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At least 19 recordsLinked to original sources
USGS2002

Employment of Gibbs-Donnan-based concepts for interpretation of the properties of linear polyelectrolyte solutions

Earlier research has shown that the acid dissociation and metal ion complexation equilibria of linear, weak-acid polyelectrolytes and their cross-linked gel analogues are similarly sensitive to the counterion concentration levels of their solutions. Gibbs-Donnan-based concepts, applicable to the gel, are equally applicable to the linear polyelectrolyte for the accommodation of this sensitivity to ionic strength. This result is presumed to indicate that the linear polyelectrolyte in solution develops counterion-concentrating regions that closely resemble the gel phase of their analogues. Advantage has been taken of this description of linear polyelectrolytes to estimate the solvent uptake by these regions. ?? 1991 American Chemical Society.

Journal of Physical Chemistry↗
USGS2002

Vapor-liquid phase equilibria of potassium chloride-water mixtures: Equation-of-state representation for KCl-H2O and NaCl-H2O

Measurements of isothermal vapor-liquid compositions for KCl-H2O as a function of pressure are reported. An equation of state, which was originally proposed by Pitzer and was improved and used by Tanger and Pitzer to fit the vapor-liquid coexistence surface for NaCl-H2O, has been used for representation of the KCl-H2O system from 300 to 410??C. Improved parameters are also reported for NaCl-H2O from 300 to 500??C. ?? 1990 American Chemical Society.

Journal of Physical Chemistry↗
USGS2002

Infrared spectral behavior of fine particulate solids

Transmission and emission spectra of clouds and layers of fine particulate samples of quartz, magnesium oxide, and aluminum oxide in the 6.5-35-??m wavelength range are presented. They demonstrate that the behavior of layers of particles constitutes a good analogue for a cloud of particles; that individual micrometer-sized particles emit most where they absorb most; that as the size of the particle is increased, the emission features reverse polarity and the spectrum approaches that of one obtained from a polished plate; and that as the particle layer-thickness increases, radiative interaction becomes increasingly important so that the emission maximum shifts from the strongest to weaker features, or produces a maximum at the Christiansen wavelength.

Journal of Physical Chemistry↗
USGS2002

Heat capacity from 12 to 305°K and entropy of talc and tremolite

The heat capacities of talc, Mg 3 Si 4 O 10 (OH) 2 , and tremolite, Ca 2 Mg 6 Si 8 O 22 (OH) 2 , have been measured between 12 and 305°K. Smoothed values of heat capacity, entropy, enthalpy, and free energy are tabulated. At 298.15° K. the values of the thermodynamic functions are: talc, C p °= 76.89 ± 0.23 cal. deg. -1 mole -1 , S° = 62.33 ± 0.19 cal. deg. -1 mole -1 , H° - H 0 ° = 11,206 ± 34 cal. mole -1 ; tremolite, Cp° = 156.7 ± 0.6 cal. deg. -1 mole -1 , S° = 131.2 ± 0.5 cal. deg. -1 mole -1 , H° - H 0 ° = 23,335 ± 90 cal. mole -1 . From the equilibrium data of Bowen and Tuttle and the entropy of talc, the heat of formation of talc from MgO, SiO 2 , and H 2 O (liq.) is calculated to be Δ H°f 298 = -43.6 ± 1 kcal.

Journal of Physical Chemistry↗
USGS2002

The addition of iodine to tetramethylammonium iodide

The system tetramethylammonium iodide-iodine-toluene has been studied by the solubility method at 6 and at 25°. The compounds (CH 3 ) 4 NI 3 , (CH 3 ) 4 NI 5 and (CH 3 ) 4 NI 11 were found to be stable phases at both temperatures. In addition, the compound (CH 3 ) 4 NI 10 was found at 6° and the compound (CH 3 ) 4 NI 9 at 25°. The dissociation pressures of the compounds at these temperatures were calculated from the solubility data.

Journal of Physical Chemistry↗
USGS2001

Diamond-anvil cell observations of a new methane hydrate phase in the 100-MPa pressure range

A new high-pressure phase of methane hydrate has been identified based on its high optical relief, distinct pressure-temperature phase relations, and Raman spectra. In-situ optical observations were made in a hydrothermal diamond-anvil cell at temperatures between -40?? and 60 ??C and at pressures up to 900 MPa. Two new invariant points were located at -8.7 ??C and 99 MPa for the assemblage consisting of the new phase, structure I methane hydrate, ice Ih, and water, and at 35.3 ??C and 137 MPa for the new phase-structure I methane hydrate-water-methane vapor. Existence of the new phase is critical for understanding the phase relations among the hydrates at low to moderate pressures, and may also have important implications for understanding the hydrogen bonding in H2O and the behavior of water in the planetary bodies, such as Europa, of the outer solar system.

Journal of Physical Chemistry A↗
USGS2003

CO2 hydrate: Synthesis, composition, structure, dissociation behavior, and a comparison to structure I CH4 hydrate

Structure I (sI) carbon dioxide (CO 2 ) hydrate exhibits markedly different dissociation behavior from sI methane (CH 4 ) hydrate in experiments in which equilibrated samples at 0.1 MPa are heated isobarically at 13 K/h from 210 K through the H 2 O melting point (273.15 K). The CO 2 hydrate samples release only about 3% of their gas content up to temperatures of 240 K, which is 22 K above the hydrate phase boundary. Up to 20% is released by 270 K, and the remaining CO 2 is released at 271.0 plusmn; 0.5 K, where the sample temperature is buffered until hydrate dissociation ceases. This reproducible buffering temperature for the dissociation reaction CO 2 ·nH 2 O = CO 2 (g) + nH 2 O(1 to s) is measurably distinct from the pure H 2 O melting point at 273.15 K, which is reached as gas evolution ceases. In contrast, when si CH 4 hydrate is heated at the same rate at 0.1 MPa, >95% of the gas is released within 25 K of the equilibrium temperature (193 K at 0.1 MPa). In conjunction with the dissociation study, a method for efficient and reproducible synthesis of pure polycrystalline CO 2 hydrate with suitable characteristics for material properties testing was developed, and the material was characterized. CO 2 hydrate was synthesized from CO 2 liquid and H 2 O solid and liquid reactants at pressures between 5 and 25 MPa and temperatures between 250 and 281 K. Scanning electron microscopy (SEM) examination indicates that the samples consist of dense crystalline hydrate and 50-300 μm diameter pores that are lined with euhedral cubic hydrate crystals. Deuterated hydrate samples made by this same procedure were analyzed by neutron diffraction at temperatures between 4 and 215 K; results confirm that complete conversion of water to hydrate has occurred and that the measured unit cell parameter and thermal expansion are consistent with previously reported values. On the basis of measured weight gain after synthesis and gas yields from the dissociation experiments, approximately all cages in the hydrate structure are filled such that n ≈ 5.75.

Journal of Physical Chemistry B↗
USGS2005

Direct measurement of methane hydrate composition along the hydrate equilibrium boundary

The composition of methane hydrate, namely n w for CH 4 · n w H 2 O, was directly measured along the hydrate equilibrium boundary under conditions of excess methane gas. Pressure and temperature conditions ranged from 1.9 to 9.7 MPa and 263 to 285 K. Within experimental error, there is no change in hydrate composition with increasing pressure along the equilibrium boundary, but n w may show a slight systematic decrease away from this boundary. A hydrate stoichiometry of n w = 5.81−6.10 H 2 O describes the entire range of measured values, with an average composition of CH 4 ·5.99(±0.07)H 2 O along the equilibrium boundary. These results, consistent with previously measured values, are discussed with respect to the widely ranging values obtained by thermodynamic analysis. The relatively constant composition of methane hydrate over the geologically relevant pressure and temperature range investigated suggests that in situ methane hydrate compositions may be estimated with some confidence.

Journal of Physical Chemistry B↗
USGS2006

Cometary impact and amino acid survival - Chemical kinetics and thermochemistry

The Arrhenius parameters for the initiating reactions in butane thermolysis and the formation of soot, reliable to at least 3000 K, have been applied to the question of the survival of amino acids in cometary impacts on early Earth. The pressure/temperature/time course employed here was that developed in hydrocode simulations for kilometer-sized comets (Pierazzo and Chyba, 1999), with attention to the track below 3000 K where it is shown that potential stabilizing effects of high pressure become unimportant kinetically. The question of survival can then be considered without the need for assignment of activation volumes and the related uncertainties in their application to extreme conditions. The exercise shows that the characteristic times for soot formation in the interval fall well below the cooling periods for impacts ranging from fully vertical down to about 9?? above horizontal. Decarboxylation, which emerges as more rapid than soot formation below 2000-3000 K, continues further down to extremely narrow impact angles, and accordingly cometa??ry delivery of amino acids to early Earth is highly unlikely. ?? 2006 American Chemical Society.

Journal of Physical Chemistry A↗
USGS2006

Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria

Using the Gibbs function of reaction, equilibrium pressure, temperature conditions for the formation of methane clathrate hydrate have been calculated from the thermodynamic properties of phases in the system CH4-H 2O. The thermodynamic model accurately reproduces the published phase-equilibria data to within ??2 K of the observed equilibrium boundaries in the range 0.08-117 MPa and 190-307 K. The model also provides an estimate of the third-law entropy of methane hydrate at 273.15 K, 0.1 MPa of 56.2 J mol-1 K-1 for 1/n CH4??H 2O, where n is the hydrate number. Agreement between the calculated and published phase-equilibria data is optimized when the hydrate composition is fixed and independent of the pressure and temperature for the conditions modeled. ?? 2006 American Chemical Society.

Journal of Physical Chemistry B↗