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I.-M. Chou

Publications and source records attributed to I.-M. Chou.

At least 55 records · Page 3Linked to original sources
USGS2002

Determination of melanterite-rozenite and chalcanthite-bonattite equilibria by humidity measurements at 0.1 MPa

Melanterite (FeSO 4 ·7H 2 O)-rozenite (FeSO 4 ·4H 2 O) and chalcanthite (CuSO 4 ·5H 2 O)-bonattite (CuSO 4 ·3H 2 O) equilibria were determined by humidity measurements at 0.1 MPa. Two methods were used; one is the gas-flow-cell method (between 21 and 98 °C), and the other is the humiditybuffer method (between 21 and 70 °C). The first method has a larger temperature uncertainty even though it is more efficient. With the aid of humidity buffers, which correspond to a series of saturated binary salt solutions, the second method yields reliable results as demonstrated by very tight reversals along each humidity buffer. These results are consistent with those obtained by the first method, and also with the solubility data reported in the literature. Thermodynamic analysis of these data yields values of 29.231 ± 0.025 and 22.593 ± 0.040 kJ/mol for standard Gibbs free energy of reaction at 298.15 K and 0.1 MPa for melanterite-rozenite and chalcanthite-bonattite equilibria, respectively. The methods used in this study hold great potential for unraveling the thermodynamic properties of sulfate salts involved in dehydration reactions at near ambient conditions.

American Mineralogist↗
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↗
USGS2001

Hydrogen bond breaking in aqueous solutions near the critical point

The nature of water-anion bonding is examined using X-ray absorption fine structure spectroscopy on a 1mZnBr2/6m NaBr aqueous solution, to near critical conditions. Analyses show that upon heating the solution from 25??C to 500??C, a 63% reduction of waters occurs in the solvation shell of ZnBr42-, which is the predominant complex at all pressure-temperature conditions investigated. A similar reduction in the hydration shell of waters in the Br- aqua ion was found. Our results indicate that the water-anion and water-water bond breaking mechanisms occurring at high temperatures are essentially the same. This is consistent with the hydration waters being weakly hydrogen bonded to halide anions in electrolyte solutions. ?? 2001 Elsevier Science B.V.

Chemical Physics Letters↗
USGS2001

Analysis of radiation-induced small Cu particle cluster formation in aqueous CuCl2

Radition-induced small Cu particle cluster formation in aqueous CuCl2 was analyzed. It was noticed that nearest neighbor distance increased with the increase in the time of irradiation. This showed that the clusters approached the lattice dimension of bulk copper. As the average cluster size approached its bulk dimensions, an increase in the nearest neighbor coordination number was found with the decrease in the surface to volume ratio. Radiolysis of water by incident x-ray beam led to the reduction of copper ions in the solution to themetallic state.

Journal of Chemical Physics↗
USGS2001

Chemical and engineering properties of fired bricks containing 50 weight percent of class F fly ash

The generation of fly ash during coal combustion represents a considerable solid waste disposal problem in the state of Illinois and nationwide. In fact, the majority of the three million tons of fly ash produced from burning Illinois bituminous coals is disposed of in landfills. The purpose of this study was to obtain a preliminary assessment of the technical feasibility of mitigating this solid waste problem by making fired bricks with the large volume of fly ash generated from burning Illinois coals. Test bricks were produced by the extrusion method with increasing amounts (20-50% by weight) of fly ash as a replacement for conventional raw materials. The chemical characteristics and engineering properties of the test bricks produced with and without 50 wt% of fly ash substitutions were analyzed and compared. The properties of the test bricks containing fly ash were at least comparable to, if not better than, those of standard test bricks made without fly ash and met the commercial specifications for fired bricks. The positive results of this study suggest that further study on test bricks with fly ash substitutions of greater than 50wt% is warranted. Successful results could have an important impact in reducing the waste disposal problem related to class F fly ash while providing the brick industry with a new low cost raw material.

Energy Sources↗
USGS2000

Transformations in methane hydrates

Detailed study of pure methane hydrate in a diamond cell with in situ optical, Raman, and x-ray microprobe techniques reveals two previously unknown structures, structure II and structure H, at high pressures. The structure II methane hydrate at 250 MPa has a cubic unit cell of a = 17.158(2) A?? and volume V = 5051.3(13) A??3; structure H at 600 MPa has a hexagonal unit cell of a = 11.980(2) A??, c = 9.992(3) A??, and V = 1241.9(5) A??3. The compositions of these two investigated phases are still not known. With the effects of pressure and the presence of other gases in the structure, the structure II phase is likely to dominate over the known structure I methane hydrate within deep hydrate-bearing sediments underlying continental margins.

Proceedings of the National Academy of Sciences of↗
USGS2000

Hydrothermal diamond anvil cell for XAFS studies of first-row transition elements in aqueous solutions up to supercritical conditions

A hydrothermal diamond anvil cell (HDAC) has been modified by drilling holes with a laser to within 150 ??m of the anvil face to minimize the loss of X-rays due to absorption and scatter by diamond. This modification enables acquisition of K-edge X-ray absorption fine structure (XAFS) spectra from first-row transition metal ions in aqueous solutions at temperatures ranging from 25??C to 660??C and pressures up to 800 MPa. These pressure-temperature (P-T) conditions are more than sufficient for carrying out experimental measurements that can provide data valuable in the interpretation of fluid inclusions in minerals found in ore-forming hydrothermal systems as well as other important lithospheric processes involving water. (C) 2000 Elsevier Science B.V. All rights reserved.

Conference Paper↗
USGS2000

Corrosivities in a pilot-scale combustor of a British and two Illinois coals with varying chlorine contents

Many US boiler manufacturers have recommended limits on the chlorine (Cl) content (< 0.25% or < 0.3%) of coals to be used in their boilers. These limits were based primarily on extrapolation of British coal data to predict the probable corrosion behavior of US coals. Even though Cl-related boiler corrosion has not been reported by US utilities burning high-Cl Illinois coals, the manufacturer's limits affect the marketability of high-Cl Illinois coals. This study measured the relative rates of corrosion caused by two high-Cl coals (British and Illinois) and one low-Cl Illinois baseline coal under identical pilot-scale combustion conditions for about 1000 h which gave reliable comparisons. Temperatures used reflected conditions in boiler superheaters. The corrosion probes were fabricated from commercial alloy 304SS frequently used at the hottest superheater section of utility boilers. The results showed no evidence of direct correlation between the coal chlorine content and rate of corrosion. A correlation between the rate of corrosion and the metal temperature was obvious. The results suggested that the different field histories of corrosivity from burning high-Cl Illinois coal and high-Cl British coal occurred because of different metal temperatures operated in US and UK utility boilers. The results of this study can be combined into a database, which could be used for lifting the limits on chlorine contents of coals burned in utility boilers in the US.

Fuel Processing Technology↗
USGS1999

XAFS measurements on zinc chloride aqueous solutions from ambient to supercritical conditions using the diamond anvil cell

The structure and bonding properties of metal complexes in subcritical and supercritical fluids are still largely unknown. Conventional high pressure and temperature cell designs impose considerable limitations on the pressure, temperature, and concentration of metal salts required for measurements on solutions under supercritical conditions. In this study, we demonstrate the first application of the diamond anvil cell, specially designed for x-ray absorption studies of first-row transition metal ions in supercritical fluids. Zn K-edge XAFS spectra were measured from aqueous solutions of 1-2 m ZnCl 2 and up to 6 m NaCl, at temperatures ranging from 25-660 °C and pressures up to 800 MPa. Our results indicate that the ZnCl 4 2- complex is predominant in the 1 m ZnCl 2 /6 m NaCl solution, while ZnCl 2 (H 2 O) 2 is similarly predominant in the 2 m ZnCl 2 solution, at all temperatures and pressures. The Zn-Cl bond length of both types of chlorozinc(II) complexes was found to decrease at a rate of about 0.01 Å/100 °C.

Journal of Synchrotron Radiation↗
USGS1999

Utilization of the gypsum from a wet limestone flue gas desulfurization process

The authors have been developing a process which converts FGD-gypsum to ammonium sulfate fertilizer with precipitated calcium carbonate as a by-product during the conversion. Preliminary cost estimates suggest that the process is economically feasible when ammonium sulfate crystals are produced in a granular size (1.2 to 3.3 mm), instead of a powder form. However, if additional revenue from the sale of the PCC for higher-value commercial application is applicable, this could further improve the economics of the process. Ammonium sulfate is known to be an excellent source of nitrogen and sulfur in fertilizer for corn and wheat production. It was not known what impurities might co-exist in ammonium sulfate derived from scrubber gypsum. Before the product could be recommended for use on farm land, the impurities and their impact on soil productivity had to be assessed. The objectives of this phase of the study were to evaluate the chemical properties of ammonium sulfate made from the FGD-gypsum, to estimate its effects on soil productivity, and to survey the marketability of the two products. The results of this phase of the study indicated that the impurities in the ammonium sulfate produced would not impose any practical limitations on its use at application levels used by farmers. The market survey showed that the sale price of solid ammonium sulfate fertilizer increased significantly from 1974 at $110/ton to 1998 at $187/ton. Utilities currently pay $16 to $20/ton for the calcium carbonate they use in their flue gas scrubber system. The industries making animal-feed grade calcium supplement pay $30/ton to $67/m-ton for their source of calcium carbonate. Paper, paint, and plastic industries pay as much as $200 to $300/ton for their calcium carbonate filers. The increased sale price of solid ammonium sulfate fertilizer and the possible additional revenue from the sale of the PCC by-product could further improve the economics of producing ammonium sulfate from FGD-gypsum.

Conference Paper↗
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↗
USGS1998

Fluid-deposited graphitic inclusions in quartz: Comparison between KTB (German Continental Deep-Drilling) core samples and artificially reequilibrated natural inclusions

We used Raman microsampling spectroscopy (RMS) to determine the degree of crystallinity of minute (2–15 μm) graphite inclusions in quartz in two sets of samples: experimentally reequilibrated fluid inclusions in a natural quartz grain and biotite-bearing paragneisses from the KTB deep drillhole in SE Germany. Our sequential reequilibration experiments at 725°C on initially pure CO 2 inclusions in a quartz wafer and the J. Krautheim 1993 experiments at 900–1100°C on organic compounds heated in gold or platinum capsules suggest that, at a given temperature, (1) fluid-deposited graphite will have a lower crystallinity than metamorphosed organic matter and (2) that the crystallinity of fluid-deposited graphite is affected by the composition of the fluid from which it was deposited. We determined that the precipitation of more-crystalline graphite is favored by lower f H 2 (higher f O 2 ), and that the crystallinity of graphite is established by the conditions (including gas fugacities) that pertain as the fluid first reaches graphite saturation. Graphite inclusions within quartz grains in the KTB rocks show a wide range in crystallinity index, reflecting three episodes of carbon entrapment under different metamorphic conditions. Isolated graphite inclusions have the spectral properties of totally ordered, completely crystalline graphite. Such crystallinity suggests that the graphite was incorporated from the surrounding metasedimentary rocks, which underwent metamorphism at upper amphibolite-facies conditions. Much of the fluid-deposited graphite in fluid inclusions, however, shows some spectral disorder. The properties of that graphite resemble those of experimental precipitates at temperatures in excess of 700°C and at elevated pressures, suggesting that the inclusions represent precipitates from C-O-H fluids trapped under conditions near those of peak metamorphism at the KTB site. In contrast, graphite that is intimately associated with chlorite and other (presumably low-temperature) silicates in inclusions is highly disordered and spectrally resembles kerogens. This graphite probably was deposited during later greenschist-facies retrograde metamorphism at about 400–500°C. The degree of crystallinity of fluid-deposited graphite is shown to be a much more complex function of temperature than is the crystallinity of metamorphic graphite. To some extent, experiments can provide temperature-calibration of the crystallinity index. However, the difference in time scales between experimental runs and geologic processes makes it difficult to infer specific temperatures for naturally precipitated graphite.

Bohemian Massif↗
USGS1998

In situ observations of a high-pressure phase of H2O ice

A previously unknown solid phase of H2O has been identified by its peculiar growth patterns, distinct pressure-temperature melting relations, and vibrational Raman spectra. Morphologies of ice crystals and their pressure-temperature melting relations were directly observed in a hydrothermal diamond-anvil cell for H2O bulk densities between 1203 and 1257 kilograms per cubic meter at temperatures between -10??and 50??C. Under these conditions, four different ice forms were observed to melt: two stable phases, ice V and ice VI, and two metastable phases, ice IV and the new ice phase. The Raman spectra and crystal morphology are consistent with a disordered anisotropic structure with some similarities to ice VI.

Science↗
USGS1997

An occurrence of metastable cristobalite in high-pressure garnet Granulite

High-pressure (0.8 gigapascals) granulite facies garnet from Gore Mountain, New York, hosts multiple solid inclusions containing the low- pressure silica polymorph cristobalite along with albite and minor ilmenite. Identification of cristobalite is based on Raman spectra, electron microprobe analysis, and microthermometric measurements on the ??/?? phase transformation. The cristobalite plus albite inclusions may have originated as small, trapped samples of hydrous sodium-aluminum-siliceous melt. Diffusive loss of water from these inclusions under isothermal, isochoric conditions may have resulted in a large enough internal pressure decrease to promote the metastable crystallization of cristobalite.

Science↗
USGS1997

The forms of trace metals in an Illinois basin coal by x-ray absorption fine structure spectroscopy

Utilities burning Illinois coals currently do not consider trace elements in their flue gas emissions. After the US EPA completes an investigation on trace elements, however, this may change and flue gas emission standards may be established. The mode of occurrence of a trace element may determine its cleanability and Hue gas emission potential. X-ray Absorption Fine Structure (XAFS) is a spectroscopic technique that can differentiate the mode of occurrence of an element, even at the low concentrations that trace elements are found in coal. This is principally accomplished by comparing the XAFS spectra of a coal to a database of reference sample spectra. This study evaluated the technique as a potential tool to examine six trace elements in an Illinois #6 coal. For the elements As and Zn, the present database provides a definitive interpretation on their mode of occurrence. For the elements Ti, V, Cr, and Mn the database of XAFS spectra of trace elements in coal was still too limited to allow a definitive interpretation. The data obtained on these elements, however, was sufficient to rule out several of the mineralogical possibilities that have been suggested previously. The results indicate that XAFS is a promising technique for the study of trace elements in coal.

ACS Division of Fuel Chemistry, Preprints↗
USGS1996

Raman spectroscopic characterization of gas mixtures. II. Quantitative composition and pressure determination of the CO2-CH4 system

Raman spectral parameters were determined for the v 1 band of CH4 and the v 1 and 2 v 2 bands (Fermi diad) of CO 2 in pure CO 2 and CO 2 -CH 4 mixtures at pressures up to 700 bars and room temperature. Peak position, area, height, and width were investigated as functions of pressure and composition. The peak positions of the CH 4 and CO 2 bands shift to lower relative wavenumbers as fluid pressure is increased. The peak position of the lower-wavenumber member of the Fermi diad for CO 2 is sensitive to fluid composition, whereas the peak positions of the CH 4 band and the upper Fermi diad member for CO 2 are relatively insensitive in the CO 2 -CH 4 system. The magnitude of the shifts in each of the three peak positions (as a function of pressure) is sufficient to be useful as a monitor of fluid pressure. The relative molar proportions in a CO 2 -CH 4 mixture may be determined from the peak areas: the ratio of the peak areas of the CH 4 band and the CO 2 upper Fermi diad member is very sensitive to composition, whereas above about 100 bars, it is insensitive to pressure. Likewise, the peak height ratio is very sensitive to composition but also to fluid pressure. The individual peak widths of CO 2 and CH 4 , as well as the ratios of the widths of the CH 4 peak to the CO 2 peaks are a sensitive function of pressure and, to a lesser extent, composition. Thus, upon determination of fluid composition, the peak width ratios may be used as a monitor of fluid pressure. The application of these spectral parameters to a suite of natural CO 2 -CH 4 inclusions has yielded internally-consistent, quantitative determinations of the fluid composition and density.

American Journal of Science↗
USGS1996

Manufacture of ammonium sulfate fertilizer from gypsum-rich byproduct of flue gas desulfurization - A prefeasibility cost estimate

Costs for constructing and operating a conceptual plant based on a proposed process that converts flue gas desulfurization (FGD)-gypsum to ammonium sulfate fertilizer has been calculated and used to estimate a market price for the product. The average market price of granular ammonium sulfate ($138/ton) exceeds the rough estimated cost of ammonium sulfate from the proposed process ($111/ ton), by 25 percent, if granular size ammonium sulfate crystals of 1.2 to 3.3 millimeters in diameters can be produced by the proposed process. However, there was at least ??30% margin in the cost estimate calculations. The additional costs for compaction, if needed to create granules of the required size, would make the process uneconomical unless considerable efficiency gains are achieved to balance the additional costs. This study suggests the need both to refine the crystallization process and to find potential markets for the calcium carbonate produced by the process.

ACS Division of Fuel Chemistry, Preprints↗