. The fluid is a multi-species mixture which is undergoing finite rate chemical reactions. The spatial stability of an infinitesimal disturbance in the fluid is considered. Numerical solutions of the eigenvalue stability equations for both reactive and nonreactive supersonic flows are presented and discussed. The chemical reactions have significant influence on the stability behavior. For instance, a neutral eigenvalue is observed near the freestream Mach number of 2.375 for the nonreactive case, but disappears when the reaction is turned on. For reactive flows, the eigenvalues are not very dependent on the free stream Mach number.
An algorithm has been developed for the forced convective diffusion-reaction problem for convection inside and outside a droplet by a recirculating flow field hydrodynamically coupled at the droplet interface with an external flow field that at infinity becomes a uniform streaming flow. The concentration field inside the droplet is likewise coupled with that outside by boundary conditions at the interface. A chemical reaction can take place either inside or outside the droplet or reactions can take place in both phases. The algorithm has been implemented and results are shown here for the case of no reaction and for the case of an external first order reaction, both for unsteady behavior. For pure interphase mass transfer, concentration isocontours, local and average Sherwood numbers, and average droplet concentrations have been obtained as a function of the physical properties and external flow field. For mass transfer enhanced by an external reaction, in addition to the above forms of results, we present the enhancement factor, with the results now also depending upon the (dimensionless) rate of reaction.
An algorithm has been developed for time-dependent forced convective diffusion-reaction having convection by a recirculating flow field within the drop that is hydrodynamically coupled at the interface with a convective external flow field that at infinity becomes a uniform free-streaming flow. The concentration field inside the droplet is likewise coupled with that outside by boundary conditions at the interface. A chemical reaction can take place either inside or outside the droplet, or reactions can take place in both phases. The algorithm has been implemented, and for comparison results are shown here for the case of no reaction in either phase and for the case of an external first order reaction, both for unsteady behavior. For pure interphase mass transfer, concentration isocontours, local and average Sherwood numbers, and average droplet concentrations have been obtained as a function of the physical properties and external flow field. For mass transfer enhanced by an external reaction, in addition to the above forms of results, we present the enhancement factor, with the results now also depending upon the (dimensionless) rate of reaction.
An explicit finite-rate code was developed to compute hypersonic viscous chemically reacting flows about three-dimensional bodies. Equations describing the finite-rate chemical reactions were fully coupled to the gas dynamic equations using a new coupling technique. The new technique maintains stability in the explicit finite-rate formulation while permitting relatively large global time steps.
The rate constants for the reaction CH3O2 + CH3O2 yields products (1) were measured in the temperature range from 248 to 417 K, taking into consideration pressures in the range from 60 to 700 torr of N2. The experimental investigation was carried out in a Pyrex flash photolysis system employing ultraviolet absorption detection. Methylperoxy radicals (CH3O2) were produced by the photolysis of Cl2-CH4-O2 mixtures. Rate constants were measured by observing the second-order disappearance of CH3O2 radicals. Plots of 1/(CH3O2 optical density) vs. time were observed to be linear over a concentration change of a factor of 10-50. Results of the kinetic runs at each temperature are summarized in a table, and an Arrhenius plot of the data is shown in a graph.
The rate constant for the reaction HO2 + HO2 yields H2O2 + O2 was measured at 298 K and 1 torr total pressure of helium by using the discharge flow technique. A quadrupole mass spectrometer was used to detect HO2 in conjunction with in situ long-path ultraviolet absorption which was used for calibration. A value of 1.5 + or - 0.4 x 10 to the -12th per molecule/s was obtained for k1 where the rate constant is defined by the relation -d(HO2)/dt = 2K1(HO2)HO2.
Evaluation of two daytime D-region positive-ion composition measurements performed at Thumba, India, for solar zenith angles of 53.2 and 27.8 deg. Comparison of upleg ram with downleg wake data shows a large increase in the concentration of heavy ions 48(+), NO(+) . H2O; 55(+), H3O(+) . (H2O)2; and M(+) greater than 65(+) for the downleg reduced shock condition. Peak concentrations of 48(+) and 55(+) occur at unit optical depth for Lyman alpha radiation. The ion 37(+), H3O(+) . H2O, is dominant for chi = 27.8 deg, but not for chi = 53.2 deg, consistent above 80 km with an origin from the X-ray production of O2(+). Laboratory measurements have shown that the ion, NO(+), can be transferred to heavy hydrates 48(+), 55(+), and M(+) greater than 65(+) by a reaction chain starting with NO(+) + X + M = NO(+) . X + M, where X can be O2, N2, CO2 or a combination of all three, depending on the rate of reaction. This chain, together with a similar reaction scheme starting with O2(+) and ending in 19(+), 37(+), and heavier clusters, is used to provide a consistent explanation for the hydrated ions observed in the D region.
Silicon aluminum oxynitride solid solutions (sialons) based on beta-Si3N4 and Si2N2O behave differently in contact with molten silicon. The Si2N2O-based sialons convert to almost pure Si3N4, apparently through a two-step decomposition and solution-precipitation reaction, whereas the beta-Si3N4 sialons are preferentially attacked at the grain boundaries. The composition of the grain-boundary phase appears to control the rate of reaction.
This study presents a three-dimensional explicit, finite-difference, shock-capturing numerical algorithm applied to viscous hypersonic flows in thermochemical nonequilibrium. The algorithm employs a two-temperature physical model. Equations governing the finite-rate chemical reactions are fully-coupled to the gas dynamic equations using a novel coupling technique. The new coupling method maintains stability in the explicit, finite-rate formulation while allowing relatively large global time steps. The code uses flux-vector accuracy. Comparisons with experimental data and other numerical computations verify the accuracy of the present method. The code is used to compute the three-dimensional flowfield over the Aeroassist Flight Experiment (AFE) vehicle at one of its trajectory points.
An ongoing research program aims to characterize the solidification of several Ni- and Co-based commercial wrought type alloys. The techniques used and the data items sought are: (1) thermal analysis, liquidus, nonequilibrium solidus as a function of cooling rate, secondary reactions temperatures, incipient melting, progress of solidification as a function of temperature; (2) optical metallography, characteristic structures and secondary dendrite arm spacing as a function of cooling rate; (3) X-ray diffraction, identification of precipitates; and (4) SEM/EDAX, measure of microsegregation.
Simple theory predicts compositions of alloys that exhibit maximum catalytic activities in presence of certain reactants. Method used to select best catalysts for electrochemical batteries and fuel cells. Oxygen-electrode overvoltage plotted against solubility parameter of lead/platinum electrode in acidic and basic solutions. Electrode formed by plating mixtures of lead and platinum, corresponding to various solubility parameters. Method based on one used to analyze activities of nonelectrical catalysts in reactions involving hydrogen or oxygen. Rate of such reaction increases when solubility parameter of catalyst matches reactant.
A comprehensive homogeneous gas phase photochemical model is developed to study the problem of stability of the Martian atmosphere. The one-dimensional model extends from the ground up to 220 km, passing through the homopause at 125 km. The model thus couples the lower (neutral) atmosphere to the ionosphere above which provides significant downward flux of carbon monoxide and oxygen atoms. It is concluded on the basic of currently accepted values for globally and seasonally averaged water vapor abundance, dust opacity and the middle atmospheric eddy mixing coefficient, as well as the relevant laboratory data (particularly the temperature dependence of CO2 absorption cross section and the rate constant for CO+OH reaction), that the rate of re-formation of carbon dioxide exceeds its photolytic destruction rate by about 40%. Furthermore, it is found that this result is virtually independent of the choice of eddy mixing coefficient, unless its value in the middle atmosphere exceeds 10(exp 8) sq cm/sec or is far smaller than 10(exp 5)sq cm/sec, or the dust opacity, unless it exceeds unity, or the water vapor mixing ratio at the surface, unless it is far smaller (less than or = 1 ppm) or far greater (greater than or = 500 ppm) than the average value (approximately 150 ppm). Since none of these extremes represent globally and seasonally averaged conditions on Mars, we propose that the present model requires existence of a mechanism to throttle down the recycling rate of carbon dioxide on Mars. Therefore, it is suggested that a heterogeneous process which provides a sink to the species that participate in the recycling of CO2, i.e., H2O, H2O2, OH, CO or O, in particular, may be necessary to bring about the balance between the CO2 recycling rate and its photolytic destruction rate. Aerosols of dust or ice (pure or doped water or carbon dioxide ice present in the atmosphere of Mars) can provide the appropriate adsorption sites for the above heterogeneous process. Despite our conclusion that some heterogeneous process may be needed, it is important to recognize that one-dimensional models can only provide first-order results which, most likely, represent globally and seasonally averaged conditions. However, it is only after actual temporal, latitudinal and longitudinal variations of relevant atmospheric parameters are included in the model that one can determine fuly whether the problem of atmospheric stabiltiy still continues to persist and whether some heterogeneous process is required to correct it.
In the laboratory, ice films formed by freezing from the liquid or more frequently by deposition from the vapor phase have been used to simulate stratospheric cloud surfaces for measurements of reaction and uptake rates. To obtain intrinsic surface reaction probabilities that can be used in atmospheric models, the area of the film surface that actually takes part in the reaction must be known. It is important to know not only the total surface area but also the film morphology in order to determine where and how the surface is situated and, thus, what fraction of it is available for reaction. Information on the structure of these ice films has been obtained by using several experimental methods. In the sections that follow, these methods will be discussed, then the results will be used to construct a working model of the ice films, and finally the model will be applied to an experimental study of HC1 uptake by H_2O ice.
A second-order differential Reynolds Stress turbulence model has been applied to the Favre-averaged Navier-Stokes equations for the study of supersonic flows with finite-rate chemistry and radiation. An assumed Beta Probability Density Function is applied to account for the chemical source terms and the radiative flux terms in the conservation equations. A seven-species, seven-reaction finite rate chemistry mechanism is used to simulate the combustion process. The tangent slab approximation is used in radiative flux formulation. A pseudo-gray gas model is used to represent the absorption-emission characteristics of the participating species. The turbulence/radiation interaction is achieved via a new formulation. The resulting formulation is validated by comparison with experimental data on reacting supersonic axisymmetric jets. Results obtained for specific conditions indicate that the effect of chemical reaction on the turbulence is significant. Also, the radiative heat transfer is enhanced by the turbulence.
The inhibition of the oligomerization of HCN by montmorillonite clays is shown to be caused by oxidation of diaminomaleonitrile (DAMN) by ferric ion in the clay lattice, with ferrous ion and oxalic acid the reaction products. It is demonstrated that diiminosuccinonitrile is the initial reaction product and is rapidly hydrolized to oxalic acid and HCN. The same oxidative transformations are effected by ferric ion bound to Dowex 50, ferric ion in solution, and Ni(NH3)6(2+). The rate of reaction of DAMN indicates no catalytic role for the clay in the oxidation of DAMN, and little reaction of the latter was observed with montmorillonite in which the bulk of the iron was in the divalent state. The possible significance of these redox reactions to chemical evolution is discussed.
A second-order differential Reynolds Stress turbulence model has been applied to the Favre-averaged Navier-Stokes equations for the study of supersonic flows undergoing hydrogen-air chemical reactions. An assumed Beta Probability Density Function is applied to account for the chemical source terms in the conservation equations. An algebraic Reynolds Flux model is used for the fluctuating density-velocity as well as the species mass fraction-velocity correlations. The variances of temperature and species fluctuations are also modelled using an algebraic flux technique. A seven-species, seven-reaction finite rate chemistry mechanism is used to simulate the combustion processes. The resulting formulation is validated by comparison with experimental data on reacting supersonic axisymmetric jets. Results obtained for specific conditions indicate that the effect of chemical reaction on the turbulence is significant.