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NASA NTRS1980

The infrared spectrum of matrix isolated hydrogen and deuterium

The induced infrared spectra of H2 and D2, trapped in matrices of Ar, Kr, N2, CO, have been investigated. It is found that in Ar and Kr, the pure rotation spectrum is always readily observable. Portions of the fundamental region, however, are induced by impurities, while the entire spectrum is impurity induced in N2 matrices. These results are discussed in light of a recent Raman study of this system, and in comparison with several single crystal studies. Effective rotational and vibrational constants for matrix isolated H2 are also given.

Warren, J. A.↗
NASA NTRS1980

Electron impact cross sections for v = 0-1 vibrational excitation in CO at electron energies of 3 to 100 eV

The paper discusses the measurements of normalized, absolute differential cross-sections for electron-impact vibrational transition in CO. Integral and momentum-transfer cross-sections were obtained from these differential results; incident electron energies were in the 3 to 100 eV range, and the scattering angles were 10 to 135 deg. A comparison of these results with measurements made with pure vibrationally elastic cross-sections in N2, and with the data based on a two-potential theory for electron scattering from diatomic molecules showed that the present CO cross-sections are similar to those in N2. This indicates that the long-range effect of the small CO dipole moment is negligible in promoting vibrational excitation; moreover, a significant peak in the integral and momentum-transfer cross-sections is observed at 20 eV. Finally, the low-energy integral cross-sections are compared with a recent set of swarm data for vibrational excitation.

Chutjian, A.↗
NASA NTRS1980

Synergistic effects in trace gas-aerosol interactions

The reaction of SO2 and NO2 with soot has been studied experimentally by gravimetric determination of chemisorption with subsequent analysis of the chemisorbed species by various techniques. When samples of commercially available carbon black (used as soot surrogate) are exposed to SO2 or NO2 in dry air or N2 as carrier gas, no quantitative chemisorption (less than 5 micrograms per mg of substrate) is observed. However, exposure of the same grade of carbon to a combination of SO2 and NO2 in dry air of N2 results in significant chemisorption (180-200 micrograms/mg), a major fraction of which is analyzed as sulfate.

Schryer, D. R.↗
NASA NTRS1980

Trace constituents in the middle atmosphere by high resolution UV spectroscopy

An array of 5 autonomous spectrometers, the imaging spectrometric observatory covers a broad wavelength range (approximately 200 to 12,000 A), has a resolution selectable down to approximately 0.5 A, and a dynamic range of approximately 10 to the 7th power and is designed to select experiment measurement sequences by software control. Because current models of thermospheric ionic processes produce too much N2(+) ionization, the N2(+) reaction with O and the chemistry of metastable (N(+) ions and of O2(+) ions are objects of study on Spacelab 1.

Torr, D. G.↗
NASA NTRS1980

Shock tube propellant reactions: Ignition of M-9 and catalysis of RDX

The preliminary results of shock tube experiments to study RDX catalysis are presented. It is shown that using N2 as the test gas (P approximately equal to 90 KPa, T bar approximately equal to 650K), the replacement of RDX powder with NaBH4 (20% by weight) leads to a large increase in the amount of RDX reacting and a small decrease in ignition delays T sub i. It is further shown that higher temperatures due to exothermic pyrolysis reactions of NaBH4 are not responsible for these effects. Replacement of N2 by NO2 (10% by volume) in the environment of RDX powders (T bar approximately equal to 650K, P = 90-400 KPa) leads to an increase in T sub i and T sub i is directly proportional to NO2 pressure. Inhibition appears to be initiated by reactions between NO2 and either RDX or the RDX decomposition products.

Cohen, A.↗
NASA NTRS1981

Chemical kinetic analysis of hydrogen-air ignition and reaction times

An anaytical study of hydrogen air kinetics was performed. Calculations were made over a range of pressure from 0.2 to 4.0 atm, temperatures from 850 to 2000 K, and mixture equivalence ratios from 0.2 to 2.0. The finite rate chemistry model included 60 reactions in 20 species of the H2-O2-N2 system. The calculations also included an assessment of how small amounts of the chemicals H2O, NOx, H2O2, and O3 in the initial mixture affect ignition and reaction times, and how the variation of the third body efficiency of H2O relative of N2 in certain key reactions may affect reaction time. The results indicate that for mixture equivalence ratios between 0.5 and 1.7, ignition times are nearly constant; however, the presence of H2O and NO can have significant effects on ignition times, depending on the mixture temperature. Reaction time is dominantly influenced by pressure but is nearly independent of initial temperature, equivalence ratio, and the addition of chemicals. Effects of kinetics on reaction at supersonic combustor conditions are discussed.

Rogers, R. C.↗
NASA NTRS1981

Effect of water vapor on sound absorption in nitrogen at low frequency/pressure ratios

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.

Zuckerwar, A. J.↗
NASA NTRS1981

Analyses of atomic oxygen, the green line, and Herzberg bands in the lower thermosphere

Measured altitude profiles of atomic oxygen, 557.7-nm emissions, and Herzberg I emission between 80 and 120 km were used to test the proposed mechanisms leading to these emissions. As generally assumed, the O2(A 3 Sigma u +) that emits the Herzberg I bands is excited by three-body recombination of atomic oxygen. The quenching of this state is by N2 or O2; for N2 the lifetime times the rate is 2.75 x 10 to the -13th per cu cm; other quenchers are insignificant. It is found that the atomic oxygen O(1S) emitting the green line is excited by the Barth mechanism.

Thomas, R. J.↗
NASA NTRS1980

Mass spectrometric measurements of the neutral gas composition of the thermosphere and exosphere of Venus

The neutral gas composition and density in the thermosphere of Venus is being measured with a quadrupole mass spectrometer on the Pioneer Venus orbiter. Data are obtained near periapsis once per day approximately 150-250 km above the surface. The principal gases in the thermosphere are CO2, CO, N2, O, N, and He. Atomic oxygen is the major constituent above 155 km on the dayside and also on the nightside up to 180 km when helium becomes the major constituent. The average values of CO2, CO, N2, O, and N remain nearly constant during day and night, but an abrupt change occurs across the terminator from a high dayside value to a low nightside value. The helium density varies in the opposite way, and a distinct bulge was observed at night near the morning terminator. The data have been used as the basis of an empirical model. Large orbit to orbit variations in densities were also observed on the nightside, suggesting perhaps strong turbulent motion in the atmosphere below. Kinetic temperatures inferred from scale heights are approximately 285 K on the dayside and 110 K at night. The average global temperature obtained from the model is 199 K.

Niemann, H. B.↗
NASA NTRS1980

The upper atmosphere of Venus during morning conditions

The structure and composition of the Venus upper atmosphere between 130- and 650-km altitude were measured for a solar zenith angle of approximately 60 deg by the neutral gas mass spectrometer on board the Pioneer Venus multiprobe bus. Below 180 km a wavelike structure is quite evident in the CO2 and He number density profiles. For altitudes above 100 km a one-dimensional model of the Venus upper atmosphere during morningside conditions (MS model) is presented. Number densities at 150-km altitude are as follows: CO2 equals 4.2 x 10 to the 9th, N2 equals 1.1 x 10 to the 9th, CO equals 2.8 x 10 to the 9th, and He equals 4.8 x 10 to the 6th per cu cm. The homopause altitudes for N2 and He are at 136 and 130 km, respectively.

Von Zahn, U.↗
NASA NTRS1981

Measurement of metastable N/+/1S/ 5755-A emission in the twilight thermosphere

Measurements are reported of the 5755-A emission arising from the transition N(+)(1D-1S) made at Sutherland, South Africa (32.4 deg S, 20.8 deg E). The surface brightness of the emission in mid-November 1977 decayed from approximately 5 R at 10 solar depression angle (SDA) to approximately 1 R at 15 deg SDA. By the use of these data, it has been determined that less than 5% of all N2 ionizations result in the production of N(+) ions in the 1S state. Quenching of N(+)(1S) by neutral constituents and electrons is found to be negligible above 220 km in the twilight thermosphere in November and December 1977. Measurements of the 5755-A emission therefore potentially provide a ground based means of measuring the N2 density in the twilight thermosphere.

Torr, D. G.↗
NASA NTRS1980

Evolution of Io's volatile inventory

Voyager data are used to make crude estimates of the rate at which Io loses volatiles, by a variety of processes, to the surrounding magnetosphere, for the case of both the current, SO2-dominated atmosphere and hypothetical paleoatmospheres in which such other gases as N2 may have been the dominant constituent. Among the mechanisms making significant contributions to the prodigious rate at which Io is losing volatiles are: the interaction of the magnetospheric plasma with volcanic plume particles and the background atmosphere; the sputtering of ices on the surface, if the nightside atmospheric pressure is low enough; and Jeans' escape of O as a dissociation product of SO2 gas. It is also argued that in the case of paleoatmospheres only the first two alternatives would have been possible and, nevertheless, insufficient to account for N2 loss over the life of the satellite.

Pollack, J. B.↗
NASA NTRS1981

Spectroscopy of the extreme ultraviolet dayglow during active solar conditions

The spectral characteristics of the mid-latitude daytime airglow observed between 530 and 1500 A under conditions of high solar activity are compared with those obtained at the same location during markedly lower solar activity. The spectral observations were made by two scanning spectrometers and an N2 3371 A photometer carried aboard Astrobee-F rockets launched from White Sands Missile Range, NM, on January 9, 1978 and June 27, 1980. The more recent data allow the partial resolution of the emission spectrum between 800 and 1200 A into a large number of weak N I, O I and N2 transitions. Data taken at 220 km altitude suggest an increase in atomic nitrogen density of more than a factor of 3 between the two observations, along with a doubling of the solar EUV flux at wavelengths less than 688 A. No evidence of a corresponding increase in the 10 to 50 eV photoelectron flux is found, however, an ionospheric sounding data indicate the peak electron density to have decreased during this period. The mechanism for this electron flux decrease in the face of increased EUV flux and only a three-fold increase in N concentration remains unknown.

Gentieu, E. P.↗
NASA NTRS1982

Radiative lifetimes and quenching rate coefficients for directly excited rotational levels of OH/A 2Sigma +, v-prime = 0/

A narrow-bandwidth pulsed dye laser was used to excite OH X 2Pi i radicals to the A 2Sigma(+) state by pumping in the (0, 0) vibrational band around 308 nm. The radiative lifetimes of specific (K-prime, J-prime) rotational levels in v-prime = 0 were measured at low pressures (not greater than 1 mtorr), which yielded a mean lifetime of 0.71 + or - 0.009 microsec (2 sigma). Electronic quenching rate constants for N2, O2, H2O, and H2 were measured for a range of initially excited rotational levels. A strong dependence of this rate constant on the initially excited rotational level was found for N2, and less markedly for O2, with the rate constant tending to increase for the lowest rotational levels K-prime not greater than 3. The implications of these results for the laser-induced fluorescence detection of atmospheric OH are discussed.

Mcdermid, I. S.↗
NASA NTRS1982

Titan's upper atmosphere - Composition and temperature from the EUV solar occultation results

It is inferred from observation of an occultation of the sun by Titan, using the Voyager 1 UV spectrometer, that temperatures are 176 + or - 20 K near the evening terminator and 196 + or - 20 K near the morning terminator, and that the major atmospheric constituent is N2, with a density of 2.7 + or - 0.2 x 10 to the 8th/cu cm at 3840 km. A layer of absorbing molecules, possibly polymers, is found near both morning and evening terminators. A photochemical model suggests that the homopause is located at 3500 + or - 70 km, with an eddy diffusion coefficient of 1(+2, -0.7) x 10 to the 8th/sq cm per sec, which decreases to about 1000 sq cm/sec in the lower stratosphere as N2 to the -2/3 power.

Smith, G. R.↗
NASA NTRS1982

The ultraviolet spectrum of an aurora 530-1520 A

Ultraviolet spectra between 530 and 1520 A of an active auroral arc were obtained at 6.5-A instrumental resolution. Several new emission features are identified, including several bands of the N2 Birge-Hopfield (1, v-double-prime) progression and numerous N I multiplets, the latter being preponderant at low altitudes. The improved instrumental resolution over previous experiments in the wavelength region below 1200 A allows for a partial resolution of the complex structure between 900 and 1100 A reported in earlier work. The ratio of O I 1356 to N2 Lyman-Birge-Hopfield is smaller than in the dayglow at a similar altitude, and this is interpreted as evidence for a depletion of atomic oxygen in the auroral ionosphere relative to mid-latitude composition.

Feldman, P. D.↗
NASA NTRS1982

Determination of photoionization branching ratios and total photoionization cross sections at 304 A from experimental ionospheric photoelectron fluxes

High-resolution measurements of the ionospheric photoelectron spectrum are used to derive photoionization cross sections and branching ratios for N2 and O at 304 A, the wavelength of the intense He II solar radiation. Based on a theory in which the measured fluxes at energies 22.5, 24.5, 25.5 and 27.5 eV are determined by the ratio of the production rate and the loss rate coefficient, values are obtained for the ratio of molecular nitrogen density to atomic oxygen density as a function of altitude, the sum of the total photoionization cross sections, the 2P/4S and 2D/4S branching ratios for O and the B/X and A/X branching ratios for N2 photoionization and the ratios and the interspecies cross section ratios 2D/A, 4S/X and 2P/B. The values obtained are in accord with the photoionization cross sections of Kirby et al. (1979).

Richards, P. G.↗
NASA NTRS1982

The combined effects of Fe and H2 on the nitridation of silicon

In view of the support offered by previous work for the suggestion that Fe may affect alpha-Si3N4 formation and microstructural development, a two-part study was conducted to differentiate the effects of H2 and Fe in, first, the nitridation of pure and of Fe-containing powder in N2 and N2-4% H2, and then the nitridation of (1 1 1) Si single crystal wafers with and without Fe powder on the surface. The degree of nitridation is most strongly affected by H2 at 1200 C, but by Fe at 1375 C, where Fe-containing samples in either atmosphere were almost completely nitrided. While neither H2 nor Fe alone changed the ratio of alpha-Si3N4 to beta-Si3N4, the combination of H2 and Fe increased it at both temperatures.

Shaw, N. J.↗