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At least 1,369 records · Page 76
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NASA NTRS1987

Production of Cl2O2 from the self-reaction of the ClO radical

The species Cl2O2 has been generated in a gaseous flow system at 220-240 K by reacting Cl atoms with one of three different ClO precursors: O3, Cl2O, or OClO. The infrared spectra of the reactive mixture indicate that at least two different dimers are produced: a predominant form with bands centered at 1225 and 1057/cm attributed to ClOOCl, and a second form with a band at 650/cm attributed to ClOClO. The UV spectrum of the predominant form shows a maximum absorption cross section of about 6.5 x 10 to the -18th sq cm/molecule around 270 nm, with a wing extending beyond 300 nm. The implications of these results for the chemistry of the stratosphere are discussed.

Molina, L. T.↗
NASA NTRS1987

A simple interpretation of the Fe2(-) photoelectron spectrum

The photoelectron spectrum of Fe2(-) can be simply interpreted in terms of electron detachment from the mildly bonding 4s sigma sup * sub u orbital of a (4s sigma sub s)(sup 2) (4s sigma sup * sub u)(sup 2) (3d)(sup 13) anion. This interpretation implies a (4s sigma sub g)(sup 2) (4s sigma sup * sub u)(sup1) (3d)(sup13) configuration for the ground state of Fe2, correlating with one ground state (4s2 3d6) and one excited state (4s1 3d7) Fe atom. A comparison of the bond length and vibrational frequency of Fe2 to values for transition metal dimers containing single 4s-4s bonds is suggestive of 3d-3d bonding in this molecule. The results of preliminary full-valence configuration interaction calculations provide stron support for the proposed Fe2 and Fe2(-) configurations.

Leopold, Doreen G.↗
NASA NTRS1987

Non-enzymatic transcription of an oligodeoxynucleotide 14 residues long

Nonenzymatic synthesis of oligodeoxynucleotides up to 14 residues long from 2-MeImpG and 2-MeImpC mononucleotides was demonstrated. The synthesis is primed by 14-mer and 15-mer oligonucleotides d(C3GC3GC3GC2) and d(C3GC3GC3GC3) as templates. The predominant products are a series of 3-prime-5-prime-linked oligonucleotides, complementary to the template, ranging in length from GGC to GGCGGGCGGGCGGG. The 15-mer template directed the synthesis of the same family of products that were formed on the 14-mer template. This finding is explained by the preferential conversion of the dimer GG to GGC rather than to GGG. In the context of molecular evolution, these results suggest that the detailed kinetics of template-directed synthesis could form the basis for the selection of one replicating oligonucleotide from a family of closely related oligonucleotides.

Acevedo, Oscar L.↗
NASA NTRS1988

Electron-temperature dependence of the recombination of electrons with O4(+) ions

The coefficient for recombination of O4(+) ions with electrons has been measured as a function of Te by analyzing electron- and ion-density decays in microwave-generated afterglow plasmas in neon-oxygen mixtures. Te values in the afterglow were elevated above those of the neutral species and ions by continuous application of microwave power. The data analysis included effects on the Te arising from inelastic collisions of electrons with the minority oxygen molecules and spatial nonuniformities of Te due to the spatially nonuniform microwave heating field. Over the temperature range Te = 143-5500 K the recombination coefficients were found to have a Te exp -z dependence, with z = 0.48 + 0.1 or - 0.05. While the values of the recombination coefficients for this dimer ion are an order of magnitude larger than those of the monomer ions, the temperature dependence is close to the Te exp -0.5 dependence predicted and often observed for diatomic ions.

Dulaney, J. L.↗
NASA NTRS1988

Photochemical trajectory modelling studies of the 1987 Antarctic spring vortex

Simulations of Antarctic ozone photochemistry performed using a photochemical model integrated along air parcel trajectories are described. This type of model has a major advantage at high latitudes of being able to simulate correctly the complex interaction between photolysis and temperature fields, which, because of the polar night cannot be represented accurately in a zonally averaged framework. Isentropic air parcel trajectories were computed using Meteorological Office global model analyses and forecast fields from positions along the ER-2 flight paths during the Airborne Antarctic Ozone Experiment in Austral Spring 1987. A photochemical model is integrated along these trajectories using the aircraft observations to initialize constituent concentrations. The model includes additional reactions of the ClO dimer and also bromine reactions, which are thought to play a significant role in Antarctica. The model also includes heterogeneous reactions which are invoked when the air parcel passes through a polar stratospheric cloud (PSC). The existence of a PSC is determined throughout the course of the model integration from the parcel temperature and the saturated vapour pressure of water over an assumed H2O/HNO3 mixture. The air parcel temperature is used to determine the saturated vapor pressure of HNO3 over the same mixture. Mixing ratios which exceed saturation result in condensation of the excess in the model and hence lead to a reduction of the amount of gas phase NO2 available for chemical reaction.

Austin, J.↗
NASA NTRS1988

Studies of ClO and BrO reactions important in the polar stratosphere: Kinetics and mechanism of the ClO+BrO and ClO+ClO reactions

The reactions, BrO + ClO yields Br + ClOO (1a) yields Br + OClO (1b) yields BrCl + O2 (1c) and ClO + ClO yields Cl + CiOO (2a) yields Cl + OClO (2b) yields Cl2 + O2 (2c) yields (ClO)2 (2d) have assumed new importance in explaining the unusual springtime depletion of ozone observed in the Antarctic stratosphere. The mechanisms of these reactions involve the formation of metastable intermediates which subsequently decompose through several energetically allowed products providing the motivation to study these reactions using both the discharge flow-mass spectrometric and flash photolysis - ultraviolet absorption techniques. These methods have also been used to explore aspects of the kinetics and spectroscopy of the ClO dimer.

Friedl, Randall R.↗
NASA NTRS1988

Measurements of the ClO radical vibrational band intensity and the ClO + ClO + M reaction product

There is considerable interest in the kinetics and concentrations of free radicals in the stratosphere. Chlorine monoxide is a critically important radical because of its role in catalytic cycles for ozone depletion. Depletion occurs under a wide variety of conditions including the Antarctic spring when unusual mechanisms such as the BrO sub x/ClO sub x, ClO dimer (Cl sub 2 O sub 2), and ClO sub x/HO sub x cycles are suggested to operate. Infrared spectroscopy is one of the methods used to measure ClO in the stratosphere (Menzies 1979 and 1983; Mumma et al., 1983). To aid the quantification of such infrared measurements, researchers measured the ClO ground state fundamental band intensity.

Burkholder, James B.↗
NASA NTRS1988

Modelling the Antarctic lower stratosphere

Results form modeling studies of the Antarctic lower stratosphere which have attempted to simulate the large springtime ozone losses and corresponding changes in other trace constituents are given. These studies were carried out in a photochemical box model, a one-dimensional model without transport and in a two-dimensional photochemical-dynamical-radiation model. The photochemical studies have investigated inter alia the sensitivity of ozone to inclusion in the model of heterogeneous chemistry, and to the inclusion of the ClO dimer. When both of these are incorporated in the model, ozone depletions resembling whose found in Halley Bay in 1987 (J.C. Farman, Nature, 329, 1987) can be reproduced. The temporal variations (both diurnal and during the August to October period) of a number of important tracers including HCl, ClONO2, OClO and BrO are discussed. The two-dimensional study concentrated on the difficulty of establishing in the model the dynamical preconditioning of the lower polar stratosphere - low temperatures, low N2O, etc., high ClOx. Calculations are presented to show: (1) the depletion of ozone during the springtime season, (2) the effect of large ozone losses on lower latitudes, and (3) the longer term (multi-year) variations of ozone in Antarctica, assuming realistic increases in the atmospheric halogen burden.

Chipperfield, M. P.↗
NASA NTRS1988

The chemistry of Antarctic ozone 1960-1987

The factors that influence Antarctic ozone are examined with a view to understanding the observed historical trend. Researchers show that reduced ambient temperatures can dramatically enhance the efficiency of chemical removal processes. Attention is focused on positive feedback between levels of ozone, temperature, and rates of heterogeneous chemical reactions. ClO and its dimer, and high levels of these gases are maintained until the clouds evaporate, on 15 September for the simulation shown here.

Salawitch, R. J.↗
NASA NTRS1989

New observations of a large concentration of ClO in the springtime lower stratosphere over Antarctica and its implications for ozone-depleting chemistry

New measurements of stratospheric chlorine monoxide (ClO) were made at McMurdo Station, Antarctica, during the austral spring of 1987. Rotational emission line spectroscopy, employing a ground-based detector, was used to determine mixing ratio profiles over the range about 17-45 km. A spectral band pass double that was used for similar measurements in 1986 allowed an improvement to be made in the definition of the anomalous low-altitude stratospheric ClO layer associated with springtime ozone depletion. A peak mixing ratio of 1.6 + or - 0.4 parts per billion by volume (ppbv) (95 percent confidence level) was found at 19.5 + or - 1 km at midday during the period September 20-24, 1987. The observed peak mixing ratio and diurnal behavior are discussed in relation to chemical depletion theories. Calculations indicate that the large observed ClO concentration provides an efficient closure for a catalytic Cl cycle through the ClO dimer mechanism, yielding good agreement with various observed features of O3 depletion.

De Zafra, R. L.↗
NASA NTRS1989

Kinetics of O3 destruction by ClO and BrO within the Antarctic vortex - An analysis based on in situ ER-2 data

The kinetics of ozone destruction within the Antarctic polar vortex are studied via simultaneous in situ observations of ClO, BrO, O3, N2O, pressure, and temperature. It is found that the chlorine dimer mechanism rate, limited by the reaction ClO + ClO + M yields ClOOCl + M, contributes the most to the integrated rate of ozone destruction within the vortex on isentropic surfaces between altitudes of 14 and 18.3 km.

Anderson, J. G.↗
NASA NTRS1989

Lagrangian photochemical modeling studies of the 1987 Antarctic spring vortex. I - Comparison with AAOE observations

Results from the Lagrangian photochemical model integrated along computed air parcel trajectories intersected by the ER-2 aircraft are presented and compared with AAOE observations. According to the model, the BrO observations made from the ER-2 within the dehydrated denitrified region are consistent with there being approximately 5 parts per trillion by volume of BrO(y) at 428 K in spring. Within the high ClO region, ozone destruction rates are expected to exceed 2 percent/d with approximately 80 percent due to the ClO dimer mechanism.

Jones, R. L.↗
NASA NTRS1989

Lagrangian photochemical modeling studies of the 1987 Antarctic spring vortex. II - Seasonal trends in ozone

A photochemical model consisting of 40 species and 107 reactions is integrated along 80-day air parcel trajectories calculated in the lower stratosphere for the springtime Antarctic. For the trajectory starting at 58 deg S, which may be regarded as outside the circumpolar vortex, only a small change in O3 occurs in the model. In contrast, for the air parcel starting in the vortex at 74 deg S, the O3 concentration is reduced by 93 percent during the 80 days from the beginning of August to late October. The model results for several species are compared with measurements from the Airborne Antarctic Ozone Experiment and, in general, good agreement is obtained. In the model, the dentrification of the air parcels in polar stratospheric clouds increases the amount of chlorine present in active form. Heterogeneous reactions maintain high active chlorine which destroys O3 via the formation of the ClO dimer. Results of calculations with reduced concentrations of inorganic chlorine show considerably reduced O3 destruction rates and compare favorably with the behavior of total O3 since the late 1970s. The remaining major uncertainties in the photochemical aspects of the Antarctic ozone hole are highlighted.

Austin, J.↗
NASA NTRS1989

Stratospheric ozone - Impact of human activity

The current knowledge of the chemistry of the stratosphere is reviewed, with particular consideration given to the measurements from the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment and from the Airborne Antarctic Ozone Experiment. Analysis of the ATMOS data at 30 deg N suggests that the current understanding of the contemporary-stratosphere chemistry at mid-latitudes is relatively complete, except for possible problems with the diurnal variations of N2O5 at low altitudes, and with ClNO3 at higher altitudes. Except for some difficulties with these two compounds, the data from ATMOS agree well with the gas phase models for nitrogen and chlorine species at 30 deg N in spring. It is emphasized that, in addition to the HOCl mechanism proposed by Solomon et al. (1986), the ClO-BrO scheme proposed by McElroy et al. (1986), and the ClO dimer mechanism introduced by Molina and Molina (1987), other processes exist that are responsible for ozone removal.

Mcelroy, Michael B.↗
NASA NTRS1990

Vibrational frequencies for Be3 and Be4

The harmonic frequencies of Be3 and Be4, evaluated by multireference configuration-interaction (MRCI) and singles and doubles coupled-cluster (CCSD) methods, are reported, as are IR intensities evaluated by using the double harmonic approximation. A comparison of the results shows that the CCSD method augmented with a correction for connected triple excitations, CCSD(T), can be a viable alternative to MRCI for determining the ground-state properties of small Be clusters (other than the dimer). Results of normal mode analyses indicate that the anharmonic vibrational frequencies of Be3 and Be4 are reasonably consistent at the CCSD, CCSD(T), or MRCI levels of treatment.

Rendell, Alistair P.↗
NASA NTRS1990

Oligomerization reactions of deoxyribonucleotides on montmorillonite clay - The effect of mononucleotide structure, phosphate activation and montmorillonite composition on phosphodiester bond formation

The 2(prime)-d-5(prime)-GMP and 2(prime)-d-5(prime)-AMP bind 2 times more strongly to montmorillonite 22A than do 2(prime)-d-5(prime)-CMP and 5(prime)-TMP. The dinucleotide d(pG)2 forms in 9.2 percent yield and the cyclic dinucleotide c(dpG)2 in 5.4 percent yield in the reaction of 2(prime)-d-5(prime)-GMP with EDAC in the presence of montmorillonite 22A. The yield of dimers which contain the phosphodiester bond decreases as the reaction medium is changed from 0.2 M NaCl to a mixture of 0.2 M NaCl and 0.075 M MgCl2. A low yield of d(pA)2 was observed in the condensation reaction of 5(prime)-ImdpA on montmorillonite 22A. The yield of d(pA)2 obtained when EDAC is used as the condensing agent increases with increasing iron content of the Na(+)-montmorillonite used as catalyst. Evidence is presented which shows that the acidity of the Na(+)-montmorillonite is a necessary but not sufficient factor for the montmorillonite catalysis of phosphodiester bond formation.

Ferris, James P.↗
NASA NTRS1990

Use of moments of momentum to predict the crystal habit in potassium hydrogen phthalate

A relatively simple calculation of the moments of momentum predicts the morphological order of crystal faces for potassium hydrogen phthalate. The effects on the habit caused by the addition of monomeric, dimeric, and larger aggregates during crystal growth are considered. The first six of the seven observed crystal faces are predicted with this method.

Barber, Patrick G.↗
NASA NTRS1992

NASA Lewis steady-state heat pipe code users manual

The NASA Lewis heat pipe code was developed to predict the performance of heat pipes in the steady state. The code can be used as a design tool on a personal computer or with a suitable calling routine, as a subroutine for a mainframe radiator code. A variety of wick structures, including a user input option, can be used. Heat pipes with multiple evaporators, condensers, and adiabatic sections in series and with wick structures that differ among sections can be modeled. Several working fluids can be chosen, including potassium, sodium, and lithium, for which monomer-dimer equilibrium is considered. The code incorporates a vapor flow algorithm that treats compressibility and axially varying heat input. This code facilitates the determination of heat pipe operating temperatures and heat pipe limits that may be encountered at the specified heat input and environment temperature. Data are input to the computer through a user-interactive input subroutine. Output, such as liquid and vapor pressures and temperatures, is printed at equally spaced axial positions along the pipe as determined by the user.

Tower, Leonard K.↗