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Lanthanide-Polyaminopolycarboxylate Complexation Kinetics in High Lactate Media

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Lanthanide-Polyaminopolycarboxylate Complexation Kinetics in High Lactate Media LANTHANIDE-POLYAMINOPOLYCARBOXYLATE COMPLEXATION KINETICS IN HIGH LACTATE MEDIA: INVESTIGATING THE AQUEOUS PHASE OF TALSPEAK By DEREK MACKENZIE BRIGHAM A dissertation submitted in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY WASHINGTON STATE UNIVERSITY Department of Chemistry May 2013 © Copyright by DEREK MACKENZIE BRIGHAM, 2013 All Rights Reserved © Copyright by DEREK MACKENZIE BRIGHAM, 2013 All Rights Reserved To the Faculty of Washington State University: The members of the Committee appointed to examine the dissertation of DEREK MACKENZIE BRIGHAM find it satisfactory and recommend that it be accepted. ___________________________________ Kenneth L. Nash, Ph.D., Chair ___________________________________ Scot E. Wherland, Ph.D. ___________________________________ Sue B. Clark, Ph.D. ___________________________________ Jeremy J. Lessmann, Ph.D. ii ACKNOWLEDGMENTS “Faith in your partner, your fellow men, your friends, is very important, because without it there's no mutual component to your relationship, and relationships are important. So faith plays an important role, but faith in people you don't know, faith in religious or political leaders or even people on stages, people who are popular in the public eye, you shouldn't have faith in those people. You should listen to what they have to say and use it. It might give you some ideas on how to view the world, but ultimately you have to base your views on evidence. Evidence comes from your own eyes and ears.” Dr. Greg Graffin When I first arrived at WSU to begin my undergraduate studies I had very different ambitions and could not have predicted where I would end up. I certainly would not have guessed that I would still be in Pullman nearly ten years later. While this journey has been long and at times arduous, I am glad for all the experiences it has afforded me. I want to thank my friends and family back home in Oregon for always being there for me. I certainly would not be where I am today without the ever present love and support of my parents, Larry and Marie Brigham. I am especially grateful of their patience with me throughout my life. I am deeply appreciative for all they have done for me, and hope to always make them proud. When I would come home to visit my friends made it feel like I had never left. This always gave me something to look forward to, and left me refreshed and ready to return. My life would not be the same without them. My time at WSU has left me with some of the closest friends I could have ever asked for. The ones I have trained with, studied with, laughed, cried, suffered, and been triumphant with, I will never forget them. It is rare to make this kind of connection, and it is something I will always cherish. iii I wish to express my deepest gratitude to my committee members. I would first like to thank Dr. Sue Clark, not only for being on my committee but for helping to set me on the path that has brought me to this point. If not for her involvement in the undergraduate chemistry program I would not have been introduced to radiochemistry. Dr. Jeremy Lessmann has been a welcome presence throughout both my undergraduate and graduate experience. It has been a pleasure to work for and to work with him. I am especially grateful of Dr. Scot Wherland. Not only has he been an excellent teacher, who taught me most of what I know about kinetics, but he was always welcoming and insightful when I would come to his door unannounced to discuss my results. I would not have come this far without his assistance. And finally I wish to thank Dr. Ken Nash, who has been an excellent mentor, teacher, and friend. I truly believe I would not have made it through the graduate program without his belief in, and patience with, me. I wish to make special mention of the late James “Sully” Sullivan. He was the one to first foster my interest in chemical kinetics, and he showed me what a true passion for science was. As the last student Sully took on, I hope to honor his memory and pass on his passion for research and discovery. iv LANTHANIDE-POLYAMINOPOLYCARBOXYLATE COMPLEXATION KINETICS IN HIGH LACTATE MEDIA: INVESTIGATING THE AQUEOUS PHASE OF TALSPEAK Abstract by Derek Mackenzie Brigham, Ph.D. Washington State University May 2013 Chair: Kenneth L. Nash In advanced nuclear fuel reprocessing schemes, the TALSPEAK (Trivalent Actinide Lanthanide Separation with Phosphorus-reagent Extraction from Aqueous Komplexes) process has been proposed as a means to separate Am and Cm from the lanthanides. One significant limitation of the TALSPEAK process is slow phase transfer kinetics of the lanthanides to the organic phase. Increasing the lactic acid buffer concentration is found to improve the solvent extraction kinetics. However, concentrations of greater than 1 M are necessary to achieve rates of mass transfer fast enough for TALSPEAK to be applicable on an industrial scale. The TALSPEAK process employs diethylenetriaminepentaacetic acid (DTPA) as an aqueous phase complexant to selectively bind to the actinides and prevent their extraction, however, DTPA also binds with the lanthanides. Understanding the mechanism of the interaction between DTPA and the lanthanides in high total lactate will help to explain the accelerative effect of increased total lactate on TALSPEAK mass transfer rates. This dissertation describes the homogeneous aqueous complexation kinetics of the lanthanides Pr3+, Nd3+, Sm3+-Lu3+ and the polyaminopolycarboxylate ligands DTPA, v ethylenediaminetetraacetic acid (EDTA), and (hydroxyethyl)ethylenediaminetriacetic acid (HEDTA) in 1 M total lactate aqueous media similar to that found in the aqueous phase of a TALSPEAK separation system. Temperature studies on the interactions of select lanthanides with DTPA, EDTA, and HEDTA were performed to obtain activation parameters associated with the complex formation reaction. Additional studies on the interaction of Eu3+ with DTPA were performed under varying total lactate conditions at several different constant concentrations of lactate ion and pH values to determine the mechanistic role of the species in the lactate/lactic acid buffer system. Kinetic data were obtained using the method of equilibrium perturbation by ligand displacement via stopped-flow spectrophotometry employing the colorimetric dye arsenazo III. This work provides an increased understanding of lanthanide interactions with polyaminopolycarboxylate ligands in TALSPEAK-like aqueous media. From the insights gained in these studies, a possible explanation for the accelerative effect of lactate on TALSPEAK phase transfer rates is proposed. The overall conclusion of this work is that under high concentrations of total lactate the lactate ion governs the aqueous phase complexation kinetics. vi TABLE OF CONTENTS ACKNOWLEDGMENTS ............................................................................................................. iii ABSTRACT .....................................................................................................................................v LIST OF TABLES ......................................................................................................................... ix LIST OF FIGURES ....................................................................................................................... xi CHAPTER 1. INTRODUCTION ...........................................................................................................1 Electricity in the U.S ................................................................................................1 Nuclear Power ..........................................................................................................1 Nuclear Fuel Reprocessing ......................................................................................2 TALSPEAK .............................................................................................................4 Kinetics of Extraction in TALSPEAK .....................................................................6 Research Aims .........................................................................................................9 2. EXPERIMENTAL .........................................................................................................13 Reagents .................................................................................................................19 Procedure ...............................................................................................................20 Trans-lanthanide Study ..........................................................................................21 Temperature Studies ..............................................................................................22 Total Lactate Experiments .....................................................................................22 AAIII Independence...............................................................................................23 3. EXPERIMENTAL RESULTS.......................................................................................28 DTPA Lanthanide Series Study ............................................................................29 Temperature Study .....................................................................................33 vii EDTA Lanthanide Series Study ............................................................................35 Temperature Study .....................................................................................39
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