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A Quantitative Raman and Density Functional Theory Investigation of Uranyl Sulfate Complexation and Liquid-Liquid Phase Separation Under Hydrothermal Conditions

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A Quantitative Raman and Density Functional Theory Investigation of Uranyl Sulfate Complexation and Liquid-Liquid Phase Separation Under Hydrothermal Conditions A Quantitative Raman and Density Functional Theory Investigation of Uranyl Sulfate Complexation and Liquid-Liquid Phase Separation under Hydrothermal Conditions by Christopher D. Alcorn A Thesis presented to The University of Guelph In partial fulfillment of the requirements for the degree of Doctor of Philosophy In Chemistry Guelph, Ontario, Canada © Christopher D. Alcorn, May 2018 ABSTRACT A Quantitative Raman and Density Functional Theory Investigation of Uranyl Sulfate Complexation and Liquid-Liquid Phase Separation under Hydrothermal Conditions Christopher D. Alcorn Advisor: University of Guelph, 2017 Professor P. R. Tremaine State-of-the-art Raman spectroscopic techniques have been employed to quantitatively measure (i) the temperature-dependent Raman properties and thermal decomposition of several non-complexing anions in acidic and neutral solutions at temperatures up to 400 oC, (ii) the first and second formation constants of the uranyl sulfate system from 25 – 375 °C, and (iii) the speciation and concentrations of liquid-liquid phase separated mixtures of uranyl sulfate and sulfuric acid up to 425 °C. - The results of the first study show the stability followed the order HSO4 (stable) > - - - o ReO4 > ClO4 > CF3SO3 in acidic solution, with half-lives over 7 h at 300 C. In neutral - - - - solutions, the order was HSO4 (stable) > CF3SO3 > ReO4 > ClO4 , with half-lives over 8 h at 350 oC. Raman vibrational frequencies and relative Raman scattering coefficients of these anions were determined, providing temperature-dependent data for frequency calibration and for determining the efficiency of these anions to scatter Raman light. To our knowledge, this manuscript is the first of its kind to report quantitative values using this methodology. The first and second formation constants of the uranyl sulfate system were quantitatively determined for the first time at t > 75 °C up to supercritical conditions. A drastic increase in both constants is observed, compared to an extrapolation of literature values, owing to the formation of uranyl sulfate complexes at high temperature. At t > 375 °C, uranyl sulfate solutions separated into two immiscible liquids, rich and deficient in uranium, respectively. A solid, presumed to be UO3·H2O(s), formed in the rich phase of solutions without excess sulfuric acid. Analysis shows the uranyl ion is 0 completely complexed in both phases, forming UO2SO4 (aq) and minor amounts of 2- 0 UO2(SO4)2 (aq). The relative abundance of UO2SO4 (aq) increases with temperature. At - t ≥ 400 °C, excess HSO4 (aq) forms in the uranium rich phase. For the uranium deficient phase, no uranium or sulfur species are detectable at 400 °C. Concentrations in both phases were quantified by using the homogeneous phase spectra as an external standard, together with densities calculated using the Helgeson-Kirkham-Flowers equation of state, and a reasonable density estimation using apparent molar volumes. To The Great Reverend Elijah Craig, Who Discovered Bourbon, And With It, My Sanity. iv Acknowledgements As far as acknowledgements towards my academic success, the first and foremost recognition has to go to my parents Bernie and Roberta Alcorn, and my grandparents Vaughan and Sylvia Milton. Without their unquestioning support, the education that this dissertation culminates on would have literally been impossible. I don’t know where I would be without them, but it most certainly wouldn’t be here. My supervisor Prof. Peter Tremaine and informal co-supervisor Dr. Jenny Cox deserve acknowledgement for not only being mentors in physical chemistry, but for also their understanding when providing allowances regarding my physical day-to-day limitations. As much as I resist and dislike admitting it, these limitations are real, and their understanding on the matter is greatly appreciated. Dr. Lucas Applegarth deserves a heartfelt acknowledgement for not only being a mentor in Raman spectroscopy, but for also being a straight-shooting English “gentleman”. “Pip pip, cheerio!”, or whatever it is your backwards cave-people say to acknowledge gratitude. I would also like to thank my Examining Committee Prof. Peter Tremaine, Prof. Marcel Schlaf, Prof. W. Scott Hopkins (U. Waterloo) and my external examiner Prof. David Shoesmith (Western U.) for an engaging thesis defence. Prof. Peter Tremaine, Prof. W. Scott Hopkins, Prof. Paul Rowntree and Prof. Dan Thomas also deserve thanks for serving on my Advisory Committee, and for helpful guidance in that role when needed. v The Tremaine Research Group deserve a warm acknowledgement for making the daily grind as enjoyable as possible. My initial labmates Dr. Hugues Arcis, Dr. Kristy Erickson, Dr. Alex Lowe, Katie Bissonette, Jeff Plumridge and Michael Yacyshyn were beyond excellent co-workers, and were later replaced by the outstanding Dr. Yohann Coulier, Dr. Olivia Fandiño-Torres, Dr. Swaroop Sasidharanpillai, Jacy Conrad, Jane Ferguson, Christine McGregor, Daniel Nieto-Roca, John Nöel, Avinaash Persaud, and Jason Sylvester. You people literally made all the difference. My sanity is intact thanks to efforts by my friends Phil Burgess, Malcolm McAvoy and Valerie Seeglitz. After a long week, Phil and I found simple pleasure from ruining someone elses’ day, armed with nothing but an endless supply of spite, and we did so frequently and without remorse. Malcolm contributes in much the same way, but also by simply existing on a statistically impossible tail of the Gaussian distribution of luck, I get to see how my own personal luck could be a whole lot worse. And finally, I always ended up walking away from early morning conversations with Val feeling a lot better, even if the next day I couldn’t even say what was talked about. You guys are simply the best. vi Table of Contents Abstract ........................................................................................................................... ii Dedication ...................................................................................................................... iv Acknowledgements ......................................................................................................... v Table of Contents .......................................................................................................... vii List of Tables ............................................................................................................... xiii List of Figures ............................................................................................................. xvii List of Abbreviations and Figures ................................................................................. xxi Chapter I General Introduction ...................................................................................... 1 I.1 Physical Properties of High Temperature Water .................................................... 1 I.2 High Temperature Aqueous Chemistry ................................................................. 3 I.2.1 Historical Context .......................................................................................... 3 I.2.2 Thermodynamic Standard States .................................................................... 3 I.2.3 Activity Coefficient Models ........................................................................... 4 I.2.4 Solvation Effects: Modelling Implicit and Explicit Solvation ......................... 6 I.2.5 Liquid-Liquid Phase Separation of Ionic Species ............................................ 9 I.3 Scientific and Industrial Interest in High Temperature Aqueous Uranium Chemistry .................................................................................................................. 10 I.4 Literature Review of Uranyl Coordination Chemistry ......................................... 12 I.4.1 Complexation of Uranyl with Sulfate ........................................................... 14 I.4.2 Complexation of Uranyl with Carbonate....................................................... 16 I.4.3 Complexation of Uranyl with Chloride ......................................................... 18 I.4.4 Complexation of Uranyl with Hydroxide ...................................................... 20 I.5 Methods for Probing Aqueous Uranyl Chemistry ................................................ 21 I.6 Raman Spectroscopy ........................................................................................... 22 I.6.1 Raman Effect, Polarizability Tensor and Raman Selection Rules .................. 22 I.6.2 Raman Intensities Using Plane Polarized Incident Light ............................... 25 I.6.3 Horiba Jobin Yvon Labram HR 800 ............................................................. 28 I.6.4 Methods for Obtaining Quantitative Raman Spectra ..................................... 30 vii I.6.5 Quantification of Difference Between Reduced Isotropic Spectra Using -3 -4 Different Correction Factors: (ṽo – ṽi) ṽi vs. (ṽo – ṽi) ṽi ....................................... 33 I.6.6 Deconvolution of Raman Spectra ................................................................. 34 I.7 Density Functional Theory Methods ................................................................... 35 I.8 Objectives and Organization of the Thesis .......................................................... 37 I.8.1 Objectives of the Thesis ............................................................................... 37 I.8.2 Organization of the Thesis ...........................................................................
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