Chemical Thermodynamics of Uranium - OECD Nuclear Energy

735 Pages·2004·4.08 MB·English

CHEMICAL THERMODYNAMICS
OF URANIUM
Ingmar GRENTHE (Chairman)
Royal Institute of Technology
Stockholm (Sweden)
Jean FUGER
Commission of the European Communities, JRC
European Institute for Transuranium Elements
Karlsruhe (Federal Republic of Germany)
Rudy J.M. KONINGS
Netherlands Energy Research Foundation ECN
Petten (The Netherlands)
Robert J. LEMIRE
AECL Research, Whiteshell Laboratories
Pinawa, Manitoba (Canada)
Anthony B. MULLER
Science Applications International Corporation
McLean, Virginia (USA)
Chinh NGUYEN-TRUNG
CREGU
Vandœuvre-l`es-Nancy (France)
Hans WANNER
OECD Nuclear Energy Agency, Data Bank
Issy-les-Moulineaux (France)
Edited by
Hans WANNER and Isabelle FOREST
OECD Nuclear Energy Agency, Data Bank
Issy-les-Moulineaux (France)
NUCLEAR ENERGY AGENCY
ORGANISATION FOR ECONOMIC CO-OPERATION AND DEVELOPMENT
ORGANISATION FOR ECONOMIC CO-OPERATION AND DEVELOPMENT
Pursuant to Article 1 of the Convention signed in Paris on 14th December 1960, and which came into force
on 30th September 1961, the Organisation for Economic Co-operation and Development (OECD) shall promote
policies designed:
(cid:16)
to achieve the highest sustainable economic growth and employment and a rising standard of living in
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The original member countries of the OECD are Austria, Belgium, Canada, Denmark, France, Germany,
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The Commission of the European Communities takes part in the work of the OECD (Article 13 of the OECD
Convention).

NUCLEAR ENERGY AGENCY
The OECD Nuclear Energy Agency (NEA) was established on 1st February 1958 under the name of the
OEEC European Nuclear Energy Agency. It received its present designation on 20th April 1972, when Japan became
its first non-European full member. NEA membership today consists of 28 OECD member countries: Australia,
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to assist its member countries in maintaining and further developing, through international co-
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(cid:16)
to provide authoritative assessments and to forge common understandings on key issues, as input to
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In these and related tasks, the NEA works in close collaboration with the International Atomic Energy
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© OECD 2004
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iii
Preface to the 2004 reprint

Chemical Thermodynamics of Uranium is the first book in a series of monographs providing a
critical review of the thermodynamic properties of the actinide elements and their
compounds; it was followed by monographs on neptunium, plutonium, americium and
technetium and their compounds. Other monographs dealing with selenium, nickel and
actinide complexes with organic ligands are in preparation. Chemical Thermodynamics of
Uranium was published in 1992 and an update that also contains new thermodynamic data for
neptunium, plutonium and americium is due to be published in 2003. The characteristic
feature of this series is the extensive discussions of experimental data obtained from the
original publications and reports. In some cases the review teams have reinterpreted the
original data, which have also been recalculated to zero ionic strength using the specific ion
interaction method. The methodology used for activity factor corrections and statistical
analysis is described in the appendices. The detailed discussion of the experimental data
allows the user to follow the reasoning behind the selection and thus agree or disagree with
the thermodynamic values selected.
Why the need for a reprint of the first volume? The answer is simple - the first edition is sold
out. However, there are other reasons, too. The most important is that the 2003 Update only
contains discussions of the thermodynamic data that has been published since the cut-off date
for the original 1992 edition. When the new literature has not led to an update of the selected
values, the 1992 edition still provides the detailed discussions leading to the retained
selections. This volume is an identical reprint of the first edition. It contains some errors and
other mistakes that have been corrected in the 2003 Update. I was gratified, as were the other
members of the first uranium team, that the new experimental data reported in the 2003
Update have resulted in few major changes in the thermodynamic data and in the chemical
models used to describe the complex formation with different ligands. Our quantitative
understanding of the chemistry of uranium in the form of thermodynamic data is with some
exceptions good, and should provide a sound basis for applications. However, there are still
some areas where additional experimental data are needed as discussed in the 2003 Update.
On behalf of the review team I would like to thank the readers that have pointed out errors in
the first edition. These have been corrected in the 2003 Update, but not in this reprint.

Ingmar Grenthe

Stockholm, 5 May 2003
iv
Editor’s note to the 2004 reprint

The present volume is a reprint of the 1992 edition of Chemical Thermodynamics of
Uranium by Ingmar Grenthe, Jean Fuger, Rudy J. M. Konings, Robert J. Lemire,
Anthony B. Muller, Chinh Nguyen-Trung and Hans Wanner. The book was edited at
the NEA Data Bank by Hans Wanner and Isabelle Forest and published by Elsevier
under the North-Holland imprint.
As part of Phase II of the NEA Thermochemical Database Project (TDB), a new
publication entitled Update on the Chemical Thermodynamics of Uranium,
Neptunium, Plutonium, Americium and Technetium and authored by Robert
Guillaumont, Thomas Fanghänel, Jean Fuger, Ingmar Grenthe, Volker Neck, Donald
A. Palmer and Malcolm H. Rand, was published by Elsevier in 2003. For uranium,
this Update contains a review of the literature published since the cut-off date for the
literature reviewed in the 1992 edition cited above. As a consequence of this new
TDB Review, some of the values selected in the earlier publication have been
superseded while others have retained their validity. The 2003 Update is self-
contained with respect to any new data selections but the discussions leading to the
retained selections can in most cases only be found in the 1992 publication. Since the
latter is no longer available from its original publisher, the NEA is making the present
reprint available to the scientific community. Consequently, it is important to note
that the Tables of Selected Values contained in this reprint ARE OUTDATED AND
SHOULD NOT BE USED. The updated Tables and the rationale behind the new
and updated selections can be consulted in the above-mentioned 2003 Update.
This reprint has been prepared at the NEA Data Bank by Federico Mompean,
Myriam Illemassene and Jane Perrone by reprocessing the files employed in the
production of the 1992 edition. Every effort has been made to preserve the original
layout and page numbering. We are grateful to the many readers who have provided
feedback and pointed out errors in the 1992 book. In particular, Dr. Lionel Bion and
Dr. Pierre Vitorge from the Commissariat à l’Énergie Atomique (France) identified
an error in Figure V.19, page 325, due to the interchange of the labels for the species
U(OH) (aq) and UO CO (aq). In an attempt to make this reprint as close a
4 2 3
reproduction of the original publication as possible, we have not implemented any
corrections.
v
Preface
This is the first volume in a series of critical reviews of the chemical thermodynam-
ics of those elements that are of particular importance in the safety assessment of
radioactive waste disposal systems. The NEA Thermochemical Data Base (TDB)
project was begun seven years ago by the OECD Nuclear Energy Agency (NEA) as
a result of discussions that had taken place during radioactive waste management
conferences held in the United States and France. Anthony Muller initiated the
project and, at first, he coordinated it at the NEA; in 1986 he was succeeded by
Hans Wanner.
In late 1986, two years after the preliminary talks, a meeting was held at which
the first drafts of some of the sections in this volume were discussed. This resulted in
some major revisions, updates, and also improved documentation of the evaluation
and selection procedures. Since then the review team has met twice for extensive
discussions.
This volume is a collective effort: each participant contributedsections correspond-
ing to his area of expertise. Robert Lemire has drafted the sections on the oxide and
hydroxide compounds and complexes, the uranium nitrides, the solid uranium ni-
trates and the arsenic-containing uranium compounds, and he has contributed to
the sections on uranates in the final stage. He has also written Appendix D and
established the procedures used for consistent estimation of entropies. The sections
on gaseous and solid uranium halides were originally drafted by Anthony Muller,
then commented upon by Jean Fuger, and finally thoroughly revised and extended
by Rudy Konings, who joined the review team in 1990, and who has also drafted
the section on gaseous uranium oxides and contributed to the sections on uranates in
the final stage. Chinh Nguyen-Trung, who joined the review team in 1988, has con-
tributed to the section on solid phosphorus-containing uranium compounds and the
one on alkali metal uranates. Hans Wanner has developed the procedures, drafted
the sections on uncertainties and on standards and conventions, and has verified
and checked the consistency of data submitted by the project participants. My con-
tribution consists of the sections on aqueous complexes (including Section V.2 but
excluding the hydroxide complexes) and the parts of the sections on uranium miner-
als that deal with solubility products. Hans Wanner and I drafted Appendix B on
ionic strength corrections.
Hans Wanner has been responsible for editing this volume. He was assisted by his
colleagues from the NEA Data Bank: Isabelle Muller (formerly Poirot), succeeded
by Isabelle Forest in 1989; Mikazu Yui, succeeded by Kaname Miyahara in 1990; and
vi
Pierre Nagel, who has developed the computerized data base system.
I would also like to acknowledge contributions made by Donald Langmuir who
participated in our first meeting. Unfortunately, because of insufficient funding, he
was unable to take part in subsequent activities.
The project has taken a long time to complete, partly because of lack of proper
fundinginitsinitialstages. IamgratefultotheNEARadioactiveWasteManagement
Committee for its assistance in recent years in seeking this financial support. The
effortsbyMr.Jean-PierreOlivier, HeadoftheNEADivisionforRadiationProtection
and Radioactive Waste Management, to establish the TDB project at the NEA,
are acknowledged. Dr. Kunihiko Uematsu, Director General of the NEA, has been
instrumental in bringing this project to its successful conclusion. Mr. Johnny Ros´en,
HeadoftheNEADataBank,hasalwaysbeenasourceofsupportandencouragement.
On behalf of the review team, I want to thank not only those named above, but also
all the colleagues and co-workers who have helped us complete our task.
Stockholm, November 1991 Ingmar Grenthe, Chairman
vii
Acknowledgments
I.GrenthethankstheSwedishNuclearFuelandWasteManagementCompany(SKB)
for financial support.
R.J. Lemire’s participation in this project was jointly funded by AECL Research
and Ontario Hydro under the auspices of the CANDU Owners Group. He also wishes
to express appreciation to P. Taylor and J. Paquette for helpful discussions, and to
N.D. Haworth for assistance with the literature searches.
C. Nguyen-Trung’s participation in this project was funded by CREGU. He wishes
to thank R.E. Mesmer, D.A. Palmer and C.F. Baes, Jr., for helpful discussions and
logistic support while he was at the Oak Ridge National Laboratory.
H. Wanner wishes to thank Nathalie Cramer for entering thousands of data into
the computerized data base, as well as S´everine Girod and Lionel Morel for their help
in formatting and editing the text.
The following eight independent experts have reviewed the contents of the present
book according to the peer review procedures [90WAN2] prepared for this purpose in
theframeworkoftheNEAThermochemicalDataBaseproject. Theyhaveviewedand
approved the modifications made by the authors according to their comments. The
peer review comment records may be obtained on request from the OECD Nuclear
Energy Agency.
Prof. S. Ahrland University of Lund, Lund, Sweden
Dr. C.F. Baes, Jr. Oak Ridge National Laboratory, Oak Ridge,
Tennessee, USA (Retired)
Prof. L. Ciavatta University of Naples, Naples, Italy
Prof. E.H.P. Cordfunke Netherlands Energy Research Foundation ECN,
Petten, The Netherlands
Prof. F.P. Glasser University of Aberdeen, Aberdeen, United Kingdom
Prof. F. Grønvold University of Oslo, Oslo, Norway
Dr. D.L. Hildenbrand SRI International, Menlo Park, California, USA
Dr. F.J. Pearson, Jr. Ground-Water Geochemistry, Irving, Texas, USA
We are grateful to I. Puigdomenech (Studsvik AB, Nykoeping, Sweden) for the
production of the distribution and predominance diagrams, i.e., Figures V.4, V.5,
V.6, V.7, V.8, V.17, V.18, V.19, V.20.
In addition, we thank the following for their technical comments and suggestions
in the course of the project: P.L. Brown, Australian Nuclear Science and Technology
viii
Organization, Lucas Heights, New South Wales, Australia; M.W. Chase, National In-
stitute of Standards and Technology, Gaithersburg, Maryland, USA; K. Czyscinski,
Roy F. Weston Inc., Washington, D.C., USA; D. Garvin, National Institute of Stan-
dards and Technology, Gaithersburg, Maryland, USA; I. Khodakovsky, Vernadsky
Institute, USSR Academy of Sciences, Moscow, USSR; O. Kubaschewski, Aachen,
Germany; L. Maya, Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA;
L.R. Morss, Argonne National Laboratory, Argonne, Illinois, USA; T.W. Newton,
Los Alamos National Laboratory, Los Alamos, New Mexico, USA; D.K. Nordstrom,
US Geological Survey, Menlo Park, California, USA; V.B. Parker, National Institute
of Standards and Technology, Gaithersburg, Maryland, USA; S.L. Phillips, Lawrence
Berkeley Laboratory, Berkeley, California, USA; M.H. Rand, Harwell Laboratory,
Didcot, United Kingdom; J.A. Rard, Lawrence Livermore National Laboratory, Liv-
ermore, California, USA; W.J. Ullman, University of Delaware, Lewes, Delaware,
USA; P. Vitorge, Commissariat a` l’Energie Atomique, Fontenay-aux-Roses, France;
E.F. Westrum, Jr., University of Michigan, Ann Arbor, Michigan, USA;
We are indebted to the following for permission to reproduce copyright material:
American Institute of Physics and the authors for Figure II.1 (from D.D. Wagman
et al. [82WAG/EVA]), and John Wiley & Sons, Inc., for Table II.5 (from C.J. Baes,
Jr., and R.E. Mesmer [76BAE/MES]).
Paris, January 1992 The Editors
ix
Foreword
The present volume starts a series of detailed expert reviews of the chemical ther-
modynamics of key elements in nuclear technology and waste management. Volumes
on americium, technetium, neptunium and plutonium are currently in progress. The
recommendedthermodynamicdataaretheresultof a critical assessmentof published
information. The data network developed at the Data Bank of the OECD Nuclear
Energy Agency (NEA), cf. Section I.4, ensures consistency not only within the rec-
ommended data set on uranium but also among all the data sets to be published in
the series.
The NEA Data Bank provides a number of services that may be useful to the
reader of this book.
• The recommended data can be obtained on eletronic media (PC diskettes, mag-
netic tape, or via computer networks) directly from the NEA Data Bank. The
special formatting of the data allows easy conversion to any specific formats
convenient to the user.
• TheNEADataBankmaintainsalibraryoftestedcomputerprogramsinvarious
areas. This includes geochemical codes such as PHREEQE, EQ3/6, MINEQL,
MINTEQ, PHRQPITZ, etc., in which chemical thermodynamic data like those
presented in this book are required as the basic input data. These computer
codes can be obtained on request from the NEA Data Bank.
• Short courses on the use of geochemical codes and thermodynamic data have
been organized at the NEA Data Bank since 1985, tought by the authors of the
codes PHREEQE, MINEQL and EQ3/6. It is planned to give further courses
on the codes mentioned above or on new ones, corresponding to the interest
expressed by the user’s community. Persons interested in further courses are
advised to contact the NEA Data Bank.
For requests of data, computer programs, on-line access, and for further informa-
tion, please write to:
OECD Nuclear Energy Agency
Data Bank
Le Seine St. Germain
2-12, Rue Jean-Pierre Timbaud
F-92130 Issy-les-Moulineaux
France