13 C H E M I C A L VOLUME a T H E R M O D Y N A M I C S CHEMICAL THERMODYNAMICS OF IRON Part 1 C T I HEMICAL HERMODYNAMICS OF RON 1 PART Robert J. LEMIRE (CHAIRMAN) Deep River ON K0J 1P0 (Canada) Urs BERNER Claude MUSIKAS Paul Scherrer Institut 5 Avenue Moissan Villigen 91440 Bures-sur-Yvette (Switzerland) (France) Donald A. PALMER Peter TAYLOR Oliver Springs Tennessee Pinawa TN 37840 Manitoba R0E 1L0 (USA) (Canada) Osamu TOCHIYAMA Nuclear Safety Research Association 5-18-7 Shimbashi Minato-ku Tokyo 105-0004 (Japan) Edited by Jane Perrone (Project Co-ordinator and Volume Editor) OECD Nuclear Energy Agency, Data Bank Issy-les-Moulineaux (France) ORGANISATION FOR ECONOMIC CO-OPERATION AND DEVELOPMENT The OECD is a unique forum where the governments of 34 democracies work together to address the economic, social and environmental challenges of globalisation. 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In these and related tasks, the NEA works in close collaboration with the International Atomic Energy Agency in Vienna, with which it has a Co-operation Agreement, as well as with other international organisations in the nuclear field. Corrigenda to OECD publications may be found online at: www.oecd.org/publishing/corrigenda. © OECD 2013 You can copy, download or print OECD content for your own use, and you can include excerpts from OECD publications, databases and multimedia products in your own documents, presentations, blogs, websites and teaching materials, provided that suitable acknowledgment of the OECD as source and copyright owner is given. All requests for public or commercial use and translation rights should be submitted to [email protected]. Requests for permission to photocopy portions of this material for public or commercial use shall be addressed directly to the Copyright Clearance Center (CCC) at [email protected] or the Centre français d'exploitation du droit de copie (CFC) [email protected]. CHEMICAL THERMODYNAMICS Vol. 1. Chemical Thermodynamics of Uranium, Wanner, H., Forest, I., OECD Nuclear Energy Agency Data Bank, Eds., North Holland Elsevier Science Publishers B. V., Amsterdam, The Netherlands, (1992). Vol. 2. Chemical Thermodynamics of Americium, OECD Nuclear Energy Agency Data Bank, Eds., North Holland Elsevier Science Publishers B. V., Amsterdam, The Netherlands, (1995). Vol. 3. Chemical Thermodynamics of Technetium, Sandino, M. C. A., Östhols, E., OECD Nuclear Energy Agency Data Bank, Eds., North Holland Elsevier Science Publishers B. V., Amsterdam, The Netherlands, (1999). Vol. 4. Chemical Thermodynamics of Neptunium and Plutonium, OECD Nuclear Energy Agency Data Bank, Eds., North Holland Elsevier Science Publishers B. V., Amsterdam, The Netherlands, (2001). Vol. 5. Update on the Chemical Thermodynamics of Uranium, Neptunium, Plutonium, Americium and Technetium, OECD Nuclear Energy Agency Data Bank, Eds., North Holland Elsevier Science Publishers B. V., Amsterdam, The Netherlands, (2003). Vol. 6. Chemical Thermodynamics of Nickel, OECD Nuclear Energy Agency Data Bank, Eds., North Holland Elsevier Science Publishers B. V., Amsterdam, The Netherlands, (2005). Vol. 7. Chemical Thermodynamics of Selenium, OECD Nuclear Energy Agency Data Bank, Eds., North Holland Elsevier Science Publishers B. V., Amsterdam, The Netherlands, (2005). Vol. 8. Chemical Thermodynamics of Zirconium, OECD Nuclear Energy Agency Data Bank, Eds., North Holland Elsevier Science Publishers B. V., Amsterdam, The Netherlands, (2005). Vol. 9. Chemical Thermodynamics of complexes and compounds of U, Np, Pu, Am, Tc, Zr, Ni and Se with selected organic ligands, OECD Nuclear Energy Agency Data Bank, Eds., North Holland Elsevier Science Publishers B. V., Amsterdam, The Netherlands, (2005). Vol. 10. Chemical Thermodynamics of Solid Solutions of Interest in Nuclear Waste Management. A State-of-the-Art Report, OECD Nuclear Energy Agency Data Bank, Eds., OECD Publications, Paris, France, (2007). Vol. 11. Chemical Thermodynamics of Thorium, OECD Nuclear Energy Agency Data Bank, Eds., OECD Publications, Paris, France, (2008). Vol. 12. Chemical Thermodynamics of Tin, OECD Nuclear Energy Agency Data Bank, Eds., OECD Publications, Paris, France, (2012). Preface Volume 13a of the “Chemical Thermodynamics” (TDB) series, edited by the OECD Nuclear Energy Agency (NEA), is the first of two volumes describing the selection of chemical thermodynamic data for species of iron. After an initiation report for iron was presented to the NEA in late 2004, it was decided (and confirmed in 2008) that because of the voluminous information in the literature, it would be more efficient to prepare the review in two (unequal) parts. This larger first part contains assessments of data for the metal, simple ions, aqueous hydroxido, chlorido, sulfido, sulfato and carbonato complexes, and for solid oxides and hydroxides, halides, sulfates, carbonates and simple silicates. As this volume goes to press, work is well underway on the second part of the review, which will provide assessments of data for other aqueous halido species, sulfide solids, and solid and solution species with nitrate, phosphate and arsenate, as well as address some aspects of solid solutions in iron-oxide and iron-sulfide systems. Originally the iron Review Team included Urs Berner, Robert Lemire (chairperson), Claude Musikas, Donald Palmer, Nobuaki Sato and Peter Taylor, with Kastriot Spahiu as the NEA TDB Executive Group Liaison. A first meeting of the Review Team was held at the NEA offices in Issy-les-Moulineaux, France in February 2005. Subsequent meetings were held in Toronto, Canada in December 2005, and again in Issy-les-Moulineaux in July 2006 and February 2007. In mid-2007, time constraints and the pressure of other commitments forced Nobuaki Sato to resign from the Review Team, and Osamu Tochiyama joined as a new member. A final sub-group meeting was held at Issy-les-Moulineaux in February 2008. Editorial work was done in late 2008 and through 2009, and the draft was submitted for peer review in January 2010. By the time the peer review comments were received and addressed, several of the members of the iron Review Team were already involved in new NEA reviews or had other commitments. Also, resources at the NEA have been limited. Therefore, it has taken considerable time to put this volume into its final form. The co-ordination of the iron project at the NEA was initially done by Federico Mompean, and between 2008 and 2010 by Mireille Defranceschi. Since then, Jane Perrone has taken on the duties of co-ordinator, and from the beginning of the project in 2005 she also carried out the arduous task of incorporating the drafts submitted by the iron team into the full manuscript. Without her persistence, it is doubtful whether this work would have been published. Although almost all of the final Review Team members contributed text and comments to several of the chapters, primary responsibility for the different chapters CHEMICAL THERMODYNAMICS OF IRON, PART 1, NEA No. 6355, © OECD 2013 vi Preface was divided as follows: Peter Taylor for the section on oxides, Urs Berner for the sections on iron(II) complexes with chloride, fluoride, sulfate and carbonate, Osamu Tochiyama for the section on iron sulfide complexes, Claude Musikas for the sections on the electrochemistry of the aquo ions and the iron(III) complexes with chloride, sulfate and carbonate, Donald Palmer for the sections on hydrolysis and, with the chairman, for other sections on the aquo ions. The chairman took the lead for the sections on iron metal and the halide, sulfate, carbonate and silicate solids, and also was the main author for the section on resolution of inconsistent values from different chemical thermodynamic cycles. As is the case with databases for many other elements, “key” iron-species values are often based on very limited experimental values. For example, careful studies of the Fe(III)/Fe(II) couple as a function of ionic medium are surprisingly sparse, and most are rather dated. A further complication has been that many of the experimentally determined thermodynamic quantities for different iron species are related. To maintain database consistency it was necessary to consider many of these quantities together as part of the related chemical thermodynamic cycles (cf. Chapter XI). After an initial consistency calculation, three of the experimental results were reassessed, and minor adjustments were made to four other assessed uncertainties to generate a final set of selected values. These selected values are consistent with the input experimental quantities within the stated uncertainties. Any chemical thermodynamic database does no more than represent a survey of what is known at a particular time. The time required to carefully compile and consider data dictates that any database is at least slightly “out-of-date” when it appears in print. The current version is no exception. Although an arbitrary cut-off date of 2008 was set for papers used in this review, a few later papers have been included. Unfortunately, despite extensive literature searches, it is likely that a few significant earlier papers have been missed; some of these may be reviewed in TDB Iron Part 2. Deep River, Canada, March 2013 Robert J. Lemire, Chairman CHEMICAL THERMODYNAMICS OF IRON, PART 1, NEA No. 6355, © OECD 2013 Acknowledgements For the preparation of this publication, the authors have received financial support from the NEA TDB Phase III Project. The following organisations have taken part in the project: ONDRAF/NIRAS, Belgium NWMO, Canada RAWRA, Czech Republic POSIVA, Finland ANDRA, France CEA, France KIT, Germany JAEA, Japan ENRESA, Spain SKB, Sweden SKI, Sweden ENSI, Switzerland NAGRA, Switzerland PSI, Switzerland NDA, United Kingdom Nexia Solutions, United Kingdom DoE, United States The authors wish to thank the TDB III Management Board, Executive Committee and the staff at the OECD Nuclear Energy Agency Data Bank for shepherding this volume to completion. In particular we are grateful for the assistance of Jane Perrone, who has worked with us throughout the iron review, initially as volume editor and finally as series editor and project co-ordinator. Robert Lemire would like to thank Atomic Energy of Canada Limited (AECL) for its support in the form of a researcher emeritus position between 2009 and 2013, as well as the library staff at AECL Chalk River Laboratories, especially Suzanne Sell, Jo-Anne Festarini and Monica Lim. He also appreciates the considerable assistance provided (prior to 2010) by the staff of the Canada Institute for Scientific and Technical Information in obtaining access to journals and “grey-literature” documents. This assistance helped clarify many journal references. He is also grateful to Professor CHEMICAL THERMODYNAMICS OF IRON, PART 1, NEA No. 6355, © OECD 2013 viii Acknowledgements Heinz Gamsjäger and Dr. Malcolm Rand for many useful discussions, particularly concerning possible modifications to Chapter 2 and Appendix B. Claude Musikas wishes to thank Federico Mompean and Robert Lemire for introducing him to the TDB project. He is also grateful to the NEA TDB staff for providing him with the necessary documents. The CEA (Saclay) is also acknowledged for allowing the use of its library. Peter Taylor expresses his thanks to Professor Juraj Majzlan for providing unpublished data, and the University of Manitoba for allowing the use of its library. Urs Berner thanks Professor Christoph A. Heinrich, Institut für Geochemie und Petrologie, ETH Zürich, who provided a collection of original data (including evaluation steps) for the FeCl -water system. He also expresses his appreciation to the Paul Scherrer Institut, 2 5232 Villigen PSI, Switzerland and the National Cooperative for the Disposal of Radioactive Waste, Nagra, Hardstrasse 73, 5430 Wettingen, Switzerland for their support. The authors and editors are grateful to Elsevier for its permission to produce one of the figures found in this volume. The entire manuscript has undergone a peer review by an independent, international group of reviewers, according to the procedures in the TDB-6 Guidelines, available from the NEA. The peer reviewers have seen and approved the modifications made by the authors in response to their comments. The peer review comment records may be obtained on request from the NEA. The peer reviewers were Professor Juraj Majzlan (Institute of Earth Sciences, Jena, Germany), Dr. Valérie Moulin (CEA, Saclay, France), and Professor R. Fernández-Prini (University of Buenos Aires, Argentina). Their valuable contributions to this review are gratefully acknowledged. CHEMICAL THERMODYNAMICS OF IRON, PART 1, NEA No.6355, © OECD 2013