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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
NASA NTRS1995

Rate constants and temperature dependences for the reactions of hydroxyl radical with several halogenated methanes, ethanes, and propanes by relative rate measurements

Rate constants of 15 OH reactions with halogen-substituted alkanes, C1 to C3, were studied using a relative rate technique in the temperature range 283-403 K. Compounds studied were CHF2Cl (22), CHF2Br (22B), CH3F (41), CH2F2 (32), CHF3 (23), CHClFCCl2F (122a), CHCl2CF3 (123), CHClFCF3 (124), CH3CF3 (143a), CH3CH2F (161), CF3CHFCF3 (227ea), CF3CH2CF3 (236fa), CF3CHFCHF2 (236ea), and CHF2CF2CH2F (245ca). Using CH4, CH3CCl3, CF3CF2H, and C2H6 as primary reference standards (JPL 92-20 rate constants), absolute rate constants are derived. Results are in good agreement with previous experimental results for six of the compounds studied, including CHF2Cl, CHF2Br, CH2F2, CH3CF3, CHFClCFCl2, and CF3CHFCF3. For the remainder the relative rate constants are lower than those derived from experiments in which OH loss was used to measure the reaction rate. Comparisons of the derived Arrhenius A factors with previous literature transition-state calculations show order of magnitude agreement in most cases. However, the experimental A factors show a much closer proportionality to the number of H atoms in the molecule than is evident from the transition state calculations. For most of the compounds studied, an A factor of (8 +/- 3)E-13 cm(exp 3)/(molecule s) per C-H bond is observed. A new measurement of the ratio k(CH3CCl3)/k(CH4) is reported that is in good agreement with previous data.

Hsu, K.-J.↗
NASA NTRS1994

Temperature dependence of the ozone obsorption spectrum over the wavelength range 410 to 760 nm

The ozone, O3, absorption cross sections between 410 and 760 nm, the Chappuis band, were measured at 220, 240, 260, and 280 K relative to that at room temperature using a diode array spectrometer. The measured cross sections varied very slightly, less than 1%, with decreasing temperature between 550 and 660 nm, near the peak of the Chappuis band. At wavelengths away from the peak, the absorption cross sections decreased with decreasing temperature; e.g., about 40% at 420 nm between 298 and 220 K. These results are compared with previous measurements and the impact on atmospheric measurements are discussed.

Burkholder, James B.↗
NASA NTRS1997

Efficiency and temperature dependence of water removal by membrane dryers

The vapor pressure of water in equilibrium with sorption sites within a Nafion membrane is given by log P(WN) = -3580/T + 10.01, where P(WN) is expressed in Torr and T is the membrane temperature, in kelvin. The efficiency of dryers based on selective permeation of water through Nafion can thus be enhanced by cooling the membrane. Residual water in effluents exceeds equilibrium levels if insufficient time is allowed for water to diffuse to the membrane surface as gas passes through the dryer. For tubular configurations, this limitation can be avoided if L > or = Fc(10(3.8)/120 pi D), where L is the length of the tubular membrane, in centimeters, Fc is the gas flow rate, in mL/ min, and D is the diffusion coefficient for water in the carrier gas at the operating temperature of the dryer, in cm2/s. An efficient dryer that at room temperature dries gas to a dew point of -61 degrees C is described; the same dryer maintained at 0 degrees C yields a dew point of -80 degrees C and removes water as effectively as Mg(ClO4)2 or a dry ice/acetone slush. The use of Nafion membranes to construct devices capable of delivering gas streams with low but precisely controlled humidities is discussed.

Non-NASA Center↗
NASA NTRS1976

Temperature dependency of the photoabsorption cross section for CF2Cl2

The photoabsorption cross section for CF2CL2 is measured at 297 K and 200 K. Cross sections are obtained for the ground and first two vibrationally excited states, allowing for a determination of the photoabsorption as a function of temperature over the range of stratospheric interest.

Boitnott, C. A.↗
NASA NTRS2007

Temperature Dependent E2 Raman Modes in the ZnCoO Ternary Alloy

The anharmonic properties of low and high frequency E2 modes of ZnO and Co doped ZnO were investigated using Raman scattering spectroscopy. We have determined the behavior of frequency, linewidths, and lifetime of E2 modes in the temperature range from 80 to 800 K. In the case of E2(high) mode the frequency shift towards the lower energy side was analyzed in light of the theory of anharmonic phonon-phonon interaction and thermal expansion of the lattice, and the linewidth behavior was analyzed in terms of anharmonic effect of three-phonon decay mechanism. But in the case of E2(low), the linewidth and frequency behaved practically harmonic with respect to temperature and independent of Co substitutions. It is found that the E2(high) phonon anharmonicity is higher for ZnCoO alloys than in pure ZnO and it increases with the compositional disorder. The low temperature lifetime of E2 phonon in ZnO, 1 % and 3% Co doped ZnO were found to be 1.S2, 1.74, and 1.54 ps, respectively.

Samanta, K.↗
NASA NTRS1991

The mechanisms and temperature dependence of superlattice stacking fault formation in the single-crystal superalloy PWA 1480

The mechanism of the formation of superlattice staking faults in the single-crystal nickel-base superalloy PWA 1480 was investigated by observing deformation microstructures in the superalloy single crystals in the temperature range 20-1100 C. Results showed that, in addition to superlattice stacking faults observed after slow strain rate deformation at temperatures from 700 to 950 C, a high-density of superlattice staking faults formed after deformation at 200 C and below. The mechanisms of fault formation, which are different in the high- and the low-temperature regimes, are discussed.

Milligan, Walter W.↗
NASA NTRS1973

Temperature-dependent hyperfine interactions in Fe2B.

Moessbauer absorption spectra have been observed for Fe2B from 290 to 1175 K. A change in the electric quadrupole interaction was observed from 460 to 480 K and interpreted as a result of the rotation of the easy axis of magnetization as a function of temperature. The effective magnetic hyperfine field is defined as a function of temperature. A discontinuity in the isomer shift of 0.018 (plus or minus 0.010) mm/sec was found across the ferromagnetic transition.

Murphy, K. A.↗
NASA NTRS1974

Temperature dependence of vibrational relaxation in the HF, DF, HF-CO2, and DF-CO2 systems

The laser excited fluorescence method has been employed to determine rate constants for V to V, R and V to R, T relaxation HF (nu = 1) and DF(nu = 1) by CO2 over the temperature range from 295 to 670 K. The self-deactivation rates for HF(nu = 1) and DF(nu = 1) by ground state molecules and the rate of V to V, R transfer from HF(nu = 1) and DF(nu = 1) to the CO2 (00/0/1) state exhibit a marked decrease with increasing temperature. The results provide additional evidence for the conversion of the large vibrational energy defects of the present systems into rotational motion of the hydrogen halide under the influence of a sizable attractive intermolecular potential well.

Lucht, R. A.↗
NASA NTRS1981

Temperature dependent UV absorption cross sections for carbonyl sulfide

The ultraviolet absorption spectrum of carbonyl sulfide is investigated in order to assess the importance of the photolytic sink for OCS in the troposphere. Absorption cross sections were measured at wavelengths between 185 and 300 nm in a double-beam spectrometer at temperatures of 295 and 225 K. The results are found to be in good agreement with previous reports in the short wavelength region, but significantly lower than the value of 2 x 10 to the 22nd sq cm/molecule proposed by Rudolf and Inn (1981) between 280 and 300 nm, which may be attributed to trace contaminants or dimerization. A marked temperature effect is noted at wavelengths greater than 240 nm and below 190 nm. As no evidence of absorption at wavelengths greater than 270 nm was found, estimates of the solar photodissociation rate of tropospheric OCS based on the present cross sections yield a value of about 2 x 10 to the -9th/sec, corresponding to a tropospheric lifetime of about 20 years. It is therefore concluded that solar photolysis represents a negligible sink for OCS.

Molina, L. T.↗
NASA NTRS2001

Exploiting the Temperature Dependence of Magnetic Susceptibility to Control Convective in Fundamental Studies of Solidification Phenomena

It is well known that convection is a dominant mass transport mechanism when materials are solidified on Earth's surface. This convection is caused by gradients in density (and therefore gravitational force) that are brought about by gradients in temperature, composition or both. Diffusion of solute is therefore dwarfed by convection and the study of fundamental parameters, such as dendrite tip shape and growth velocity in the absence of convection is nearly impossible. Significant experimental work has therefore been carried out in orbiting laboratories with the intent of minimizing convection by minimizing gravity. One of the best known experiments of this kind is the Isothermal Dendritic Growth Experiment (IDGE), supported by NASA. Naturally such experiments are costly and one objective of the present investigation is to develop an experimental method whereby convection can be halted, in solidification and other experiments, on the Earth's surface. A second objective is to use the method to minimize convection resulting from the residual accelerations suffered by experiments in microgravity.

Seybert, C.↗
NASA NTRS1991

The temperature dependence of collision-induced absorption by oxygen near 6 microns

Coefficients for oxygen absorption in the infrared induced by collisions with O2 and N2 are reported over the range 1400-1800/cm and 225-356 K. These coefficients are used to calculate the absorption for O2 in air as a function of temperature and wavenumber, and comparisons are made with previous determinations. In addition, structured absorption features superimposed on the broad collision-induced absorption band, which were observed at all temperatures studied, are interpreted in terms of the presence of (O2)2 and O2-N2 van der Waals molecules.

Orlando, John J.↗
NASA NTRS1987

High temperature (900-1300 C) mechanical behaviour of dendritic web grown silicon ribbons - Strain rate and temperature dependence of the yield stress

The mechanical behavior of dendritic web Si ribbons close the melting point was studied experimentally. The goal of the study was to generate data for modeling the generation of stresses and dislocation structures during growth of dendritic web Si ribbons, thereby permitting modifications to the production process, i.e., the temperature profile, to lower production costs for the photovoltaic ribbons. A laser was used to cut specimens in the direction of growth of sample ribbons, which were then subjected to tensile tests at temperatures up to 1300 C in an Ar atmosphere. The tensile strengths of the samples increased when the temperature rose above 1200 C, a phenomena which was attributed to the diffusion of oxygen atoms to the quasi-dislocation sites. The migration to the potential dislocations sites effectively locked the dislocations.

Mathews, V. K.↗
NASA NTRS1994

Temperature dependent absorption cross-sections of HNO3 and N2O5

Absorption cross-sections for HNO3 and N2O5 have been measured in the wavelength region 220-450 nm, using a dual beam diode array spectrometer with a spectral resolution of 0.3 nm. The results for both compounds are in good agreement with recommended values at room temperature. However, the cross-sections of both HNO3 and N2O5 show a marked reduction with decreasing temperature in the range 295-233 K. The calculated photolysis rate of HNO3 at the low temperatures and high solar zenith angles characteristic of the polar winter and spring is significantly lower than previously estimated.

Rattigan, Oliver V.↗
NASA NTRS1995

The reaction O((3)P) + HOBr: Temperature dependence of the rate constant and importance of the reaction as an HOBr stratospheric loss process

The absolute rate constant for the reaction O((3)P) + HOBr has been measured between T = 233K and 423K using the discharge-flow kinetic technique coupled to mass spectrometric detection. The value of the rate coefficient at room temperature is (2.5 +/- 0.6) x 10(exp -11)cu cm/molecule/s and the derived Arrhenius expression is (1.4 +/- 0.5) x 10(exp -10) exp((-430 +/- 260)/T)cu cm/molecule/s. From these rate data the atmospheric lifetime of HOBr with respect to reaction with O((3)P) is about 0.6h at z = 25 km which is comparable to the photolysis lifetime based on recent measurements of the UV cross section for HOBr. Implications for HOBr loss in the stratosphere have been tested using a 1D photochemical box model. With the inclusion of the rate parameters and products for the O + HOBr reaction, calculated concentration profiles of BrO increase by up to 33% around z = 35 km. This result indicates that the inclusion of the O + HOBr reaction in global atmospheric chemistry models may have an impact on bromine partitioning in the middle atmosphere.

Nesbitt, F. L.↗