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At least 1,099 records · Page 61

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NASA NTRS1976

Products of the reaction of chlorine atoms and ozone

Preliminary matrix-isolation infrared spectroscopic studies of the gas-phase reaction of chlorine atoms and ozone are reported. It was shown that the major product of the reaction is the symmetric OClO radical, while very little of the asymmetric ClOO radical is produced. It was also shown that the presence of O2 enhances the OClO production and the ClOO is the primary product in the reaction of Cl atoms and pure O2. The radical ClO was observed for the first time in a gas-phase reaction of Cl and O3. A mechanism for these observations is proposed.

Hall, J. H., Jr.↗

NASA NTRS1975

The electrical and magnetic properties of /TTF//I/-sub 0.71

The synthesis and transport properties of the salts (TTF) (iodine)-sub x have been investigated. These salts are quasi-one-dimensional compounds containing cation radicals only, in contrast to the cation radical-anion radical systems such as (TTF)(TCNQ). The phase diagram of (TTF)(I)-sub x is discussed, and found to consist of two nonconducting, stoichiometric phases, x = 2.0 and 3.0, and two conducting, nonstoichiometric phases, x = 0.71 and 2.3. The transport properties of (TTF)(I)-sub 0.71 are discussed in detail. This phase is highly conducting, undergoes a sharp transition to a less conducting state at 210 K, and exhibits an unusual hysteresis in some of the transport properties upon thermal cycling. The nature of the high-temperature ground state is examined.

Somoano, R. B.↗

NASA NTRS1975

Comparison of magnetospheres and radio emissions of Jupiter with earth

The magnetosphere and radio emission of Jupiter is compared with those of the earth. It was predicted that Jupiter would have a Van Allen belt at a radius such that its magnetic field strength would be about equal to that in earth's Van Allen belt and that Jupiter's moon Io travels in the Van Allen belt. Because of Io's low conductivity, plasma sweeping past hits Io, producing a turbulent plasma proboscis which forms hydrodynamic shocks. These shocks travel down the magnetic field lines to the Jovian magnetosphere where they stimulate electron cyclotron emission and free radical spin-flip emission. The free radicals likely to exist abundantly and the richness of the likely decametric frequencies resulting from the many g values of the free radicals are discussed.

Libby, L. M.↗

NASA NTRS1977

Electrical, magnetic, and optical properties of the tetrathiafulvalene /TTF/ pseudohalides, /TTF/12/SCN/7 and /TTF/12/SeCN/7

The electrical, magnetic, and optical properties of charge-transfer salts containing tetrathiafulvalene (TTF) and the pseudohalides, thiocyanate (SCN) and selenocyanate (SeCN), have been investigated. These salts are quasi-one-dimensional compounds containing cation radicals only, in contrast to a cation-radical-anion-radical system, such as tetrathiafulvalene tetracyanoquinodimethane (TTF) (TCNQ). Measurements of electrical conductivity, thermoelectric power, and optical reflectivity of single crystals of the nonstoichiometric salts (TTF)12(SCN)7 and (TTF)12(SeCN)7 show metal-like characteristics above 200 K (high-temperature region). The conductivities at room temperature are approximately 750 mho/cm comparable to those found in (TTF) (TCNQ), and increase with decreasing temperature down to approximately 200 K. The thermoelectric power at room temperature is small and positive (approximately 9 microvolts/deg K), and decreases linearly with decreasing temperature in this region (as expected for metal-like hole conduction along the TTF chains). The ESR intensity, however, decreases with decreasing temperature above 200 K. At 170 K a metal-nonmetal transition occurs, and the transport and magnetic properties below this temperature are characteristic of a semiconducting state.

Somoano, R. B.↗

NASA NTRS1979

Preparation of heterocyclic block copolymer from perfluoroalkylene oxide alpha, omega-diamidoximes

Diamidoxime monomers are intermolecularly and thermally condensed to form a heat and chemical resistant polymer containing 1,2,4-oxadiazole linkages with identical bivalent organic radicals or any combination of bivalent organic radicals selected from the group consisting of -(CX(sub 2))p-, wherein P ranges from 2 to 8 when X is fluorine and 2 to 18 when X is hydrogen, chlorine, nitro or aryl; arylene; and an oligometric or polymeric radical prepared by reacting a dicarboxylic acid halide with a fluorinated epoxide and having the formula: (CFY(OCF(sub 2)CFY)sub m)O(CX(sub 2))(sub p)O(CFYCF(sub 2)O)(sub n)CFY wherein Y is flourine or tryifluoromethyl, X is nitro, aryl, hydrogen, chlorine or fluorine, preferably the latter, p ranges from 1 to 18 and m+n ranges from 2 to 7.

Ross, L. O.↗

NASA NTRS1981

Curing agent for polyepoxides and epoxy resins and composites cured therewith

A curing for a polyepoxide is described which contains a divalent aryl radical such as phenylene a tetravalent aryl radical such as a tetravalent benzene radical. An epoxide is cured by admixture with the curing agent. The cured epoxy product retains the usual properties of cured epoxides and, in addition, has a higher char residue after burning, on the order of 45% by weight. The higher char residue is of value in preventing release to the atmosphere of carbon fibers from carbon fiber-epoxy resin composites in the event of burning of the composite.

Serafini, T. T.↗

NASA NTRS1981

Matrix spectroscopic studies of chlorine atom-ozone reaction products

A spectroscopic study is presented of the matrix-isolated products of the direct combination reaction of chlorine atoms with ozone and of the microwave discharge reaction of chlorine and oxygen. Infrared spectra in the wavenumber range 2000 to 200 per cm were recorded for reaction products trapped by the condensation of a matrix of solid argon. Evidence for the formation of the ClO radical as well as the ClOO and ClClO radicals during the direct chlorine-ozone reaction is obtained, however no evidence is found for the presence of asymmetric ClO3 under conditions thought favorable for its formation. The ClO molecule is also observed following the microwave discharge reaction of chlorine and oxygen in argon in the isotopic forms (Cl-35)(O-16), (Cl-37)(O-16), (Cl-35)(O-18), and (Cl-37)(O-18). It is noted that the vibrational frequency for the (Cl-35)(O-16) radical at 849.2 per cm is blue-shifted 5 per cm above its gas-phase fundamental.

Carter, R. O., III↗

NASA NTRS1982

A photochemical study of the kinetics of the reactions of NH2 with phosphine, ethylene, and acetylene using flash photolysis-laser induced fluorescence

The photochemistry of the reactions of NH2 was investigated in an attempt to explain the existence of an abundance of ammonia in the Jovian atmosphere. The production of ammonia reservoirs from the coupling of ammonia with other atmospheric constituents was considered. The rate constants for the reactions of NH2 radicals with phosphine, acetylene, and ethylene were measured. Flash photolysis was used for the production of NH2 radicals and laser induced fluorescence was employed for radical detection. It was determined that the rates of the reactions were too slow to be significant as a source of ammonia reservoirs in the Jovian atmosphere.

Bosco, S. R.↗

NASA NTRS1983

Theoretical studies of photodissociation of small molecules of astrophysical importance

The radicals and ions observed in comets result from photodissociation and photoionization of molecules. According to current models, a comet is composed chiefly of a large, solid nucelus of frozen gases (parent molecules) such as H2O, HCN, and NH3. It is believed comets were formed at the same time and in the same region of space as the major planets and that their chemical composition is the same as that of the early solar system. As the comet nears the Sun, the surface heats up, liberating the frozen gases as well as dust particles. Solar radiation photodissociates the parent molecules into fragments that are observed by resonance fluorescence. Both polyatomic molecules, present in the interstellar medium, and cometary radicals were observed. Using laboratory photo-dissociation data and computer models, astronomers are attempting to identify the parent molecules that account for all observed radicals and ions.

Saxon, R. P.↗

NASA NTRS1982

Modelling of photodegradation in solar cell modules of substrate and superstrate design made with ethylene-vinyl acetate as pottant material

A computer model which simulates, in principle, the chemical changes in the photooxidation of hydrocarbons using as input data a set of elementary reactions, corresponding kinetic rate data and appropriate initial conditions was developed. The Model was refined and exploited to examine more closely the photooxidation and photostabilization of a hydrocarbon polymer. The results lead to the following observations. (1) The time to failure, tau sub f (chosen as the level of 5% C-H bond oxidation which is within the range anticipated for marked change in mechanical properties) varies as the inverse square root of the light intensity. However, tau sub f is almost unaffected by both the photoinitiator type and concentration. (2) The time to failure decreases with the rate of abstraction of C-H by peroxy radicals but increases with the rate of bimolecular radical termination controlled by diffusion. (3) Of the various stabilization mechanisms considered, the trapping of peroxy radicals is distinctly the most effective, although the concommitant decomposition of hydroperoxide is also desirable.

Somersall, A. C.↗

NASA NTRS1983

Pulsed laser photolysis study of the reaction between O(3P) and HO2

It is pointed out that bimolecular reactions involving two free radicals are of great interest because both reactants have unpaired electrons and hence could interact at distances longer than those typical of radical-molecule encounters. A method based on laser photolysis is being developed to produce selectively free radicals in the homogeneous gas phase. This is to be done in such a way as to isolate the reaction of interest and subsequently follow the course of the reaction using spectroscopic techniques. The present investigation is concerned with a study in which the rate coefficient for the reaction of O(3P) with HO2, has been measured at N2 pressures ranging from 10 to 500 torr, taking into account the reaction O(3P)+HO2 yields OH-O2. In the described study, O(3P) and HO2 were produced by cophotolysis of O3 and H2O2 in N2 at 248.5 nm using a KrF excimer laser.

Ravishankara, A. R.↗

NASA NTRS1983

The photochemistry of anthropogenic nonmethane hydrocarbons in the troposphere

A lumped, nonmethane hydrocarbon (NMHC) chemical mechanism is presently applied to a one-dimensional photochemical model of the troposphere. The profiles of OH, HO2, NO(x), and HNO3, showed only slight changes when NMHC chemistry was added. The integrated column of peroxyacetylnitrate (PAN), when NMHC chemistry was included, comprised 17 percent of the odd nitrogen budget. Advection is noted as an important possible mechanism for the removal of PAN at midlatitudes. The inclusion of such intermediate lifetime species as aldehydes and olefins has both provided additional sources of short-lived NMHC radicals, such as the peroxyacetyl radical that is the radical precursor of PAN, and offered a more detailed description of the concentrations of short-lived species and the overall NMHC chemistry.

Brewer, D. A.↗

NASA NTRS1984

Saturated laser fluorescence in turbulent sooting flames at high pressure

The primary objective was to develop a quantitative, single pulse, laser-saturated fluorescence (LSF) technique for measurement of radical species concentrations in practical flames. The species of immediate interest was the hydroxyl radical. Measurements were made in both turbulent premixed diffusion flames at pressures between 1 and 20 atm. Interferences from Mie scattering were assessed by doping with particles or by controlling soot loading through variation of equivalence ratio and fuel type. The efficacy of the LSF method at high pressure was addressed by comparing fluorescence and adsorption measurements in a premixed, laminar flat flame at 1-20 atm. Signal-averaging over many laser shots is sufficient to determine the local concentration of radical species in laminar flames. However, for turbulent flames, single pulse measurements are more appropriate since a statistically significant number of laser pulses is needed to determine the probability function (PDF). PDFs can be analyzed to give true average properties and true local kinetics in turbulent, chemically reactive flows.

King, G. B.↗

NASA NTRS1984

Simulation of lubricating behavior of a thioether liquid lubricant by an electrochemical method

An electrochemical cell was constructed to explore the possible radical anion forming behavior of a thioether liquid lubricant. The electrochemical behavior of the thioether was compared with the electrochemical behavior of biphenyl, which is known to form radical anions. Under controlled conditions biphenyl undergoes a reversible reaction to a radical anion, whereas the thioether undergoes an irreversible reduction yielding several products. These results are discussed in relation to boundary lubrication.

Morales, W.↗

NASA NTRS1984

CN and C2H in IRC +10216

The effects of the production of the radicals CN and C2H from the dissociation of HCN and C2H2 by ambient UV photons in the outer envelope of IRC +10216 are investigated. The spatial distribution of the radicals and their observable millimeter emission-line characteristics are calculated from the inferred abundances of the progenitor species in the envelope of IRC +10216 using photochemical and radiative transfer models. These are compared with available observations to examine whether photoproduction is a possible explanation of the observed emission from these species. The results suggest that the variable abundances induced by photodestruction of their progenitors do affect the observed emission from the radicals.

Huggins, P. J.↗

NASA NTRS1984

Importance of formaldehyde in cloud chemistry

A physical-chemical model which is an extension of that of Hong and Carmichael (1983) is used to investigate the role of formaldehyde in cloud chemistry. This model takes into account the mass transfer of SO2, O3, NH3, HNO3, H2O2, CO2, HCl, HCHO, O2, OH and HO2 into cloud droplets and their subsequent chemical reactions. The model is used to assess the importance of S(IV)-HCHO adduct formation, the reduction of H2O2 by HCHO, HCHO-free radical interactions, and the formation of HCOOH in the presence of HCHO in cloud droplets. Illustrative calculations indicate that the presence of HCHO inhibits sulfate production rate in cloud droplets. The direct inhibition of sulfate production rate in cloudwater due to nucleophilic addition of HSO3(-) to HCHO(aq) to form hydroxymethanesulfonate is generally low for concentrations of HCHO typical of ambient air. However, inhibition of sulfate production due to formaldehyde-free radical interactions in solution can be important. These formaldehyde-free radical reactions can also generate appreciable quantities of formic acid.

Adewuyi, Y. G.↗

NASA NTRS1986

Simulation of lubricating behavior of a thioether liquid lubricant by an electrochemical method

Morales, W.↗

NASA NTRS1987

Spectroscopic comparison of effects of electron radiation on mechanical properties of two polyimides

The differences in the radiation durabilities of two polyimide materials, Du Pont Kapton and General Electric Ultem, are compared. An explanation of the basic mechanisms which occur during exposure to electron radiation from analyses of infrared (IR) and electron paramagnetic resonance (EPR) spectroscopic data for each material is provided. The molecular model for Kapton was, in part, established from earlier modeling for Ultem (pp. 1293-1298 of IEEE Transactions on Nuclear Science, December 1984). Techniques for understanding the durability of one complex polymer based on the understanding of a different and equally complex polymer are demonstrated. The spectroscopic data showed that the primary radiation-generated change in the tensile properties of Ultem (a large reduction in tensile elongation) was due to crosslinking, which followed the capture by phenyl radicals of hydrogen atoms removed from gem-dimethyl groups. In contrast, the tensile properties of Kapton remained unchanged because radical-radical recombination, a self-mending process, took place.

Long, Edward R., Jr.↗