Photolysis of formaldehyde at 1470 and 1236 A
Formaldehyde vapor photodecomposition modes by end product analysis, utilizing mixed isotope, radical scavenger, inert gas pressurization and lamp intensity attenuation
Glicker, S.↗
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Photochemistry and lifetimes of interstellar molecules.
Quantitative discussion of the photochemistry and lifetime against photodecomposition of five interstellar molecules: H2CO, NH3, H2O, CH4, and CO. For the first four molecules, primary photochemical decomposition processes yielding atomic and molecular hydrogen are considered in addition to photoionization. The quantum yield for decomposition of these molecules is unity. For CO, only decomposition to ground-state carbon and oxygen atoms occur, but the quantum yield is not known and may be considerably less than unity. The radiation field in obscuring clouds is estimated, using an interstellar extinction curve for the Perseus region.
Stief, L. J.↗
Photolysis of CO-NH3 mixtures and the Martian atmosphere
It has already been noted (Ferris and Nicodem, 1972) that although neither CO2 nor H2O affected the rate of NH3 photolysis, CO accelerated the photodecomposition of ammonia, with the formation of a solid product. The photolysis of NH3 in the presence of CO is investigated in greater detail not only because of the potential significance to atmospheric photochemistry on Mars, but also because of the possibility of photocatalytic reactions of NH3 and CO on the Martian surface and in the interstellar medium. These photoreactions may also have occurred on the primitive earth.
Ferris, J. P.↗
Photochemistry of interstellar molecules
The role of photochemistry in determining the lifetime of interstellar molecules is considered. The probability of photodecomposition depends on three factors, including the absorption cross section, the quantum yield or probability of dissociation following photon absorption, and the interstellar radiation field. A more detailed discussion of the photochemistry of five molecules is presented, giving attention to carbonyl sulfide, methyl acetylene, nitric oxide, acetylene, and benzene. Lifetimes of interstellar molecules in unobscured regions are in the range from 5 to 100 years. It is concluded that polyatomic molecules can exist only in dense clouds which protect them from the full interstellar radiation field.
Stief, L. J.↗
Absolute rate parameters for the reaction of ground state atomic oxygen with dimethyl sulfide and episulfide
It is pointed out that the investigated reaction of oxygen with dimethyl sulfide may play an important role in photochemical smog formation and in the chemical evolution of dense interstellar clouds. Kinetic data were obtained with the aid of the flash photolysis-resonance fluorescence method. The photodecomposition of molecular oxygen provided the oxygen atoms for the experiments. The decay of atomic oxygen was studied on the basis of resonance fluorescence observations. Both reactions investigated were found to be fast processes. A negative temperature dependence of the rate constants for reactions with dimethyl sulfide was observed.
Lee, J. H.↗
The sodium and hydrogen gas clouds of Io
Models are developed to describe the spatial distribution of gases emitted by Io and are applied to recent observations which indicate extensive gas clouds of hydrogen and sodium in orbit around Jupiter. Hydrogen and sodium atoms are emitted from Io with velocities in the range from 2 to 3 km/sec, with fluxes of about 10 billion and 100 million per sq cm/sec for hydrogen and sodium, respectively. Hydrogen atoms may be formed by photodecomposition of gases such as NH3 or H2S released from the satellite surface and may escape thermally from an exosphere whose temperature is about 500 K. Sodium may be ejected from the surface by energetic particles or by ultraviolet radiation, and it appears that a nonthermal mechanism drawing energy from Jupiter's magnetic field is required in order to account for its release to space.
Smyth, W. H.↗
The potential impact on atmospheric ozone and temperature of increasing trace gas concentrations
The response of the atmosphere to emissions of chlorofluorocarbons (CFCs) and other chlorocarbons, and to increasing concentrations of other radiatively active trace gases such as CO2, CH4, and N2O is calculated by a coupled chemical-radiative transport one-dimensional model. It is shown that significant reductions in the ozone concentration and in the temperature are expected in the upper stratosphere as a result of increasing concentrations of active chlorine produced by photodecomposition of the CFCs. The ozone content is expected to increase in the troposphere, as a consequence of increasing concentrations of methane and nitrogen oxides. Due to enhanced greenhouse effects, the Earth's surface should warm up by several degrees. The amplitude and even the sign of future changes in the ozone column are difficult to predict as they are strongly scenario-dependent. An early detection system to prevent noticeable ozone changes as a result of increasing concentrations of source gases should thus be based on a continuous monitoring of the ozone amount in the upper stratosphere rather than on measurements of the ozone column only. Measurements of NOx, Clx, and HOx are also required for unambiguous trend detection and interpretation.
Brasseur, G.↗
Chemistry of the CO dimer at low temperatures
Researchers conducted a series of experiments on the chlorine-catalyzed photodecomposition of O sub 3 both in the gas and in inert solvents such as CF sub 4 and CO sub 2 in the temperature range about 190 to 225 K. The liquid medium was chosen in order to minimize possible surface loss of long-lived ClO dimer, and to aid in the stabilization of transient excited intermediates. The mechanism of dimer formation was as follows: (1) Cl sub 2 + hv yields Cl + Cl; (2) Cl + O sub 3 yields ClO + O sub 2; (3) ClO + ClO yields Cl sub 2 O sub 2. The experiments were done in cooled low temperature cells, with irradiation from an Osram high pressure mercury arc, filtered to remove radiation below 325 nm. Spectral analysis was by means of a Cary Model 2200 UV spectrometer. The principal objectives were: (1) to determine the lifetime of the dimer as a function of temperature; (2) to observe spectral changes in the mixtures which could be attributed to dimer or related products; and (3) to observe chemical or photochemical reactions of the dimer.
Demore, W. B.↗
A laboratory investigation of the production and properties of molecular and radical species pertinent to planetary atmospheres
Vinylidene (H2C=C) is shown to be the largest photodecomposition channel in the direct photolysis of both C2H2 and C2H4. The chemistry of H2C=C as it relates to planetary atmospheres is discussed. The vinyl radical (C2H3), important in the acetylene chemistry cycle, has been directly observed spectroscopically and the kinetics of several key reactions of this species measured.
Fahr, Askar↗
Deposition of tantalum carbide coatings on graphite by laser interactions
Graphite surfaces can be hardened and protected from erosion by hydrogen at high temperatures by refractory metal carbide coatings, which are usually prepared by chemical vapor deposition (CVD) or chemical vapor reaction (CVR) methods. These techniques rely on heating the substrate to a temperature where a volatile metal halide decomposes and reacts with either a hydrocarbon gas or with carbon from the substrate. For CVR techniques, deposition temperatures must be in excess of 2000 C in order to achieve favorable deposition kinetics. In an effort to lower the bulk substrate deposition temperature, the use of laser interactions with both the substrate and the metal halide deposition gas has been employed. Initial testing involved the use of a CO2 laser to heat the surface of a graphite substrate and a KrF excimer laser to accomplish a photodecomposition of TaCl5 gas near the substrate. The results of preliminary experiments using these techniques are described.
Veligdan, James↗
Formation and Survival of Amino Acids in Space
The detection of deuterium enrichments in meteoritic hydroxy and amino acids demonstrates that there is a connection between organic material in the interstellar medium and in primitive meteorites. It has generally been assumed that such molecules formed via reactions of small deuterium enriched insterstellar precursors in liquid water on a large asteroidal or cometary parent body. We have recently show that the W photolysis of interstellar/presolar ices can produce the amino acids alanine, serine, and glycine, as well as hydroxy acids, and glycerol, all of which have been extracted from the Murchison meteorite. Thus, some of the probiologically interesting organic compounds, compounds found in meteorites may have formed in presolar ice and have not solely been a product of parent body liquid water chemistry. We will report on our isotopic labeling studies of the mechanism of formation of these interesting compounds, and on astrophysically relevant kinetic studies UV photodecomposition of amino acid precursors in the solid state. This is our first year of exobiology funding on this project.
Bernstein, M. P.↗
Degradation Characterization of Unsteady Pressure-Sensitive Paint Under Various Pressures
The lifetime and intensity techniques are two distinct methods used to measure the surface pressure of wind tunnel models with pressure-sensitive paint (PSP). When exposed to 405 nm light for extended periods, both the luminescence and the lifetime ratio were observed to decrease, affecting perceived pressure values. To help further the implementation of the uPSP, this paper describes the efforts to characterize the degradation of both the intensity of the paint and its lifetime ratio, as well as the change in intensity calibration. It was found that the paint degrades at different rates depending on the partial pressure of oxygen during excitation. It was also found that the calibration curves exhibit greater changes when under higher oxygen concentrations, both indicating photodegradation due to photodecomposition and photo-oxidation processes. These effects are observed on models in a subsonic 14” × 14” wind tunnel. The work provides insight into the dynamic degradation behavior of PSP and uPSP, paving the way to reduce the error in pressure measurements obtained through these techniques.
Pressure-Sensitive Paint↗
Multi-Messenger In-situ Tolerance Optimization of Mixed Perovskite Photovoltaics. Final Report
The main objectives for this project were to formulate, validate and disseminate a new procedure based on Environmental X-ray Photoelectron Spectroscopy (EXPS) for the accelerated degradation testing of metal hybrid perovskite (MHP) PV materials. With this capability, we can aid US efforts to improve MHP tolerance for illumination in damp heat conditions. This capability will benefit the public by supporting new industry efforts to create stable MHP formulations.
14 SOLAR ENERGY↗
PLANETARY ATMOSPHERE STUDIES V- PHOTOCHEMISTRY OF SULFUR-OXYGEN SYSTEMS
Planetary atmosphere studies v - photochemistry of sulfur-oxygen systems
OXYGEN↗
Reactions of carbon atoms with N sub 2, H sub 2, and D sub 2 at 4.2 deg K.
Photochemical decomposition of carbon suboxide and spectroscopic observation of carbon atom reactions with nitrogen, hydrogen and deuterium at 4.2 degrees K
CARBON↗
Photodesorption of oxygen from nickel oxide powder
Photodesorption of oxygen from nickel oxide at room temperature using 635, 705, and 1070 millimicron light
DESORPTION↗