Chemical Thermodynamics Volume 11, Chemical Thermodynamics

945 Pages·2008·11.19 MB·English

11
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T H E R M O D Y N A M I C S
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This volume is the eleventh in the OECD Nuclear Energy Agency (NEA) C CHEMICAL
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Cover_f.fm Page 1 Wednesday, April 7, 2004 11:00 AM
CHEMICAL THERMODYNAMICS
OF THORIUM
Malcolm RAND
WintersHill Consultancy
Dry Sandford, Abingdon
(United Kingdom)

Jean FUGER Ingmar GRENTHE
Institute of Radiochemistry Royal Institute of Technology (KTH)
University of Liège-Sart Tilman Department of Chemistry
Liège (Belgium) Stockholm (Sweden)

Volker NECK Dhanpat RAI
Forschungszentrum Karlsruhe Rai Enviro-Chem, LLC
Institut für Nukleare Entsorgung (INE) Retired from
Karlsruhe (Germany) Pacific Northwest National Laboratory
Richland, WA (USA)

Edited by
Federico J. Mompean (Series Editor and Project Co-ordinator)
Jane Perrone (Volume Editor) and Myriam Illemassène
OECD Nuclear Energy Agency, Data Bank
Issy-les-Moulineaux, (France)
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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, Ed., 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, Ed., 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, Ed., North
Holland Elsevier Science Publishers B. V., Amsterdam, The Netherlands, (2003).
Vol. 6. Chemical Thermodynamics of Nickel, OECD Nuclear Energy Agency Data Bank,
Ed., North Holland Elsevier Science Publishers B. V., Amsterdam, The Netherlands,
(2005).
Vol. 7. Chemical Thermodynamics of Selenium, OECD Nuclear Energy Agency Data
Bank, Ed., North Holland Elsevier Science Publishers B. V., Amsterdam, The
Netherlands, (2005).
Vol. 8. Chemical Thermodynamics of Zirconium, OECD Nuclear Energy Agency Data
Bank, Ed., 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,
Ed., 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).

Preface

This volume is the eleventh in the series "Chemical Thermodynamics" edited by the
OECD Nuclear Energy Agency (NEA). It is a critical review of the thermodynamic
properties of thorium, its compounds and aqueous complexes, initiated by the
Management Board of the NEA Thermochemical Database Project Phase III
(NEA-TDB III). The first meeting of the review team was held in May 2004 at the
OECD Headquarters, Paris at which the scope of the review and the distribution of the
responsibilities for the assessments and text were determined. Three further meetings
were held, and several of the review team met at various scientific conferences during
the review period, particularly those in the “Migration” series. All the members
contributed fully to the main text and the discussions, but the workload was distributed
according to the expertise of each member. Malcolm Rand and Jean Fuger reviewed gas
and solid-state thermodynamics, while the other members were involved in solution
thermodynamics. Cindy Atkins-Duffin participated in the meetings of the review team
as the designated member of the Executive Group.
At the NEA Data Bank the responsibility for the overall co-ordination of the
Project was with Federico Mompean who until his departure in September 2007, was in
charge of the preparation of the successive drafts to the semifinal version, and updating
the NEA thermodynamic database. Myriam Illemassène (until December 2006) and
Jane Perrone, (who also oversaw the production of the final version) were responsible,
most capably, for the editing of the numerous drafts. The present volume owes a great
deal to the invaluable efforts of these NEA staff.
One aspect of the final assessment that should be noted is that we have
increased the standard entropy of Th(cr) slightly from that given in the seminal
CODATA Key Values volume [1989COX/WAG]. Naturally, such a change in an
important selected value was very carefully considered, and a full justification for the
change is presented. It is clear that new measurements of the low temperature specific
heat of Th(cr) are required to define the standard entropy more precisely.
Most of the recent experimental work on the detailed thermodynamic
properties of thorium compounds has been on solubilities and aqueous solutions. The
large number of hydroxide complexes of Th(IV) and the propensity to form colloidal
solutions, makes the interpretation of these studies a challenging task. As noted in
previous reviews, the development of laser-based spectroscopic techniques has been a
useful tool in our increased understanding of these phenomena, and it is gratifying that
v
vi Preface
data obtained by these new techniques in general agrees very well with data obtained by
more traditional methods. Quantum chemical methods are also emerging as tools to
understand the coordination chemistry of f-elements, thereby providing further valuable
information when discussing speciation. Such calculations are also providing more
reliable estimates for the vibrational properties of gases (for example, for the thorium
tetrahalide gases)
This volume provides the first detailed, well-documented and comprehensive
review of the thermodynamic properties of thorium, its compounds and aqueous
species, supplementing the earlier, less-detailed reviews noted in the Introduction
(Chapter I).

Dry Sandford, Oxford, England, October, 2008 Malcolm Rand, Chairman
Acknowledgements

For the preparation of this report, the authors have received financial support from the
NEA-TDB III Project. The following organisations take part in the Project:
ONDRAF/NIRAS, Belgium
NWMO, Canada
RAWRA, Czech Republic
POSIVA, Finland
ANDRA, France
CEA, France
FZK, Germany
JAEA, Japan
ENRESA, Spain
SKB, Sweden
SKI, Sweden
HSK, Switzerland
Nagra, Switzerland
PSI, Switzerland
Nexia Solutions, UK
NDA, UK
DoE, USA

Malcolm Rand and Jean Fuger would like to acknowledge valuable
contributions from John Arblaster and Mike Mortimer in the U.K. and Georgii Bergman
at the Glushko Thermocenter in Moscow concerning the low temperature specific heat
of Th(cr). John Arblaster first drew the reviewers’ attention to the need for additional
precise data in this area and provided us with full details of his assessment, which has
been adopted by the review. Georgii Bergman kindly provided us with full details of the
CODATA assessment of the heat capacity of Th(cr) and made helpful comments on the
discrepancy, and Mike Mortimer gave us helpful advice about low-temperature heat
capacity measurements and the general behaviour of Debye temperatures as a function
of temperature. We are also grateful to Paul Potter (Oxford) for help with some Russian
translations and Rudy Konings (ITU, Karlsruhe, Germany), who kindly provided a
preprint of a paper on the ab initio calculations of the structures of ThC (g) and
2
ThC (g), and made many other helpful comments.
4
vii
viii Acknowledgements
Dhan Rai would like to thank Dr. Andrew Felmy of the Pacific Northwest National
Laboratory for making the NONLINT-SIT program available to the review and for
providing help in its correct application.
The entire manuscript of this book has undergone a peer review by four
independent reviewers, according to the procedures in the TDB-6 Guideline, 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 OECD Nuclear Energy Agency. The peer reviewers were:
Pr. Robert Guillaumont, French Academy of Sciences, former Professor at
Université de Paris, XI, Orsay, France
Dr. Rudy Konings, Institute for Transuranium Elements (Joint Research
Centre, European Commission), Karlsruhe, Germany.
Dr. Leslie Pettit, University of Leeds, England,
Dr. Tom Wolery, Lawrence Livermore National Laboratory, Livermore, CA,
USA
Their valuable contributions to the quality of this review are gratefully
acknowledged.