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Gas phase ion-molecule phosphine reactions in pure and binary mixtures by ion cyclotron resonance spectroscopy, considering acidity and basicity
The Brayton rotating unit (BRU), operating on a gas bearing system, has been designed, fabricated, and demonstrated for use in a closed Brayton cycle space power conversion system. The BRU uses a binary mixture of xenon and helium (molecular weight, 83.8) as the cycle working fluid and bearing lubricating medium and was designed to produce from 2.25 to 10.5 kw sub e of 1200 Hz three-phase electrical power. The single-shaft rotating assembly operates at a design speed of 36,000 rpm and comprises a radial single-stage compressor, a four-pole Rice alternator rotor, and a radial inflow turbine. Four units, a dynamic simulator and three component research packages, were supplied to the NASA Lewis Research Center for performance testing and further development.
The relaxation of the accelerating-gas boundary layer to the test-gas boundary layer over a flat plate in an expansion tube is analyzed. Several combinations of test gas and acceleration gas are considered. The problem is treated in two conically similar limits: (1) when the time lag between the arrival of the shock and the interface at the leading edge of the plate is very large, and (2) when this lag is negligible. The time-dependent laminar-boundary-layer equations of a binary mixture of perfect gases are taken as the flow-governing equations. This coupled set of differential equations, written in terms of the Lam-Crocco variables, has been solved by a line-relaxation finite-difference techniques. The results presented include the Stanton number and the local skin-friction coefficient as functions of shock Mach number and the nondimensional distance-time variable. The results indicate that more than 95 percent of the test-gas boundary layer exists over a length, measured from the leading edge of the plate, equal to about three-tenths of the distance traversed by the interface in the free stream.
Infrared absorption spectra of ten individual contaminant materials and four binary mixtures of these have been studied using the internal reflection spectroscopy technique. The effect of ultraviolet radiation on these contaminants has also been studied. It has been observed that all siloxanes, silanes, and esters are drastically affected by ultraviolet irradiation. In most cases polymerization and tar formation results.
We solve the familiar Langevin equation with stochastic damping to represent the motion of a Brownian particle in a fluctuating medium. A connection between the damping and the random driving forces is proposed which preserves quite generally the Einstein relation between the diffusion and mobility coefficients. We present an application to the case of a Brownian particle in a critical binary mixture.
The paper describes a resonant tube for measuring sound absorption in gases, with specific emphasis on the vibrational relaxation peak of N2, over a range of frequency/pressure ratios from 0.1 to 2500 Hz/atm. The experimental background losses measured in argon agree with the theoretical wall losses except at few isolated frequencies. Rigid cavity terminations, external excitation, and a differential technique of background evaluation were used to minimize spurious contributions to the background losses. Room temperature measurements of sound absorption in binary mixtures of N2-CO2 in which both components are excitable resulted in the maximum frequency/pressure ratio in Hz/atm of 0.063 + 123m for the N2 vibrational relaxation peak, where m is mole percent of added CO2; the maximum ratio for the CO2 peak was 34,500 268m where m is mole percent of added N2.
Sound absorption measurements were made in N2-H2O binary mixtures at 297 K over the frequency/pressure range f/P of 0.1-2500 Hz/atm to investigate the vibrational relaxation peak of N2 and its location on f/P axis as a function of humidity. At low humidities the best fit to a linear relationship between the f/P(max) and humidity yields an intercept of 0.013 Hz/atm and a slope of 20,000 Hz/atm-mole fraction. The reaction rate constants derived from this model are lower than those obtained from the extrapolation of previous high-temperature data.
Thomson's ion nucleation theory was modified to include the effects of curvature dependence of the microscopic surface tension of field dependent, nonlinear, dielectric properties of the liquid; and of sulfuric acid hydrate formation in binary mixtures of water and sulfuric acid vapors. The modified theory leads to a broadening of the ion cluster spectrum, and shifts it towards larger numbers of H2O and H2SO4 molecules. Whether there is more shifting towards larger numbers of H2O or H2SO4 molecules depends on the relative humidity and relative acidity of the mixture. Usually, a broadening of the spectrum is accompanied by a lowering of the mean cluster intensity. For fixed values of relative humidity and relative acidity, a similar broadening pattern is observed when the temperature is lowered. These features of the modified theory illustrate that a trace of sulfuric acid can facilitate the formation of ultrafine, stable, prenucleation ion clusters as well as the growth of the prenucleation ion clusters towards the critical saddle point conditions, even with low values of relative humidity and relative acidity.
The aerosol nucleation phenomenon is studied in a binary mixture of H2O and H2SO4 vapors in a carrier stream of N2 gas in the presence of ions produced by a low energy beta source. Cluster spectra of the form (H2SO4)n.(H2O)m.H(+) are identified from the measurements of the cluster masses using a quadrupole mass spectrometer. Results show that the number of H2SO4 molecules in the clusters ranged from 0 to 6 whereas the number of H2O molecules ranged from 1 to 20 depending on the concentration of H2SO4 and H2O vapors in the reaction chamber. Among other conclusions, it is noted that a large number of clusters of the type investigated are formed in the presence of an ionization source even when the partial pressures of H2SO4 and H2O are very low. The cluster composition is found to be strongly dependent on the r.h. and r.a. values in the reaction cell. The cluster spectrum (n, m, l) contains a large number of low n- and low m-value clusters when the reaction cell pressure is high.
The goal of the study described here is to determine new criteria for improved target discrimination in areas of hydrothermal mineralization. It is noted that the portion of materials, that is, geological surfaces detected by sensing devices, must be accurately determined before elemental and mineralogical characterization. The depth from which visible-near infrared radiation is reflected from target surfaces depends on composition and fabric. Reflectance spectra are obtained from binary mixtures of hematite, goethite, kaolinite and montmorillonite with a reflecting sphere spectrometer over a wavelength range of 400-2500 nm. The reflection (or absorption) intensity is plotted vs. the sample thickness (determined by scanning electron microscopy) to determine the sample thickness at which absorption saturates. The optical depth is seen to vary as a function of mineralogy and wavelength. In general, the maximum depth from which reflection features are discerned is from 12 to 47 microns measured in the visible-near infrared spectral region.
The effect of solid-liquid interface shape on lateral solute segregation during steady-state unidirectional solidification of a binary mixture is calculated under the assumption of no convection in the liquid. A finite element technique is employed to compute the concentration field in the liquid and the lateral segregation in the solid with a curved boundary between the liquid and solid phases. The computational model is constructed assuming knowledge of the solid-liquid interface shape; no attempt is made to relate this shape to the thermal field. The influence of interface curvature on the lateral compositional variation is investigated over a range of system parameters including diffusivity, growth speed, distribution coefficient, and geometric factors of the system. In the limiting case of a slightly nonplanar interface, numerical results from the finite element technique are in good agreement with the analytical solutions of Coriell and Sekerka obtained by using linear theory. For the general case of highly non-planar interface shapes, the linear theory fails and the concentration field in the liquid as well as the lateral solute segregation in the solid can be calculated by using the finite element method.
The theories of diffusion-controlled dendritic crystallization will be reviewed briefly, along with recently published critical experiments on the kinetics and morphology of dendritic growth in pure substances. The influence of the gravitational body force on dendrite growth kinetics will be shown to be highly dependent on the growth orientation with respect to the gravity vector and on the level of the thermal supercooling. In fact, an abrupt transition occurs at a critical supercooling, above which diffusional transport dominates the growth process and below which convective transport dominates. Our most recent work on binary mixtures shows that dilute solute additions influence the crystallization process indirectly, by altering the interfacial stability, rather than by directly affecting the transport mode. Directions for future studies in this field will also be discussed.
Xe isotopic measurements are described. The samples analyzed were bulk chips of the Murray (C2) and Murchison (C2) carbonaceous chondrites that had been freeze-thaw disaggregated, etched with H2O2, and then split into colloidal and noncolloidal fractions using methanol. The etching removed a substantial portion of the trapped Xe and increased variations in measured isotopic ratios compared with bulk sample analyses. The Murray samples appeared to contain a binary mixture of U-Xe and H+L-Xe. The Murchison data concur with the Murray data for the heavy isotopes, but the structure at the light isotopes is obscured by spallation Xe. There is no evidence in these data for the separability of H-Xe and L-Xe. The fact that H2O2 etching removes Xe without prior demineralization supports the view that the carrier of a substantial portion of trapped Xe may reside on grain surfaces.
Equations are presented for the surface-slip (or jump) values of species concentration, pressure, velocity, and temperature in the low Reynolds number, high-altitude flight regime of a space vehicle. These are obtained from closed-form solutions of the mass, momentum, and energy flux equations by using the Chapman-Enskog velocity distribution function. This function represents a solution of the Boltzmann equation in the Navier-Stokes approximation. The analysis, obtained for nonequilibrium multicomponent airflow, includes the finite-rare surface catalytic recombination and changes in the internal energy during reflection from the surface. Expressions for the various slip quantities have been obtained in a form which can readily be employed in flow-field computations. A consistent set of equations is provided for multicomponent and binary mixtures and single-species gas. An expression is also provided for the finite-rate species-concentration boundary condition for a multicomponent mixture in the absence of slip.
The surprising funguslike morphology which occurs at the liquid(1)/liquid(2)/solid triple junction in directionally solidifying miscibility gap systems at the monotectic temperature is described. The monotectic temperature in a binary mixture is the one at which two immiscible solutions of the same two components form phases in equilibrium with the solid phase of one of the components. The growth of this morphology is described, and a similarity between it and that of a known crystal growth morphology is pointed out.
The viscosity of the following binary mixtures was measured near their consolute points: (1) methanol + cyclohexane, (2) isobutyric acid + water, (3) nitroethane + 3-methylpentane, and (4) 2-butoxyethanol + water. It is shown that the multiplicative hypothesis is valid for these mixtures. It is also found that the concentration closest to critical has the largest viscosity enhancement.
Calculations of sound absorption in air are traditionally based on the assumption that molecular relaxations in N2 and O2 are independent. In binary mixtures of these two gases, however, they are not independent; rather, molecular relaxation is known to be controlled by a very strong vibrational-vibrational (V-V) coupling, which influences both the relaxation frequencies and the relaxation strengths. This article shows that small concentrations of the air constituents CO2 and H2O, which themselves possess a strong V-V coupling to N2 and O2, serve to decouple the N2 and O2 relaxations. To characterize the N2-O2 coupling a coupling strength is derived which depends upon the constituent concentrations and the related reaction rate constants. It is found that the molecular relaxations associated with N2 and O2 in air experience a gradual transition from strong to weak coupling as the humidity increases beyond approximately 0.001 mole percent.
The buoyancy-driven instability of a monocomponent or binary fluid completely contained in a vertical circular cylinder is investigated, including the influence of the Soret effect for the binary mixture. The Boussinesq approximation is used, and the resulting linear stability problem is solved using a Galerkin technique. The analysis considers fluid mixtures ranging from gases to liquid metals. The flow structure is found to depend strongly on both the cylinder aspect ratio and the magnitude of the Soret effect. The predicted stability limits are shown to agree closely with experimental observations.