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Microstructural Characterization of Water-Rich Boehmite (AlO(OH)): TEM Correlation of Apparently Divergent XRD and TGA Results

Description: An understanding of the solid-phase thermodynamics and aqueous speciation of aluminum is critical to our ability to understand and predict processes in a wide variety of geologic and industrial settings. Boehmite (AIO(OH)) is an important phase in the system Al<sub>2</sub>O<sub>3</sub>-H<sub>2</sub>O that has been the subject of a number of structural and thermodynamic studies since its initial synthesis [l] and discovery in nature [2]. Unfortunately, it has long been recognized that thermogravimetric analysis (TGA) of both synthetic and natural boehmite samples (that appear well crystallized by powder XRD methods) yields significant excess water - typically losing 16-16.5 wt. % on heating as compared with a nominal expected weight loss of 15.0 wt. % [3,4]. The boehmite used in our experiments was synthesized hydrothermally from acid-washed gibbsite (Al(OH)<suv>3</sub>) at 200°C. Powder XRD and SEM examination showed no evidence of the presence a contaminant phase. The TGA patterns do not suggest that this is due to adsorbed water, so a structural source is likely. We therefore undertook to examine this material by TEM to clarify this phenomenon.
Date: August 1999
Creator: Allard, L. F.; Anovitz, L. M.; Benezeth, P.; Coffey, D. W.; Palmer, D. A.; Porter, W. D. et al.
Partner: UNT Libraries Government Documents Department

Geochemistry of Aluminum in High Temperature Brines

Description: The objective ofthis research is to provide quantitative data on the equilibrium and thermodynamic properties of aluminum minerals required to model changes in permeability and brine chemistry associated with fluid/rock interactions in the recharge, reservoir, and discharge zones of active geothermal systems. This requires a precise knowledge of the thermodynamics and speciation of aluminum in aqueous brines, spanning the temperature and fluid composition rangesencountered in active systems. The empirical and semi-empirical treatments of the solubility/hydrolysis experimental results on single aluminum mineral phases form the basis for the ultimate investigation of the behavior of complex aluminosilicate minerals. The principal objective in FY 1998 was to complete the solubility measurements on boehmite (AIOOH) inNaC1 media( 1 .O and 5.0 molal ionic strength, IOO-250°C). However, additional measurements were also made on boehmite solubility in pure NaOH solutions in order to bolster the database for fitting in-house isopiestic data on this system. Preliminary kinetic Measurements of the dissolution/precipitation of boehmite was also carried out, although these were also not planned in the earlier objective. The 1999 objectives are to incorporate these treatments into existing codes used by the geothermal industry to predict the chemistry ofthe reservoirs; these calculations will be tested for reliability against our laboratory results and field observations. Moreover, based on the success of the experimental methods developed in this program, we intend to use our unique high temperature pH easurement capabilities to make kinetic and equilibrium studies of pH-dependent aluminosilicate transformation reactions and other pH-dependent heterogeneous reactions.
Date: May 18, 1999
Creator: Benezeth, P.; Palmer, D. A. & Wesolowski, D. J.
Partner: UNT Libraries Government Documents Department

Solubility and Reaction Rates of Aluminum Solid Phases Under Hydrothermal Conditions

Description: Experimental studies involving equilibrium solubility and dissolution/precipitation rates were initiated on boehmite (AIOOH) using a hydrogen-electrode concentration cell (HECC). This cell provides continuous, accurate in situ pH measurements of solid/solution mixtures to 295 C with provision for either removing solution samples for analysis of the metal content, or adding either of two titrants. This cell has been recently used to measure the solubility of minerals such as brucite; boehmite, zincite, arid magnetite. The ability to perturb pH, isothermally by addition of acidic or basic titrant opens the door for studies of the kinetics of dissolution/precipitation, even for relatively fast reactions. By monitoring the change in pH, with time, detailed kinetic information can be obtained without the need for sampling.
Date: November 14, 1999
Creator: Benezeth, P.; Palmer, D.A. & Wesolowski, D.
Partner: UNT Libraries Government Documents Department

A Flow-Through High-Pressure Electrical Conductance Cell for Determining of Ion Association of Aqueous Electrolyte Solutions at High Temperature and Pressure

Description: A flow-through high-pressure electrical conductance cell was designed and constructed to measure limiting molar conductances and ion association constants of dilute aqueous solutions with high precision at high temperatures and pressures. The basic concept of the cell employs the principle developed at the University of Delaware in 1995, but overall targets higher temperatures (to 600 C) and pressures (to 300 MPa). At present the cell has been tested by measuring aqueous NaCl and LiOH solutions (10{sup {minus}3} to 10{sup {minus}5} mol.kg{sup {minus}1}) to 405 C and 33 MPa with good results.
Date: September 12, 1999
Creator: Bianchi, H.; Ho, P.C.; Palmer, D.A. & Wood, R.H.
Partner: UNT Libraries Government Documents Department

The Partitioning of Acetic, Formic, and Phosphoric Acids Between Liquid Water and Steam

Description: The chemical carryover of impurities and treatment chemicals from the boiler to the steam phase, and ultimately to the low-pressure turbine and condenser, can be quantified based on laboratory experiments preformed over ranges of temperature, pH, and composition. The two major assumptions are that thermodynamic equilibrium is maintained and no deposition, adsorption or decomposition occurs. The most recent results on acetic, formic and phosphoric acids are presented with consideration of the effects of hydrolysis and dimerization reactions. Complications arising from thermal decomposition of the organic acids are discussed. The partitioning constants for these acids and other solutes measured in this program have been incorporated into a simple thermodynamic computer code that calculates the effect of chemical and mechanical carryover on the composition of the condensate formed to varying extents in the water/steam cycle.
Date: June 22, 1999
Creator: Gruszkiewicz, M. S.; Marshall, S. L.; Palmer, D. A. & Simonson, J. M.
Partner: UNT Libraries Government Documents Department