This thesis is an investigation of the relative differences of acid ionization constants and ion mobility in D2O versus H2O under hydrothermal conditions, for acetic acid and phosphoric acid. Values of specific conductivity were measured for each acid in H2O and D2O, as well as for a series of strong electrolytes using a high-temperature high-pressure AC conductivity flow cell that was originally designed at the University of Delaware. The Fuoss-Hsai-Fernández-Prini (FHFP) equation was fitted to the experimental values of molar conductivity, Λ, to obtain molar conductivities at infinite dilution, Λo. The molar conductivities at infinite dilution for each acid were used to calculate degrees of dissociation and ionization constants in D2O versus H2O from 298 K to 571 K. Measured values of differences in pKaq in D2O vs H2O, ΔpKaq = [pKaq,D2O – pKaq,H2O], become relatively independent of temperature above 423 K, with values of: ΔpKaq 0.45 for acetic acid and ΔpKaq 0.35 for phosphoric acid. The Density Model was then fitted to the values of pKaq in H2O and D2O to represent their temperature dependence to a precision of ± 0.01 in ΔpKaq. Comparisons of the molar conductivities and ionic molar conductivities at infinite dilution for the strong electrolytes in H2O and D2O as a function of temperature have also been made, based on Walden’s rule correlations, (λ°•η)D2O / (λ°•η)H2O. Changes in values of (λ°•η)D2O / (λ°•η)H2O as a function of temperature are consistent with a change in the relative hydration behavior of ions, where the effective Stokes’ radii of the ions in D2O versus H2O changes at temperatures above ~ 450 K. Changes in values of (λ°•η)D2O / (λ°•η)H2O for D+/H+ and OD-/OH- suggest that proton hopping “Grotthuss” mechanisms become more efficient in D2O versus H2O with increasing temperature. / University Network of Excellence in Nuclear Engineering, Ontario Power Generation Ltd, Natural Science and Engineering Research Council of Canada

Polarized Raman spectroscopy has been used to measure the deuterium isotope effect, (delta)pK = pKD2O – pKH2O, for the second ionization constant of sulfuric acid in the temperature range of 25 °C to 200 °C at saturation pressure. Results for pK in light water agree with the literature within ± 0.034 pK units at alltemperatures under study, confirming the reliability of the method. The ionization constant of deuterated bisulfate, DSO4-, differs significantly from previous literature results at elevated temperatures. This results in an almost constant (delta)pK ≈ 0.425 ± 0.076 over the temperature range under study. Differences in (delta)pK values between the literature and current results can be attributed to the effect of dissolved silica from cell components. The new results are consistent with (delta)pK models that treat the temperature dependence of (delta)pK by considering differences in the zero-point energy of hydrogen bonds in the hydrated product and reactant species. The phosphate hydrolysis equilibrium was measured between the temperatures of 5 °C and 80 °C and the borate/boric acid equilibrium between the temperatures of 25 °C and 200 °C. The high alkalinity and temperatures experienced by these two systems had a significant impact on the glass dissolution and equilibrium. / Raman spectroscopy was used to measure the small differences in ionization constants for weak acids/bases as a function of temperature. / University of Guelph, Atomic Energy of Canada Limited (AECL), Bruce Power, University Network of Excellence in Nuclear Engineering (UNENE), National Sciences and Engineering Research Council of Canada (NSERC), Natural Resources Canada, Ontario Power Generation (OPG), Canada Foundation for Innovation

State of the art conductivity equipment has been used to measure deuterium isotope effects on the molar conductivity of strong electrolytes in the temperature range of 298 K to 598 K as a means of exploring solvation effects under hydrothermal conditions. Individual ionic contributions were determined by extrapolation of published transference number data to elevated temperature. The temperature dependence of the Walden product ratio indicates that there is little difference in the transport of ions between light and heavy water . Excess conductivity observed in hydrogen and deuterium compounds arising from proton hopping in hydrogen-bonded networks has been determined in the temperature range of 318 K to 598 K for the first time