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The Raman spectra of N-14O2 and N-15O2 have been studied at 20 K. The far infrared of N-14O2 at 20 K was also measured. The data were assigned on the basis of a C-sub 2 nu molecular model. Normal coordinate calculations were performed for a variety of assignments. The assignment that yielded the best fit is presented. The solid state effects are discussed.
Absolute rate constants for the reaction of atomic hydrogen with ozone were obtained over the temperature range 219-360 K by the flash photolysis-resonance fluorescence technique. The results can be expressed in Arrhenius form by K = (1.33 plus or minus 0.32)x10 to the minus 10 power exp (-449 plus or minus 58/T) cu cm/molecule/s (two standard deviations). The present work is compared to two previous determinations and is discussed theoretically.
Classical trajectory calculations are presented for the reaction ClO + O yields Cl + O2, a reaction which is an important step in the chlorine-catalyzed destruction of ozone which is thought to occur in the 220 and 1000 K. The calculated rate constant is 4.36 x 10 to the minus 11th power exp (-191/T)cu cm molecule (-1)s(-1) and its value at 300 K is 2.3 plus or minus 10 to the 11th power cu cm molecule (-1)s(-1), about a factor of 2 lower than recent experimental data. The empirical potential energy surface used in the calculations was constructed to fit experimental data for ClO, O2 and ClOO molecules. Other important features of this potential surface, such as the barrier to reaction, were varied systematically and calculations were performed for a range of conditions to determine the best theoretical rate constants. Results demonstrate the utility of classical trajectory methods for determining activation energies and other kinetic data for important atmospheric reactions.
High-spectral-resolution echellograms confirm the existence of an asymmetric emission core in the K line of Deneb that may be due to chromospheric emission from this A-type supergiant or that may be due to scattering from a circumstellar shell. If the core is due to chromospheric emission, its width does not agree with what is predicted using the Wilson-Bappu relation for late-type stars. This would indicate that the chromospheres of hotter stars are qualitatively different from those of cooler stars. A K-emission-core profile for Aldebaran is also presented.
A study of the 1365 K tensile properties, creep characteristics and residual room temperature properties after creep testing of the experimental oxide dispersion strengthened iron-base alloy MA-956E (Fe-20Cr-4.5Al-0.5Ti-0.5Y2O3) was conducted. The 1365 K tensile properties, particularly ductility, are strongly dependent on strain rate. It appears that MA-956E does not easily undergo slow plastic deformation. Rather than deform under creep loading conditions, the alloy apparently fails by a crack nucleation and growth mechanism. Fortunately, there appears to be a threshold stress below which crack nucleation and/or growth does not occur.
Variation of the equatorial K-corona radiance at 2.5 solar radii from the sun center was studied on a daily basis during the Skylab mission (May 1973 to February 1974). The radiance data may be divided into three periods, the first characterized by a smooth variation in time, the second by a signal that is neither persistent in the short term nor recurrent from one limb passage to the next, and the third (and longest period) by a signal exhibiting an orderly, periodically increasing intensity. The data may be interpreted as indicating a general simplification of the coronal magnetic field; harmonic analysis of the surface field provides additional information on the evolution of the equatorial K-corona structures.
The rate constant for the reaction Br + O3 yields BrO + O2 has been measured from 200 to 360 K by the technique of flash photolysis coupled to time resolved detection of bromine atoms by resonance fluorescence (FP-RF). Br atoms were produced by the flash photolysis of CH3Br at a wavelength of 165 nm. O3 concentration was monitored continuously under reaction conditions by absorption at 253.7 nm. At each of five temperatures the results were independent of substantial variations in O3 concentration, total pressure (Ar), and limited variations in flash intensity (i.e., initial Br concentration). The measured rate constants obey the Arrhenius expression, k = (7.74 plus or minus 0.50) x 10 to the -12th exp(-603 plus or minus 16/T) cu cm/molecule/sec, where the error quoted is two standard deviations.
Absolute rate constants for the reaction of atomic hydrogen with ozone were obtained over the temperature range 219-360 K by the flash photolysis-resonance fluorescence (FP-RF) technique. The results can be expressed in Arrhenius form by k = (1.33 + or - 0.32) times (10 to the minus tenth power) exp(-449 + or - 58/T) cu cm/molecule per sec (two standard deviations). The present work is compared to two previous determinations and is theoretically discussed.
Rate constants for the reaction of atomic hydrogen with ketene have been measured at room temperature by two techniques, flash photolysis-resonance fluorescence and discharge flow-resonance fluorescence. The measured values are (6.19 + or - 1.68) x 10 to the -14th and (7.3 + or - 1.3) x 10 to the -14th cu cm/molecule/s, respectively. In addition, rate constants as a function of temperature have been measured over the range 298-500 K using the FP-RF technique. The results are best represented by the Arrhenius expression k = (1.88 + or - 1.12) x 10 to the -11th exp(-1725 + or - 190/T) cu cm/molecule/s, where the indicated errors are at the two standard deviation level.
Measurements are made of the rate constant for the reaction H + NO2 yielding OH + NO over significant temperature ranges with the flash photolysis-resonance fluorescence (FP-RF) technique and also with the discharge flow-resonance fluorescence (DF-RF) technique. Since it is important to study chemical reactions with more than one technique, the above reaction is investigated with the FP-RF technique over the temperature range 230-400 K. The results reported do not agree with earlier determinations. Accordingly, a separate set of measurements is made with the DF-RF technique over the temperature range 195-368 K; the results are also reported. The reaction is also considered theoretically, especially with regard to the question of temperature dependence and absolute magnitude of the rate constant.
The absolute rate constant of the reaction between chlorine (2P) atoms and hydrogen peroxide was determined from 298 to 424 K, using the discharge flow resonance fluorescence technique. Pseudo-first-order conditions were used with hydrogen peroxide in large excess. A fast flow-sampling procedure limited hydrogen peroxide decomposition to less than 5% over the temperature range studied. At 298 K, the rate constant is (4.1 plus or minus 0.2) x 10 to the minus 13th cu cm/molecule-sec.
A simplified procedure is proposed for calculating the cross section for photoionization from the K-shell for a general atomic system that contains an arbitrary number of outer-shell electrons. The procedure retains the formalism of the one-electron atom case (pure Coulomb-field problem) by determining the effective nuclear charge reduced from Z by 'screening parameters' associated with the other K-shell electron and the outer-bound electrons. The parameters are determined essentially by fitting the atom's radial electric field to Coulomb form at the distance from the nucleus where the integrand of the dipole radial integral is peaked.
The results of the most extensive set to date of thermodynamic calculations on the equilibrium chemistry of several hundred compounds of the elements Na, K, F, Cl, Br, and P in a solar composition system are reported. Two extreme models of accretion are investigated. In one extreme complete chemical equilibrium between condensates and gases is maintained because the time scale for accretion is long compared to the time scale for cooling or dissipation of the nebula. Condensates formed in this homogeneous accretion model include several phases such as whitlockite, alkali feldspars, and apatite minerals which are found in chondrites. In the other extreme complete isolation of newly formed condensates from prior condensates and gases occurs due to a time scale for accretion that is short relative to the time required for nebular cooling or dissipation. The condensates produced in this heterogeneous accretion model include alkali sulfides, ammonium halides, and ammonium phosphates. None of these phases are found in chondrites. Available observations of the Na, K, F, Cl, Br, and P elemental abundances in the terrestrial planets are found to be compatible with the predictions of the homogeneous accretion model.
Fluxes in 1 A bands at the centers of the H and K lines are being measured in main-sequence F-G-K-M stars in the northern half of the Woolley et al. (1970) 'Catalog of stars within twenty-five parsecs of the sun', in a survey not yet completed. Results for 486 stars are presented in the form of flux-color diagrams and discussed in light of evidence that chromospheric activity declines with age in main-sequence stars. Support is noted for the reality of the Sirius moving group. The relative numbers of more-active (Hyades-like) and less-active (solar-like) F-G stars are tolerably in agreement with a nearly constant rate of formation, but there exists an apparent deficiency in the number of F-G stars exhibiting intermediate activity. The possibility that the gap is an accidental characteristic of the sample will be investigated by extending the survey to southern declinations and greater distances.
Conditions were determined in a premixing prevaporizing fuel preparation duct at which ignition occurred. An air blast type fuel injector with nineteen fuel injection points was used to provide a uniform spatial fuel air mixture. The range of inlet conditions where ignition occurred were: inlet air temperatures of 600 to 1000 K air pressures of 180 to 660 kPa, equivalence ratios (fuel air ratio divided by stoichiometric fuel air ratio) from 0.12 to 1.05, and velocities from 3.5 to 30 m/s. The duct was insulated and the diameter was 12 cm. Mixing lengths were varied from 16.5 to 47.6 and residence times ranged from 4.6 to 107 ms. The fuel was no. 2 diesel. Results show a strong effect of equivalence ratio, pressure and temperature on the conditions where ignition occurred. The data did not fit the most commonly used model of auto-ignition. A correlation of the conditions where ignition would occur which apply to this test apparatus over the conditions tested is (p/V) phi to the 1.3 power = 0.62 e to the 2804/T power where p is the pressure in kPa, V is the velocity in m/e, phi is the equivalence ratio, and T is the temperature in K. The data scatter was considerable, varying by a maximum value of 5 at a given temperature and equivalence ratio. There was wide spread in the autoignition data contained in the references.
The central results of a survey of the Mg II resonance line emission in a sample of over 50 evolved late type stars, including spectral-luminosity type F8 to M5 and La to IV are presented. Observed and surface fluxes are derived and correlations noted. The major findings include: (1) Mg II k emission core asymmetry transition near K1 III, analogous to that known for Ca II K; (2) a small gravity and temperature dependence of the Mg II chromospheric radiative loss rate.
The current field strength characteristic, E(1), and a large number of radial temperature distributions, T(r,I), measured in a 5 mm N2 cascade arc at normal pressure are used to evaluate the transport properties of nitrogen up to 26,000 K. The electrical conductivity sigma (T) and the Coulomb cross section are determined directly from the E(I) and several T(r,I) curves. Between 10,000 and 15,000 K the radiative energy flux for different arc current, the thermal conductivity, and from this the charge exchange cross section are determined in a good approximation utilizing the large number of measured temperature distributions. It turns out, that at the highest measured arc current, i.e., 570 A, in the axial region of the arc about 95% of the supplied energy is carried off by radiation.
Low-dispersion ultraviolet spectra (1150-2000 A) of a representative sample of cool stars, including dwarfs and giants of spectral types F-K, obtained with the IUE, are examined. The observation and the absolute calibration procedures are described. Correlation diagrams are constructed that compare chromospheric and transition-region emission line strengths and broadband coronal soft X-ray fluxes. The transition-region and coronal emission in the G-K dwarfs and G giants is well correlated with the Mg II (wavelength 2800) doublet emission strength, which is symptomatic of chromospheric energy losses. The power-law slopes are steeper than unity, particularly for soft X-rays. The implications of the correlations are discussed with respect to the weakening or disappearance of transition regions and hot coronae in the cool half of the red-giant branch and possible chromospheric and coronal heating mechanisms. It is proposed that the weakness of outer atmospheres in the red giants compared with the yellow giants can be understood as a consequence of stellar evolution, since it is possible that stars of slightly different spectral type in the giant branch have very different main-sequence progenitors.