Acid-Base Ionization and Metal Complexation under Hydrothermal Conditions by UV-Visible and Raman Spectroscopy

UV-visible spectroscopy, Raman spectroscopy, and vibrating tube densimetry have been used in our laboratory to determine equilibrium constants of aqueous species at temperatures as high as 325 °C. The UV-visible and Raman spectra of solutions containing metal complexes and ionized acids or bases can be used to yield formation constants by applying curve fitting methods to resolve the contribution of each species. Colorimetric pH indicators identified by Johnston and coworkers at the University of Texas (Austin) provide an alternative means of determining ionization constants and the pH of complex mixtures. High precision density measurements over the same range yield standard partial molar volumes, which are key parameters for "equations of state" for aqueous species. Examples are given for the copper-ammonia system, simple carboxylic acids, and the iron-sulphate system.