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Estimates in excellent agreement with experimental values. Simple method proposed for estimating solubility of gases in electrolytes of lithium batteries using expressions for energy of vaporization and for molar volume.
The solubility of sulfur dioxide in 50% (wt./wt.) sulfuric acid was evaluated by regular solution theory, and the results verified by experimental measurements in the temperature range of 25 C to 70 C at pressures of 60 to 200 PSIA. The percent (wt./wt.) of sulfur dioxide in 50% (wt./wt.) sulfuric acid is given by the equation %SO2 = 2.2350 + 0.0903P - 0.00026P 10 to the 2nd power with P in PSIA.
A model for a prebiotic environment in which concentration, condensation, and chemical evolution of biomolecules could have occurred is proposed. The principal reactions expected of proteins, nucleic acids, lipids, and some of their precursors in this environment are discussed. The model is based on the concept of a fluctuating system in which hydration and dehydration processes occur in a cyclic manner, with allowance for high concentrations of soluble salts, such as chlorides and sulfates. It is concluded that the proposed prebiotic environment with its dynamical characteristics is a plausible model for the chemical evolution from biomonomers through random oligomers toward self-replicating chemical systems.
The adsorption of 5-prime-AMP onto solid CaSO4-2H2O was studied in a saturated suspension as a function of pH and electrolyte concentration. The adsorption is pH-dependent and is directly correlated with the charge on the 5-prime-AMP molecule which is determined by the state of protonation of the N-1 nitrogen of the purine ring and the phosphate oxygens. It is proposed that the binding that occurs between the nucleotide and the salt is electrostatic in nature. The adsorption decreases with increasing ionic strength of the solution which means that in a fluctuating environment of wetting and drying cycles, a biomolecule similar to 5-prime-AMP could be expected to desorb during the drying phase. The results indicate that CaSO4-2H2O can serve as a concentrating surface for biomolecules. The significance of this is discussed with regard to the possible role of soluble minerals and their surfaces in a geochemical model consistent with the evolution of the earth and the origin of life.
The directed synthesis of biopolymers in an abiotic environment is presumably a cyclic sequence of steps which may be realized in a fluctuating environment such as a prebiotic pond undergoing wetting-drying cycles. Soluble mineral salts have been proposed as an essential component of this fluctuating environment. The following sequence may be considered as a most primitive mechanism of information transfer in a fluctuating environment: (1) adsorption of a biomolecule onto a soluable mineral salt surface to act as an adsorbed template; (2) specific adsorption of biomonomers onto the adsorbed template; (3) condensation of the adsorbed biomonomers; and (4) desorption of the elongated oligomer. In this investigation, the salts selected for study were CaSO4.2H2O(gypsum), SrSO4, and several other metal sulfates and chlorides. Adsorption of the monomeric species, gly, 5'AMP 5'GMP, and 5'CMP was investigated. The adsorbed template biopolymers used were Poly-A, Poly-G, Poly-C, and Poly-U. The results of studies involving these experimental participants, the first two steps of the proposed primitive information transfer mechanism, and condensation of amino acids to form oligomers in a fluctuating environment are to be reported.
Optical absorption, fluorescence emission, Raman scattering, and time-resolved emission experiments are reported on a new liquid form of soluble polyacetylene. This liquid consists of separate polyene chains, grown on activated sites of a polybutadiene chain. The depolarization ratios as well as the time-resolved spectrum of the secondary emission were measured. The relevant spectral features are discussed and analyzed in terms of the lack of interchain interactions which characterize the polymer in solution.
The rainout-determined lifetimes of highly soluble particulate and gaseous atmospheric compounds are investigated using general circulation model simulations in which removal is explicitly calculated in terms of the local, model-produced precipitation rates. The calculations indicate that because of the episodic and asymmetric nature of rainout, species' lifetimes depend not only on the amount of precipitation but also on the characteristics of the precipitation regime (such as duration and frequency of the precipitation events) and on the direction of the tracer main flow (determined by the species' average mixing ratio gradient). For this reason, averaged rainout lifetimes of tracers flowing downstream from the stratosphere are found to differ substantially from those of tracers of surface origin flowing upward or tracers of a more ubiquitous tropospheric source. These results imply that the use of a first-order parameterization to simulate rainout in a photochemical model that does not explicitly calculate precipitation can be inadequate in representing this process. A computationally efficient parameterization that includes the effects of intermittence and asymmetry of rainout is proposed, and it is shown how this parameterization can be used to estimate rainout-determined tropospheric residence times from observational data sets. A review of published estimates of submicron aerosol tropospheric residence times based on observations shows that these are consistent with the model results.
Several soluble aromatic poly(amic acid) films were staged at intervals to 325 C and characterized by IR spectroscopy and various solution property techniques. A series of films in which the polymer had been endcapped in an effort to control chain extension was also examined. Much of the behavior observed is consistent with an interpretation that a reduction in molecular weight occurred during cure before the ultimate molecular weight was achieved as a polyimide.
Because of toughness, flexibility, and remarkable thermal stability, linear all-aromatic polyimides excellent candidate film and coating materials for advanced electronic circuitry and wires. Study determined effects on solubility of changing isomeric points of attachment of phenoxy units in diamine portions of several all-aromatic polyimides. Tough, flexible, transparent films produced by thermally converting polyamic acids to polyimides at 300 degree C in air. Potential for electronic applications excellent.
Polyimide-metal oxide (Co3O4 or CuO) composite films have been prepared via in situ thermal decomposition of cobalt (II) chloride or bis(trifluoroacetylacetonato)copper(II). A soluble polyimide (XU-218) and its corresponding prepolymer (polyamide acid) were individually employed as the reaction matrix. The resulting composites exhibited a greater metal oxide concentration at the air interface with polyamide acid as the reaction matrix. The water of imidization that is released during the concurrent polyamide acid cure and additive decomposition is believed to promote metal migration and oxide formation. In contrast, XU-218 doped with either HAuCl4.3H2O or AgNO3 yields surface gold or silver when thermolyzed (300 C).
Results are reported in the form of reaction diagrams, graphs, and tables of research being conducted to synthesize and characterize linear aromatic polyimides which are soluble in common organic solvents and optically transparent in the 400-600 nm spectral range. These flexible and high-temperature polymeric films and coatings are needed for specific applications on space components such as antennas, solar cells, and thermal control coating systems. Several series of these polyimide films have been produced by making variations in the polymer molecular structure aimed at reducing the electronic interactions between the polymer chains.
A series of fine-grain and amorphous Ni3Al-X alloys, where X is a solute of 1 to 45 at. pct hf, C, or Hf+C in continuously graded compositions, was formed simultaneously into a 0.2 mm-thick disk by high-rate sputter codeposition. The as-deposited Ni3Al-X alloys exhibited a disordered L1(2) structure and extended solid solubility limits beyond which amorphous phases were formed. Heat-treatment of the alloys at 900 C resulted in fine grain size of 0.5 micron to 1.5 microns. Ultra fine dispersoids less than 500 A in size were observed, and they seemed resistant to coarsening.
The solubility of hydrogen, at a fixed hydrogen pressure, was measured in two different heat treatment conditions in both IN-100 and Waspaloy by equilibrium and analysis. The diffusion coefficients were determined by measuring the rate of hydrogen evolution in a vacuum. Hydrogen evolution appeared to be a diffusion-controlled process in all cases. For hydrogen diffusion in Waspaloy, Delta H was 38.5 kJ and D0 was 2.6 x 10 to the -7th sq/s. For IN-100, Delta H was 68.2 kJ and D0 was 59 x 10 to the -7th sq/s. The values for Waspaloy are close to those for pure nickel. The values for IN-100 are more similar to high nickel alloys that show trapping or surface layer impedance.
The Martian atmosphere has a high X-129/Xe-132 ratio compared to the Martian mantle. As Xe-129 is the daughter product of the extinct nuclide I-129, a means of fractionating iodine from xenon early in Martian history appears necessary to account for the X-129/Xe-132 ratios of its known reservoirs. A model is presented here to account for the Marian xenon data which relies on the very different solubilities of xenon and iodine in water to fractionate them after outgassing. Atmospheric xenon is lost by impact erosion during heavy bombardment, followed by release of Xe-129 produced from I-129 decay in the crust.
The large-scale spatial distribution from 0.15-to 6 km altitude in the North American Arctic troposphere of several soluble acidic gases and major aerosol species during the summertime is reported. The distribution is found to be compositionally consistent on a large spatial scale. The summertime troposphere is an acidic environment, with HCOOH and CH3COOH the principal acidic gases while acidic sulfate aerosols dominate the particulate phase. There appears to be a surface source of NH3 over the pack ice which may originate from decay of dead marine organisms on the ice surface, evolution from surface ocean waters in open ice leads, or release from rotting sea ice. At low altitude over the pack ice this NH34 appears to partially neutralize aerosol acidity. Over sub-Arctic tundra in southeastern Alaska, inputs of marine biogenic sulfur from the Bering Sea appear to be an important source of boundary layer aerosol SO4(2-). The rainwater acidity over the tundra is typical of remote regions.
The solid phase thermal imidization of a soluble 4,4-prime-bis (3,4-dicarboxyphynoxy) diphenyl sulfide dianhydride plus 2,2-bis 4-(4-aminophenoxyl)phenyl hexafluoropropane (BDSDA-BDAF) polyimide precursor staged between 40 and 325 C was characterized by gel permeation chromatography, inherent viscosity, and number average molecular weight measurements. The information obtained indicated that this polyamic acid experienced an initial reduction in molecular weight during cure before achieving its ultimate molecular weight as a polyimide. The event was most likely related to the development of an anhydride band that appeared in the infrared spectrum around 1850/cm as the material cured. Correlation through infrared spectroscopy with a previous study dealing with several common, but insoluble, polyimide precursors, suggested that polyimides, in general, exhibit this trend in molecular weight behavior.
On 19 January 1992, heterogeneous loss of HNO3, ClNO3, and HCl was observed in part of the Mount Pinatubo volcanic cloud that had cooled as a result of forced ascent. Portions of the volcanic cloud froze near 191 kelvin. The reaction probability of ClNO3 and the solubility of HNO3 were close to laboratory measurements on liquid sulfuric acid. The magnitude of the observed loss of HCl suggests that it underwent a heterogeneous reaction. Such reactions could lead to substantial loss of HCl on background sulfuric acid particles and so be important for polar ozone loss.
The solubility of HCl in sulfuric acid was measured using a Knudsen cell technique. Effective Henry's law constants are reported for sulfuric acid concentrations between 50 and 60 weight percent and for temperatures between 220 and 230 K. The measured values indicate that very little HCl will be dissolved in the stratospheric sulfate aerosol particles.