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At least 37 records · Page 2Linked to original sources
USGS2004

The role of water in gas hydrate dissociation

When raised to temperatures above the ice melting point, gas hydrates release their gas in well-defined, reproducible events that occur within self-maintained temperature ranges slightly below the ice point. This behavior is observed for structure I (carbon dioxide, methane) and structure II gas hydrates (methane-ethane, and propane), including those formed with either H2O- or D2O-host frameworks, and dissociated at either ambient or elevated pressure conditions. We hypothesize that at temperatures above the H2O (or D2O) melting point: (1) hydrate dissociation produces water + gas instead of ice + gas, (2) the endothermic dissociation reaction lowers the temperature of the sample, causing the water product to freeze, (3) this phase transition buffers the sample temperatures within a narrow temperature range just below the ice point until dissociation goes to completion, and (4) the temperature depression below the pure ice melting point correlates with the average rate of dissociation and arises from solution of the hydrate-forming gas, released by dissociation, in the water phase at elevated concentrations. In addition, for hydrate that is partially dissociated to ice + gas at lower temperatures and then heated to temperatures above the ice point, all remaining hydrate dissociates to gas + liquid water as existing barriers to dissociation disappear. The enhanced dissociation rates at warmer temperatures are probably associated with faster gas transport pathways arising from the formation of water product.

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↗
USGS2012

Molecular dynamics simulation of nitric oxide in myoglobin

The infrared (IR) spectroscopy and ligand migration of photodissociated nitric oxide (NO) in and around the active sites in myoglobin (Mb) are investigated. A distributed multipolar model for open-shell systems is developed and used, which allows one to realistically describe the charge distribution around the diatomic probe molecule. The IR spectra were computed from the trajectories for two conformational substates at various temperatures. The lines are narrow (width of 3–7 cm –1 at 20–100 K), in agreement with the experimental observations where they have widths of 4–5 cm –1 at 4 K. It is found that within one conformational substate (B or C) the splitting of the spectrum can be correctly described compared with recent experiments. Similar to photodissociated CO in Mb, additional substates exist for NO in Mb, which are separated by barriers below 1 kcal/mol. Contrary to full quantum mechanical calculations, however, the force field and mixed QM/MM simulations do not correctly describe the relative shifts between the B- and C-states relative to gas-phase NO. Free energy simulations establish that NO preferably localizes in the distal site and the barrier for migration to the neighboring Xe4 pocket is Δ G B→C = 1.7–2.0 kcal/mol. The reverse barrier is Δ G B←C = 0.7 kcal/mol, which agrees well with the experimental value of 0.7 kcal/mol, estimated from kinetic data.

Journal of Physical Chemistry↗
USGS1997

Measurement of clathrate hydrates via Raman spectroscopy

Raman spectra of clathrate hydrate guest molecules are presented for three known structures ( I ( sI ), II ( sII ), and H ( sH )) in the following systems: CH 4 ( sI ), CO 2 ( sI ), C 3 H 8 ( sII ), CH 4 + CO 2 ( sI ), CD 4 + C 3 H 8 ( sII ), CH 4 + N 2 ( sI ), CH 4 + THF- d 8 ( sII ), and CH 4 + C 7 D 14 ( sH ). Relative occupancy of CH 4 in the large and small cavities of sI were determined by deconvoluting the ν 1 symmetric bands, resulting in hydration numbers of 6.04 ± 0.03. The frequency of the ν 1 bands for CH 4 in structures I, II, and H differ statistically, so that Raman spectroscopy is a potential tool to identify hydrate crystal structure. Hydrate guest compositions were also measured for two vapor compositions of the CH 4 + CO 2 system, and they compared favorably with predictions. The large cavities were measured to be almost fully occupied by CH 4 and CO 2 , whereas only a small fraction of the small cavities are occupied by CH 4 . No CO 2 was found in the small cavities. Hydration numbers from 7.27 to 7.45 were calculated for the mixed hydrate.

Journal of Physical Chemistry B↗
USGS1998

Optical-cell evidence for superheated ice under gas-hydrate-forming conditions

We previously reported indirect but compelling evidence that fine-grained H 2 O ice under elevated CH 4 gas pressure can persist to temperatures well above its ordinary melting point while slowly reacting to form methane clathrate hydrate. This phenomenon has now been visually verified by duplicating these experiments in an optical cell while observing the very slow hydrate-forming process as the reactants were warmed from 250 to 290 K at methane pressures of 23 to 30 MPa. Limited hydrate growth occurred rapidly after initial exposure of the methane gas to the ice grains at temperatures well within the ice subsolidus region. No evidence for continued growth of the hydrate phase was observed until samples were warmed above the equilibrium H 2 O melting curve. With continued heating, no bulk melting of the ice grains or free liquid water was detected anywhere within the optical cell until hydrate dissociation conditions were reached (292 K at 30 MPa), even though full conversion of the ice grains to hydrate requires 6−8 h at temperatures approaching 290 K. In a separate experimental sequence, unreacted portions of H 2 O ice grains that had persisted to temperatures above their ordinary melting point were successfully induced to melt, without dissociating the coexisting hydrate in the sample tube, by reducing the pressure overstep of the equilibrium phase boundary and thereby reducing the rate of hydrate growth at the ice−hydrate interface. Results from similar tests using CO 2 as the hydrate-forming species demonstrated that this superheating effect is not unique to the CH 4 −H 2 O system.

Journal of Physical Chemistry B↗
USGS1967

Pressure derivatives of elastic moduli of fused quartz to 10 kb

Measurements of the longitudinal and shear moduli were made on fused quartz to 10 kb at 24·5°C. The anomalous behavior of the bulk modulus K at low pressure, &#x2202;K &#x2202;P &lt; 0 "> ∂K∂P< 0 , begins to approach the “normal” behavior of solids, &#x2202;K &#x2202;P &gt; 0 "> ∂K∂P> 0 , at higher pressures. The pressure derivative of the rigidity modulus &#x2202;G &#x2202;P "> ∂G∂P remains constant and negative for the pressure range covered. A 15-kb hydrostatic pressure vessel is described for use with ultrasonic pulse instrumentation for precise measurements of elastic moduli and density changes with pressure. The placing of the transducer outside the pressure medium, and the use of C -ring pressure seals result in ease of operation and simplicity of design.

Journal of Physics and Chemistry of Solids↗
USGS1969

Magnetic susceptibility and exchange coupling in the mineral ardennite

Ardennite, a rare silicate mineral, contains about 19 wt.% manganese. Some of the manganese atoms are in positions which are close enough to allow negative exchange and hence a reduction of the total magnetic susceptibility. It is shown that the susceptibility can be accounted for approximately by the treatment of Earnshaw and Lewis (1958) for S = 5 2 "> S =52 and a Hamiltonian H = −2 g μ H b −2 JS 1 · S 2 .

Journal of Physics and Chemistry of Solids↗
USGS1977

Cell dimensions and antiferromagnetism of lunar and terrestrial ilmenite single crystals

X-Ray diffraction and anisotropic magnetic measurements have been made on single crystals of lunar ilmenite and on terrestrial ilmenite from Bancroft, Ontario, Canada and the Ilmen Mountains, U.S.S.R. The elongated c "> c -axis of lunar ilmenite, previously reported, is confirmed by new measurements. The shorter c "> c -axis found in terrestrial specimens is ascribed to Fe 3+ substitution for Ti 4+ in the titanium layer. Magnetic measurements on the same specimens show that, in agreement with the Ishikawa-Shirane et al . model, the initial shortening of the c "> c -axis by the above substitution of small amounts of Fe 3+ (<8%) causes an increase in Fe 2+ −Fe 2+ exchange coupling through Fe 3+ in the titanium layer that lowers the Néel transition temperature. The Weiss temperatures and other magnetic parameters confirm this model proposed by Ishikawa and Shirane et al . Additional transitions found in one of the terrestrial specimens (Bancroft) have been ascribed to a small amount of an exsolved spinel phase, possibly a solid solution phase of magnetite-ülvospinel. The spinel phase is localized in hematite-rich blebs which exsolved from the host ilmenite-rich phase.

Journal of Physics and Chemistry of Solids↗
USGS1977

Anisotropic magnetic susceptibility of erbium and ytterbium in zircon, ZrSiO4

Magnetic susceptibility measurements have been made for both Er- and Yb-doped (1&#x0303;0 3 ppm) zircon single crystals with the magnetic field perpendicular and parallel to the [001] axis. Large susceptibility anisotropies were found in both cases. Our observed anisotropies of ZrSiO 4 : Yb indicate small populations (1&#x0303;9%) of Yb ions at the axial (tetragonal) sites, as the susceptibility of ZrSiO 4 : Yb would be nearly isotropic if the Yb ions only occupied the orthorhombic sites. For Er 3+ in orthorhombic sites of zircon, our data indicate that the first excited state is paramagnetic with g x = 9 and g y 5&#x0303; at 20 cm −1 above the ground state ( g x 0&#x0303;, g y 1&#x0303;5). The first excited state is quite similar to the ground states observed for Er 3+ in many host lattices

Journal of Physics and Chemistry of Solids↗
USGS1971

Magnetic susceptibility and triangular exchange coupling in the tourmaline mineral group

Magnetic susceptibilities of three iron-rich tourmaline crystals from Mexquitic (Mexico), Pierpont (New York), and Madagascar with different and known chemical compositions have been studied from 8° to 300°K. The iron atoms in the tourmaline crystal structure, space group R3m , a∼15·9, c∼7·2 , are situated at the three corners of an equilateral triangle and are close enough for magnetic exchange interaction. For buergerite, the Mexquitic sample, the susceptibility data lead to an exchange constant J/k of 7·5°K. Although the amount of aluminum would be sufficient to fill point position 18(c) exactly, the magnetic data are consistent with some substitution of ferric iron for aluminum, as previously determined from X-ray and neutron diffraction studies. Some aluminum thus replaces iron in position 9(b). Exchange constants were also estimated for the other two magnesium-iron specimens, of which the madagascar sample is aluminum deficient. The results agree with the evidence from optical spectra that there is considerable deviation from octahedral symmetry in the oxygen coordination polyhedra about the 9(b) and 18(c) point positions.

New York↗
USGS1984

Adsorption of goethite onto quartz and kaolinite

The adsorption of colloidal goethite onto quartz and kaolinite substrates has been studied as a function of pH and NaCl concentration. Goethite adsorption was measured quantitatively by Fourier-transform infrared spectroscopy. The results indicate that adsorption onto both substrates is due primarily to coulombic forces; however, the pH dependence of adsorption is very different for the two substrates. This is explained by the fact that the surface charge on quartz is entirely pH-dependent, while kaolinite has surface faces which carry a permanent negative charge. Adsorption of goethite on to kaolinite increases markedly with increasing NaCl concentration, while adsorption onto quartz is relatively independent of NaCl concentration. This can be explained by the influence of NaCl concentration upon the development of surface charge on the substrates. A method is described for separating surface-bound goethite from free goethite.

Journal of the Chemical Society, Faraday Transacti↗
USGS1989

Shape-selective adsorption of aromatic molecules from water by tetramethylammonium-smectite

The adsorption of aromatic compounds by smectite exchanged with tetramethylammonium (TMA) has been studied. Aromatic compounds adsorbed by TMA-smectite are assumed to adopt a tilted orientation in a face-to-face arrangment with the TMA tetrahedra. The sorptive characteristics of TMA-smectite were influenced strongly by the presence of water. The dry TMA-smectite showed little selectivity in the uptake of benzen, toluene and xylene. In the presence of water, TMA-smectite showed a high degree of selectivity based on molecular size/shape, resulting in high uptake of benzene and progressively lower uptake of larger aromatic molecules. This selectivity appeared to result from the shrinkage of interlamellar cavities by water.

Journal of the Chemical Society, Faraday Transacti↗
USGS1987

Mineralogy and petrology of the Cretaceous- Tertiary boundary clay bed and adjacent clay-rich rocks, Raton Basin, New Mexico and Colorado.

The Cretaceous-Tertiary (K-T) boundary is preserved in a sequence of coal-bearing, fluvial rocks in the lower part of the Raton Formation (Late Cretaceous and Paleocene) at several sites in the east-central part of the Raton Basin. The K-T boundary occurs at the top of a kaolinitic claystone layer, commonly referred to as the "boundary clay layer," in an interval of coal and carbonaceous shale. The boundary is defined by the disappearance of certain fossil-pollen taxa. The boundary clay layer also contains shocked quartz grains and abundance anomalies of iridium, chromium, and other elements. Each of these characteristics support the hypothesis of an asteroid impact at the end of the Cretaceous. Small goyazite spheres were also found in the boundary clay bed; however, their origin is uncertain. X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and thin-section petrography have shown that the boundary clay bed exhibits unique mineralogic and petrologic characteristics not possessed by other clay-rich beds in coal-bearing rocks of the Raton Basin. The boundary clay bed is composed primarily of well-crystallized kaolinite but also contains subordinate, randomly interstratified, mixed-layer illite/smectite, both of which appear to have been formed by the alteration of vitreous material in a coal-swamp environment. The bulk mineralogy of the boundary clay bed is similar to that of other kaolinite-rich clay beds (tonsteins) that altered in coal swamps from airfall volcanic ash. The alteration process and diagenetic products of the host material in the boundary clay bed, however, differed from those of the tonsteins, resulting in a unique petrographic fabric. The boundary clay bed is characterized by an overall imbricate fabric that may reflect an original vitreous material that included shards, bubbles, and spheres. The original fallout material of the boundary clay bed first altered to "cabbage-like" microspherules, indicating a halloysite or allophane precursor, and then to well-crystallized kaolinite; the well-crystallized kaolinite is the diagenetic stable phase for these rocks at their maximum burial conditions. In comparison, the vitreous components of the tonsteins were altered directly to coarse vermicular and platey kaolinite. Alteration of the original fallout material in the boundary bed was probably rapid, leading to hydrated, disordered, fine-grained clay minerals that formed into curled spherical or tubular shapes. The factors that produced these unique fabrics in the boundary clay bed existed at all K-T sites in the Raton Basin and were much different from those that formed the coarse platey and vermicular fabrics of ordinary tonsteins. The distinctive character of the boundary clay may be due to the unique nature and chemistry of the fallout material and (or) physical or chemical conditions existing shortly after its deposition.

Journal of Sedimentary Petrology↗
USGS2003

Temperature, pressure, and compositional effects on anomalous or "self" preservation of gas hydrates

We previously reported on a thermal regime where pure, polycrystalline methane hydrate is preserved metastably in bulk at up to 75 K above its nominal temperature stability limit of 193 K at 0.1 MPa, following rapid release of the sample pore pressure. Large fractions (>50 vol.%) of methane hydrate can be preserved for 2-3 weeks by this method, reflecting the greatly suppressed rates of dissociation that characterize this "anomalous preservation" regime. This behavior contrasts that exhibited by methane hydrate at both colder (193-240 K) and warmer (272-290 K) isothermal test conditions, where dissociation rates increase monotonically with increasing temperature. Here, we report on recent experiments that further investigate the effects of temperature, pressure, and composition on anomalous preservation behavior. All tests conducted on sI methane hydrate yielded self-consistent results that confirm the highly temperature-sensitive but reproducible nature of anomalous preservation behavior. Temperature-stepping experiments conducted between 250 and 268 K corroborate the relative rates measured previously in isothermal preservation tests, and elevated pore-pressure tests showed that, as expected, dissociation rates are further reduced with increasing pressure. Surprisingly, sII methane-ethane hydrate was found to exhibit no comparable preservation effect when rapidly depressurized at 268 K, even though it is thermodynamically stable at higher temperatures and lower pressures than sI methane hydrate. These results, coupled with SEM imaging of quenched sample material from a variety of dissociation tests, strongly support our earlier arguments that ice-"shielding" effects provided by partial dissociation along hydrate grain surfaces do not serve as the primary mechanism for anomalous preservation. The underlying physical-chemistry mechanism(s) of anomalous preservation remains elusive, but appears to be based more on textural or morphological changes within the hydrate material itself, rather than on compositional zoning or ice-rind development.

Canadian Journal of Physics↗
USGS2006

Description, Properties, and Degradation of Selected Volatile Organic Compounds Detected in Ground Water--A Review of Selected Literature

This report provides abridged information describing the most salient properties and biodegradation of 27 chlorinated volatile organic compounds detected during ground-water studies in the United States. This information is condensed from an extensive list of reports, papers, and literature published by the U.S. Government, various State governments, and peer-reviewed journals. The list includes literature reviews, compilations, and summaries describing volatile organic compounds in ground water. This report cross-references common names and synonyms associated with volatile organic compounds with the naming conventions supported by the International Union of Pure and Applied Chemistry. In addition, the report describes basic physical characteristics of those compounds such as Henry's Law constant, water solubility, density, octanol-water partition (log Kow), and organic carbon partition (log Koc) coefficients. Descriptions and illustrations are provided for natural and laboratory biodegradation rates, chemical by-products, and degradation pathways.

Open-File Report↗