Browsing Chemistry Faculty Publications by Author "Fulton, John L."
Short-Pathlength, High-Pressure Flow Cell for Static and Time-Resolved Infrared Spectroscopy Suitable for Supercritical Fluid Solutions Including Hydrothermal SystemsHoffmann, Markus M.; Addleman, R. Shane; Fulton, John L.; Pacific Northwest National Laboratory; The College at Brockport (2000-03-01)An optical flow cell for high pressures and temperatures is described. The use of a novel window design allows for a precise, fixed optical pathlength that can be varied by use of spacers that range from a few micrometers to several millimeters. The cell pathlength is not affected by changes in pressure or temperature. The novel window design may be applicable to other high-pressure spectroscopic cells. The flow-cell design has a minimal sample dead volume, which is important for kinetic studies. The design eliminates the need for brazing or for a soft-sealing material for the optical windows, thereby minimizing the number of materials in contact with the sample. Using only diamond and platinum or platinum alloys as the corrosion resistant materials, the design is optimized for the study of aqueous solutions at high temperatures. Infrared spectra of an aqueous sodium tungstate solution up to 400?°C and 380 bar pressure are presented. Time-resolved infrared data are also presented for the ultraviolet photolysis reaction of ?-naphthoyl azide in supercritical carbon dioxide.
X-Ray Absorption Spectroscopy and Imaging of Heterogeneous Hydrothermal Mixtures Using a Diamond Microreactor CellFulton, John L.; Darab, John G.; Hoffmann, Markus M.; Pacific Northwest National Laboratory; The College at Brockport (2001-04-01)Hydrothermal synthesis is an important route to novel materials. Hydrothermal chemistry is also an important aspect of geochemistry and a variety of waste remediation technologies. There is a significant lack of information about the speciation of inorganic compounds under hydrothermal conditions. For these reasons we describe a high-temperature, high-pressure cell that allows one to acquire both x-ray absorption fine structure (XAFS) spectra and x-ray transmission and absorption images of heterogeneous hydrothermal mixtures. We demonstrate the utility of the method by measuring the Cu(I) speciation in a solution containing both solid and dissolved Cu phases at temperatures up to 325?°C. X-ray imaging of the various hydrothermal phases allows micro-XAFS to be collected from different phases within the heterogeneous mixture. The complete structural characterization of a soluble bichloro-cuprous species was determined. In situ XAFS measurements were used to define the oxidation state and the first-shell coordination structure. The Cu–Cl distance was determined to be 2.12 Å for the CuCl2? species and the complete loss of tightly bound waters of hydration in the first shell was observed. The microreactor cell described here can be used to test thermodynamic models of solubility and redox chemistry of a variety of different hydrothermal mixtures.