Data and Knowledge in A Changing World: Scientific Publication Committee

Data and Knowledge in a Changing World
Scientific Publication Committee
Chairman: H. Behrens (Germany)

Members: A. Gaye (Senegal)
H. Kehiaian (France)
T. Kunisawa (Japan)
K. Lal (India)
J.-J. Royer (France)
CODATA Secretariat
Executive Director: K. Cass
51 Boulevard de Montmorency
75016 Paris, France
E-mail: codata@dial.oleane.com
http://www.codata.org
Springer-Verlag Berlin Heidelberg GmbH
0. B. Fabrichnaya · S.K. Saxena
P. Richet · E.F. Westrum
Thermodynamic Data, Models,

and Phase Diagrams
in Multicomponent Oxide Systems
An Assessment for Materials and Planetary Scientists Based on

Calorimetric, Volumetric and Phase Equilibrium Data
~Springer
CODATA Secretariat
K. Cass, Exec. Director
51, Boulevard de Montmorency
F-75016 Paris
ISBN 978-3-642-05730-4 ISBN 978-J-662-10504-7 (eBook)

DOI 10.1007/978-2-662-10504-7
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Introduction to the Series
CODATA is an interdisciplinary Scientific Committee of the International Council

for Science (ICSU). It works to improve the quality, reliability, management and
accessibility of data of importance to all fields of science and technology.
CODATA is a resource that provides scientists and engineers with access to inter-
national data activities for increased awareness, direct cooperation and new
knowledge. CODATA, established over 33 years ago by ICSU, promotes and en-
courages on a world-wide basis the compilation, evaluation and dissemination of
reliable numerical data of importance to science and technology. This includes
data initiatives and modeling of an interdisciplinary nature such as that encoun-
tered in far-reaching projects e.g. Global Change, various Genome projects, envi-
ronmental and biodiversity issues, etc .. Today 22 countries are members, 15 Inter-
national Scientific Unions have assigned liaison delegates, there are 4 co-opted
delegates and 20 supporting organizations from industry, government and acade-
mia.
CODATA is concerned with all types of data resulting from experimental
measurements, observations and calculations in every field of science and tech-
nology, including the physical sciences, biology, geology, astronomy, engineering,
environmental science, ecology and others. Particular emphasis is given to data
management problems common to different disciplines and to data used outside
the field in which they were generated.
CODATA's primary purpose in launching the series "Data and Knowledge in a
changing World" is to collect data and the wealth of information pertaining to the
intelligent exploitation of data in the conduct of science and technology and to
make these data and information available to a multidisciplinary community. This
series in support of that goal provides a forum made up of many contributions
which can be theoretical treatments, compilations or applied outlines. This in-
cludes computer related handling and visualization of data to the major scientific
and technical fields.
To this end, the series on Data and Knowledge is open to contributions of vari-
ous kinds, in particular:
Fostering the improvement of the accessibility and quality of quantitative and

qualitative data;
Treating classical and ground breaking methods by which numeric and sym-
bolic data are acquired, analyzed and managed;
Presenting new data and knowledge interfaces designed to optimize interop-
erability and thereby increase the potential for sharing data among databases
and networks;
VI Introduction to the Series
Promoting international cooperation in communication and data sharing. This

includes works dealing with standardization, data quality agreements and con-
ceptual data descriptions (metadata, syntactic and semantic approaches) along
with papers dealing with the evolution of internet based facilities, other forms
of worldwide communications and electronic publishing;
Providing new insights into, or interpretations of, processes leading to creative
design in the field of concurrent and/or cooperative engineering, including
cognitive aspects critical to data based decision making.
In the evolving information world we live in, where the traditional ways of trans-
ferring information as an essential resource are rapidly changing, this Series aims
to identity emerging and innovative concepts for data compilation, handling, man-
agement, and evaluation. Its ambition is to be a catalyst for change while simulta-
neously nurturing a thought-provoking forum.
Acknowledgments
Our special thanks go to Mrs. Mary Browning who computerized the manuscript
and provided much editorial assistance on many details.
The work incorporated and reviewed here reflects endeavors of a very distin-
guished group of research scientists. We thank them for sharing this international
endeavor in thermophysics and thermochemistry especially within a geochemical
framework. We thank the International Council for Science through CODATA
(Committee on Data for Science and Technology) for modest support through the
Geochemistry Task Group over the years and support earmarked more recently
especially for this project.
Preface
This book involves application of the Calphad method for derivation of a self-
consistent thermodynamic database for the geologically important system Mg0-
Fe0-Fe203-Alz03-Si02 at pressures and temperatures of Earth's upper mantle and
the transition zone of that mantle for Earth. The created thermodynamic database
reproduces phase relations at 1 bar and at pressures up to 30 GPa. The minerals
are modelled by compound energy formalism, which gives realistic descriptions of
their Gibbs energy and takes into account crystal structure data.
It incorporates a detailed review of diverse types of experimental data which
are used to derive the thermodynamic database: phase equilibria, calorimetric stud-
ies, and thermoelastic property measurements. The book also contains tables of
thermodynamic properties at 1 bar (enthalpy and Gibbs energy of formation from
the elements, entropy, and heat capacity, and equation of state data at pressures
from 1 bar to 30 GPa. Mixing parameters of solid solutions are also provided by
the book.
Table of Contents
Introduction to the Series ....................................................................................... V
Acknowledgments ................................................................................................ VII
Preface ................................................................................................................... IX
Table of Contents .................................................................................................. XI
Co-Authors ......................................................................................................... XIII
Vitae of Co-Authors ............................................................................................. XV
CODATA Task Group on Geothermodynamic Data ....................................... XXIII
Chapter 1. Thermodynamics and Modeling .......................................................... 1

1.1 Introduction ....................................................................................... 1
1.2 Thermodynamic Modeling ................................................................ 1
1.3 Experimental Data ............................................................................ 3
1.4 Programs and Assessment. ................................................................ 4
1.5 System and Phases ............................................................................ 5
Chapter 2. Experimental Phase Equilibrium Data ................................................. 7

2.1 The Si02 System ............................................................................... 7
2.2 The Fe-0 System .............................................................................. 8
2.3 The Fe-Si-0 System ........................................................................ 10
2.4 The Mg0-Si0 2 System ................................................................... 11
2.5 The Fe-Mg-Si-0 System ................................................................. 12
2.6 The Ah0 3-Si02 System .................................................................. 15
2.7 The FAS (Fe0-Ah03-Si02) System ............................................... 15
2.8 The MAS (Mg0-Ab0 3-Si0 2) System ............................................ 16
2.9 The FMAS (Fe0-Mg0-Ah0 3-Si0 2) System .................................. 19
Chapter 3. Thermodynamic Data for Stoichiometric Phases

and End-members of Solid Solutions ................................................ 25
3.1 Introduction ..................................................................................... 25
3.2 Data for Compounds ....................................................................... 25
Si02 Tables ..................................................................................... 26
Fe Tables ......................................................................................... 38
AbSi0 5 Tables ................................................................................ 42
XII Table of Contents
Fe20 3 Tables .................................................................................... 48

Magnesioferrite S.S. Tables ............................................................ 50
Spinel S.S. Tables ........................................................................... 54
Magnesiowustite S.S. Tables .......................................................... 58
Olivine S.S., ~-andy-Spinel S.S. Tables ........................................ 64
Protopyroxene S.S. and Hpclinopyroxene S.S.Tables .................... 76
Orthopyroxene S.S. Tables ............................................................. 84
Garnet S.S. Tables ........................................................................... 90
Ilmenite S.S. Tables ........................................................................ 98
Perovskite S.S. Tables ................................................................... 104
3.3 Comments on Equation of State Tables ........................................ 110
3.4 Comments on Thermodynamic Tables .......................................... 119
Chapter 4. Solid Solution Models and Data ....................................................... 129

4.1 Olivine/ ~-, y-spinel. ...................................................................... 129
4.2 Pyroxene ........................................................................................ 130
4.3 Magnesiowustite ........................................................................... 131
4.4 Spinel ............................................................................................ 132
4.5 Garnet ............................................................................................ 132
4.6 Ilmenite/Perovskite ....................................................................... 135
Chapter 5. Calculation of Phase Diagrams ......................................................... 137

5.1 The Si02 System ........................................................................... 137
5.2 The Fe-0 System ........................................................................... 138
5.3 The Fe0-Si0r02 System .............................................................. 140
5.4 The Mg0-Si02 System.................................................................. 142
5.5 The Fe0-Mg0-Si02 System ......................................................... 143
5.6 The FAS System ........................................................................... 153
5.7 The MAS System .......................................................................... 155
5.8 The FMAS System at Pressures up to 5 GPa ................................ 158 ,
5.9 The FMAS System at Pressures up to 30 GPa .............................. 163
References ........................................................................................................... 173
Subject and Substance Index ............................................................................... 191
Glossary ............................................................................................................... 197

Co-Authors
Fabrichnaya, Olga, Ph.D.

Max-Planck-Institut fUr Metallforschung, Pullvermetallurgische Laboratorium
Heisenbergstr. 3, 70659 Stuttgart, Germany
Phone: +49-711-689-31 06
Fax: +49-711-689-3131
Richet, Pascal, Ph.D.

Laboratoire des Geomateriaux, Institute de Physique du Globe de Paris
4 Place Jussieu, F-75252 Paris cedex 5, France
Phone: +33-1-4427-4938
Fax: +33-1-4427-2487
Saxena, Surendra K., Ph.D.

Director CeSMEC, Center for the Study of Matter at Extreme Conditions,
Florida
International University, VH150, University Park
Miami, Florida, 33199, U.S.A.
Phone:+ 1-305-348-3030
Fax:+ 1-305-348-3070
Westrum, Edgar F. Jr., Ph.D.

Department of Chemistry, University ofMichigan
Ann Arbor, MI 48109-1055, U.S.A.
Phone: +1-734-764-7357
Fax: +1-734-647-4865
E-mail: westrum@umich.edu
Vitae of Co-Authors
Olga B. Fabricbnaya
Born November 1, 1960; Moscow, Russia
Education
1978-1983 Moscow State University, Chemistry Department; Master of
Science in Physical Chemistry
1983-1987 Post Graduate Course in Vernadsky Institute of Geochemis-
try and Analytical Chemistry, the USSR Academy of Sci-
ences, Moscow
1988 Candidate of Science. Thesis: "Phase relations in olivine and
pyroxene systems at P-T conditions of the mantle transition
zone" in the Vernadsky Institute of Geochemistry and Ana-
lytical Chemistry
1995-1998 Ph.D. Student in Uppsala University, Sweden; Ph.D. in Min-
eralogy, Petrology and Tectonics. Thesis: "Thermodynamic
study of the FeO- MgO-AhOrSi02 system. Data assessment
and phase diagram calculation"
Employment
1987-1989 Junior Scientist in Vernadsky Institute, Moscow, USSR
1989-1992 Research Scientist
1992-1995 Senior Scientist, Moscow, Russia; Visiting Scientist in the
Institute of Earth Sciences, Uppsala University, Sweden
1995-1998 Doctorand in the Institute of Earth Sciences, Uppsala Univer-
sity, Sweden
1998-1999 Researcher in Royal Institute of Technology, Stockholm
1999-present Guest Scientist in Max-Planck-Institute fiir Metallforschung,
Stuttgart, Germany
Publications (26 total)

4. O.L. Kuskov and O.B. Fabrichnaya, "Phase relations in the Fe0-Mg0-Si02
system: The thermodynamic parameters of virtual ~-Fe2 Si04 , and petrologi-
cal and geophysical applications." Geochem. Intern. 24, No 9, 56--72 (1987)
10. O.B. Fabrichnaya and O.L. Kuskov, "Constitution of the mantle: 1. Phase
relations in the Fe0-Mg0-Si02 system at 10-30 GPa." Phys. Earth Planet.
Intern. 69, 56-71 (1991)
18. O.B. Fabrichnaya, "Thermodynamic data for phases in the FeO-MgO-SiOz
system and phase relations in the mantle transition zone." Phys. Chern. Min-
erals 22, 323-332 (1995)
XVI Vitae of Co-Authors
23. 0. Fabrichnaya and I. Nerad, "CaO·Si02 - CaO·Alz03·2Si02 - 2Ca0 Alz0 3

Si02 system." J. Eur. Ceram. Soc. 20,505-515 (2000)
25. O.B. Fabrichnaya, H.J. Seifert, T. Ludwig, F. Aldinger, and A. Navrotsky,
"The assessment of thermodynamic parameters in the Alz03- Y20 3 system
and phase relations in the Y-Al-0 system." Scand. J. Metallurgy 30, 175-
183 (2001)
Surendra K. Saxena
Education and Employment

1963-1964 Research Fellow, Uppsala University
1964-1967 Doctoral research
1967 Ph.D., Uppsala University, Uppsala, Sweden
1967-1968 Assistant Professor, Institute of Mineralogy and Geology,
Uppsala
1968-1969 Research Scientist, Institute of Mineralogy and Geology,
Uppsala
1969-1971 Senior Research Associate, National Academy of Science, at
Goddard Space Flight Center, Greenbelt, Maryland
1971-1972 Research Associate, Virginia Polytechnic Institute and State
University
1973-1976 Associate Professor, Brooklyn College, City University of
New York
1977-1996 Professor, Brooklyn College, City University of New York
1983-1996 Professor, Graduate Center of the City University of New
York
1989-2001 Professor, Univesity ofUppsala, Sweden
1999--present Professor, Florida International University, Miami, Florida
Professional Affiliations
Member, Royal Swedish Academy of Science
Laurea Honoris causa dall 'Universita di Padova (200 1)
Books
1. Thermodynamics of rock-forming crystalline solutions. Springer-Verlag,
New York, 1973. Published in Russian by MIR publishers, 1975, Ed. L.L.
Perchuk. Translated into Chinese, 1979
2. Chemical Petrology: With applications to terrestrial planets and meteorites,
R.F. Mueller and S.K. Saxena. Springer-Verlag, New York, 1977. Translated
into Russian by MIR publishers in 1979. Translated into Chinese in 1983
3. Mixtures and Mineral Reactions, J. Ganguly and S.K. Saxena. Springer-
Verlag, 1987
Vitae of Co-Authors XVII
4. Thermodynamic Data on Oxides and Silicates, S.K. Saxena, N. Chatterjee,

Y. Fei and G. Shen. Springer-Verlag, New York, 1993
5. Energetics of Geological Processes. Hans Ramberg Volume. Editors: S.K.
Saxena and 1. Bhattacharji. Springer-Verlag, New York, 1977
6. Advances in Physical Geochemistry. APG Series Editor: S.K. Saxena. Sprin-
ger-Verlag
7. APG Volume 2. Fe-Mg Order-Disorder in Silicates and Other Topics, 1982
8. APG Volume 3. Kinetics and Equilibrium in Mineral Reactions, 1983
9. APG Volume 6. Chemistry and Physics of Terrestrial Planets, 1986
10. APG Volume 10. Thermodynamic Data Systematics, 1992.
Selected Journal Publications

77. Y. Fei and S.K. Saxena, "Fluids at crustal pressures and temperatures," Con-
trib. Mineral. Petrol. 95, 370-375 (1987)
104. S.K. Saxena, G. Shen and P. Lazor, "Experimental evidence for a new iron
phase and implications for Earth's core," Science 260, 1312-1314 (1993)
112. S.K. Saxena, "Earth mineralogical model: Gibbs free energy minimization
computation in the system Mg0-Fe0-Si0 2," Geochim. Cosmochim. Acta 60,
2379-2395 (1996)
129. M. Hillert, B. Burton, S.K. Saxena, S. Degterov, K.C.H. Kumar, H. Ohtani,
F. Aldinger, and A. Kussmaul, Workshop in thermodynamic modelling of
solutions and alloys-Shloss Ringberg, March 10-16 (1996)-Group 4: model-
ling of oxides, Calphad-Computer Coupling of Phase Diagrams and Ther-
mochemistry 21,247-263 (1997)
180. S.K. Saxena, "Thermodynamics of epsilon iron at core physical conditions,"
Geophysical Monographs, American Geophysical Union, in press (2002)
Pascal Richet
Education
1972-1977 Student, Ecole Normale Superieure, Science section
1974 Master, Fundamental Geochemistry, University Paris 7
1976 3rd Cycle Doctorate, Chemistry, University Paris 7; Thesis:
"Calcul des fractionnements isotopiques des molecules sim-
ples d'interet geochimique. Applications geochimiques et
cosmochimiques."
1982 State Doctorate, Physics, University Paris 7; Thesis: "Pro-
prietes termodynamiques des silciates fondus."
XVIII Vitae of Co-Authors
Employment
1977-1983 CNRS Research Scientist at the Institut de Physique du
Globe de Paris, Paris
1983-1985 Postdoctoral Fellow at the Geophysical Laboratory, Carnegie
Institution of Washington, Washington, D.C., U.S.A.
1986-present Physicist at the Institut de Physique du Globe de Paris, Paris
1996-1997 Alan Cox Visiting Professor, Stanford University, California,
U.S.A.
2001 Visiting Professor, Tokyo Institute of Technology, Japan
Books
1. P. Richet, L 'age du monde-A Ia decouverte de l'immensite du temps, Edi-
tions du Seuil, Paris (1999)
2. P. Richet, Les bases physiques de Ia thermodynamique, Belin, Paris (2000)
3. P. Richet, L 'age du verre, Decouvertes Gallimard, Paris (2000)
4. P. Richet, The Physical Basis of Thermodynamics, Plenum Publishing, New
York (2001)
Selected Popularizations (15 total)

2. P. Richet, La Terre, temps des contrastes, in L 'an 2000 entre autres ... , Air
France Magazine, p. 131-140 (December 1999)
5. P. Richet, articles dealing with earth sciences, physics and literature in Dic-
tionnaire culture/ des sciences, ed. by N. Witkowski, Editions du Seuil et du
Regard, Paris (200 1)
8. P. Richet, articles dealing with earth sciences in Dictionnaire culture! de Ia
langue fran~aise, ed. by A. Rey, Dictionnaires Le Robert, Paris (2002)
Selected Research Publications (120 Total)

5. Y. Bottinga and P. Richet, "Thermodynamics of liquid silicates: a prelimi-
nary report," Earth Planet. Sci. Lett. 40, 382-400 (1978)
14. Y. Bottinga, P. Richet and D.F. Weill, "Calculation of the density and ther-
mal expansion coefficient of silicate liquids," Bull. Mineral. 106, 129-138
(1983)
24. P. Richet, R.A. Robie and B.S. Hemingway, "Low-temperature heat capacity
of diopside glass: A calorimetric test of the configurational entropy theory as
applied to the viscosity of liquid silicates," Geochim. Cosmochim. Acta 50,
1521-1533 (1986)
35. P. Richet and G. Fiquet, "High-temperature heat capacity and premelting of
minerals in the system MgO-CaO-AlzOrSi02," J Geophys. Res. 96, 445-
456 (1991)
44. G. Fiquet, Ph. Gillet and P. Richet, "Anharmonic contribution to the high-
temperature heat capacity of crystals - Application to Ca2Ge04 , Mg2Ge04
and CaMgGe04 olivines," Phys. Chem. Minerals 18,469-479 (1992)
Vitae of Co-Authors XIX
56. P. Richet, J. Ingrin, B.O. Mysen, P. Courtial and Ph. Gillet, "Premelting of
minerals: an experimental study," Earth Planet. Sci. Lett. 121, 589--600
(1994)
75. B. Champagnon, C. Chemarin and P. Richet, "Fictive temperature and me-
dium range order in silicate glasses: heat capacity measurements and Boson
peak," Phil. Mag. B77, 663--669 (1998)
82. A. George, P. Richet and J.F. Stebbins, "Cation dynamics and premelting in
lithium metasilicate (Li2Si03) and sodium metasilicate (Na2Si03): a High-
Temperature NMR Study," Amer. Mineral83, 1277-1284 (1998)
108. D. deLigny, P. Richet, E.F. Westrum, Jr. and J. Roux, "Heat capacity and en-
tropy of rutile (Ti02) and of nepheline (NaA1Si04)," Phys. Chem. Minerals
29, 267-272 (2002)
Chapters in Books (6 total)

5. P. Richet, "Glasses and the glass transition," Mineralogical Notes, 3, 419-
447, European Mineralogy Union (2001)
Edgar F. Westrum, Jr.

Born March 16, 1919, Albert Lea, Minn.
Education and Employment

1937-1938 Hamline University, St. Paul, Minn.
1939-1941 Institute of Technology, University of Minnesota, Minneapo-
lis, Minn., B. Chern., Physical Chemistry
1941-1944 University of California-Berkeley (Mentorship of Prof. K.S.
Pitzer, Ph.D. 1944), Thermodynamics
1945 University of Chicago, 1945. Post-doctoral work in optical
crystallography
1944-1947 University of Chicago, Metallurgical Laboratory, Plutonium
research, nuclear physics, and chemistry
1947-1952 University of California Radiation Laboratory with Prof.
G. T. Seaborg (and subsequently as a consultant and faculty
member)
1946-1989 University of Michigan, Assistant Professor, 1946; Associate
Professor, 1951; Professor of Chemistry, 1957
1989- Professor Emeritus-Consulting; for industry; government;
International Atomic Energy Agency (Vienna, Austria);
Seiko Seikosha (Tokyo, Japan), Joint U.S.-Japan Atomic En-
ergy Commission; etc.
XX Vitae of Co-Authors
Academic Endeavors
Teaching. Undergraduate courses: General Chemistry, Physical Chemistry, Lit-
erature, Chemical History, Scientific Writing, Honors Physical Chemistry, Physi-
cal Chemistry Laboratory. Graduate Courses: Thermodynamics, Statistical Me-
chanics, Kinetics, Advanced Thermodynamics, Special Topics, etc.
1966-1992 Member, Executive Board of the (War Memorial) Phoenix

Project, peacetime uses of nuclear energy, University of
Michigan
1983-1993 Coordinator, Physical Chemistry Division
1983-1989 Urban/Minority Program in Scholarly Research (for under-
represented minority high school students)
1991-1993 S.E. Michigan Research Mentorships
National Scientific Activities

1964-1968 Advisory Review Committee for the Heat Division, National
Bureau of Standards
1965-1971 U.S. National Committee for the International Institute of Re-
frigeration, Member
1969-1974 National Research Council Committee on Weights, Units,
and Terminology (under the general aegis of the Numerical
Data Advisory Board), Member
1970-1973 U.S. National committee for CODATA: Member, 1970-72;
Chairman 1972-73; National Delegate (U.S.) to International
General Assembly CODATA, 1973
1970-1973 Chairman, Ad hoc IUPAC Committee for the Updating, Ex-
tension, Revision and Internationalization of the Resolution
on the Publication of Calorimetric Data
1972-1979 Advisory Review Committee for the Physical Chemistry Di-
vision, National Bureau of Standards
1975-1976 Organizer and first Chairman, Gordon Research Conference
on Orientational Disorder in Crystals
1982-1992 Education Panel of the (U.S.) Numerical Data Advisory
Board (NDAB)
International Scientific Involvement

1963 Continuous association with IUPAC since 1963 including
service as Commission Chairman
1971-1976 ICSU/CODATA Task Group for Primary Data Publication,
Chairman
1973-1976 ICSU/CODATA Representative to ICSU AB/CODATA
Joint Working Group on Data Tagging and Flagging
1975-1979 ICSU Policy Group on Scientific Information, Chairman
Vitae of Co-Authors XXI
1982- ICSU/CODATA Task Group for Chemical Thermodynamic

Tables
1985-1989 ICSU/CODATA Task Group for Geothermodynamic Data,
Chairman
1985-1993 ICSUICODATA Task Group for Referral Data, Chairman
1985-1994 A prime involvement in the ICSUICODATA international
activity was being the initial holder of the newly created post
of Secretary General for the maximum statutory terms total-
ing eight years and-by unanimous vote of the General As-
sembly-an additional one year term. He was also Editor-in-
Chief for CODATA 1994-1999.
Scientific Unions
1969-1973 IUP AC Commission 1.2 on Thermodynamics and Thermo-
chemistry, Titular Member and Chairman 1997-77, Secretary
1969-73, Associate Member 1963--69, Past Chairman (pre-
sent at all international conferences)
1973-1975 IUPAC Division of Physical Chemistry, Divisional Commit-
tee
1982-1988 IUPAC Delegate to ICSU/CODATA
Professional and Other Society Memberships and Offices

Honorary Societies: Alpha Chi Sigma, Phi Lambda Upsilon, Society of Sigma Xi
Fellow: American Physical Society, American Institute of Chemists,
American Association for the Advancement of Science
Scientific Societies: American Chemical Society, Faraday Society, The Chemical
Society (U.K.), Netherlands Physical Society, The Calo-
rimetry Conference (U.S.) (Initiator, Chairman, and other of-
fices including Directorship, 1955-1971)
Editorial Endeavors
1962-1970 The Thermophysical Bulletin merged in 1962 with the Bulle-
tin of Thermochemistry and Thermodynamics to become
what was designated as the Bulletin of Chemical Thermody-
namics. This "zeroth order critical table" of some 600 pages
per year provides a survey of the approximately 6000 articles
in chemical thermodynamics, as well as a summary of com-
pleted-but-unpublished-experimentation
1966-1984 With Prof. Max McGlashan and Henry Skinner, he launched
the prestigeous Journal of Chemical Thermodynamics pub-
lished by Academic Press and shared the editorship with
Prof. McGlashan during eight formative years, by the end of
XXII Vitae of Co-Authors
which it had grown to its present page count and 12 issues

per year.
1967-1978 Editor, The Bulletin of Thermodynamics and Thermochemis-
try, 1967-77; Associate Editor, 1978, (renamed) Bulletin of
Chemical Thermodynamics
1969-1977 Initiator and Co-Editor, The Journal of Chemical Themody-
namics
1976-1979 Advisory Editorial Board, Member, Journal of Physical and
Chemical Reference Data
1981-1995 Editor-in-Chief, ICSU/CODATA; Editor, CODATA Direc-
tory of Data Sources for Science and Technology; editor,
CODATA Newsletter Thermodynamics of Organic Sub-
stances, D.W. Stull, G.A. Sinke, E.F. Westrum, Jr.
1971 Edition in Russian: Thermodynamics of Organic Substances.
D.W. Stull, G.A. Sinke, E. F. Westrum jr. Isdatelsvo Mir
Moscow 936 pp.
1985-2002 Author or editor on 13 ICSU/CODATA books on data han-
dling, database management, regional and environmental
data, etc.
Journal Publications
A total of 545 papers (13 during 2002) have been published. These cover nuclear
physics and chemistry, data management and the application of chemical and ther-
mophysical reaction calorimetry, and especially adiabatic heat-capacity calo-
rimetry above the ambient temperatures to those within a few degrees above 0 K.
Many deal with oxides, vitreous phases, plastic crystals behaviors, etc. [A copy of
the 51 page list of reprints will be supplied on requests from scientists.]
CODATA Task Group on Geothermodynamic Data
1984-1998
Terms of Reference:
For Geothermodynamics, it is important to consider the calorimetric data along
with the experimental phase equilibrium data in a system of interest. In extrapola-
tions to high temperatures and pressures beyond the experimental range, calcu-
lated data (e.g., by molecular dynamics) need to be introduced. Mineral physicists
use spectroscopic and other experimental methods to measure the temperature-
pressure dependence of physical properties. These data cannot remain isolated
pieces of information and must be integrated into one internally consistent data-
base. This is one important respect in which the work of this Task Group differed
from others.
Chairman Corresponding Members

Prof. E.F. Westrum, Jr. Prof. E. Essene
Prof. F. Gr0nvold
Prof. B.S. Hemingway
Prof. I. Khodakovsky
Prof. R. Powell
Members Executive Committee Liaison

Dr. R. Berman Prof. M. Tasumi
Dr. T.J.B. Holland
Dr. P. Richet
Prof. S.K. Saxena
Chapter 1
Thermodynamics and Modeling
1.1
Introduction
In metallurgical and ceramics studies work on data assessment has been in pro-
gress for many years (see [70KAU], [87ANS/SUN), [94PEL], [96SEIIALD]).
Helgeson et al. [78HEL/DEL], Berman [88BER], Holland and Powell [90HOLI
POW], Gottschalk [97GOT], Saxena et al. [93SAX/CHA] created geochemical
databases. The recent studies of Berman [88BER], Holland and Powell [90HOLI
POW] and Gottschalk [97GOT] describe phase equilibria at low and medium pres-
sures and temperatures. In the database of Saxena et al. [93SAX/CHA], thermo-
dynamic data for high-pressure phases were presented. However, melting at 1 bar
was not considered by Saxena et al. [93SAX/CHA]. They also did not consider all
solid solutions; for example, data on garnet solid solutions were not included. The
available databases were created for special applications such as the calculation of
equilibria between iron and oxide slag and between rocks and fluids. A serious
limitation of these specialized databases is that it is impossible to combine data
from different databases. They have different descriptions for the same phase or
different values for the same thermodynamic parameter. Using data from different
databases requires reassessment of thermodynamic data for almost all phases in-
volving experimental data used in the assessed databases.
The aim of this study is to create a database that reproduces experimental data
on subsolidus phase relations and melting at 1 bar as well as one with phase rela-
tions at high pressures and temperature which is equally useful to geo- and materi-
als-scientists. The solid solutions are described by a molecular model and a com-
pound energy model whereas liquid phases are described by the two-sublattice
ionic model [68HIL].
1.2
Thermodynamic Modeling
In the present work the Gibbs energy of each phase is described as a function of
temperature, pressure and composition. The Gibbs energy (G) of a pure phase and
end members of solid solutions at a certain
P and Tis expressed as
O. B. Fabrichnaya et al., Thermodynamic Data, Models, and Phase Diagrams in Multicomponent Oxide Systems
2 Thermodynamics and Modeling
where so298 is the entropy, .1.,H298

0 is the enthalpy of formation from the elements
and Cp is the heat capacity given by
Cp =a+ bT + cT-2 + dT 2 + eT-3 + p-0.5 + gT-1
The molar volume as a function of pressure and temperature is calculated using

the Murnaghan equation,
, )-IlK~
(1+~:
V(P,T)=V(l,T)
where K Tis isothermal bulk modulus expressed as
and K'p is the pressure derivative of bulk modulus which in some cases has a tem-
perature dependence:
K~ = K~rr + K~r (T - Tr) ln(TjTr)
K' PTr is the pressure derivative of bulk modulus at T,.=298 .15 K, K' PT is its tem-
perature derivative.
The molar volume at I bar is expressed as a function of temperature
T
V(l, T) = v;~rr exp( fa(T)dT)
Tr
where v.o I,Tr

is the molar volume at 1 bar and Tr-298.15 K. a(l) is the temperature
dependent thermal expansion
Fabrichnaya [95FAB] showed that the Murnaghan and Birch-Murnaghan equa-

tions of state give results very close to each other over the P and T ranges consid-
ered in this work.
The simplest non-ideal solution model is the molecular model with Gibbs en-
ergy of mixing expressed as follows:
.1-Gmix = 'LX1G1 + RT'LX1 In X 1 + .1-Gex

i i
Experimental Data 3
where Xi are the mole fractions, Gi is the Gibbs energy of an end-member i and
the excess Gibbs energy of mixing is expressed by:
~Gex = LX;XiL(X; -Xi)"L7,j

i-."'j,i<j n
where Ln.
1,)
is the mixing parameter between end-members i and j. In the present
work this model is applied to orthopyroxene.
The sublattice model concept was outlined by Temkin [45TEM]. The model
was developed by Hillert [68HIL], Hillert and Staffansson [70HILISTA] for two
sublattice substances and then by Harvig [71HAR], and by Sundman and Agren
[81SUN/AGR] for several sublattices. The sublattice model used for ionic solid
phases is called the compound energy model. The Gibbs energy of solution in the
sublattice model is given by
~Gmix = L L LY/Yj1YkuGijk + RTL U 5 LY/ In Y;" + ~Gex

; j k s ;
where Yi s is the mole fraction of constituent i on sub lattice s, us is the number of

sites on sublattice s per mole of formula unit of phase and AGex is the excess
Gibbs energy of mixing expressed as
~Gex = L L (LY/ Jq~

s i
Ls.
1,)
="(Ys
~I
- y•J )e.
1,)
n
where e . are binary interaction parameters. Higher-order interaction parameters

1,)
could also be included giving more complicated excess Gibbs energy terms.
1.3
Experimental Data
Diverse kind of experimental information is used to derive internally consistent

data sets phase equilibrium data, calorimetric, electrochemical, volumetric and
thermophysical measurements. The original thermodynamic data and phase dia-
grams are usually in conflict, i.e. it is impossible to reproduce experimental phase
diagrams using the calorimetric values of thermodynamic parameters. The reason
is that calorimetric data often have large errors and each phase is treated inde-
pendently of the others. The content of a phase diagram is very sensitive to exact
thermodynamic properties of phases. Changing Gibbs energy of a phase within
uncertainty limits of calorimetric data may lead to drastic changes in the phase dia-
grams. Using only experimental phase equilibrium data could give values outside
the uncertainty limits of calorimetric data and poor extrapolation to higher order
systems. Both direct measurement of thermodynamic properties and phase dia-
grams are included in optimization to get an internally consistent database.
To describe pressure dependent terms in Gibbs energy information on volume,
compressibility, pressure derivative of bulk modulus and thermal expansion is
necessary. Those data could be obtained using different experimental techniques.
They should be internally consistent as it is described in Saxena et al.
[93SAX/CHA]. Heat capacity at constant pressure, determined in calorimetric
studies should be consistent with heat capacity at constant volume, calculated from
vibrational spectra and acoustic velocities using Kieffer's model [79KIE], bulk
modus, thermal expansion and molar volume
Cp = Cv+a2VKTT
The phases considered in this study can be classified into four groups:
l. Phases with well determined calorimetric data, e.g. MgO.

2. Phases, for which thermochemical properties have been measured calorimetri-
cally by different workers with different results, e.g. forsterite and fayalite.
3. Phases whose thermochemical data are not available, but phase equilibrium
data do exist.
4. Fictive end-members, which are not stable at all P-T conditions. Their thermo-
dynamic parameters could be obtained from experimental data on solid solu-
tions.
1.4
Programs and Principles of Assessment
In the last decade, general computer programs for optimization of thermodynamic

data have been developed, which make it possible to take into account all available
experimental information on a system simultaneously (e.g. BINGSS and TERGSS
of Lukas et al. [77LUKIHEN), THERMO-CALC set of Sundman et al. [85SUN/
JAN). In this study the PARROT-program in THERMO-CALC set (Jansson
[84JAN], Sundman et al. [85SUN/JAN]) is used for thermodynamic data assess-
ment. Phase diagrams are calculated by total Gibbs energy minimization, using the
POLY-3 program in the THERMO-CALC set and the CHEMSAGE program of
Eriksson and Hack [90ERIIHAC).
The optimization program gives the best fit of experimental data taking into
account the error of every data point. However, the real situation is usually more
complicated and including all-available data in optimization does not necessarily
lead to satisfactory results. Some sets of experimental data could be in conflict and
System and Phases 5
show large systematic errors. By changing weights for the data points one may
recognize the influence of different experiments on the result of optimization. This
procedure helps to identify which data are contradictory.
However, it is usually impossible to optimize all parameters simultaneously.
There are too many parameters and they have different influence on phase dia-
grams. In this study we start assessment from phases of constant composition in
end-member systems. For each end member we reach consistency between volu-
metric properties and heat capacities at constant volume and pressure. Enthalpies
and entropies for such oxides as MgO, Al 20 3 and Si02 are accepted from calo-
rimetric measurements. Entropies usually are quite precisely determined by adia-
batic calorimetry and are accepted in this study. If such data are not available en-
tropies are assessed from phase equilibria. Enthalpies of formation are assessed
from phase equilibrium data, taking into account available calorimetric data. How-
ever, the uncertainty of calorimetric measurements of l!.rlJO is high and the result is
mainly influenced by phase equilibrium data.
For some solid solution phases calorimetric measurement of excess enthalpy of
mixing or activity data are available. However, they are very often contradictory.
At the last stage of assessment mixing properties of solid solutions are optimized
using available data on phase equilibria, excess enthalpy of mixing and activity
data.
1.5
System and Phases
In this book we selected the system Mg0-Fe0-Ah0 3-Si0 2 and considered ther-
modynamic properties and phase relations in this system. Phase relations in the
above mentioned system are important for Earth sciences and materials sciences.
To model mineral structure of the Earth interior it is necessary to know properties
of phases at high pressures and temperatures and to have information about phase
transformations. The phase relations at 1 bar are important for industrial applica-
tions. Chapter 1 contains review of phase equilibrium data.
The principal phases considered in the book are Si02 polymorphs (a-, ~
quartz, tridymite, cristobalite, coesite, stishovite), two modifications of Fe (bee,
fcc), AhSi0 5 polymorphs (andalusite, sillimanite, kyanite ), hematite, magnesiofer-
rite, spinel, magnesiowustite, olivine, ~-, y-spinel, orthopyroxene, hpclinopyrox-
ene, protopyroxene, garnet, ilmenite, perovskite. Polymorphs of Si02, iron,
AhSi0 5 and hematite have constant composition, other phases are solid solutions.
Chapter 3 contains information for stoichiometric phases and end-member of solid
solutions. The following systems were considered Si02, Fe, AhSi0 5, Fe203,
Fe30 4-MgFe204, FeAh04-MgAh04, MgO-Fe0-0, Fe2Si04-Mg2Si04, FeSi03-
MgSi03, Ah0 3-FeSiOrMgSi03. For each end member or stoichiometric phase
data on heat capacity, entropy, enthalpy increment, enthalpy and Gibbs energy of
formation from elements and equation of state parameters (volume, thermal ex-
pansion, compressibility, pressure derivative of bulk modulus) are presented.

Chapter 4 contains information about models of solid solution and mixing parame-
ters. The results of the calculations are presented in Chapter 5.
Chapter 2
Experimental Phase Equilibrium Data
2.1
The Si02 System
Several polymorphs of silica are known and their phase relations are reviewed by
a number of authors (see [79WEA/CHI], [84TAY], [86LIU/BAS], [86KUS/FAB],
[94SWA/SAX]). The principal polymorphs stable at pressures below 3 GPa are
quartz, tridymite and cristobalite; each of them have a low-temperature (a) and a
high-temperature (p) form. The a = P-quartz transformation occurs at temperature
of 846.5 ± 1.5 K at atmospheric pressure (see [49TUT]), P-quartz transforms to
tridymite at temperature of 1140 K (see [13FEN]). Cristobalite is stable from
1743 K (see [13FEN]) up the to melting point 1999 ± 5 K (see
[82RIC/BOT]).
Several modifications of low-temperature tridymite are known (see [13FEN],
[84TAY]). According to the available experimental phase equilibrium data of Fen-
ner [13FEN], Kennedy eta/. [62KEN/WAS], Ostrovsky [660ST], Grattan-Bellew
[78GRA] the triple point of P-quartz + high-tridymite + P-cristobalite is placed at
about 1460 K and 0.15 GPa. Tridymite is not stable above 0.15 GPa, cristobalite is
stable up to 0.6 GPa according to data of Jackson [76JAC]. Quartz polymorphs are
stable at pressures up to 3.5 ± 1 GPa (see [80MIRIMAS], [90KAN]). The P-T
boundary of a = P-quartz transformation was studied by Cohen and Klement
([67COHIKLE]), they determined the triple point a-quartz+ p-quartz + coesite at
3.75 GPa and 1673 K.
At pressures from 3 to 3.5 GPa quartz transforms to coesite, which transforms
to stishovite at 9-10 GPa. The a-quartz = P-quartz and quartz = coesite transfor-
mations have been extensively investigated (see review by Weaver et a/.
[79WEA/CHI]) and later by Mirwald and Massone [80MIRIMAS], Bohlen and
Boettcher [82BOH/BOE] and Kanzaki [90KAN]. The coesite = stishovite trans-
formation was studied by Ostrovsky [650ST], Akimoto and Syono [69AKI/SYO],
Yagi and Akimoto [76YAG/AKI], Suito [77SUI], Pacolo and Gasparik [90PAC/-
GAS], Zhang et a/. [93ZHAILIE], Serghiou et at. [95SER/ZER] and Zhang et at.
[96ZHAILI]. There are discrepancies in slope dP/dT of coesite = stishovite be-
tween investigations made using different experimental techniques. According to
the data of Yagi and Akimoto [76YAG/AKI] made by in situ X-ray diffraction
studies dP/dT = 0.0011 GPa!K, it is in agreement with new data of Serghiou et al.
[95SER/ZER], obtained in laser-heated, diamond, anvil cell. The other data ob-
tained in quench experiments (see [69AKI/SYO], [77SUI], [93ZHAILIE]) are in
8 Experimental Phase Equilibrium Data
agreement with new data of Zhang et al. [96ZHA/LI] obtained by in situ X-ray
diffraction studies (dP/dT = 0.0026 GPa!K). At very high pressures probably an
even more dense polymorphic modification of Si02 is stable (see [73GERIPRO],
[78LIU/BAS], [89TSUNAG]). The structure of this phase is still under discussion
and other information is not reliable.
Experimental data on the anhydrous melting of Si02 are available. Jackson
[76JAC] determined the melting curve of cristobalite and ~-quartz and located the
triple point of cristobalite, ~-quartz and liquid at about 1973 K and 0.6 GPa. Kan-
zaki [90KAN] studied the melting curve of ~-quartz and coesite at pressures from
3 to 7 GPa and located the quartz + coesite + liquid triple point at 4.5 GPa and
2723 K. Zhang et al. [93ZHA/LIE] determined the melting curve of coesite and
stishovite at 9-14 GPa and located the coesite + stishovite + liquid triple point at
13.7 GPa and 3073 K. Shen and Lazor [95SHE/LAZ] studied the melting ofSi02
at pressures of6.5-37 GPa and temperatures of2750-4250 K.
2.2
The Fe-0 System
The phase relations in the Fe-0 system have been extensively studied. The stabil-
ity of phase assemblages depends on pressure, temperature and oxygen activity.
Different techniques were used to determine conditions of equilibrium and phase
compositions. In experiments on phase equilibria the oxygen activity was fixed
using solid-solid buffers or mixture of gases of known composition and oxygen
activity. Another way to determine oxygen activity is electrochemical methods
based on emf measurement.
Darken and Gurry ([45DAR/GUR], [46DAR/GUR]) studied the experimental
phase diagram of the Fe-0 system at 1 bar in details. They measured phase com-
positions and oxygen activity for solid-solid and solid-liquid equilibria and in one-
phase stability region. Later studies ([65VAL/RAC], [73GID/GOR] and others)
are in a good agreement with the results of Darken and Gurry [45DAR/GUR].
Vallet and Raccah [65VAL/RAC] and Carel [67CAR] considered multiple phase
regions to exist within the single-phase wustite field, which were separated by
second order transitions. Kubaschewsky [82KUB] reviewed the available data on
phase relations in the Fe-0 system. Hazen and Jeanloz [84HAZ/JEA] reviewed the
physical properties of wustite
They assumed that wustite exists in a variety of structure types characterized
by different partition Fe+J between tetrahedral and octahedral sites and different
extent of short-range and long-range order of clustered defects. Dieckmann
[82DIE] presented the data on nonstoichiometry and defect structure of magnetite.
Katsura et a/. [67KATIIWA], Simmons and Seifert [79SIM/SEI], Simmons
[80SIM], Shen et al. [83SHE/BAS], Me Cammon and Liu [84MCC/LIU] found
The Fe-0 System 9
that wustite become more stoichiometric when the pressure increases up to

10 GPa. According to experiments at pressures higher than 10 GPa deviations
from stoichiometry grow with pressure (see [76bLIU], [83SHE/BAS],
[84MCCILIU]). Later experiments of Me Cammon [93MCC] in split-sphere appa-
ratus showed that at pressures of 10-18 GPa the deviation from stoichiometry
practically did not change with pressure increases. Me Cammon and Liu
[84MCC/LIU] and McCammon [93MCC] showed that to reproduce the pressure
dependence ofwustite composition in calculations, the bulk modulus ofFe,O must
vary strongly with the composition at x>0.96, but should be almost constant at
x<0.96. Hazen and Jeanloz [84HAZ/JEA] also assumed nonlinear dependencies of
physical properties on composition. However, the new experiments ofFei [96FEI]
showed that the effect of wustite composition on bulk modulus is small. Shen et
a/. [83SHE/BAS] found that iron + wustite + magnetite univariant equilibrium
shifted towards lower temperatures with the pressure increase.
Jeanloz and Ahrens [80JEA/AHR] found a phase transformation in wustite at
pressure of 70 GPa. According to Liu et a/. [82LIU/SHE] the features on Hugo-
niot curve for wustite interpreted as a phase transition at 70 GPa could be also ex-
plained by changing stoichiometry. Fei and Mao [94FEI/MAO] studied phase
transformations in FeO by in-situ synchrotron X-ray diffraction measurements.
They detected a transformation of cubic structure to rhombohedral phase at room
temperature and 16 GPa with a positive slope. Transformation of rhombohedral
phase to NiAs structure took place at 70-100 GPa with a negative slope. Magnet-
ite and hematite according to Mao et a/. [74MAO/TAK] transform to high-
pressure phases. It was assumed that magnetite transformed to its monoclinic form
at 25 GPa and room temperature and that this transition had negative slope (see
[74MAO/TAK], [77SYO/GOT] and [86HUA/BAS]). According to shock-wave
data hematite transformed to a high-pressure phase at 60 GPa [82GOT/SAT]. A
phase transition was also observed in static compression experiments in a diamond
anvil cell. Yagi and Akimoto [82YAG/AK1], Olsen eta/. [910LS/COU] and oth-
ers reported X-ray diffraction studies. According to Olsen eta/. [910LS/COU] the
transition of corundum to orthorhombic perovskite type of structure takes place at
55 GPa. However, the information about high-pressure phases in the Fe-0 system
is still poor for making thermodynamic calculations.
The melting of pure iron and wustite at high pressures was experimentally
studied by Boehler [92BOE] and by Shen et al. [93SHEILAZ]. Ringwood and
Hibberson [90RIN/HIB] studied the liquidus phase relations in the Fe-FeO system
at pressure 16 GPa. They found two eutectic equilibria: iron + wustite + metallic
liquid (1943 K) and metallic liquid+ oxide liquid+ wustite (2033 K).
2.3
The Fe-Si-0 System
Since the solid phase relations in the Fe0-Si02-02 system have many metallurgi-
cal and geological applications they were extensively studied. The temperature
dependence of the oxygen activity for solid phase buffers, such as silica-iron-
fayalite, iron-wustite, wustite-magnetite, silica-fayalite-magnetite, magnetite-
hematite were measured by different techniques in many works. For example, they
were studied by the emf method ([81JAC/ROS], [81SCHIKUS], [85JAC],
[870NE], [880NE], [89JACIKAL]), by the CO/C02 gas equilibria method
([32SCH/FRA], [46CIR], [66SCHIMUA]), by the H2-membrane method
([78HEW]), and by the thermogravimetric method ([65VAL/RAC], [67SWAI
WAG]). A detailed review of different studies of liquidus relations in the Fe0-
Si02-02 system is presented by Selleby [93SEL] and by Fabrichnaya and Sund-
man [97FAB/SUN].
Subsolidus phase relations and melting in the Fe2Si04 system at high pressures
were studied by Lindsley [67LIN], Hsu [67HSU], Akimoto et al. [67AKIIKOM]
and Ohtani [790HT]. Lindsley [67LIN] and Hsu [67HSU] observed incongruent
melting of fayalite with separation of metallic iron up to 4 GPa. Akimoto et al.
[67AKI/KOM] reported that fayalite melted congruently up to 6.2 GPa, where fay-
alite transformed to a phase with spinel structure. Study of melting behavior of
Fe2 Si04 has been extended to the range between 5 to 16 GPa by Ohtani [790HT],
who reported that both olivine and spinel melted congruently in the pressure range
between 5 and 13 GPa and at higher pressure spinel melted incongruently forming
liquid and stishovite. Akimoto et al. ([65AKI/FUJ], [67AKIIKOM], and
[77AKINAG]). Yagi et al. [87YAG/AKA] studied fayalite = y-spinel transition.
Mao and Bell [71MAO/BEL] and Bassett and Ming [72BAS/MIN] have found
that Fe2 Si04 (y-spinel) disproportionates to stishovite and nonstoichiometric
wustite Ft;cO with x = 0.91-0.95 at 25 GPa and 1073 K. Later experiments of
Ohtani [790HT] confirmed the negative slope of this transformation. Subsolidus
relations in the system FeSi03 were studied in several works (see [80BOHIESS],
[92KOC/CEM], [70AKI/SYO], [76LIU]). Lindsley [65LIN] carried out a detailed
study of ferrosilite phase diagram. Transition boundaries between different modi-
fications of ferrosilite as found in Lindsley [65LIN] are drastically different from
data of Akimoto et al. [65AKI/FUJ]. A new study of Hugh-Jones et al.
[94HUG/WOO] showed the existence of two forms of clinoferrosilite. This al-
lowed reconciling previous experimental data ([65LIN] and [65AKI/FUJ]).
[94HUG/WOO) studied boundary of transformation of orthoferrosilite to different
forms of clinoferrosilite. According to data of Bohlen et a/. [80BOH/ESS] and
Koch-Muller et al. [92KOC/CEM], ferrosilite forms from a mixture offayalite and
quartz at temperatures of 973-1323 K and pressures of 1-1.5 GPa. Ringwood and
The Mg0-Si02 System 11
Major [66RIN/MAJ] found decomposition of ferrosilite toy-spinel and stishovite.

Experiments of Akimoto and Syono [70AKI/SYO] confirmed this result and
showed that ferrosilite decomposition occurred at pressures about 9 GPa and tem-
perature of 1273 K. The phase boundary of this transformation is very close to the
coesite = stishovite boundary.
2.4
The MgO-Si02 System
The phase relations in the Mg2 Si04 polymorphs (olivine, ~-phase and y-spinel)
have been experimentally studied by many authors ([70RINIMAJ], [72AKI],
[77SUI], [77KAW], [790HT], [79YAG/MAO], [82FUK], [86SAW], [82ITO/
YAM], [89KATIITO], [89ITO/TAK], [90GAS], [94MORIKAT] and [98IRI/
NIS]). It was found by Ringwood and Major [70RIN/MAJ], that at 1273 K and a
pressure of 13 GPa olivine transforms to ~-phase (structure of modified spinel).
The latest determinations of Morishima et al. [94MORIKAT] are in reasonable
agreement with data of Katsura and Ito [89KATIITO]. At a pressure of about
18 GPa the ~-phase transforms to y-spinel according to Ringwood and Major
[70RIN/MAJ]. Liu [75aLIU] was the first who found that y-spinel decomposes to
a mixture ofMgSi03 (perovskite structure) and MgO (periclase). This transforma-
tion has a negative slope dP/dT (see [82ITONAM], [89ITO/TAK], [98IRI/NIS]).
The differences between measurements, which were made using different experi-
mental techniques do not exceed 1 GPa except latest data of lrifune et al.
[98IRIINIS], which indicate that y-spinel decomposition takes place at a pressure,
which is 2 GPa lower than obtained in previous studies. If it is true, phase equilib-
ria in the Mg0-Si0 2 system, which occur at about 20-25 GPa, should be re-
determined.
Phase relations in the MgSi0 3 system are quite complex; the principal phases
are enstatite, phases with ilmenite, perovskite and garnet structure. There are four
different modifications of enstatite at 1 bar - low-T-clino, high-T-clino, ortho and
proto. At pressures of 7-12 GPa, high-P-clinoenstatite is stable (see [90PAC/
GAS]). The phase relations among modifications of enstatite are still controver-
sial. These phase transformations are difftcult to study because of the small
changes in enthalpy, entropy and volume. The transitions are very sluggish and
sensitive to influence of impurities and shear stress.
At pressures about 15-25 GPa, the sequence of phase transformations depends
on temperature. It was found that at 1273 K and pressures about 15 GPa enstatite
transforms to ~-phase + Si02 (stishovite). This equilibrium was studied in Aki-
moto and Syono [70AKI/SYO], Akaogi and Akimoto [77AKA/AKI]. At higher
pressure the ~-phase transforms to the y-phase; at pressures about 20 GPa a mix-
ture of y-spinel and Si02 transform to MgSi0 3-ilmenite, which transforms to
perovskite at pressures 23-24 GPa. Transformation of y-spinel + Si02 was studied

by Ito and Navrotsky [85ITO/NAV], Kanzaki [87KAN], Irifune and Ringwood
[871RIIRIN]. Depending on temperature ~-spinel+ Si02 mixture could transform
directly to ilmenite ([87SAW], [90GAS]). Liu [76cLIU] was the first who found
high-pressure polymorphs of MgSi03 with ilmenite and perovskite structure. The
transformation of ilmenite to perovskite was studied in detail by Ito and Yamada
[82ITONAM], Ito and Takahashi [89ITO!fAK] who indicated a negative slope
dP/dT for this transition. Tetragonal garnet MgSi0 3 was found to be stable at high
temperature by Kato and Kumazawa ([85KAT/KUM], [86KAT/KUM]). Sawa-
moto [87SA W] and Gasparik [90GAS] studied the phase relations of garnet in de-
tail. Comparison ofGasparik's [90GAS] results with data ofKato and Kumazawa
[85KAT/KUM] and Sawamoto [87SAW] shows systematic discrepancies in the
slopes of univariant curves. The reason could be differences in temperature de-
pendence of pressure calibrations. At temperatures above 1973 K enstatite trans-
forms directly to garnet. Presnall and Gasparik [90PRE/GAS] found that this tran-
sition has a negative slope dP/dT, in contrast to the positive slope reported by Kato
and Kumazawa [85KAT/KUM] and Sawamoto [87SAW]. According to calcula-
tions of Fei et al. [90FEI/SAX] and Saxena [96SAX], the slope of the ensta-
tite=garnet transition should be slightly negative, otherwise the topology of phase
diagram becomes inconsistent with experimental data. Depending on temperature
garnet transforms to a mixture of ~-spinel and stishovite, which transforms to il-
menite and then to perovskite with a pressure increase, or garnet transforms di-
rectly to ilmenite and then to perovskite with a pressure increase, or garnet trans-
forms directly to perovskite. When adding other components in the Mg0-Si02
system such as Alz0 3 or FeO garnet solid solutions have cubic structures. How-
ever, in the pure MgSi03 system a garnet with cubic structure was not found.
2.5
The Fe-Mg-Si-0 System
Magnesiowustite solid solutions in equilibrium with iron were studied for different
temperatures and oxygen fugacities ifo 2) by Hahn and Muan [62HAHIMUA], Ka-
tsura and Kimura [65KATIKIM], Simons [80SIM], Srecec et al. [87SRE/END].
These data, obtained at 1 bar, show how the total iron and Fe+3 contents in magne-
siowustite depend on oxygen fugacity and temperature. Hahn and Muan [62HAW
MUA] estimated the uncertainty of composition determination as ± 1.5 mol per
cent at low FeO contents and ± 3 mol. per cent at high FeO contents. Brynestad
and Flood [58BRY/FLO], Katsura and Kimura [65KATIKIM], and Speidel
[67SPE] for temperatures at 1673, 1433 and 1573 K studied the complete phase
diagram of the Fe-Mg-0 system at various oxygen fugacities, respectively. Ex-
perimental data are the bulk compositions along lines of equal oxygen fugacity in
The Fe-Mg-Si-0 System 13
the stability fields of magnesiowustite, magnesiowustite + magnesioferrite, mag-

nesioferrite, and hematite + magnesioferrite. The uncertainty of such experiments
was estimated by Speidel [67SPE] as ± 3 K in temperature, ± 0.05 in log fo 2 ,
± 0.15 wt per cent for oxide components. The elastic properties of wustite and
magnesiowustite were studied by different methods (see [89RICIMAO]), because
of geophysical importance of magnesiowustite.
Nafziger and Muan [67NAFIMUA], Wiser and Wood [91WIS/WOO] and Fei
et al. [91FEI/MAO] studied the exchange reaction olivine + magnesiowustite at
pressures between 1 bar and 9 GPa. Phase equilibria and electrochemical data
show deviations from ideality in magnesiowustite ([67NAF/MUA], [87SRE/
END], [91FEI/MAO]).
The Fe-Mg exchange reaction between olivine and pyroxene and the divariant
equilibrium olivine+ pyroxene+ silica were studied experimentally at different P,
T, X conditions by Nafziger and Muan [67NAFIMUA], Matsui and Nishizawa
[74MAT/NIS], Bohlen and Boettcher [81BOH/BOE], Koch-Muller et al.
[92KOC/CEM] and von Seckendorff and O'Neill [93SEC/ONE] at pressure be-
tween 1 bar and 3 GPa. The uncertainties in composition determinations of olivine
and pyroxene were ± 1.5 mol. per cent [92KOC/CEM].
Phase transformations in the Fe-Mg-Si-0 system at pressures of 10---30 GPa
were studied experimentally by Ringwood and Major [70RINIMAJ], Akimoto
[72AKI], Ito and Yamada [82ITO/YAM], Katsura and Ito [89KATIITO] and Ito
and Takahashi [89ITO/TAK]. Experimental uncertainties under these conditions
were ± 1-1.5 GPa in pressure, ± 75° in temperature, and ± 0.015 in mole frac-
tions. The review of experimental studies was presented by Fabrichnaya [95F AB].
Ringwood and Major [70RIN/MAJ] and Akimoto [72AKI] were the first who
obtained phase diagrams of the Fe2 Si04-Mg2 Si04 system experimentally at tem-
peratures 1273, 1473 K and pressures up to 18 GPa. The phase diagrams of the
FeSi03-MgSi03 system were determined by Akimoto and Syono [70AKI/SYO] at
pressures up to 10 GPa and temperatures 1073 and 1273 K. In both systems for-
mation of solid solutions of ~-spinel andy-spinel were found, which participate in
the univariant equilibium olivine + y-spinel = ~-spinel in the Fe 2Si04-Mg2Si04
system and in the equilibrium pyroxene + y-spinel = ~-spinel + stishovite in the
FeSi03-MgSi03 system. Exchange equilibrium pyroxene + y-spinel at pressures
6-12 GPa was studied by Nishizawa and Akimoto [73NIS/AKI] and exchange
equilibria between magnesiowustite and ~-spinel or y-spinel were studied by Fei et
al. [91FEIIMAO].
Liu ([75aLIU], [76aLIU]) studied the phase relations in the FeSiOrMgSi03
and Fe2Si04-Mg2Si04 systems and obtained solid solutions of perovskite at pres-
sures of 25-30 GPa. Yagi et al. [79YAG/MAO] studied both systems in diamond
anvil cell with laser heating at 1273 K and pressures up to 30 GPa. Yagi et al.
[79YAG/MAO] found univariant reaction y-spine1 + stishovite = perovskite +
magnesiowustite in the system of olivine composition at pressures of 24-25 GPa.

In the system of pyroxene composition two univariant reactions were found at
pressure above 20 GPa, one mentioned above, and another one ilmenite = y-spinel
+ stishovite + perovskite. Ito and Yamada [82ITO/YAM] studied the system of
pyroxene composition in multi anvil high-pressure apparatus at pressure above
20 GPa and 1373 K. The results obtained by Ito and Yamada were in contradiction
with data ofYagi et al. [79YAG/MAO]. They obtained maximal solubility ofFe-
Si03 in perovskite 10 mol per cent, while Yagi et al. [79YAG/MAO] obtained 20
per cent. Ito and Yamada obtained univariant transformations y-spinel + stishovite
= ilmenite + magnesiowustite and ilmenite = perovskite + stishovite + magne-
siowustite, different from those obtained by Yagi et al. [79YAG/MAO]. Accord-
ing to Ito and Yamada [82ITO/YAM] those reactions occur in very narrow pres-
sure ranges. Later Ito and Takahashi [89ITO/TAK] studied system of olivine com-
position and obtained the same reaction as Yagi et al. [79YAG/MAO]. However,
maximal content of FeSi03 in perovskite was in agreement with data of Ito and
Yamada [821TO/YAM], Ito et al. [84ITO/TAK] and Fei et al. [91FEIIMAO].
Recently, new data on the Fe-Mg partition between perovskite and magne-
siowustite (Katsura and Ito [96KATIITO], Martinez et al. (97MARIWAN]) and
on the maximal content of FeSi03 in perovskite (Fei et al. [96FEIIWAN]) have
been published. Fei et al. [96FEI/WAN] claimed that xi;= Fe/(Fe+Mg) in
perovskite changed from 0.064-0.076 at 1473K to 0.119-0.125 at 2013 K. The
new data ofKatsura and Ito [96KAT/ITO] and Martinez eta/. [97MARIWAN] on
K 0 (Pv/Mw) = (xFPve 1xFMw
e
)(xPv
Mg
1xMw)
Mg
disagree with previous studies oflto and Ya-
mada [82ITO/YAM], Ito et al. [84ITO/TAK], Ito and Takahashi [891TO/TAK],
and Fei et al. [91FEI/MAO]. According to the measurements of Katsura and Ito
[96KATliTO] and Martinez eta/. [97MARIWAN] the K 0 value is twice as high as
obtained before by Ito and Yamada [821TO/YAM], Ito et al. [84ITO/TAK], Ito
and Takahashi [89ITO/TAK], and Fei et al. [91FEI/MAO]. The reason for the dis-
agreement between the two groups of experimental data could be attributed to dif-
ferences in experimental and analytical techniques. Data obtained in a diamond
anvil cell (Guyot et al. [88GUY/MAD], Kesson and Fitz Gerald [91KES/FIT])
were less precise; temperature was not measured and the obtained range of K 0
values was wide (from 0.125 to 0.5).
Kato [86KAT] studied the FeSiOrMgSi03 system at pressure of 20 GPa and
temperature up to 2473 K and obtained stability fields of garnet phase with cubic
and tetragonal structures. Ohtani et al. [910HT/KAG] studied the phase relations
in this system at 2073 K and pressures up to 25 GPa and only tetragonal garnet
was found. Ohtani et al. [910HT/KAG] determined phase compositions in equi-
libria garnet + y-spinel + stishovite and garnet + pyroxene. The univariant reaction
pyroxene + y-spinel + stishovite = garnet was obtained at pressure of 16 GPa.
2.6
The Al203-Si02 System
The principal phases in the A}z03-Si02 system are the A}zSi0 5 polymorphs (anda-
lusite, sillimanite, kyanite) and mullite. Mullite is a stable phase at 1 atm. It exhib-
its a range of composition between 3A}z03 • 2Si02 and 2A}z03 • 3Si02 • Data on po-
lymorphic transformations in the A}zSi0 5 are available in studies of Newton
([66aNEW], [66bNEW], [69NEW]), Althaus [67ALT], Richardson et a/.
[69RlC/GIL] and Holdaway [71HOL]. Review of experimental studies is pre-
sented in a book by Kerrik [90KER]. The transformation of sillimanite to kyanite
was reinvestigated by Bohlen eta/. [91BOH/MON] and a curvature in the bound-
ary was indicated at 873-1273 K. This was the result of increasing aluminum and
silicon disorder in sillimanite with temperature. The triple point was determined at
0.42 GPa and 803 K. Metastable decomposition of kyanite and andalusite to a
mixture of corundum and quartz was studied by Harlov and Newton [93HAR/
NEW] in presence of H20 flux. Liu [74LIU] found that kyanite decomposed to
stishovite and corundum at pressures about 14 GPa. Later this reaction was studied
by Irifune et a/. [95IR1/KUR] and phase boundary was described by equation
P(GPa) = 11.9 + 0.0008-T (K). According to measurements of Schmidt et a/.
[97SCHIPOL] decomposition of kyanite occured at 14 GPa and 1273 K and at
17.5 GPa and 2273 K.
2.7
The FAS (FeO-Al203-Si02) System
Principal phases in the Fe0-Al20 3-Si02 (FAS) system are hercynite FeA}z04
(structure of spinel), almandine Fe3AhSh012 (garnet), pyroxene FeSiOrA120 3,
ferrocordierite Fe2A4Si 50 18 , and fayalite Fe2Si04 •
The reactions between stoichiometric phases in the FAS system were experi-
mentally studied. Shulters and Bohlen [89SHU/BOH] studied equilibrium her-
cynite + sillimanite = almandine + A}z0 3 in a piston-cylinder apparatus at 850-
1100 °C and pressures 0.7-1.2 GPa. The equilibrium hercynite +quartz= alman-
dine+ sillimanite was studied by Bohlen eta/. [86BOHIDOL] in piston-cylinder
apparatus at temperatures 880-1030 °C and pressures 0.52-0.88 GPa. Muk-
hopadhyay and Holdaway [94MUKIHOL] studied the reaction Fe-cordierite = ~
quartz + almandine + sillimanite. The equilibrium kyanite + magnetite + ~-quartz
= almandine + 0 2 buffered to magnetite + hematite oxygen fugacity was studied
by Harlow and Newton [92HAR/NEW] at 650-900 °C and pressures of2-3 GPa.
The alumina content in orthopyroxene in equilibrium with garnet was experi-
mentally studied by Kawasaki and Matsui [83KAWIMAT] at 5 GPa and by Ara-
novich and Berman (97ARAIBER]) at 1123-1373 K and pressures of 1-2 GPa.
The univariant reaction pyroxene = almandine + fayalite + quartz determining the

lower stability limit for orthopyroxene was studied by Aranovich and Berman
[97 ARAIBER]. The new data of Aranovich and Berman [97 ARAIBER] indicate
significantly lower A}z03 solubility in orthopyroxene in Fe-bearing system com-
pared with Mg-system.
The Fe4S40 1rFe3AlzSh0 12 * (Fs-Alm) system at pressures from 6 to 11 GPa
was experimentally studied by Akaogi and Akimoto [77AKA/AKI]. Phase rela-
tions in this join are simpler than ones in the enstatite-pyrope join, described be-
low. Phases with ~-spinel, ilmenite and perovskite structure are not found in the
Fs-Alm join. Kesson et al. [95K.ES/FIT] found that at ~60 GPa the products of
almandine disproportionation were wustite, stishovite and FeA}z04 (Ca-ferrite
structure) or wustite, stishovite and corundum. Akaogi et al. [98AKA/OHM]
found that almandine decomposed to a mixture of oxides at 21-22 GPa in the tem-
perature range 1473-1873 K.
The experimental uncertainty in the end-member systems due to errors in tem-
perature and composition measurements are high under the conditions of transition
zone. The DAC technique makes it possible to study phase relations at pressures
of the lower mantle. Kesson et al. [95K.ES/FIT] estimated the uncertainty of pres-
sure measurement at 50-70 GPa to be 5-10 GPa. They did not try to measure the
temperature, because short-term fluctuations in sample temperature could exceed
1000 °C.
2.8
The MAS (MgO-Al203-Si02) System
Fawset and Yoder [66FAWNOD], Herzberg [83HER] and Seifert [74SEI] have
studied phase equilibria in the Mg0-Alz0 3-Si02 (MAS) system at pressures up to
0.5 GPa. They have determined the univariant transformation of anhydrous Mg-
cordierite to orthoenstatite +quartz at pressures of0.2-0.3 GPa. At moderate pres-
sures orthoenstatite was found to contain Alz03 forming solid solutions. McGregor
[74MCG] carried out an extensive study of the MAS system in the range 900-
1800 °C and 0.5-4 GPa. This study provided data on univariant boundary and or-
thopyroxene composition in spinel and garnet peridotite phase assemblages. The
data of McGregor [74MCG] required pressure correction, for more accurate de-
termination it was necessary to use frictionless NaCl assemblies. Gasparik and
Newton [84GAS/NEW] studied the composition of pyroxene in equilibrium with
spinel and forsterite at 1030-1600 °C and 1.0-2.8 GPa. It was shown that alumina
* The Fs-Alm join is an abbreviation used in original papers concerning the

composition of the system Fe4 S40 12-Fe3AlzSh0 12 . The end members of the garnet
s.s. are garnet (Fe4 Si40 12 ) and almandine.
The MAS (MgO-Al20rSi02) System 17
solubility is practically independent of pressure. They also found that at 1123 K

and pressure of 1.625 GPa a univariant reaction between spinel and garnet peri-
dotite field was terminated by the breakdown of pyrope to orthopyroxene and co-
rundum. The alumina contents of orthopyroxene coexisting with pyrope were first
determined by Boyd and England [64BOY/ENG] and later by McGregor
[74MCG]. However, the compositions obtained by McGregor could not be con-
sidered as reversed. Lane and Ganguly [80LAN/GAN] and Perkins et al.
[81PERIHOL] obtained true reversals. Perkins et al. [81PER!HOL] studied Alz03
content in orthopyroxene being in equilibrium with garnet at temperatures of
1173-1873 K and pressures of 2-4 GPa. Kawasaki and Matsui [83KAWIMA T]
studied this equilibrium at 5 GPa. It was shown that the Alz03 content in orthopy-
roxene in equilibrium with garnet decreases with the pressure increase. MacGre-
gor [74MCG] studied univariant reaction separating spinel and garnet peridotite
fields. Within the temperature range of experiment ( 1000-1700 °C) the boundary
was approximated by a straight line. Danckwerth and Newton [78DAN/NEW]
studied the same univariant reaction at temperatures between 900 and 11 00 oc and
found the boundary is curved reaching pressure minimum. The compositions of
orthopyroxene in equilibrium with forsterite and spinel were determined hydro-
thermally at 950, 1000 and 1080 °C and 2 GPa.
Ringwood and Major [66RlN/MAJ] studied the solubility ofM~Si4 0 12 in gar-
net at high pressures and they found that it increased with pressure. Phase relations
in the Mg4 Si40 12-Mg3AlzSh0 12 (En-Py)* system at 1273 K were investigated by
Akaogi and Akimoto [77AKA/AKl] and Liu [77aLIU]. The maximal solubility of
Mg4Si40 12 in garnet is reached at the pressure where enstatite decomposes to a
mixture of P-spinel and stishovite (St). At higher pressures garnet is in equilibria
with 13-spinel + St and y-spinel + St phases and the solubility of M~Si40 12 in gar-
net decreases with pressure. Liu [77aLIU] obtained phases with ilmenite and
perovskite structure in the En-Py join at pressures of 24 and 30 GPa, respectively.
Data ofLiu [77aLIU] obtained in a laser-heated diamond cell have mainly qualita-
tive character, because they are poorly defined.
The En-Py join was studied again by Kanzaki [87KAN], ten years after Akaogi
and Akimoto [77 AKA/AKl]. There are inconsistencies in maximal solubility of
Mg4 Si40 12 in garnet between different experimental studies (75 mol. per cent- Liu
[75aLIU]; 60 mol. per cent- Akaogi and Akimoto [77AKA/AKl]; 83 mol. per
cent - Kanzaki [87KAN]). According to Kanzaki [87KAN] the maximal solubility
of the Mg4 S40 12 in garnet in equilibria Gar + P + St and Gar + '{ + St did not
change significantly with pressure. Liu [77bLIU] synthesized a series of ilmenite
*The En-Py join is an abbreviation used in original papers concerning the composition of
the system M~Si40 12 -Mg3 AlzSi0 12 . End members of garnet are pyrope and garnet
(M~Si 4 0 12 ) (or majorite ).
solid solutions in the composition range between M~S40 12 and pyrope. It was
shown that ilmenite had non-zero volume of mixing, since linear extrapolation to
Alz0 3 composition gave larger volume than for corundum. Liu [75bLIU] found
that spinel MgAlz04 decomposed to mixture ofMgO and Alz03 at pressures below
18 GPa.
Liu [77aLIU] and Kanzaki [87KAN] studied the En-Py system at 1273 K and
found Gar + Ilm loop up to pyrope composition at 20-24 GPa. At higher pressures
Liu [77aLIU] indicated Ilm + Pv equilibrium. These two loops did not seem to in-
tersect each other. Irifune and Ringwood [87aiRIIRIN] studied the En-Py join at
1773 K and at pressures higher than 20 GPa and found a univariant transition Gar
+ Pv = Ilm at a pressure of 24.5 GPa, being the result of intersection of Gar + Ilm
and Ilm + Pv loops. Possibly, the difference in phase relations obtained by Liu
[77aLIU] and Irifune and Ringwood [87aiRIIRIN] is caused by the difference in
temperature. At both temperatures garnet was enriched in Alz03 more than ilmen-
ite and ilmenite more than perovskite:
There is still argument whether garnet or ilmenite of pyrope composition trans-

forms directly to perovskite. Liu [77bLIU] claimed that pyrope transformed to il-
menite and then to perovskite with a pressure increase. Recent studies in the En-
Alz03 system in multi-anvil apparatus by Irifune et al. [96IRI/KOI] did not indi-
cate the direct transition of garnet to perovskite in pyrope composition at a pres-
sure of ~30 GPa. They showed that garnet decomposed to a mixture ofperovskite
and corundum solid solution with maximum content of the MgSi03 ~30 mol. per
cent at 1773 K and 27 GPa. This conclusion was also confmned by experiments of
Yagi et al. [97YAG/ONE].
Experiments at a pressure of 60 GPa are quite contradictory. Kesson et al.
[95KES/FIT] showed that perovskite of pyrope composition was stable at ~0 GPa
in diamond anvil cell (DAC). According to experiments of Yagi et al. [97YAG/
ONE], perovskite and corundum coexist at 60 GPa. Serghiou et al. [98SER/ZER]
found that at 2500 K a small amount of Alz03 coexisted with perovskite up to
43 GPa, but at higher pressure the entire Alz03 content of pyrope starting material
was accommodated in the perovskite structure. The studies of Ahmed-Zaid and
Madon ([91AHMIMAD], [95AHMIMAD]) showed that pyrope decomposed at a
pressure of 40 GPa forming silicate perovskite and either MgAlzSi06 or AlzSi05
(high pressure polymorph) depending on temperature. Ito and Takahashi [87ITO/
TAK] and Takahashi and Ito [87TAK/ITO] reported the presence of an unknown
aluminous phase in synthetic basalt and natural peridotite. Irifune et al. [96IRIIKOI]
proposed that this Al-rich silicate, also reported by Ahmed-Zaid and Madon
[95AHMIMAD], was a corundum solid solution MgSiOrAlz03.
The FMAS (FeO-MgO-Al20rSi02) System 19
2.9
The FMAS (FeO-MgO-Al203-Si02) System
The Fe-Mg exchange equilibrium between olivine and pyroxene was studied by
Kawasaki and Matsui [77KAW/MAT] at 1373 K and 5 GPa, O'Neill and Wood
[790NE/WOO] at 1273-1400 K and 3 GPa, and by Hackler and Wood
[89HAC/WOO] at 1273 K and 0.91 GPa. O'Neill and Wood [790NE/WOO]
made mainly synthetic experiments and the results were presented only graphi-
cally. Data of Hackler and Wood are more precise than obtained in previous
studies ([77KAW /MAT], [790NE/WOO]) and they are in a good agreement
with previous studies.
Jamieson and Roeder [84JAMIROE] studied Fe-Mg partition between spinel and
olivine in presence of metallic iron at 1 atm and 1573 K. It was shown that K0 for
olivine-spinel equilibrium was close to 1 and slightly dependent on composition.
The equilibrium between orthopyroxene and garnet was experimentally studied
by Kawasaki and Matsui [83KAW/MAT] at temperatures of 1373 and 1573 K and at
a pressure of 5 GPa, by Lee and Ganguly [88LEE/GAN] at temperatures of 1252-
1578 K and at pressures of 2-4.5 GPa and by Eckert and Bohlen [92ECKIBOH] at
temperatures of 1173-1373 K and at a pressure of2.2 GPa. Harley [84HAR] studied
orthopyroxene + garnet + quartz equilibrium at pressures of 1-2 GPa and tempera-
tures of 1173-1423 K. Several runs in Kawasaki and Matsui [83KAWIMA T] were
synthesis type experiments, which are not reliable enough. The Alz03 content in or-
thopyroxene at 5 GPa was small and decreased with iron enriched or temperature
decreased. The uncertainty in alumina content was large against the measured values.
Berman and Aranovich [96BER/ARA] criticized the data of Harley [84HAR], in
cases Fe capsules were used in experiments, since Fe participate in the reaction. A
PbO+PbF2 flux was used to accelerate reaction in Lee and Ganguly [88LEE/GAN]
and there is no data on heterogeneity. The data of Lee and Ganguly are mutually
consistent within ± 0.01 compositional uncertainty. Eckert and Bohlen
[92ECKIBOH] did not use any flux except in one run, where H 20 was used. The
data of Eckert and Bohlen are mutually consistent.
Gasparik [89GAS] studied the equilibrium orthopyroxene + olivine + spinel at
temperature 1613 K and pressures of 1.1 and 1.8 GPa. It was found that Al-
content of orthopyroxene slightly increased with increasing of Fe-content. The
range of the bulk Fe/(Fe+Mg) ratio producing the assemblage Opx + 01 + Sp is
limited at 1.1 GPa by melting and at 1.8 GPa by the appearance of garnet in the
assemblage 01 + Sp + Gar. At 1.8 GPa and iron-rich composition about 0.5 in
Fe/(Fe+Mg) Gasparik obtained the olivine + garnet + spinel phase assemblage,
which seem not to be in equilibrium.
In the pure Fe0-Mg0-Alz03-Si0 2 system, the equilibrium between perovskite
and magnesiowustite was the only one studied experimentally by Wood and Rubie
[96WOO/RUB]. The mixtures studied in the experiments of Akaogi and Akimoto

[79AKA/AKI], Irifune et al. [86IRI/SEC], lrifune and Ringwood ([87aiRIIRIN],
[87b IRIIRIN]), Irifune ([87IRI], [941RI]), and Bertka and Fei [97BER/FEI] con-
tained significant amounts of Ca and other elements. Akaogi and Akimoto
[79AKA/AKI] carried out phase equilibrium experiments on natural and synthetic
garnet lherzolite at 1473 K and pressures up to 20.5 GPa and examined partition
of elements among coexisting phases. Irifune et al. [86IRI/SEC], Irifune ([871RI],
[94IRI]) and Irifune and Ringwood ([87aiRIIRIN], [87biRIIRIN]) studied compo-
sitions modeling such rocks as pyrolite, harzburgite, eclogite and primitive MORB
(middle oceanic ridge basalt). The obtained data demonstrate element partitioning
mainly between garnet and pyroxene. There are few data on the assemblages Gar
+ ~ + St, Gar+ y+ St, Gar+ lim and Gar+ Pv. Irifune et al. [86IRIIRIN] studied
phase transitions in synthetic pyrolite at pressures between 23 and 28 GPa and at
temperatures between 1773 and 1873 K and found the following sequence of
phase transformations:
y+Gar+Ca-Pv y+Gar+Mw+Mg-Pv+Ca-Pv
23 GPa, 1773 K 24 GPa, 1773 K
~ Gar+Mg-Pv+Mw+Ca-Pv Mg-Pv+Mw+Ca-Pv
25 GPa, 1773 K 28 GPa, 1873 K
The presence of Ah03 in the studied mixtures was found to influence the Fe-Mg
partition between perovskite and magnesiowustite; the Fe/(Fe+Mg) ratio was al-
most the same in coexisting perovskite and magnesiowustite. In the Fe0-Mg0-
Si02 system, there was a strong Fe enrichment in magnesiowustite (see [84ITO/
TAK], [91FEI/MAO], [97MARIWAN]). The effect of Ah0 3 was confirmed by
Wood and Rubie [96WOO/RUB] who studied the Mw + Pv equilibrium in the
FMAS system.
Bertka and Fei [97BER/FEI] studied phase transformations in the composition
corresponding to Martian mantle, which had higher Fe and lower AI content than
pyrolite. For the bulk composition 3.13 weight % of Ah03 and mol. ratio of
Fe/(Fe+Mg)=0.24, magnesiowustite coexisting with perovskite was enriched in
iron. The Fe/(Fe+Mg) ratio was 0.165 in perovskite and 0.5 in magnesiowustite. It
is not clear whether this result is contradictory with data of Wood and Rubie
[96WOO/RUB] or it is a consequence of the difference in compositions.
Another important question is about the upper limit of garnet stability. O'Neill
and Jeanloz [940NE/JEA] found that 4 mol. per cent of FeO makes garnet more
stable and that it could coexist with aluminous perovskite up to a pressure of
The FMAS (FeO-Mg0-AhOrSi0 2) System 21
50 GPa. Kesson et a!. [94KES/FIT] claimed that garnet should disappear above 35 GPa.
Kesson et al. [95KES/FIT] studied the pyrope-almandine join at 55-70 GPa and
found only perovskite to be stable for mixtures containing from 0 to 50 per cent of
almandine. For Alm 0 .75 Py 0 _25 composition a mixture of perovskite and stishovite
was stable.
Table 2.1. Phase equilibrium measurements at high pressure and temperature in the system
Si0 2, Mg2Si04, MgSi0 3, Fe2Si04 and FeSi0 3.
Range T, K P(GPa)= A+ B· T(K) Ref.
System Si0 2
l. Quartz = Coesite
1073-1273 1.85 + 0.00 1-T [79AKE]
873-1653 1.8 + 0.00099· T [80MIR/MAS]
623-1273 1.944 + 0.00079· T [82BOH/BOE]
1273-1673 1.592 + 0.00111-T [84KOS/ISH]
2. Coesite = Stishovite
800-1400 7.7+0.0011-T [76YAG/AKI]
873-1473 6.854 + 0.002· T [77SUI]
2273-3073 5.0356 + 0.0028· T [93ZHA/LIE]
1273-1803 5.3902 + 0.0026·T [96ZHAILI]
2603-2903 7.727 + 0.001-T [95SER/ZER]
System Mg2Si04
Olivine= ~-Spinel
1073-1573 9.8 + 0.0035-T [77SUI]
1073-1573 5.7 + 0.0058-T [77KAW]
1073-1873 8.3172 + 0.0036· T [94MOR/KAT]
1473-1873 10.3175 +0.0025-T [89KAT/ITO]
2513 16.5 [90GAS]
~ -Spinel = y -Spinel
1073-1473 10 + 0.0055-T [77SUI]
1073-1373 7 + 0.0103-T [77KAW]
1473-1873 11.635 + 0.005-T [89KAT/ITO]
1373-1873 7.8 + 0.0063· T [87SAW]
y -Spinel= Perovskite + MgO
1273-1873 28.3644- 0.0028· T [89ITO/T AK]
1873 21.1 [98IRI/NIS]
Table 2.1 (continued)
Range T,K P(GPa)= A + B· T{K) Ref.
System Fe2Si04
Olivine = y -Spinel
1073-1793 0.9991 + 0.0033-T [67AKI/KOM]
1073-1793 2.7775 + 0.0025·T [77AKI/YAG]
1793 7 [790HT]
1073-1473 2.0675 + 0.0025· T [87YAG/AKA]
y-Spinel = FeO + Stishovite
1273-2473 18.727 -0.001·T [790HT]
System MgSi03
Clinoenst = ~-Spinel + Stishovite
1473-1920 7.4 + 0.005·T [87SAW]
1673 16.5 [90GAS]
Clinoenst = Gamet
1920-2373 14 + 0.0015·T [87SAW]
2423 16.5 [90GAS]
Gamet = ~-Spinel + Stishovite
1920-2090 -20.2 + 0.019·T [87SAW]
1873 17.5 [90GAS]
y-Spinel + Stishovite = Ilmenite
1473-1880 22.5- 0.0015·T [87SAW]
1273 19 [87KAN]
1373 19.5 [85ITO/NAV]
Gamet = Ilmenite
2090-2330 -2.8 + 0.011·T [87SAW]
2303 21.9 [90GAS]
Ilmenite = Perovskite
1473-2330 28.9 - 0.0026· T [87SAW]
1773 23 [871RIIRIN]
1273-1873 27.4825- 0.0025-T [89ITO/TAK]
Gamet = Perovskite
2673 22.4 [90GAS]
2303 22 [90GAS]
2330 22.8 [87SAW]
The FMAS (Fe0-Mg0-Ah03-Si02) System 23
Range T, K P(GPa)= A+ B·]lK) Ref.
System FeSi0 3
Olivine+ a-Quartz= Ferrosilite
973-1123 0.077 + O.OOI·T [80BOHIBOE]
1073 1.22 [93KOC/CEM]
1173 1.34 [93KOC/CEM]
Olivine+ ~-Quartz= Ferrosilite
1173-1323 --0.4604 + 0.0014667-T [80BOHIBOE]
1223 1.42 [93KOC/CEM]
1273 1.51 [93KOC/CEM]
Ferrosilite = y-Spinel + Stishovite
1073-1473 6.2448 + 0.0024· T [70AK1/SYO]
Chapter 3
Thermodynamic Data for Stoichiometric Phases and
End Members of Solid Solutions
3.1
Introduction
This chapter presents information for phases with constant composition

and end-members of solid solutions. For each compound calculated ther-
modynamic parameters and volumetric data are presented. The tables of
thermodynamic data contain information about heat capacity, entropy, en-
thalpy function J1.~ 98 Ho IT, Gibbs energy function -{G0 rJ-10 29s)/T, enthalpy
and Gibbs energy of formation from elements at atmospheric pressure and
temperature range 298-1800 K.
Tables of volumetric data contain information important for geophysics.
Data on volume, thermal expansion, compressibility, (temperature depend-
ence at 1 bar and calculated values at high pressure and temperature), pres-
sure and temperature derivatives of bulk modulus at 1 bar and sound wave
velocities at 1 bar and 298 K are presented. Comments to tables contain re-
view of available experimental information on thermodynamic values and
equation of state parameters.
3.2
Data for Compounds
Equation of state and thermochemical data tables are provided here for
mineral substances and for solid solution components (end members) and
are followed by comments.
26 Thermodynamic Data for Stoichiometric Phases ...
Table 3.1.1.1. Thermophysical and thermochemical data for a-quartz, Si02 •
a-quartz is metastable above 848 K Molar mass: 60.085 g/mol
T Cp s A~98 H' jT -(GrH298)/T l:!.rlfo l:!.tf}o

K J/(mol·K) J/(mol·K) J/(mol-K) J/(mol·K) kJ/mol kJ/mol
298.15 44.589 41.460 0.0 41.460 -910.700 -856.283

300.00 44.779 41.736 0.283 41.461 -910.707 -855.945
350.00 49.393 48.997 6.980 42.017 -910.856 -846.804
400.00 53.268 55.852 12.530 43.322 -910.869 -837.651
450.00 56.646 62.325 17.248 45.078 -910.762 -828.504
500.00 59.676 68.453 21.342 47.111 -910.552 -819.374
550.00 62.453 74.273 24.954 49.318 -910.246 -810.271
600.00 65.042 79.819 28.188 51.631 -909.852 -80l.l99
650.00 67.487 85.123 3l.ll8 54.004 -909.373 -792.163
700.00 69.821 90.210 33.800 56.410 -908.811 -783.168
750.00 72.070 95.104 36.277 58.828 -908.169 -774.215
800.00 74.251 99.820 38.582 61.243 -907.448 -765.308
848.00 76.296 104.210 40.659 63.551 -906.682 -756.803
848.00 68.134 105.206 41.654 63.552 -905.838 -756.801
850.00 68.157 105.367 41.717 63.650 -905.821 -756.450
900.00 68.721 109.282 43.202 66.077 -905.393 -747.676
950.00 69.247 113.009 44.559 68.450 -904.964 -738.925
1000.00 69.738 116.573 45.806 70.767 -904.535 -730.198
1100.00 70.631 123.263 48.023 75.240 -903.675 -712.806
1200.00 71.421 129.443 49.940 79.503 -902.819 -695.492
1300.00 72.127 135.188 51.620 83.568 -901.968 -678.249
1400.00 72.762 140.557 53.108 87.449 -90l.l25 -661.071
1500.00 73.338 145.597 54.438 9l.l59 -900.294 -643.954
1600.00 73.864 150.347 55.636 94.711 -899.476 -626.891
1700.00 74.349 154.840 56.722 98.117 -948.854 -609.492
1800.00 74.797 159.102 57.714 101.388 -947.841 -589.559
/).298
0
Ho = 6.916 ±0.02 kJ/mol Molar volume= 2.2688 ±0.0001 J/(bar·mol)
Transition in phase: a =~ Transition in reference state element
Ttrs = 848 K, ll! H' = 0.840 kJ/mol Silicon: Trus = 1690 K
Equations:
Cp= 81.1447 + 0.01828-T- 1.80986·105·T"2 + 5.4058·10-6 ·T 2 - 698.458·T--1J.s
(Valid range 298.15-848 K) [J/(K-mol)]
Cp= 78.812 + 0.001205·T- 1.731·105T-2 + 1.202·108 -T-3 - 12130·T"1
(Valid range 848-1800 K) [J/(K-mol)]
Thermodynamic Data for Stoichiometric Phases ... 27
Table 3.1.1.2. Equation of state for a-quartz, Si02•
a= 2.7513·10· 5 + 2.9868·10-8 -T + 5.5722·10·6-r- 1 + 9.1181·10·2 -r-2

Vo,298 = 22.688
fJ= 2.556·10· 11 + 1.1557-I0- 16 -T + 1.013·10-21 · T 2 + 8.89·10-241 3
K'=6.4
Volume, cm3/mol
P,GPa 1·10"4 2 5 10 20
T,K
298.15 22.688 22.156 21.702 20.637 19.406 17.836
500 22.872 22.335 21.877 20.803 19.561 17.978
1000 23.452 22.901 22.430 21.327 20.052 18.428
1500 24.226 23.655 23.167 22.025 20.707 19.027
2000 25.212 24.616 24.107 22.916 21.541 19.791
Thermal expansion, t»106, K 1
P,GPa 1·104 2 5 10 20
T,K
298.15 37.46 36.88 36.83 36.64 36.62 36.00
500 42.82 42.76 42.67 42.57 42.26 42.27
1000 57.48 57.39 57.25 57.02 56.94 56.66
1500 72.36 72.21 72.08 71.83 71.64 71.33
2000 87.27 87.09 87.01 86.81 86.32 86.17
Bulk modulus, GPa
P,GPa 1·104 2 5 10 20
T,K
298.15 39.07 45.47 51.87 71.07 103,07 167.o7
500 39.03 45.43 51.83 71.03 103,03 167.03
1000 38.93 45.33 51.73 70.93 102.93 166.93
1500 38.8 45.21 51.61 70.81 102.81 166.81
2000 38.66 45.06 51.46 70.66 102.66 166.66
(iJKp()1)p
P,GPa 1·1 04 P,GPa 1·10"4

T,K T,K
298.15 -0.0002 1000 -0.0002

500 -0.0002 1500 -0.0003
2000 -0.0003
Vp= 6.067, V,=4.11

Table 3.1.2.1. Thermophysical and thermochemical data for ~-quartz, Si0 2•
~-quartz is stable at 848-1142 K. Molar mass: 60.085 g/mol
T Cp s /!,.~9sw jr -(GrH298)/T /!,.fH 0 !!,.rGO
K J/(mol·K) J/(mol-K) J/(mol-K) J/(mol-K) kJ/mol kJ/mol
298.15 44.589 41.700 0.000 41.700 -910.495 -856.151

300.00 44.779 41.976 0.283 41.701 -910.503 -855.814
350.00 49.393 49.2373 6.980 42.257 -910.655 -846.685
400.00 53.268 56.0923 12.530 43.562 -910.666 -837.544
450.00 56.646 62.5654 17.248 45.317 -910.559 -828.409
500.00 59.676 68.6931 21.342 47.351 -910.349 -819.291
550.00 62.453 74.5128 24.955 49.558 -910.044 -810.200
600.00 65.042 80.0591 28.188 51.871 -909.649 -801.140
650.00 67.486 85.3626 31.118 54.244 -909.170 -792.116
700.00 69.821 90.450 33.800 56.650 -908.608 -783.133
750.00 72.070 95.344 36.277 59.068 -907.966 -774.192
800.00 74.251 100.065 38.582 61.483 -907.245 -765.297
847.99 76.296 104.450 40.659 63.791 -906.479 -756.804
848.00 68.134 105.446 41.654 63.792 -905.635 -756.802
850.00 68.157 105.607 41.717 63.890 -905.618 -756.451
900.00 68.721 109.519 43.202 66.317 -905.190 -747.689
950.00 69.246 113.249 44.559 68.690 -904.761 -738.950
1000.00 69.738 116.813 45.806 71.008 -904.332 -730.235
1100.00 70.631 123.503 48.023 75.480 -903.472 -712.867
1200.00 71.421 129.683 49.940 79.743 -902.616 -695.577
1300.00 72.127 135.428 51.620 83.808 -901.765 -678.358
1400.00 72.762 140.797 53.108 87.689 -900.922 -661.204
1500.00 73.338 145.837 54.438 91.400 -900.091 -644.111
1600.00 73.864 150.587 55.636 94.951 -899.273 -627.072
1700.00 74.349 155.080 56.722 98.357 -948.652 -609.697
1800.00 74.797 159.342 57.714 101.628 -947.638 -589.788
L1~98 H" = 6.916 kJ/mol Molar volume= 2.28755 ±0.0001 J/(bar·mol)

Transition in phase: a= ~ Transition in reference state element
Ttrs = 848 K, f1!H" = 0.840 kJ/mol Silicon: Trus =1690 K
Equations:
Cp = 81.1447 + 0.01828-T- 1.80986·10 51"2 + 5.4058·10·6·T 3 - 698.458-T""-O.s
Cp = 78.812 + 0.001205· T - 1.731·105·r-2 + 1.202·108 · r- 3 - 12130·T .J
Table 3.1.2.2. Equation of state for ~-quartz, Si02 •
a= 2.0604·10' 5 + 3.4694·10·8 -T+ 1.3075-104 - r-'- 1.6376·T-2

Vo,298 = 22.8755
P= 1.39699·10·" + 2.41181-10' 14 -T- 2.1518·I0' 17 -T 2 + 6.4543-10'2 'r 3
K' = 5.346
Volume, cm 3/mol
P,GPa 1-104 2
T,K
298.15 22.876 22.457 22.081
500 23.0 22.523 22.113
1000 23.5 22.987 22.542
1500 24.2 23.712 23.245
2000 25.2 24.597 24.042
Thermal expansion, a106, K 1
P,GPa 1·1 04 2
T,K
298.15 12.96 7.83 4.29
500 31.66 23.31 16.46
1000 53.79 54.05 54.17
1500 72.00 68.66 66.08
2000 89.65 77.29 67.65
Bulk modulus, GPa
P,GPa 1-10'4 2
T,K
298.15 51.50 56.85 62.19
500 46.61 51.96 57.30
1000 43.43 48.78 54.12
1500 42.52 47.87 53.21
2000 36.01 41.36 46.70
(fJKrliJ1)p
P,GPa 1·1 04 P,GPa 1·104

T,K T,K
298.15 -0.0345 1000 -0.0008

500 -0.0162 1500 -0.0057
2000 -0.0201
Table 3.1.3.1. Thermophysical and thermochemical data for tridymite, Si02•
Tridymite is stable at 1140-1743 K, a-~ transformation at 623 K

Molar mass: 60.085 g/mol
T Cp s 1!.~9sW/T -(GrHz9s)IT !!.rHO !l{;o

K J/(mol·K) J/(mol-K) J/(mo1-K) J/(mo1-K) kJ/mo1 kJ/mo1
298.15 44.254 45.116 0.000 45.116 -906.913 -853.585

300.00 44.558 45.391 0.283 45.117 -906.920 -853.254
350.00 51.096 52.788 7.110 45.678 -907.025 -844.298
400.00 55.427 59.912 12.896 47.016 -906.936 -835.341
450.00 58.473 66.626 17.800 48.826 -906.727 -826.404
500.00 60.720 72.908 21.985 50.923 -906.443 -817.494
550.00 62.446 78.780 25.588 53.192 -906.111 -808.614
600.00 63.815 84.274 28.719 55.556 -905.747 -799.767
650.00 64.933 89.428 31.463 57.965 -905.362 -790.951
700.00 65.868 94.275 33.888 60.387 -904.963 -782.164
750.00 66.667 98.847 36.047 62.800 -904.554 -773.408
800.00 67.363 103.173 37.983 65.190 -904.140 -764.678
850.00 67.978 107.275 39.730 67.546 -903.723 -755.974
900.00 68.530 11l.l77 41.315 69.862 -903.305 -747.295
950.00 69.031 114.895 42.760 72.135 -902.886 -738.639
1000.00 69.490 118.448 44.086 74.363 -902.468 -730.006
1100.00 70.314 125.111 46.433 78.678 -901.637 -712.800
1200.00 71.041 131.261 48.454 82.806 -900.815 -695.669
1300.00 71.699 136.973 50.217 86.756 -900.004 -678.607
1400.00 72.305 142.309 51.774 90.536 -899.206 -661.606
1500.00 72.870 147.317 53.162 94.156 -898.421 -644.662
1600.00 73.403 152.037 54.410 97.627 -897.650 -627.770
1700.00 73.909 156.503 55.542 100.960 -947.074 -610.539
1800.00 74.392 160.741 56.576 104.165 -946.102 -590.771
1!~ 8 H' = 7.075 ±0.100 kJ/mol Molar volume = 2.653 J/(bar·mol)

Transition in phase: a = ~ Transition in reference state element
Orthorhombic =Hexagonal, 623 K Silicon: Trus = 1690 K
Equation:
Cp = 66.6993 + 5.2779·10·3-T- 2132338-r-2 - 3.54783·10"71 2
(Valid range 298-1800) [J/(K-mol)]

Thermodynamic Data for Stoichiometric Phases . . . 31
Table 3.1.3.2. Equation of state for tridymite, Si02 •
a= 23.4923·10· 5 - 2.40434·10· 7 -r- 10750.00·10·6 -r- 1 + 12.7930·10-2·T"2 (298-623 K)

a= 2.1797-10" 5 - 1.53·10-8 -T (623-1743 K)
Vo.z9s = 26.53 Vo,623 = 27.51
P=4.0·10·11
K' = 6.0 K'pr= o
Volume, cm3/mol
P, GPa 1-10-4
T,K
298.15 26.54 25.60

500 27.14 26.18
1000 27.74 26.76
1500 27.78 26.80
2000 27.71 26.73
Thermal expansion, ~ 106, K 1
P,GPa 1·10"4
T,K
298.15 128.60 128.60

500 93.70 93.70
1000 6.50 7.00
1500 -1.01 -1.13
2000 -9.00 -9.35
Bulk modulus, GPa
P,GPa 1·104
T,K
298.15 25.0 31.0

500 25.0 31.0
1000 25.0 31.0
1500 25.0 31.0
2000 25.0 31.0
32 Thennodynamic Data for Stoichiometric Phases ...
Table 3.1.4.1. Thennophysical and thennochemical data for cristobalite, Si02 •
Cristobalite is stable at 1743-1996 K, a-~ transfonnation at 523 K,

melting point is 1996 K.
T Cp s 1!..~98 H' jr -(GrHz9s)IT !!.rHO !!.t<Jo

298.15 44.299 46.060 0.0 46.060 -906.034 -852.987

300.00 44.780 46.335 0.285 46.063 -906.040 -852.658
350.00 50.296 53.796 7.169 46.628 -906.126 -843.752
400.00 51.040 60.555 12.600 47.955 -906.175 -834.838
450.00 55.552 66.764 17.062 49.702 -906.180 -825.919
500.00 68.328 73.192 21.468 51.724 -905.823 -817.015
523.00 77.680 76.451 23.717 52.735 -905.409 -812.956
523.00 58.252 76.466 23.727 52.739 -905.406 -812.938
550.00 59.779 79.437 25.460 53.977 -905.303 -808.167
600.00 62.081 84.742 28.420 56.322 -905.047 -799.347
650.00 63.873 89.784 31.081 58.703 -904.731 -790.551
700.00 65.295 94.572 33.476 61.096 -904.372 -781.782
750.00 66.445 99.117 35.637 63.480 -903.983 -773.039
800.00 67.389 103.437 37.593 65.844 -903.574 -764.322
850.00 68.176 107.546 39.369 68.177 -903.150 -755.632
900.00 68.841 111.463 40.989 70.474 -902.719 -746.967
950.00 69.409 115.200 42.470 72.730 -902.283 -738.326
1000.00 69.901 118.773 43.830 74.944 -901.845 -729.708
1100.00 70.713 125.475 46.238 79.237 -900.972 -712.536
1200.00 71.361 131.657 48.306 83.351 -900.114 -695.444
1300.00 71.900 137.391 50.100 87.290 -899.277 -678.422
1400.00 72.366 142.736 51.674 91.062 -898.466 -661.464
1500.00 72.782 147.743 53.068 94.676 -897.683 -644.563
1600.00 73.165 152.453 54.312 98.141 -896.928 -627.713
1700.00 73.528 156.900 55.432 101.468 -946.383 -610.522
1800.00 73.878 161.112 56.447 104.665 -945.456 -590.793
/),~ 8 H' = 7.04 ±0.020 kJ/mol Molar volume at 523 K = 2.74 J/(mol·bar)
Transition in phase, a=~; Ttrs = 523 K Transition in reference state element
ftus = 1996 K; l!..ruslf' = 8.92 kJ/mol Silicon: Trus = 1690 K
Equations: Cp = 907.7209- 3.08386-T- 1.971817-107-T-2 + 3.12565·10-3-T 2

Cp = 74.9325- 1.6202·10-3 -T- 4.405322-10 6-r-2 + 9.94385·10-7·T 2
Table 3.1.4.2. Equation of state for cristobalite, Si0 2 •
a= 4.5445·10- 5 + 0.81508·10-7 -T + 441.96·10-6 -r- 1 ( 298.15-533 K)

a= 5.0·10-6 (533-1999 K)
Vo,zgs= 25.740 V0,523= 27.4
P=5.13·10-1 K'=6.0 K'PT=O
Volume, cm3/mol
P, GPa 1·10'4
T,K
298.15 25.74 24.61

500 26.21 25.06
1000 27.50 26.29
1500 27.57 26.36
2000 27.63 26.42
Thermal expansion, tl'106, K 1
P,GPa 1·10'4
T,K
298.15 85.00 89.70

500 95.00 89.70
1000 5.00 2.40
1500 5.00 2.40
2000 5.00 2.40
Bulk modulus, GPa
P,GPa 1·10'4
T,K
298.15 19.493 25.493

500 19.493 25.493
1000 19.493 25.493
1500 19.493 25.493
2000 19.493 25.493
Vp = 5.41, Vs =4.09
Table 3.1.5.1. Thermophysical and thermochemical data for coesite, Si02 •
Coesite is stable at 3-9 GPa Molar mass 60.085 g/mol
T Cp s !1~98 H' jT -(GrH29s)IT ll.tflo !!..tGO

K J/(mol·K) J/(mol·K) J/(mol·K) J/(mol·K) kJ/mol kJ/mol
298.15 43.581 40.600 0.000 40.600 -906.400 -851.726

300.00 43.738 40.870 0.276 40.601 -906.409 -851.387
350.00 48.056 47.938 6.795 41.143 -906.623 -842.198
400.00 51.959 54.616 12.203 42.414 -906.700 -832.988
450.00 55.234 60.932 16.808 44.124 -906.660 -823.775
500.00 57.928 66.895 20.789 46.106 -906.528 -814.572
550.00 60.143 72.523 24.270 48.254 -906.323 -805.385
600.00 61.975 77.838 27.338 50.500 -906.063 -796.220
650.00 63.503 82.860 30.063 52.798 -905.759 -787.079
700.00 64.789 87.615 32.499 55.116 -905.422 -777.962
750.00 65.881 92.123 34.689 57.435 -905.060 -768.870
800.00 66.817 96.406 36.668 59.738 -904.679 -759.803
850.00 67.625 100.481 38.466 62.015 -904.285 -750.760
900.00 68.329 104.367 40.106 64.261 -903.880 -741.741
950.00 68.945 108.078 41.608 66.470 -903.468 -732.745
1000.00 69.490 111.629 42.989 68.640 -903.052 -723.770
1100.00 70.404 118.296 45.441 72.855 -902.215 -705.882
1200.00 71.140 124.455 47.553 76.902 -901.384 -688.071
1300.00 71.744 130.174 49.391 80.783 -900.565 -670.328
1400.00 72.247 135.509 51.006 84.503 -899.768 -652.647
1500.00 72.672 140.509 52.437 88.072 -898.995 -635.023
1600.00 73.035 145.211 53.713 91.498 -898.252 -617.449
1700.00 73.350 149.648 54.859 94.789 -947.722 -599.534
1800.00 73.624 153.849 55.894 97.954 -946.817 -579.079
A~ 8 Ho =6.89kJ Molar volume= 2.064 ±0.001 J/(bar·mol)

Transitions in phase Transition in reference state element
Silicon: Tfus = 1690 K
Equation:
r- r-
Cp = 78.9- 5.065·106 • 2 + 0.825·109• 3 - 1.635·102 -T--{) 5
(Valid range 298-1800 K) [J/(Kmol)]
Table 3.1.5.2. Equation of state for coesite, Si02 •
a= 5.43·10-6 + 7.6·10·4 -T
Vo 298 = 20.64
f3~ 1.05-10- 11 + 1.5·10-15 -T
K' = 8.4
Volume, cm 3/mol
P,GPa 1·10 2 5
T,K
298.15 20.640 20.425 20.229 19.724
500 20.675 20.454 20.253 19.737
1000 20.790 20.554 20.340 19.796
1500 20.946 20.694 20.467 19.894
2000 21.144 20.875 20.634 20.031
Thermal expansion, a10 6, K 1
P,GPa 1·10 2 5
T,K
298.15 7.70 6.27 5.10 2.47
500 9.23 7.82 6.66 4.04
1000 13.03 11.66 10.50 7.92
1500 16.83 15.50 14.35 11.80
2000 20.63 19.34 18.20 15.68
Bulk modulus, GPa
P,GPa 1-10 2 5
T,K
298.15 91.347 99.347 108.347 133.347
500 88.889 97.289 105.689 130.889
1000 83.333 91.733 100.133 125.333
1500 78.431 86.831 95.231 120.431
2000 74.074 82.474 90.874 116.074
(iJKpCJT)p
P,GPa 1·10 P,GPa 1·10

T,K T,K
298.15 -0.0125 1000 -0.0104

500 -0.0119 1500 -0.0092
2000 -0.0082
Vp=8.19, Vs=4.59
Table 3.1.6.1. Thermophysical and thermochemical data for stishovite, Si02 .
Stishovite is stable at pressures above 9 GPa Molar mass: 60.085 g/mol
T Cp s !J.; 98 W /T -(GrHzgs)IT !J_rf!O tJ.tGO
K J/(mol-K) J/(mol-K) J/(mol-K) J/(mol-K) kJ/mol kJ/mol
298.15 42.243 24.642 0.000 24.642 -874.000 -814.567

300.00 42.491 24.904 0.272 24.643 -874.010 -814.198
350.00 48.411 31.917 6.744 25.174 -874.241 -804.208
400.00 53.028 38.696 12.253 26.443 -874.280 -794.199
450.00 56.647 45.159 16.992 28.167 -874.177 -784.194
500.00 59.524 51.282 21.107 30.175 -873.969 -774.206
550.00 61.848 57.068 24.709 32.359 -873.682 -764.243
600.00 63.756 62.534 27.886 34.648 -873.334 -754.309
650.00 65.345 67.701 30.708 36.994 -872.940 -744.406
700.00 66.686 72.594 33.231 39.364 -872.510 -734.535
750.00 67.831 77.235 35.500 41.735 -872.051 -724.695
800.00 68.819 81.645 37.553 44.093 -871.572 -714.887
850.00 69.681 85.844 39.418 46.426 -871.075 -705.110
900.00 70.438 89.849 41.121 48.728 -870.566 -695.362
950.00 71.108 93.675 42.682 50.994 -870.048 -685.642
1000.00 71.707 97.338 44.118 53.220 -869.522 -675.950
1100.00 72.729 104.222 46.674 57.548 -868.459 -656.644
1200.00 73.570 110.587 48.882 61.706 -867.389 -637.436
1300.00 74.276 116.505 50.809 65.696 -866.323 -618.316
1400.00 74.878 122.D32 52.507 69.525 -865.267 -599.278
1500.00 75.397 127.216 54.016 73.200 -864.227 -580.315
1600.00 75.851 132.097 55.367 76.730 -863.207 -561.421
1700.00 76.251 136.708 56.584 80.124 -912.391 -542.204
1800.00 76.607 141.076 57.686 83.390 -911.191 -520.463
/1298
0
Ho = 5.339±0.020 kJ/mol Molar volume= 1.401 J/(bar·mol)
Transition in phase Transition in reference state element
Silicon: Trus = 1690 K
Equation:
Cp = 85.78- 3.605·106 ·r-2 + 4.511·10 8 · r- 3 - 345.5·r-05
(Valid range 298.15-1800K) [J/(Kmol)]
Table 3 .1.6.2. Equation of state for stishovite, Si0 2 •
a= 2.3·10·6 + 1.2·10·8 · T + 0.0062· T" 1 - 1.13· r-2

V0•298 = 14.01
P= 2.954·10" 12 + 8.961·10" 16-T- 3.29·10" 19 · T 2 + 2.331·10" 22 1 3
K'=6.0 K'n= 1-10-3
Volume, cm 3/mol
P,GPa 10 2 5 10 20
T,K
298.15 14.01 13.965 13.922 13.798 13.606 13.269
500 14.1 14.007 13.962 13.831 13.631 13.283
1000 14.2 14.125 14.075 13.930 13.711 13.339
1500 14.3 14.271 14.212 14.047 13.804 13.403
2000 14.5 14.448 14.377 14.182 13.905 13.465
Thermal expansion, a106 , K 1
P,GPa 10 2 5 10 20
T,K
298.15 13.96 13.58 13.18 11.75 9.73 6.84
500 16.18 15.10 14.53 12.79 10.46 7.27
1000 19.37 18.85 17.88 15.37 12.27 8.36
1500 23.93 22.60 21.23 17.96 14.08 9.44
2000 29.12 26.35 24.58 20.54 15.88 10.53
Bulk modulus, GPa
P,GPa 10-4 2 5 10 20
T,K
298.15 312.69 318.69 324.69 342.69 372.69 432.69
500 298.60 304.60 310.60 328.60 358.60 418.60
1000 266.37 272.37 278.37 296.37 326.37 386.37
1500 230.17 236.17 242.17 260.17 290.17 350.17
2000 188.86 194.86 200.86 218.86 248.86 308.86
(iJK']fa1)p
P,GPa 1-10-4 P,GPa 1·104

T,K T,K
298.15 -0.0745 1000 -0.0665

500 -0.0662 1500 -0.0785
Vp=11.78, Vs= 7.12

Table 3.2.1.1. Thermophysical and thermochemical data for iron-bee, Fe.
Body-centered cubic crystals at 298-1184 K, 1665-1809 K, metastable 1184-1665 K,

Trus = 1809 K, Tcurie = 1042 K Molar mass: 55.847 g/mol
T Cp s !1~98 W jr -(GrH298)/T 11rH 0 11rGO

K J/(mol·K) J/(mol-K) J/(mol·K) J/(mol-K) kJ/mol kJ/mol
298.15 24.983 27.117 0.000 27.117 0.000 0.000

300.00 25.029 27.271 0.152 27.119 0.000 0.000
350.00 26.186 31.218 3.790 27.428 0.000 0.000
400.00 27.268 26.631 6.658 28.128 0.000 0.000
450.00 28.355 38.060 9.008 29.052 0.000 0.000
500.00 29.494 41.106 10.999 30.107 0.000 0.000
550.00 30.722 43.974 12.735 31.238 0.000 0.000
600.00 32.068 46.704 14.289 32.414 0.000 0.000
650.00 33.561 49.328 15.713 33.615 0.000 0.000
700.00 35.237 51.876 17.047 34.829 0.000 0.000
750.00 37.142 54.370 18.322 36.049 0.000 0.000
800.00 39.343 56.836 19.565 37.271 0.000 0.000
850.00 41.942 59.296 20.802 38.494 0.000 0.000
900.00 45.103 61.780 22.061 39.718 0.000 0.000
950.00 49.092 64.321 23.375 40.946 0.000 0.000
1000.00 54.353 66.966 24.786 42.180 0.000 0.000
1042.00 60.278 69.317 26.091 43.226 0.000 0.000
1100.00 45.723 71.959 27.284 44.674 0.000 0.000
1176.00 42.032 74.873 28.339 46.534 0.000 0.000
1176.00 42.032 74.873 28.339 46.534 -1.073 0.000
1200.00 41.381 75.716 28.607 47.109 -0.899 0.020
1300.00 39.904 78.959 29.522 49.437 -0.330 0.072
1400.00 39.496 81.897 30.245 51.652 0.096 0.086
1500.00 39.619 84.624 30.864 53.760 0.461 0.073
1600.00 40.045 87.193 31.423 55.770 0.809 0.033
1662.00 40.409 88.722 31.751 56.971 1.030 0.000
1662.00 40.409 88.722 31.751 56.971 0.000 0.000
1700.00 40.660 89.639 31.948 57.691 0.000 0.000
1800.00 41.398 91.983 32.452 59.532 0.000 0.000
!1~ 8 w = 4.489±0.015 kJ/mol Molar volume= 0.704±0.0001 J/(bar·mol)

Transition in phase: Transition in reference state element
Equations:
Cp = 23.652739 + 0.00879504-T- 154716.61"2 + 3.535614·10.71 2

Cp= 46- 2.06642745·10 33 -r- 10
Important: See Footnote A on page 110 regarding magnetic and phase change contributions.
Table 3.2.1.2. Equation of state for iron-bee, Fe.
a= 5.6124-10-5 + 4.3373·10·9 -T- 4.1187- r-2

Vo,298 = 7.04
P= 4.9·10- 12 + 1.4·10-15 -T+ 2.5·10- 19 -r-2
K'=5.4
Volume, cm3/mol
P,GPa 1-104 2 5 10
T,K
298.15 7.040 7.003 6.967 6.866 6.717
500 7.083 7.044 7.006 6.899 6.741
1000 7.267 7.220 7.175 7.050 6.869
1500 7.483 7.428 7.375 7.230 7.022
2000 7.720 7.655 7.593 7.424 7.186
Thermal expansion, Ql106, K 1
P,GPa 1-104 2 5 10
T,K
298.15 11.04 10.12 9.19 5.12 0.17
500 41.82 40.26 38.77 34.72 28.99
1000 56.34 54.43 52.65 48.18 42.21
1500 60.80 58.73 56.84 51.87 45.34
2000 63.77 61.58 59.60 54.12 46.96
Bulk modulus, GPa
P,GPa 1·10"4 2 5 10
T,K
298.15 187.287 192.687 198.087 214.000 241.287
500 176.600 182.000 187.400 203.600 230.600
1000 152.672 158.Q72 163.472 179.672 206.672
1500 132.231 137.631 143.031 159.231 186.231
2000 114.943 120.343 125.743 141.943 168.943
(i1Kpi11)p
P,GPa 1-104 P,GPa 1·10"4

T,K T,K
298.15 -0.0543 1000 -0.0443

500 -0.0515 1500 -0.0376
2000 -0.0317
Table 3.2.2.1. Thermochemical data for iron-fcc, Fe.
Fe: face-centered cubic crystals, stable 1176-1662 K Molar mass: 55.847 g/mol
T Cp s fl~ 98 W jT -(GrHz9s)IT fllfo tJ.I]O

K J/(mol-K) J/(mol·K) J/(mol·K) J/(mol-K) kJ/mol kJ/mol
298.15 25.212 35.800 0.0 35.800 7.841 5.252

300.00 25.212 35.956 0.155 35.800 7.842 5.236
350.00 25.515 39.859 3.751 36.108 7.827 4.802
400.00 26.122 43.304 6.508 36.796 7.780 4.373
450.00 26.837 46.421 8.726 37.695 7.713 3.951
500.00 27.575 49.287 10.574 38.713 7.628 3.538
550.00 28.297 51.949 12.153 39.797 7.520 3.134
600.00 28.985 54.441 13.527 40.914 7.383 2.740
650.00 29.634 56.787 14.741 42.046 7.209 2.361
700.00 30.242 59.006 15.827 43.179 6.987 1.996
750.00 30.809 61.112 16.807 44.305 6.704 1.649
800.00 31.339 63.117 17.699 45.418 6.348 1.323
850.00 31.834 65.032 18.516 46.516 5.897 1.022
900.00 32.296 66.865 19.269 47.596 5.327 0.751
950.00 32.729 68.623 19.966 48.657 4.603 0.515
1000.00 33.134 70.312 20.614 49.698 3.670 0.324
1100.00 33.872 73.505 21.787 51.719 1.793 0.091
1176.00 34.377 75.785 21.584 53.201 1.073 0.000
1176.00 34.377 75.785 21.584 53.201 0.000 0.000
1200.00 34.527 76.481 22.822 53.660 0.000 0.000
1300.00 35.111 79.268 23.745 55.523 0.000 0.000
1400.00 35.636 81.890 24.576 57.314 0.000 0.000
1500.00 36.110 84.365 25.329 59.036 0.000 0.000
1600.00 36.539 86.709 26.017 60.693 0.000 0.000
1662.00 36.786 88.103 26.414 61.689 0.000 0.000
1662.00 36.786 88.103 26.414 61.689 -1.029 0.000
1700.00 36.930 88.937 26.647 62.289 -1.170 0.024
1800.00 37.288 91.058 27.229 63.829 -1.560 0.105
d~8Ho = Molar volume= 0.68458 J/(mol·bar)

Equation: Cp = 52.2754- 3.55155·l0-4·T+ 7.9071086·l05·r-2 - 619.07·T-O.s

(Valid range 298-4000 K) [J/(Kmo1)]
Important: See Footnote A on page 110 regarding magnetic and phase change contributions.
Table 3.2.2.2. Equation of state for iron-fcc, Fe.
a= 7.1478·10·5
Vo.29S = 6.8458
/3= 5-10·12+ 4-10·15-T+ 3.5·10·19-T2
K' = 8.2
Volume, cm3/mol
P,GPa 1·10"4 2 5 10 20
T,K
298.15 6.850 6.802 6.756 6.634 6.464 6.205
500 6.950 6.897 6.847 6.714 6.533 6.258
1000 7.203 7.138 7.077 6.920 6.709 6.398
1500 7.465 7.387 7.316 7.133 6.893 6.548
2000 7.736 7.645 7.563 7.354 7.086 6.708
Thermal expansion, a<l06, K 1
P,GPa 1·10"4 2 5 10 20
T,K
298.15 71.50 68.65 66.27 6Q.43 53.73 45.26
500 71.50 68.65 66.27 60.43 53.73 45.26
1000 71.50 68.65 66.27 6Q.43 53.73 45.26
1500 71.50 68.65 66.27 6Q.43 53.73 45.26
2000 71.50 68.65 66.27 60.43 53.73 45.26
Bulk modulus, GPa
P,GPa 1·104 2 5 10 20
T,K
298.15 160.676 168.876 177.076 201.676 242.676 324.676
500 141.093 149.293 157.493 182.093 223.093 305.093
1000 106.952 115.152 123.352 147.952 188.952 270.952
1500 84.836 93.036 101.236 125.836 166.836 248.836
2000 69.444 77.644 85.844 110.444 151.444 233.444
(iJKpiJT)p
P,GPa 1-104 P,GPa 1·10"4

T,K T,K
298.15 -0.1086 1000 -0.0538
500 -0.0866 1500 -0.0363
2000 -0.0260
Table 3.3.1.1. Thermophysical and thermochemical data for andalusite, Al2 Si05 •
Andalusite is stable at 298.15 to 1800 K Molar mass: 162.046 g/mol
T Cp s ll~9sH' /T -(GrH29s)IT llcH 0 !!.eGO

K J/(mo1·K) J/(mol·K) J/(mol-K) J/(mo1·K) kJ/mo1 kJ/mo1
298.15 122.648 91.42 0.000 91.420 -2591.695 -2443.552

300.00 123.219 92.180 0.742 91.430 -2591.730 -2442.632
350.00 136.883 112.243 19.2536 92.989 -2592.408 -2417.722
400.00 147.668 131.253 34.657 96.595 -2592.649 -2392.746
450.00 156.289 149.161 47.710 101.451 -2592.573 -2367.760
500.00 163.294 166.003 58.93 107.073 -2592.262 -2342.795
550.00 169.077 181.846 68.689 113.158 -2591.780 -2317.871
600.00 173.925 196.772 77.262 119.510 -2591.171 -2292.996
650.00 178.043 210.86 84.860 126.000 -2590.470 -2268.176
700.00 181.584 224.187 91.646 132.542 -2.589706 -2.243413
750.00 184.661 236.822 97.746 139.076 -2588.903 -2218.705
800.00 187.361 248.828 103.265 145.564 -2588.091 -2194.052
850.00 189.750 260.260 108.283 151.977 -2587.301 -2169.449
900.00 191.880 271.167 112.869 158.298 -2586.560 -2144.891
950.00 193.793 281.594 117.079 164.515 -2585.879 -2120.372
1000.00 195.522 291.579 120.959 170.620 -2585.112 -2095.891
1100.00 198.529 310.359 127.878 182.481 -2583.314 -2047.054
1200.00 201.062 327.745 133.874 193.871 -2581.305 -1998.391
1300.00 203.233 343.927 139.128 204.799 -2.579166 -1.949901
1400.00 205.122 359.058 143.776 215.283 -2.576937 -1.901579
1500.00 206.786 373.268 147.922 225.346 -2.574642 -1.853419
1600.00 208.268 386.662 151.648 235.014 -2.572297 -1.805413
1700.00 209.602 399.329 155.019 244.31 -2.569912 -1.757556
1800.00 210.812 411.344 158.085 253.259 -2.567413 -1.709842
!!.~8H' = Molar volume= 5.152 J/(mol·bar)

Transition in phase Transition in reference state elements
Aluminum: Teu, = 933.47 K
Equation:
Cp= 221.7- 0.02559·T- 2.559·10 6·T-2 + 4.899·1081 2- 26690·T" 1
Table 3.3.1.2. Equation of state for andalusite, AhSi0 5•
a= 4.14736·10· 5 + 0.339116·10.8 -T- 13.3905·10-3 T 1 + 1.8129T2

Vo,298 = 51.52
fl= 6.2715·10- 12 + 1.414·10- 15 · T- 0.26279-10- 19 -T 2 + 2.366ono-22 -T 3
K=4.0 K'n=O
Volume, cm3/mol
P,GPa 1·10"4 2 5 10
T,K
298.15 51.520 51.179 50.852 49.925 48.546
500 51.736 51.377 51.036 50.068 48.636
1000 52.493 52.087 51.698 50.613 49.038
1500 53.448 52.973 52.520 51.283 49.531
2000 54.537 53.962 53.424 51.984 50.014
Thermal expansion, ao106, K 1
P,GPa 1·10"4 2 5 10
T,K
298.15 17.97 16.28 15.54 12.34 7.18
500 23.64 22.14 20.69 16.79 11.86
1000 33.29 31.38 29.50 24.96 19.30
1500 38.44 35.64 33.15 27.09 20.09
2000 42.01 38.17 34.94 26.99 18.46
Bulk modulus, GPa
P,GPa 1·10"4 2 5 10
T,K
298.15 149.320 153.320 157.320 169.320 189.320
500 142.826 146.826 150.826 162.826 182.826
1000 126.649 130.649 134.649 146.649 166.649
1500 109.506 113.506 117.506 129.506 149.506
2000 91.851 95.851 99.851 111.851 131.851
(i)Kpdl)p
P,GPa 1·1 04 P,GPa 1·1 04

T,K T,K
298.15 -0.0326 1000 -0.0332
500 -0.0319 1500 -0.0352
2000 -0.0350
Table 3.3.2.1. Thermophysical and thermochemical data for sillimanite, AI2Si05•
Sillimanite is stable at 298.15 to 1800 K Molar mass: 162.046 g/mol
T Cp s !:.~9sH' /T -(GrH29s)IT !:.rflo f:.{}o
K J/(mol-K) J/(mol-K) J/(mol-K) J/(mol·K) kJ/mol kJ/mol
298.15 121.449 95.790 0.000 95.790 -2587.765 -2440.925

300.00 122.014 96.543 0.734 95.800 -2587.803 -2440.013
350.00 135.856 116.428 19.082 97.345 -2588.538 -2415.317
400.00 146.930 135.320 34.398 100.922 -2588.823 -2390.547
450.00 155.708 153.153 47.408 105.745 -2588.779 -2365.762
500.00 162.735 169.935 58.602 111.333 -2588.496 -2340.995
550.00 168.452 185.722 68.337 117.385 -2588.040 -2316.266
600.00 173.187 200.589 76.883 123.706 -2587.468 -2291.584
650.00 177.179 214.613 84.449 130.164 -2586.808 -2266.953
700.00 180.601 227.872 91.198 136.674 -2586.090 -2242.376
750.00 183.581 240.436 97.259 143.177 -2585.338 -2217.851
800.00 186.214 252.370 102.738 149.631 -2584.583 -2193.376
850.00 188.570 263.731 107.719 156.012 -2583.851 -2168.948
900.00 190.705 274.570 112.271 162.299 -2583.169 -2144.562
950.00 192.660 284.934 116.451 168.483 -2582.545 -2120.212
1000.00 194.468 294.863 120.307 174.556 -2581.833 -2095.897
1100.00 197.738 313.554 127.201 186.353 -2580.128 -2047.383
1200.00 200.665 330.887 133.203 197.684 -2578.180 -1999.036
1300.00 203.346 347.056 138.497 208.560 -2576.056 -1950.860
1400.00 205.847 362.218 143.219 219.000 -2573.786 -1902.852
1500.00 208.213 376.502 147.474 229.028 -2571.384 -1855.011
1600.00 210.476 390.012 151.341 238.671 -2568.858 -1807.335
1700.00 212.660 402.838 154.884 247.954 -2566.210 -1759.820
1800.00 214.780 415.054 158.153 256.901 -2563.361 -1712.466
/l298 Ho = Molar volume= 4.986 J/(mol·bar)

0
Aluminum: Trus = 933.47 K
Equation:
Cp = 183.87 + 0.01815-T- 1.236·107· r-2+ 1.6024·109-T-3 + 3205.2-T-1
(Valid range 298.15-1800 K) [J/(Kmol)]
Table 3.3.2.2. Equation of state for sillimanite, AlzSi0 5•
a= 3.489·10-5 + 0.7127·10-a.r- 11.213·10-3• r' + 1.38154- r-2

Vo,298 = 49.86
P= 6.22896-10- 12 + 0.88383-10- 15 ·T + 0.96895-10-19 -T 2 + 0.38278-10-22 -T 3
K'=4.0 K'pr=4.0-104
Volume, cm3/mol
P,GPa 1-104 2 5 10 20
T,K
298.15 49.9 49.539 49.232 48.358 47.055 44.876
500 50.0 49.713 49.395 48.496 47.158 44.932
1000 50.7 50.375 50.028 49.056 47.630 45.302
1500 51.6 51.249 50.867 49.810 48.288 45.859
2000 52.7 52.281 51.858 50.702 49.072 46.539
Thermal expansion, a;106, K 1
P,GPa 1-104 2 5 10 20
T,K
298.15 14.95 13.99 12.86 10.89 7.52 2.01
500 21.55 20.64 19.68 17.29 14.13 10.04
1000 32.19 31.09 30.02 27.41 24.41 21.23
1500 38.72 37.36 36.15 33.23 30.01 27.21
2000 43.88 42.25 40.8 37.61 34.19 31.49
Bulk modulus, GPa
P,GPa 1-10-4 2 5 10 20
T,K
298.15 153.80 157.80 161.80 173.80 193.80 233.80
500 149.26 153.26 157.26 169.26 189.26 229.26
1000 137.97 141.97 145.97 157.97 177.97 217.97
1500 126.55 130.55 134.55 146.55 166.55 206.55
2000 115,07 119,07 123,07 135,07 155.07 195,07
(dKrfiJ1)p
P,Gpa 1-104 P,GPa 1-104

T,K T,K
298.15 -0.0225 1000 -0.0227

500 -0.0225 1500 -0.0229
2000 -0.0229
Vp= 9.501, Vs = 5.31

Table 3.3.3.1. Thennophysical and thennochemical data for kyanite, AlzSi0 5 .
Kyanite is stable at 298.15 to 1800 K Molar mass: 162.046 g/mol
T Cp s !J.~ 98 W jT -(GT"H298)/T D.rH 0 tJ.rGO

298.15 121.678 82.300 0.000 82.300 -2596.196 -2445.333

300.00 122.252 83.050 0.664 82.300 -2596.233 -2444.397
350.00 136.210 102.986 19.066 83.920 -2596.953 -2419.027
400.00 147.443 121.935 34.436 87.498 -2597.217 -2393.586
450.00 156.494 139.842 47.513 92.329 -2597.140 -2368.134
500.00 163.867 156.725 58.792 97.933 -2596.810 -2342.704
550.00 169.957 172.638 68.630 104.008 -2596.291 -2317.318
600.00 175.054 187.651 77.292 110.359 -2595.632 -2291.985
650.00 179.376 201.838 84.983 116.855 -2594.869 -2266.711
700.00 183.083 215.270 91.861 123.409 -2594.034 -2241.499
750.00 186.296 228.014 98.052 129.962 -2593.153 -2216.348
800.00 189.108 240.129 103.657 136.472 -2592.257 -2191.257
850.00 191.589 251.669 108.758 142.911 -2591.377 -2166.222
900.00 193.796 262.684 113.422 149.262 -2590.542 -2141.237
950.00 195.774 273.216 117.705 155.510 -2611.118 -2115.919
1000.00 197.556 283.304 121.654 161.650 -2610.106 -2089.881
1100.00 200.646 302.282 128.699 173.583 -2607.959 -2037.962
1200.00 203.239 319.855 134.806 185.049 -2605.678 -1986.243
1300.00 205.454 336.212 140.157 196.055 -2603.295 -1934.720
1400.00 207.375 351.510 144.891 206.619 -2600.831 -1883.383
1500.00 209.062 365.876 149.114 216.762 -2598.304 -1832.225
1600.00 210.562 379.418 152.909 226.509 -2595.728 -1781.237
1700.00 211.908 392.224 156.340 235.884 -2593.111 -1730.411
1800.00 213.129 404.371 159.462 244.909 -2590.380 -1679.742
tJ.~sw = Molar volume= 4.415 J/(mol·bar)

Aluminum: Tfus = 933.47 K
Equation:
Cp = 223.54 + o.002645T- 4.149·10 6-r-2 + 7.60l·l0 8-T 2 - 25240-r- 1
Table 3.3.3.2. Equation of state for kyanite, AhSi0 5•
a= 5.398·10·5 - 0.020575-10-8 - T- 15.0528-10-3 T 1 + 1.5530-!"2

Vo,zgs = 44.15
fJ= 6.37481·10- 12 + 0.97799·10- 15 -T + 3.40907·10- 19 - T 2 + 0.44305·I0-22 -T 3
K'=4.0 K'pr = 6.0-I 04
Volume, cm3/mol
P,GPa 1·104 2 5 10 20
T,K
298.15 44.15 43.857 43.577 42.783 41.601 39.633

500 44.4 44.075 43.784 42.959 41.738 39.718
1000 45.2 44.845 44.517 43.603 42.277 40.142
1500 46.2 45.766 45.392 44.370 42.927 40.682
2000 47.2 46.762 46.332 45.184 43.615 41.262
Thermal expansion, ao10 6, K 1
P,GPa 1·1 0 4 2 5 10 20
T,K
298.15 20.89 19.72 18.92 15.72 11.39 4.87

500 29.98 28.76 27.47 24.32 20.34 15.26
1000 40.27 38.64 37.05 33.31 29.06 25.05
1500 44.33 42.18 40.28 35.94 31.47 27.85
2000 46.43 43.75 41.49 36.58 31.94 28.56
Bulk modulus, GPa
P,GPa 1-10-4 2 5 10 20
T,K
298.15 149.30 153.30 157.30 169.30 189.30 229.30

500 143.79 147.79 151.79 163.79 183.79 223.79
1000 129.23 133.23 137.23 149.23 169.23 209.23
1500 114.18 118.18 122.18 134.18 154.18 194.18
2000 99.51 103.51 107.51 119.51 139.51 179.51
(i)KrfiJT)p
P,Gpa l·l 04 P,GPa 1-104

T,K T,K
298.15 -0.0266 1000 -0.0299

500 -0.0280 1500 -0.0300
2000 -0.0285
48 Thermodynamic Data for Stoichiometric Phases 000
Table 3.401.1. Thermophysical and thermochemical data for hematite, Fe20 3o
Hematite: phase transitions at 956 and 1250 K Molar Mass: 1590692 g/mol
T Cp s I':J.;9sHojT -(Gr-Hz9s)IT flrH 0 flrGO

K J/(moloK) J/(mol-K) J/(moloK) J/(moi-K) kJ/mol kJ/mol
298.15 1050050 87.400 00000 87.400 -8240782 -7420918

300000 105.334 880051 00659 87.400 -8240757 -742.410
350000 112.408 1040833 160130 88o702 -8240082 -7280736
400000 1180623 1200256 280561 91.696 -8230215 -715.173
450000 1240285 1340559 380886 95o673 -8220199 -701.727
500000 1290587 1470931 470694 1000237 -821.060 -688.401
550000 1340653 1600521 550370 1050151 -8190819 -6750195
600000 1390561 172.448 620182 1100266 -818.495 -662.105
650000 1440360 1830809 680320 115.490 -8170103 -649.128
700000 1490086 1940681 730920 1200761 -8150664 -6360261
750000 1530760 2050126 790087 1260039 -8140197 -623.497
800000 1580398 215.198 83.900 131.299 -8120728 -6100832
850000 1630011 2240939 88.418 1360522 -811.292 -5980258
900000 1670607 2340387 920689 141.698 -8090934 -5850766
950o00 172.191 2430572 960753 1460819 -8080723 -573.346
955099 1720739 2440656 970227 147.428 -8080594 -571.885
956000 1690525 2450359 970929 147.430 -8070922 -571.860
1000000 161.184 2520793 1000888 151.905 -8070511 -561.008
1100000 1480552 2670501 1050737 161.765 -8070801 -5360332
1200000 142.415 2800125 1090012 171.113 -8090047 -511.636
1249099 141.154 2850908 1100319 1750589 -8080112 -4990269
1250o00 1360046 2850910 1100319 1750590 -8080112 -4990263
1300o00 1330687 291.190 111.254 1790936 -8070573 -4860921
1400000 1360154 301.137 1120896 1880241 -8060652 -4620289
1500000 1450100 3100807 1140717 1960090 -8050279 -4370735
1600o00 1580058 3200569 1170005 2030564 -8020926 -413.302
1700000 173.472 3300604 1190864 2100740 -801.604 -3890008
1800000 1900345 3400992 1230306 2170686 -7970212 -3640857
I':J.~sw = Molar volume= 30027 J/(molobar)

Transition in phase Transitions in reference state element
Ttrs = 956 K, fY!!r = Oo670 kJ/mol Iron: Tphase = 1184 K, r;~~ase =1665 K,
Ttrs =1250 K, fY!Jr = 0 Trus = 1809 K
Equations: Cp= 79074 + 0009288°T- 3.284°106-T-2 + 20804°10 80 r-3 + 7150-T- 1

Cp= -139083 + 001449°T + l.5648o108or-2 - 1.4568°107-T-3 - 35l.6or- 1
Cp= 39408 + ooo8646-T + L2394°10 8or-2 + 40808°10 11 or-3 - 8o654ol0 5or 1
Table 3.4.1.2. Equation of state for hematite, Fe20 3 •
a = 2.453·10- 5 + 1.6702-10-8-T- 2.0-10-3 -T-2

Vo,298 = 30.26
P= 4.48627·10-' 2 + 3.68725-10-' 6-r + L2898·10-' 9.r 2 + 2.35·10-23 -T 3
K=4.53
Volume, cm3/mol
P,GPa 1·104 2 5 10 20
T,K
298.15 30.260 30.107 29.960 29.540 28.904 27.820
500 30.451 30.292 30.139 29.703 29.044 27.927
1000 31.021 30.843 30.674 30.191 29.469 28.258
1500 31.733 31.534 31.34 30.799 29.996 28.668
2000 32.598 32.367 32.144 31.524 30.616 29.141
Thermal expansion, «·106, K 1
P,GPa 1·1 04 2 5 10 20
T,K
298.15 29.53 28.34 27.50 24.99 21.22 15.97
500 32.89 32.02 31.24 28.96 25.76 20.82
1000 41.23 40.20 39.14 36.28 32.34 26.31
1500 49.58 48.21 46.81 43.19 38.16 30.74
2000 57.93 56.20 54.45 50.04 43.87 35.01
Bulk modulus, GPa
P,GPa 1-10-4 2 5 10 20
T,K
298.15 196.572 201.102 205.632 219.222 241.872 287.172
500 189.872 194.402 198.932 212.522 235.172 280.472
1000 173.457 177.987 182.517 196.107 218.757 264.057
1500 156.344 160.874 165.404 178.994 201.644 246.944
2000 138.318 142.848 147.378 160.968 183.618 228.918
(axrtanp
P,GPa 1·1 04 P,GPa 1-10-4 P,GPa 1·104
T,K T,K T,K
298.15 -0.0213 1000 -0.0278 2000 -0.0332
500 -0.0233 1500 -0.0313
Vp=7.923, V8=4.796
Table 3050 I 0I 0 Thermophysicai and thermochemical data for magnetite (FeFe20 4); for
[magnesioferrite so so].
Magnetite (FeFe20 4): phase transition at 848 K Molar mass: 231.539 g/mol
T Cp s !l;9sH' jT -( GrHz9s)IT llfH a flrGO

K J/(mol-K) J/(moloK) J/(mol-K) J/(mol-K) kJ/mol kJ/mol
298015 I490296 1450795 OoOOO I45o795 -11I5o863 -10120746

300000 I49o900 1460720 00965 1450795 -11150833 -1012.106
350000 163.512 1700909 230268 1470640 -11I4o769 -9940895
400000 1730800 I93.439 41.465 151.974 -1 I 130322 -977.866
450000 I82o500 2I4.422 560662 1570760 -Illl.618 -961.034
500000 190.596 234.072 690652 164.419 -1109o7I7 -9440403
550000 I98o742 252o6I 7 81.015 171.602 -1107o64I -9270970
600000 207.474 2700278 9l.I82 1790094 -1105.388 -9I 1.734
650000 2170366 2870265 100.500 I860765 -I 1020929 -8950695
700000 2290211 303.392 1090256 1940536 -1 I0002IO -8790854
750000 2440292 3200096 1170732 202.364 -I097.132 -864o2I9
800000 2640884 336.482 1260249 2100233 -10930516 -8480057
847099 2930680 3520688 I34o855 2I7o833 -10890246 -8340247
848000 2330356 3520693 1340859 2170834 -I089o243 -834.244
850000 232.468 3530242 1350090 2I8.152 -10890165 -8330642
900000 213.930 3660067 I40o046 2260021 -I0870884 -8I8o655
950000 2I 1.678 377.669 I43o968 2330701 -10870652 -8030708
IOOOoOO 2080236 388.431 1470259 24l.I72 -10880370 -788o749
llOOoOO 2050203 4080108 152o639 255.470 -1090.4I8 -7580657
I200o00 204.435 4250920 I560977 2680943 -I092o685 -728.449
I300o00 2040689 4420298 1600633 281.656 -10890852 -698o2I2
I400000 205.473 457.484 I63o806 2930679 -I087o197 -6680187
I500000 206o55I 471.698 I66o6I8 3050078 -10840658 -6380347
1600000 2070799 52l.I2I I690I52 315o9I3 -1082.192 -6080673
I700o00 209.149 4970704 I 71.465 3260239 -10830277 -5790080
I800o00 2100559 5090698 1730598 336.100 -10820047 -549.457
f1~ 8 H' =Molar volume= 4.452 J/(molobar)

Tcurie = 848 K Iron: Tphase = 1184 K, T~hase = 1665 K,
t!a H' = OoO kJ Tfus = 1809 K
Magnetic contribution in Gibbs energy GM = R.P(t)- Tln(~M+ 1)

t = T!Tc, Tc = 848, ~M = 44o54
298015-848 F(t) = 1 - Oo860339ot - 1- Oo17449ot 3 - Oo007755ot 9 - Oo0017449ot 15
848-1809 F(t) = -ooo4269ot -s- ooo013552ot - 15 - 20846° 10·4or25
Equation:Cp = 2409879 + 0000239045-T- 401304°10 50 T' 2

(Valid range 2980I5-I800 K) [J/(Komol)]
Table 3.5.1.2. Equation of state for magnetite (FeFe 20 4); for [magnesioferrite s.s.].
a= 1.61226·104 -3.853951·10·8· T- 0.0858241 T 1+ 14.253246·T"2
44.52
Vo,298 =
P= 6.01526·10· 12 + 4.89213-Io-' 6-T+ s.9812·10· 19 -T 2 - 3.7555·10-23 -T 3
K'=4.0
Volume, cm3/mol
P,GPa 1·1 0 4 2 5 10 20
T,K
298.15 44.520 44.246 43.983 43.235 42.113 40.226
500 44.715 44.431 44.160 43.387 42.232 40.297
1000 45.660 45.341 45.037 44.175 42.900 40.792
1500 46.885 46.519 46.167 45.183 43.744 41.407
2000 48.052 47.625 47.216 46.086 44.457 41.863
P,GPa 1·10'4 2 5 10 20
T,K
298.15 22.22 21.59 20.89 18.39 14.83 9.33
500 27.32 26.11 25.35 22.64 19.02 13.34
1000 51.12 49.63 48.19 44.24 38.75 30.51
1500 52.54 50.61 48.77 44.65 38.91 3Q.63
Bulk modulus, GPa
P,GPa J.lQ-4 2 5 10 20
T,K
298.15 160.945 164.945 168.945 180.945 200.945 240.945
500 156.135 160.135 164.135 176.135 196.135 236.135
1000 141.542 145.542 149.542 161.542 181.542 221.542
1500 125.500 129.500 133.500 145.500 165.500 205.500
(iJKTICJI)p
P,GPa 1·10'4 P,GPa 1·10'4

T,K T,K
298.15 -0.0213 1000 -0.0278

500 -0.0233 1500 -0.0313
2000 -0.0332
Table 3.5.2.1. Thermophysical and thermochemical data for magnesioferrite (MgFe20 4);
for [magnesioferrite s.s.].
Magnesioferrite (MgFe2 0 4), phase transitions at 665 K and 1230 K

T Cp s !J.~98 H' jT -(GrH29s)IT ArH 0 !J.tGO

K J/(mol-K) J/(mol-K) J/(mol·K) J/(mol-K) kJ/mol kJ/mol
298.15 143.692 121.880 0.000 121.800 -1441.500 -1329.567

300.00 144.131 122.690 0.902 121.900 -1441.500 -1328.873
350.00 154.921 145.742 22.157 123.586 -1440.763 -1310.157
400.00 164.287 167.052 39.348 127.704 -1439.730 -1291.566
450.00 172.825 186.902 53.711 133.191 -1438.438 -1273.121
500.00 180.849 205.530 66.027 139.503 -1436.921 -1254.832
550.00 188.538 223.129 76.817 146.312 -1435.207 -1236.704
600.00 195.997 239.855 86.439 153.416 -1433.318 -1218.741
650.00 203.296 255.832 95.148 160.684 -1431.273 -1200.941
665.00 205.462 260.497 97.612 162.883 -1430.633 -1195.637
665.01 186.679 260.403 97.617 162.786 -1430.632 -1195.633
700.00 187.125 269.987 102.080 167.907 -1429.829 -1183.217
750.00 187.762 282.919 107.771 175.149 -1428.869 -1165.637
800.00 188.399 295.058 112.790 182.267 -1428.149 -1148.113
850.00 189.037 306.498 117.257 189.242 -1427.700 -1130.626
900.00 189.675 317.322 121.262 196.059 -1427.571 -1113.157
950.00 190.312 327.594 124.880 202.714 -1436.356 -1095.435
1000.00 190.950 337.372 128.167 209.205 -1437.169 -1077.473
1100.00 192.225 355.631 133.933 221.698 -1438.905 -1041.397
1200.00 193.500 372.411 138.843 233.568 -1440.572 -1005.219
1230.00 193.882 377.193 140.181 237.oi2 -1440.012 -994.346
1230.00 176.930 378.147 141.142 237.005 -1438.829 -994.332
1300.00 180.930 388.050 143.177 244.873 -1438.620 -969.041
1400.00 186.644 401.667 146.078 255.589 -1565.396 -929.914
1500.00 192.358 414.739 148.973 265.766 -1562.994 -884.604
1600.00 198.072 427.336 151.863 275.473 -1560.167 -839.468
1700.00 203.786 439.515 154.749 284.766 -1559.240 -794.729
1800.00 209.500 451.325 157.632 293.693 -1556.305 -749.570
A2:sw = Molar volume= 4.457 J/(mol·bar)

Transition in phase Transitions in reference state elements
Ttrs = 665 K, ~Fr = 0.06 kJ Iron: Tphase = 1184 K, r;hase = 1665 K,
Ttrs = 1230 K, fi;.Fr = 1.183 kJ Tru, = 1809 K
Magnesium: Tru, = 923 K, Tvap = 1366 K
Equations: Cp= 178.2 + 0.01275-T (Valid range 665-1230 K [J/(K-mol)]

Cp= 119.022 + 0.1346632-T-1.376063·I0 6·r-2 (Valid range 298.15-665 K) [J/(K-mol)]
Cp = 106.648 + 0.05714-T (Valid range 1230-1800 K) [J/(K-mol)]
Thermodynamic Data for Stoichiometric Phases 000 53
Table 30502020 Equation of state for magnesioferrite (MgFe20 4); for [magnesioferrite SoSo]o
a= 1.61226°104 - 30853951°10°8 -T- 000858241° T" 1 + 14o253246-T"2

Vo 298 = 44.57
0
P= 6o01526°10o 12 + 4o89213°1o- 16 oT+ 5o9812°1o- 190 T 2 - 3o7555°10-23 oT 3

K'=4o0
Volume, cm3/mol
P,GPa 1°10"4 2 5 10 20
T,K
298.15 440570 440296 440033 43o283 42.160 40o271
500 440765 44.481 44o209 430436 420279 40.343
1000 450712 45.392 450088 44.225 420948 400838
1500 460938 46.571 460218 45.233 430793 41.453
Thermal expansion, t.f106 , K 1
P,GPa 1°104 2 5 10 20
T,K
298015 22024 21.47 20006 18.34 14o72 9o63
500 27.32 26.17 25.40 22067 19o04 13.42
1000 51.12 49063 48009 44.14 38076 30050
1500 52.54 50063 48068 44o75 38o96 29083
Bulk modulus, GPa
P,GPa 1°104 2 5 10 20
T,K
298015 1600949 1640949 168o949 1800949 2000949 2400949
500 1560135 1600135 164o135 1760135 1960135 2360135
1000 141.542 1450542 149.542 161.542 181.542 221.542
1500 1250500 1290500 1330500 1450500 1650500 2050500
(ilKpCJ1)p
P,GPa 1°10"4 P,GPa uo-4

T,K T,K
298.15 -000216 1000 -000315
500 -000258 1500 -000320
Table 3.6.1.1. Thermophysical and thermochemical data for hercynite (FeAh04); for
[spinel s.s.].
Hercynite (FeAl20 4): cubic at 298.15 to 1800 K, Trus = 2056 K

Molar mass: 173.808 glmol
T Cp s !J.~98 W /T -(GrH29s)/T !!.rHo !J.rGO

298.15 126.514 117.024 0.000 117.024 -1955.170 -1842.769

300.00 127.136 117.824 0.798 117.026 -1955.175 -1842.070
350.00 139.634 138.452 19.823 118.629 -1955.178 -1823.214
400.00 147.231 157.629 35.308 122.321 -1954.862 -1804.381
450.00 152.508 175.291 48.052 127.239 -1954.398 -1785.598
500.00 156.564 191.577 58.708 132.869 -1953.872 -1766.870
550.00 159.914 206.661 67.760 138.900 -1953.330 -1748.196
600.00 162.824 220.702 75.563 145.139 -1952.803 -1729.571
650.00 165.436 233.840 82.378 151.462 -1952.312 -1710.989
700.00 167.838 246.189 88.397 157.792 -1951.875 -1692.443
750.00 170.081 257.846 93.769 164.077 -1951.513 -1673.925
800.00 172.200 268.891 98.605 170.286 -1951.258 -1655.428
850.00 174.220 279.392 102.99 176.397 -1951.146 -1636.943
900.00 176.157 289.405 107.005 182.400 -1951.219 -1618.459
950.00 178.024 298.980 110.694 188.285 -1972.872 -1599.587
1000.00 179.831 308.157 114.106 194.051 -1973.149 -1579.934
1100.00 183.294 325.461 120.240 205.221 -1973.578 -1540.578
1200.00 186.594 341.552 125.633 215.919 -1972.842 -1501.242
1300.00 189.761 356.613 130.445 226.168 -1971.594 -1461.989
1400.00 192.820 370.789 134.792 235.997 -1970.015 -1422.847
1500.00 195.789 384.194 138.760 245.434 -1968.183 -1383.826
1600.00 198.682 396.922 142.415 254.508 -1966.142 -1344.934
1700.00 201.509 409.052 145.808 263.244 -1963.917 -1306.176
1800.00 204.281 420.649 148.980 271.669 -1961.527 -1267.553
/).~8Ho = Molar volume= 4.075 J/(mol·bar)

Aluminium: Trus = 933.47 K
Iron: Tphase = 1184 K, r;hase = 1665 K,
Trus = 1809 K
Equation:
Cp = 175.72 + 0.0222-r+ 8.1615·10 6·T-2 - 1.7335·109 ·r-3 - 2.45176·104-r-1
Table 3.6.1.2. Equation of state for hercynite (FeAh04); for [spinel s.s.].
a= 4.89524·10' 5 + 0.862·10· 8 -T- 20.549·10'3 ·T" 1 + 34.5353·10-'·T-2

V0,2 9s= 40.75
fJ= 4.59048·10· 12 + 0.85524·10- 15 -T- O.l4274·10- 19 -T 2 + o.93164·10'22 -T 3
K'=4.0 K'pr=O
Volume, cm3/mol
P,GPa 1·10'4 2 5 10 20
T,K
298.15 40.750 40.554 40.364 39.818 38.982 37.533
500 40.930 40.735 40.538 39.971 39.107 37.619
1000 41.638 41.409 41.191 40.569 39.637 38.069
1500 42.593 42.336 42.088 41.398 40.387 38.740
2000 43.740 43.447 43.163 42.386 41.283 39.546
Thermal expansion, tl'l06, K 1
P,GPa 1·1 04 2 5 10 20
T,K
298.15 21.45 21.32 20.19 17.90 14.23 9.21
500 25.98 24.87 24.19 21.94 19.08 15.11
1000 40.48 39.52 38.45 36.08 33.25 30.60
1500 49.72 48.45 47.14 44.22 41.10 38.55
2000 56.78 54.92 53.49 49.85 46.40 43.51
Bulk modulus, GPa
P,GPa 1·104 2 5 10 20
T,K
298.15 206.327 210.327 214.327 226.327 246.327 286.327
500 198.958 202.958 206.958 218.958 238.958 278.958
1000 181.008 185.008 189.008 201.008 221.008 261.008
1500 162.452 166.452 170.452 182.452 202.452 242.452
2000 143.078 147.078 151.078 163.078 183.078 223.078
(iJKTliJI)p
P,GPa 1·10'4 P,GPa 1·10'4

T,K T,K
298.15 -0.0216 1000 -0.0315
500 -0.0258 1500 -0.0320
Vp= 8.701, V8 =4.463

Table 3.6.2.1. Thermophysical and thermochemical data for spinel (MgAl20 4); for
[spinel s.s.).
Spinel (MgA}z04): cubic crystals 298.15 to 1800 K, Tfus = 2382 K

Molar mass 142.266 g/mol
T Cp s ll~98 W /T -(GrHz9s)IT flrHO fltGO

K J/(mol·K) J/(mol-K) J/(mol·K) J/(mol·K) kJ/mol kJ/mol
298.15 115.831 82.000 0.000 82.000 -2307.500 -2183.006

300.00 116.382 82.019 0.700 82.019 -2307.535 -2182.234
350.00 129.000 101.657 18.174 83.483 -2308.068 -2161.301
400.00 138.450 119.527 32.644 86.883 -2308.196 -2140.322
450.00 145.872 136.279 44.828 91.451 -2308.048 -2119.344
500.00 151.910 151.971 55.244 96.727 -2307.702 -2098.394
550.00 156.958 166.693 64.267 102.425 -2307.215 -2077.485
600.00 161.272 180.539 72.176 108.364 -2306.626 -2056.626
650.00 165.021 193.599 79.177 114.423 -2305.965 -2035.819
700.00 168.329 205.952 85.429 120.523 -2305.256 -2015.065
750.00 171.282 217.668 91.056 126.613 -2304.521 -1994.363
800.00 173.946 228.809 96.154 132.655 -2303.791 -1973.710
850.00 176.369 239.428 100.803 138.626 -2303.093 -1953.101
900.00 178.591 249.573 105.063 144.510 -2302.454 -1932.532
950.00 1.80642 259.285 108.988 150.297 -2331.177 -1911.369
1000.00 182.547 268.599 112.619 155.980 -2331.050 -1889.261
1100.00 185.990 286.163 119.136 167.027 -2329.410 -1845.160
1200.00 189.042 302.480 124.837 177.643 -2327.531 -1801.218
1300.00 191.786 317.721 129.883 187.838 -2325.437 -1757.442
1400.00 194.283 332.027 134.395 197.632 -2323.149 -1713.835
1500.00 196.577 345.510 138.465 207.045 -2320.682 -1670.398
1600.00 198.704 358.266 142.164 216.102 -2318.050 -1627.130
1700.00 200.689 370.372 145.549 224.823 -2315.261 -1584.Q32
1800.00 202.554 381.897 148.665 233.232 -2312.327 -1541.103
ll~8 W = Molar volume= 4.075 J/(mol·bar)

Aluminium: Tfus = 933.47 K
Iron: Tphase = 1184 K; r;base = 1665 K,
Tfus = 1809 K
Equation:
Cp= 175.72 + 0.0222·T+ 8.1615·106-T-2 - 1.7335·109·r-3- 2.45176·104·T- 1
(Valid range 298.15-1200 K) [J(Kmol)]
Table 3.6.2.2. Equation of state for spinel (MgA120 4); for [spinel s.s.].
a= 6.96922·10" 5- 0.108069·10- 8-T- 30.7991·10-3 ·T" 1- 5.03946·T-2

Vo,z9s= 39.71
P= 4.80091·10- 12 + 0.489213-lo-' 5-T+ 5.9812·10- 191 2 + 0.37555·10-22 -T 3
K' = 4.89 K'pr= 9.0·10-4
Volume, cm3/mol
P,GPa 1·1 04 2 5 10 20
T,K
298.15 39.710 39.513 39.324 38.784 37.970 36.590
500 39.904 39.699 39.502 38.942 38.101 36.684
1000 40.634 40.401 40.177 39.548 38.626 37.114
1500 41.595 41.321 41.060 40.344 39.324 37.714
2000 42.685 42.361 42.056 41.240 40.117 38.411
P,GPa 1·104 2 5 10 20
T,K
298.15 22.76 21.64 20.62 18.67 15.00 10.33
500 27.71 26.79 25.88 23.35 20.35 16.16
1000 42.85 41.38 39.98 36.60 32.70 28.77
1500 49.78 47.90 46.22 42.37 38.29 34.76
2000 53.39 51.20 49.34 45.17 41.29 38.23
Bulk modulus, GPa
P,GPa 1·1 o4 2 5 10 20
T,K
298.15 200.04 204.93 209.82 224.49 248.94 297.84
500 192.67 197.56 202.45 217.12 241.57 290.47
1000 170.92 175.81 180.70 195.37 219.82 268.72
1500 148,07 152.96 157.85 172.52 196.97 245.87
2000 127.04 131.93 136.82 151.49 175.94 224.84
(i)Kpa1)p
P,GPa 1·104 P,GPa 1·1 04

T,K T,K
298.15 -0.0342 1000 -0.0512
500 -0.0413 1500 -0.0517
2000 -0.0464
Vp= 9.761, Vs = 5.492

Table 3.7.1.1. Thermophysical and thermochemical data for wustite (FeO);

for [magnesiowustite s.s.].
Wustite (FeO): Fe0 _97 0 at 830 K -1644 K, Tru, = 1644 K, FeO is fictive end-member
T Cp s !1~9sH"/T -(GrH298)/T !1rHo !1rGO

298.15 49.551 59.500 0.000 59.500 -265.053 -244.125

300.00 49.572 59.807 0.304 59.502 -265.035 -243.995
350.00 50.147 67.491 7.384 60.108 -264.559 -240.527
400.00 50.721 74.225 12.765 61.460 -264.121 -237.124
450.00 51.295 80.232 17.014 63.218 -263.720 -233.774
500.00 51.869 85.666 20.471 65.195 -263.359 -230.466
550.00 52.443 90.637 23.351 67.285 -263.042 -227.193
600.00 53.017 95.224 25.800 69.425 -262.772 -223.946
650.00 53.591 99.491 27.915 71.576 -262.556 -220.720
700.00 54.165 103.483 29.770 73.714 -262.401 -217.508
750.00 54.739 107.240 31.415 75.825 -262.315 -214.305
800.00 55.313 110.791 32.891 77.900 -262.313 -211.105
850.00 55.887 114.161 34.227 79.935 -262.409 -207.902
900.00 56.461 117.372 35.446 81.926 -262.628 -204.690
950.00 57.035 120.440 36.567 83.873 -263.002 -201.462
1000.00 57.609 123.380 37.605 85.775 -263.583 -198.209
1100.00 58.757 128.925 39.476 89.449 -264.744 -191.603
1200.00 59.905 134.086 41.130 92.956 -265.800 -184.923
1300.00 61.053 138.927 42.619 96.308 -265.026 -178.214
1400.00 62.201 143.493 43.976 99.517 -264.210 -171.567
1500.00 63.349 147.824 45.230 102.594 -263.345 -164.979
1600.00 64.497 151.949 46.398 105.551 -262.423 -158.452
1700.00 65.645 155.893 47.496 108.397 -262.610 -151.959
1800.00 66.793 159.678 48.537 111.142 -261.952 -145.469
!1~sw = Molar volume= 1.225 J/(mol·bar)

Iron: Tphase = 1184 K, T~hase = 1665 K,
Trus = 1809 K
Equation:
Cp = 46.12826 + 1.14805968-1 o-2 - T
Table 3.7.1.2 Equation of state for wustite (FeO); for [magnesiowustite s.s.].
a= 2.60186·10- 5 + 1.46789-10-8-T + 2.78637·10- 3• r- 1 - 4.27635· r-2

Vo.298 = 12.25
P= 5.3304-t0- 12 + 0.932·10- 15 -T
K'=4
Volume, cm 3/mol
P,GPa 1·10'4 2 5 10 20
T,K
298.15 12.250 12.182 12.116 11.929 11.645 11.161
500 12.340 12.269 12.201 12.006 11.712 11.213
1000 12.589 12.511 12.436 12.223 11.904 11.367
1500 12.884 12.799 12.717 12.484 12.138 11.561
2000 13.231 13.137 13.048 12.794 12.419 11.801
P,GPa 1·104 2 5 10 20
T,K
298.15 34.93 34.75 34.64 30.83 27.09 21.20
500 37.22 36.08 35.21 32.89 29.58 24.36
1000 43.06 42.24 41.36 38.94 35.63 30.40
1500 49.70 48.82 48.04 45.62 42.32 37.40
2000 56.66 55.45 54.75 52.51 49.27 44.84
Bulk modulus, GPa
P,GPa 1·10'4 2 5 10 20
T,K
298.15 178.308 182.308 186.308 198.308 218.308 258.308
500 172.521 176.521 180.521 192.521 212.521 252.521
1000 159.683 163.683 167.683 179.683 199.683 239.683
1500 148.624 152.624 156.624 168.624 188.624 228.624
2000 138.997 142.997 146.997 158.997 178.997 218.997
(iJKrliJT)p
P,GPa 1·104 P,GPa 1·104

T,K T,K
298.15 -0.0296 1000 -0.0238
500 -0.0277 1500 -0.0206
2000 -0.018
Vp= 9.7, Vs=6.0

Table 3.7.2.1. Thennophysical and thennochemical data for charged

wustite, (FeO+); for
[magnesiowustite s.s.].
Charged wustite (FeO+): fictive end-member, metastable at any

conditions
T Cp s !!~9sH' /T -(GrH29s)IT l!rH 0 f!rGO

K J/(mol·K) J/(mol-K) J/(mol-K) J/(mol-K) kJ/mol kJ/mo1
298.15 61.939 39.515 0.000 39.515 -400.547 -373.660

300.00 61.966 39.898 0.382 39.516 -400.505 -373.494
350.00 62.683 49.504 9.231 40.273 -399.407 -369.079
400.00 63.401 57.921 15.957 41.964 -398.338 -364.820
450.00 64.118 65.430 21.269 44.161 -397.299 -360.693
500.00 64.836 72.223 25.590 46.633 -396.294 -356.679
550.00 65.553 78.436 29.190 49.246 -395.324 -352.765
600.00 66.271 84.171 32.250 51.920 -394.396 -348.937
650.00 66.988 89.503 34.895 54.609 -393.513 -345.185
700.00 67.706 94.494 37.213 57.281 -392.684 -341.499
750.00 68.423 99.190 39.270 59.920 -391.919 -337.870
800.00 69.141 103.629 4l.l14 62.515 -391.228 -334.290
850.00 69.858 107.842 42.784 65.058 -390.630 -330.750
900.00 70.576 111.855 44.308 67.547 -390.146 -327.243
950.00 71.294 115.690 45.709 69.981 -389.811 -323.758
1000.00 72.011 119.365 47.006 72.359 -389.675 -320.286
1100.00 73.446 126.296 49.345 76.951 -389.382 -313.349
1200.00 74.881 132.748 51.413 81.335 -388.953 -306.471
1300.00 76.316 138.798 53.274 85.525 -386.668 -299.690
1400.00 77.751 144.507 54.971 89.536 -384.312 -293.087
1500.00 79.186 149.920 56.537 93.383 -381.877 -286.656
1600.00 80.622 155.076 57.998 97.079 -379.357 -280.390
1700.00 82.057 160.007 59.371 100.636 -377.917 -274.260
1800.00 83.492 164.738 60.671 104.067 -375.604 -268.228
!!~8H' = Molar volume = 1.225 J/(mol·bar)

Tfus = 1809 K
Equation:
Cp= 57.660325 + 1.4350746·10-2-T
(Valid range 298-1644 K) [J/(Km ol)]
Table 3. 7 .2.2 Equation of state for charged wustite (FeO+); for [magnesiowustite s.s.]
a= 2.60186·10·5 + 1.46789·10·8 -T+ 2.78637-10.3 T 1- 4.27635T2

v 0,298 =12.25
fJ= 5.3304·10- 12 + 0.932·10- 15 · T
K'=4
Volume, cm3/mol
P,GPa 1-104 2 5 10 20
T,K
298.15 12.25 12.182 12.116 11.929 11.645 11.161
500 12.340 12.269 12.201 12.006 11.712 11.213
1000 12.589 12.511 12.436 12.223 11.904 11.367
1500 12.884 12.799 12.717 12.484 12.138 11.561
2000 13.231 13.137 13.048 12.794 12.419 11.801
Thermal expansion, tll106, K 1
P,GPa 1·1 04 2 5 10 20
T,K
298.15 34.93 34.75 34.64 30.83 27.09 21.20
500 37.22 36.08 35.21 32.89 29.58 24.36
1000 43.06 42.24 41.36 38.94 35.63 30.40
1500 49.70 48.82 48.04 45.62 42.32 37.40
2000 56.66 55.45 54.75 52.51 49.27 44.84
Bulk modulus, GPa
P,GPa 1-104 2 5 10 20
T,K
298.15 178.308 182.308 186.308 198.308 218.308 258.308
500 172.521 176.521 180.521 192.521 212.521 252.521
1000 159.683 163.683 167.683 179.683 199.683 239.683
1500 148.624 152.624 156.624 168.624 188.624 228.624
2000 138.997 142.997 146.997 158.997 178.997 218.997
(axr~anp
P,GPa 1·1 04 P,GPa 1-104 P,GPa 1·104

T,K T,K T,K
298.15 -0.0296 1000 -0.0238 2000 -0.018

500 -0.0277 1500 -0.0206
Table 3.7.3.1 Thermophysical thermochemical data for periclase (MgO); for

[magnesiowustite s.s.].
Periclase (MgO): 298.15-1800 K, Tfus = 3100 K

T Cp s !:.~9sH' /T -(GrHzgs)IT !:.tf{o !:.tGO

K J/(mol-K) J/(mol·K) J/(mol-K) J/(mol-K) kJ/mol kJ/mol
298.15 37.281 26.940 0.000 26.940 -601.490 -569.197

300.00 37.418 27.171 0.234 26.941 -601.493 -569.000
350.00 40.484 33.184 5.778 27.405 -601.540 -563.576
400.00 42.652 38.739 10.259 28.479 -601.499 -558.154
450.00 44.243 43.859 13.951 29.908 -601.404 -552.742
500.00 45.454 48.586 17.044 31.542 -601.278 -547.341
550.00 46.407 52.964 19.671 33.293 -601.136 -541.954
600.00 47.180 57.036 21.932 35.104 -600.990 -536.581
650.00 47.824 60.839 23.900 36.939 -600.845 -531.219
700.00 48.376 64.404 25.629 38.775 -600.709 -525.868
750.00 48.858 67.758 27.162 40.596 -600.586 -520.527
800.00 49.288 70.925 28.532 42.394 -600.480 -515.193
850.00 49.678 73.925 29.764 44.161 -600.394 -509.866
900.00 50.037 76.775 30.881 45.895 -600.331 -504.542
950.00 50.372 79.490 31.898 47.592 -608.822 -498.973
1000.00 50.688 82.081 32.829 49.252 -608.878 -493.190
1100.00 51.278 86.941 34.480 52.461 -608.963 -481.617
1200.00 51.828 91.426 35.903 55.523 -609.Dl2 -470.037
1300.00 52.351 95.595 37.149 58.447 -609.026 -458.455
1400.00 52.856 99.494 38.253 61.241 -736.417 -443.847
1500.00 53.349 103.157 39.243 63.914 -735.006 -422.998
1600.00 53.833 106.616 40.141 66.476 -733.560 -402.244
1700.00 54.310 109.894 40.961 68.934 -732.079 -381.581
1800.00 54.784 113.011 41.718 71.296 -730.560 -361.006
!:.":sH' = 5.16 kJ/mo1 Molar volume= 1.125 ±0.003 J/(bar·mol)

Ttrs = 3100 K, A-!1r = 79.84 kJ/mol Magnesium: Trus = 923 K, Tvap = 1366 K
Equation:
Cp = 45.49 + 4.773- 10·3-T- 2.16-106 -T"2 + 1.744-108 -r-3 + 2.411-103-r- 1
(Valid range 298.15-1800 K) [J/(K·mol)]
Table 3.7.3.2. Equation of state for periclase (MgO); for [magnesiowustite s.s.].
a= 3.64·10-5 + 8.35-10-9 -T+ 8.5·10-4·T' 1- 9.5·10- 1· T' 2

Vo,298 = 11.25
P= 5.875·10- 12 + 1.101·10- 15 • T+ l.37·to- 19 -T 2 + 4.8·I0-23 -T 3
K'=4.I7 K'pr=4-to-5
Volume, cm 3/mol
P,GPa 1·10'4 2 5 10 20
T,K
298.15 11.250 11.181 11.114 10.926 10.644 10.172
500 11.331 11.258 11.189 10.992 10.699 10.211
1000 11.571 11.490 11.411 11.191 10.867 10.336
1500 11.846 11.753 11.664 11.416 11.055 10.474
2000 12.153 12.046 11.944 11.662 11.259 10.621
Thermal expansion, a:106, K 1
P,GPa 1·104 2 5 10 20
T,K
298.15 31.05 28.18 29.55 25.60 20.92 13.87
500 38.48 37.45 35.93 32.66 28.39 21.95
1000 44.65 43.24 41.88 38.19 33.03 25.73
1500 49.07 47.25 45.72 41.30 35.49 27.24
2000 53.29 51.25 49.13 43.94 37.64 28.50
Bulk modulus, GPa
P,GPa 1·1 o4 2 5 10 20
T,K
298.15 160.857 165.027 169.197 181.707 202.557 244.257
500 154.661 158.831 163.001 175.511 196.361 238.061
1000 139.645 143.815 147.985 160.495 181.340 223.045
1500 125.051 129.221 133.391 145.901 166.710 208.451
2000 111.000 115.170 119.340 131.850 152.700 194.400
(iJKrfiJ1)p
P,GPa 1·1 04 P,GPa 1·104

T,K T,K
298.15 -0.0309 1000 -0.0296

500 -0,0305 1500 -0.0287
2000 -0.0274
Vp= 9.717, Vs = 6.043

Table 3.8.1.1. Thermophysical and thermochemical data for fayalite (Fe2 Si0 4);
for [olivine s.s. ].
Fayalite (Fe2Si04): 298.15-1800 K, Tfus = 1477 K.

T Cp s !l;98 H' jT -( GrH298)/T !lrH 0 !lrGO

K J/(mo1-K) J/(mol-K) J/(mol·K) J/(mol·K) kJ/mol kJ/mol
298.15 131.841 151.000 0.000 151.000 -1477.340 -1378.249

300.00 132.390 151.817 0.831 151.003 -1477.334 -1377.634
350.00 144.217 173.180 20.532 152.648 -1476.942 -1361.043
400.00 152.144 192.987 36.518 156.469 -1476.267 -1344.530
450.00 157.855 211.253 49.700 161.555 -1475.452 -1328.110
500.00 162.237 228.120 60.741 167.379 -1474.581 -1311.786
550.00 165.794 243.755 70.136 173.620 -1473.707 -1295.549
600.00 168.828 258.314 78.236 180.079 -1472.867 -1279.390
650.00 171.530 271.936 85.310 186.626 -1472.090 -1263.299
700.00 174.025 284.740 91.558 193.182 -1471.399 -1247.264
750.00 176.399 296.828 97.136 199.692 -1470.818 -1231.276
800.00 178.711 308.287 102.162 206.124 -1470.375 -1215.322
850.00 181.003 319.190 106.733 212.457 -1470.102 -1199.390
900.00 183.307 329.601 110.923 218.678 -1470.042 -1183.469
950.00 185.644 339.574 114.794 224.780 -1470.262 -1167.544
1000.00 188.033 349.157 118.396 230.761 -1470.860 -1151.598
1100.00 193.016 367.309 124.950 242.359 -1471.929 -1119.594
1200.00 198.332 384.329 130.842 253.488 -1472.587 -1087.564
1300.00 204.028 40D.427 136.250 264.177 -1469.349 -1055.608
1400.00 210.136 415.768 141.307 274.461 -1465.741 -1023.915
1477.00 215.133 427.150 145.024 282.126 -1462.672 -999.696
1500.00 216.677 430.486 146.111 284.375 -1461.702 -992.494
1600.00 223.666 444.691 150.737 293.953 -1457.173 -961.358
1700.00 231.112 458.471 155.244 303.228 -1504.615 -930.088
1800.00 239.026 471.903 159.676 312.227 -1499.484 -896.437
6~ 8 w =33.452 ± 0.100 kJ/mol Molar volume= 4.628 J/(bar·mol)

Trus = 1477 K, !lfusH0 = 88.12 kJ/mol Silicon: Tfus = 1690 K
Trus = 1809 K
Equation:
Cp = 176.02- 0.008808·T + 2.471·10. 5 · T 2 - 3889000· r· 2
(Valid range 298.15-1450 K; average absolute percent deviation: 0.5) [J/(Kmol)]
Table 30801.20 Equation of state for fayalite (Fe2 Si04); for olivine Sos.].
a= 70692223°10-5 - 2078244°10-9 -T- 3o35255°10-2 -T" 1 + 5.5494oT"2

V0,298 = 46028
fJ= 7.40354°10- 12 + 1.77968o1o- 15 or- 7.42829oi0- 19 oT 2 + 4o85647oi0-22 -T 3
K'= 5025 K'pr = 202°10-4
Volume, cm3/mol
P,GPa 1°104 2 5
T,K
298.15 46028 45092 45o58 44o65
500 46o56 46018 45083 44o86
1000 47o58 47017 46078 45072
1500 48096 48.48 48o03 46o84
2000 50o56 49098 49.44 48004
P,GPa 1·1 04 2 5
T,K
298.15 27074 26.37 26o23 23006

500 33.46 32010 30068 27.44
1000 51.73 50012 48062 45.12
1500 61.21 58o50 56012 50.45
2000 67.11 62098 59030 50071
Bulk modulus, GPa
P,GPa 1-104 2 5
T,K
298015 1260900 1320150 137.400 1530150
500 122.423 1270673 1320923 1480673
1000 1120032 1170282 1220532 1380282
1500 990594 1040844 1100094 1250844
2000 840198 89.448 94o698 110.448
(i)KpCJ1)p
P,GPa 1°104 P,GPa 1°10-4

T,K T,K
298015 -000236 1000 -00022

500 -00021 1500 -000281
2000 -000329
Vp = 6085, Vs = 3.41
Table 3080201. Thermophysical and thermochemical data for forsterite (Mg2Si04);

for [olivine Soso].
Forsterite (Mg2Si04): 298.15-1800 K, Trus = 2163 K

Molar mass: 140o694 g/mol
T Cp s tl;_98 H' jT -(GrH29s)IT !!.rHo !!.rGO

K J/(moloK) J/(moloK) J/(moloK) J/(mol-K) kJ/mol kJ/mol
298.15 118o638 95o600 00000 950600 -2174.140 -20550215

300000 119.139 96.335 Oo748 950602 -2174.153 -2054.477
350000 130.520 1150604 18.519 970085 -2174.404 -2034.505
400000 138o847 1330603 330065 1000538 -21740320 -2014.522
450000 145o211 150.340 45.187 105.153 -21740014 -1994o564
500000 1500260 1650910 550450 110.460 -2173.557 -1974o649
550000 1540395 180.432 64o263 116.168 -21720998 -19540784
600000 1570874 1940019 71.923 1220096 -2172.369 -1934o974
650000 1600870 206o777 78o653 1280124 -2171.696 -1915.218
700000 1630501 2180797 840621 134.176 -21700995 -18950515
750000 1650851 230.158 890959 1400199 -21700282 -1875o863
800o00 167o982 2400931 940770 1460161 -2169.567 -1856o258
850000 1690937 251.175 99.135 152o040 -21680862 -18360698
900o00 171.752 2600940 1030119 1570820 -2168.175 -18170179
950000 173.451 2700272 1060777 163.495 -2184.567 -17970200
1000000 1750055 2790210 1100151 1690059 -21840065 -17760825
llOOoOO 1780038 2960037 1160189 1790848 -21820935 -1736.154
l200o00 1800793 311.647 121.459 190.188 -2181.647 -1695o594
1300000 1830380 3260222 126.124 2000098 -21800211 -1655.147
1400000 1850841 3390902 130.303 2090600 -2433.454 -16080763
1500o00 1880205 352o805 1340084 2180721 -24290027 -15500010
1600000 1900492 3650025 1370538 227.487 -2424.463 -1491.557
1700000 1920719 3760641 1400719 2350922 -24690946 -14330007
1800o00 194o897 3870718 1430669 2440049 -24640887 -1372.155
!!..~ 8 H' =17 0224 ±Oo040 kJ/mol Molar volume = 4.367 ±00003 J/(baromol)
Trus = 2163 K, !l.rusH 0 =86.30 kJ/mol Silicon: Trus = 1690 K
Magnesium: Tfus = 923 K, Tvap = 1366 K
Equation:
Cp = 16508 + 1.855°10-2 oT -3971000or-2 +2086lo108 or-3 - 5610°T-1
Table 3.8.2.2. Equation of state for forsterite (Mg2Si04 ); for [olivine s.s. ].
a= 2.01·10'5 + 1.39·10'8 -T + 1.627-10'3 -T' 1 - 0.338· T"2

Vo.298 = 43.67
P= 7.427·10- 12 + 1.24·10-15 · T+ 6.9·10-20 ·T 2 + 1.702·10·22 -T 3
K'=5.2 K'pr = 2.0·1 o·4
Volume, cm3/mol
P,GPa 1·104 2 5 10 20
T,K
298.15 43.670 43.337 43.019 42.143 40.889 38.903
500 43.913 43.567 43.237 42.330 41.037 39.001
1000 44.624 44.238 43.871 42.875 41.475 39.313
1500 45.493 45.052 44.637 43.523 41.991 39.677
2000 46.534 46.017 45.536 44.269 42.569 40.074
P,GPa 1-10-4 2 5 10 20
T,K
298.15 25.90 24.63 23.94 20.79 17.13 10.81
500 28.95 27.57 26.21 23.07 18.92 13.85
1000 35.29 33.52 31.93 27.91 23.21 17.46
1500 41.88 39.42 37.27 32.04 26.13 19.26
2000 48.63 45.36 42.47 35.92 28.51 20.51
Bulk modulus, GPa
P,GPa 1·104 2 5 10 20
T,K
298.15 128.084 133.084 138.084 154.084 180.084 232.084
500 123.678 128.878 134.078 149.678 175.678 227.678
1000 112.281 117.481 122.681 138.281 164.281 216.281
1500 99.834 105.034 110.234 125.834 151.834 203.834
2000 86.621 91.821 97.021 112.621 138.621 190.621
(iJKrfCJT)p
P,GPa 1·104 P,GPa 1·1 04

T,K T,K
298.15 -0.0218 1000 -0.0238

500 -0.022 1500 -0.0259
2000 -0.0267
Vp= 8.569, Vs= 5.015

Table 3.8.3.1. Thermophysical and thermochemical data for [3-spinel (Fe2Si04);

for [[3-spinel s.s.).
[3-spinel (Fe2Si04 ): metastable end-member. Molar mass: 203.778 g/mol
T Cp s !i~9sW/T -(GrH29s)IT /:lifo /:it<Jo

K J/(mol·K) J/(mol·K) J/(mol·K) J/(mol-K) kJ/mol kJ/mol
298.15 136.066 141.800 0.000 141.800 -1468.000 -1366.160

300.00 136.464 142.643 0.855 141.788 -1467.981 -1365.529
350.00 145.000 164.366 20.880 143.486 -1467.474 -1348.490
400.00 151.130 184.145 36.794 147.351 -1466.810 -1331.537
450.00 156.151 202.243 49.784 152.459 -1466.067 -1314.671
500.00 160.539 218.927 60.645 158.283 -1465.283 -1297.891
550.00 164.494 234.417 69.909 164.508 -1464.485 -1281.191
600.00 168.113 248.887 77.944 170.943 -1463.696 -1264.563
650.00 171.454 262.477 85.010 177.467 -1462.939 -1248.000
700.00 174.553 275.298 91.296 184.001 -1462.236 -1231.492
750.00 177.440 287.440 96.944 190.496 -1461.616 -1215.033
800.00 180.138 298.979 102.060 196.919 -146l.l10 -ll98.6ll
850.00 182.666 309.976 106.728 203.248 -1460.759 -ll82.216
900.00 185.043 320.485 lll.014 209.471 -1460.614 -ll65.837
950.00 187.282 330.551 ll4.970 215.581 -1460.749 -ll49.458
1000.00 189.397 340.2ll ll8.639 221.573 -1461.271 -ll33.063
1100.00 193.300 358.449 125.252 233.197 -1462.252 -1100.170
1200.00 196.831 375.422 131.072 244.350 -1462.964 -1067.253
1300.00 200.052 391.306 136.256 255.050 -1459.995 -1034.397
1400.00 203.013 406.241 140.920 265.321 -1456.936 -1001.773
1500.00 205.753 420.342 145.152 275.190 -1453.794 -969.371
1600.00 208.306 433.704 149.020 284.684 -1450.574 -937.181
1700.00 210.698 446.405 152.579 293.826 -1499.800 -904.759
1800.00 212.951 458.512 155.870 302.642 -1496.988 -869.838
!l~sw = Molar volume = 4.314 J/(bar·mol)

Iron: Tpbase = 1184 K, r;hase = 1665 K,
Tfus = 1809 K
Equation:
Cp = 224.412 + 8.9184·10-3 T+ 1.559·107-r-2 - 1.942-109 -T-3 - 5.7576-I04·T- 1
Table 3.8.3.2. Equation of state for ~-spinel (Fe2Si04); for [~-spinel s.s.].
a = 8.774·10-5 - 2.609·1 o·9 · T- 3.398·10·2 -r- 1 + 4.435-r-2

V0•298 = 43.14
fJ= 5.54·10- 12 + 7.947·10- 16 -T + 7.069·10- 19 ·T 2 - 4.957·10-23 -T 3
K'=4.0 K'pr= 5.0·10 4
Volume, cm 3/mol
P,GPa 1-10-4 2 5 10 20
T,K
298.15 43.140 42.890 42.650 41.965 40.931 39.179

500 43.397 43.134 42.882 42.165 41.088 39.276
1000 44.441 44.136 43.842 43.019 41.808 39.826
1500 45.792 45.427 45.079 44.121 42.750 40.583
2000 47.307 46.86 46.455 45.341 43.800 41.456
Thermal expansion, t:»106, K 1
P,GPa 1·104 2 5 10 20
T,K
298.15 22.88 21.22 20.27 16.93 12.00 43.12

500 36.22 34.93 33.54 29.99 25.31 18.80
1000 55.59 53.63 51.79 47.07 41.23 34.10
1500 63.14 60.69 58.53 53.16 47.07 40.54
2000 66.64 63.82 61.35 55.56 49.66 44.34
Bulk modulus, GPa
P,GPa 1·104 2 5 10 20
T,K
298.15 171.283 175.283 179.283 191.283 211.283 251.283

500 163.723 167.723 171.723 183.723 203.723 243.723
1000 143.020 147.020 151.020 163.020 183.020 223.020
1500 122.620 126.620 130.620 142.620 162.620 202.620
2000 104.598 108.598 112.598 124.598 144.598 184.598
(iJK']'/a1)p
P,GPa J.l0-4 P,GPa 1·104

T,K T,K
298.15 -0.0353 1000 -0.0421

500 -0.0393 1500 -0.0388
2000 -0.0331
Table 3.8.4.1. Thermophysical and thermochemical data for ~-spinel (Mg2Si04);

for [~-spinel s.s.].
~-spinel (Mg2Si04): stable at 13-20 GPa; metastable at 1 bar.

T Cp s Ll~gsH' /T -(GrH298)/T LlcH 0 !J.rGO

298.15 110.694 95.000 0.000 95.000 -2140.500 -2021.400

300.00 111.294 95.687 0.698 95.002 -2140.528 -2020.657
350.00 124.451 113.899 17.500 96.398 -2141.121 -2000.625
400.00 133.574 131.146 31.471 99.675 -2141.318 -1980.537
450.00 140.312 147.286 43.207 104.079 -2141.265 -1960.441
500.00 145.533 162.350 53.189 109.161 -2141.048 -1940.359
550.00 149.730 176.424 61.781 114.644 -2140.723 -1920.306
600.00 153.208 189.606 69.259 120.347 -2140.328 -1900.285
650.00 156.159 201.989 75.833 126.156 -2139.888 -1880.299
700.00 158.714 213.657 81.664 131.993 -2139.425 -1860.347
750.00 160.965 224.685 86.877 137.808 -2138.953 -1840.430
800.00 162.975 235.139 91.572 143.568 -2138.486 -1820.544
850.00 164.794 245.075 95.826 149.249 -2138.035 -1800.686
900.00 166.457 254.542 99.705 154.838 -2137.608 -1780.854
950.00 167.991 263.584 103.259 160.325 -2154.270 -1760.548
1000.00 169.417 272.237 106.531 165.706 -2154.045 -1739.832
1100.00 172.013 288.508 112.368 176.140 -2153.497 -1698.436
1200.00 174.343 303.577 117.437 186.139 -2152.833 -1657.095
1300.00 176.473 317.617 121.898 195.719 -2152.065 -1615.814
1400.00 178.450 330.768 125.868 204.901 -2406.023 -1568.544
1500.00 180.307 343.144 129.435 213.709 -2402.359 -1508.851
1600.00 182.067 354.837 132.670 222.167 -2398.611 -1449.405
1700.00 183.748 365.926 135.626 230.300 -2444.964 -1389.810
1800.00 185.365 376.475 138.344 238.130 -2440.830 -1327.861
!J.~SH' = Molar volume = 4.054 ±0.003 J/(bar·mol)

Magnesium: Trus = 923 K, Tvap = 1366 K
Equation:
Cp =172.9 + 1.129·10-2 -T- 1077100·T"2 - 2.187 108-T"3 - 13477-T"1
(Valid range 298-1800 K) [J/(K·mol)]
Table 3.8.4.2. Equation of state for ~-spinel (Mg2 Si04); for [~-spinel s.s.].
a= 2.319·10-s + 9.04-10-9 -T- 3.966-10-3 -r-1 + 0.7496-r-2

Vo,298 = 40.54
~ = 5.5128-10- 12 + 9.2017·10- 16 -T+ 8.849·10-20 - T 2 + 1.1529·10-22 -T 3
K'=4.3 Kpr= 3.0·10·4
Volume, cm3/mol
P,GPa 1-104 2 5 10 20
T,K
298.15 40.540 40.307 40.084 39.447 38.491 36.882
500 40.718 40.475 40.243 39.583 38.596 36.943
1000 41.250 40.981 40.722 39.994 38.921 37.155
1500 41.910 41.604 41.309 40.494 39.313 37.418
2000 42.693 42.334 41.993 41.062 39.748 37.702
Thermal expansion, al06, K 1
P,GPa 1·1 04 2 5 10 20
T,K
298.15 21.02 19.77 18.78 16.89 13.24 7.93
500 22.78 21.78 20.75 17.93 14.37 9.11
1000 29.01 27.69 26.33 23.04 18.73 13.18
1500 34.44 32.56 30.81 26.48 21.16 14.77
2000 39.47 36.98 34.83 29.16 22.77 15.35
Bulk modulus, GPa
P,GPa 1-104 2 5 10 20
T,K
298.15 172.470 176.770 181.070 193.970 215.470 258.470
500 166.405 170.705 175.005 187.905 209.405 252.405
1000 150.676 154.976 159.276 172.176 193.676 236.676
1500 133.667 137.967 142.267 155.167 176.667 219.667
2000 115.882 120.182 124.482 137.382 158.882 201.882
(CJKrfCJ1)p
P,GPa 1-10 4 P,GPa 1-104 P,GPa 1-104

T,K T,K T,K
298.15 -0.0299 1000 -0.0328 2000 -0.0357
500 -0.0303 1500 -0.0351
Vp=9.66, Vs=5.71
Table 3.8.5.1. Thermophysical and thermochemical data for y-spinel (Fe2Si04);

for [y-spinel s.s. ].
y-spinel (Fe2 Si04): stable at 5-20 GPa; metastable at I bar

Molar mass 203.778 g/mol
T Cp s !1~ 98 W /T -( GrH298)/T 11rH 0 11rGO

298.15 130.198 145.826 0.0 145.826 -1465.D72 -1364.432

300.00 130.563 146.633 0.820 145.827 -1465.073 -1363.808
350.00 139.606 167.459 20.518 147.439 -1464.847 -1346.946
400.00 147.081 186.605 35.451 151.155 -1464.420 -1330.130
450.00 153.256 204.297 48.208 156.089 -1463.848 -1313.377
500.00 158.433 220.719 58.979 161.741 -1463.188 -1296.692
550.00 162.857 236.032 68.226 167.806 -1462.483 -1280.077
600.00 166.708 250.371 76.276 174.096 -1461.769 -1263.526
650.00 170.122 263.852 83.366 180.487 -1461.079 -1247.034
700.00 173.195 276.574 89.674 186.900 -1460.444 -1230.593
750.00 176.002 288.620 95.337 193.283 -1459.893 -1214.195
800.00 178.596 300.063 100.461 199.602 -1459.462 -1197.830
850.00 181.019 310.964 105.129 205.835 -1459.191 -1181.487
900.00 183.303 321.376 109.409 211.967 -1459.131 -1165.155
950.00 185.473 331.342 113.356 217.989 -1459.354 -1148.818
1000.00 187.547 340.912 117.014 223.898 -1459.967 -1132.460
1100.00 191.470 358.973 123.606 235.367 -1461.134 -1099.628
1200.00 195.164 375.793 129.417 246.376 -1462.022 -1066.756
1300.00 198.689 391.555 134.611 256.944 -1459.205 -1033.931
1400.00 202.088 406.404 139.310 267.094 -1456.262 -1001.327
1500.00 205.388 420.460 143.606 276.854 -1453.186 -968.938
1600.00 208.613 433.819 147.568 286.250 -1449.969 -936.759
1700.00 211.777 446.561 151.252 295.308 -1499.126 -904.351
1800.00 214.892 458.754 154.702 304.052 -1496.165 -869.449
11~sw = Molar volume = 4.202 J/(bar·mol)

Trus = 1809 K
Equation:
Cp = 167.86 + 0.028124·T- 5.6547·106 T 2 + 7.8238·108 T 3 - 3564.4T 1
(Valid range 298.15-1800 K; Average absolute per cent deviation: 0.5) [J/(Kmol)]
Thennodynamic Data for Stoichiometric Phases ... 73
Table 3.8.5.2. Equation of state for y-spinel (Fe 2Si04); for [y-spinel s.s.].
a= 8.897·10·5 + 2.803-10. 9 ·T- 3.426·10·2 ·T" 1 + 3.813·T"2

Vo,298 = 42.02
P= 3.86·10" 12 + 3.978·10" 15 -T- 6.304-10" 19 ·T 2 + 8.275-10"23 1 3
K' = 4.0 K'pr = 8.0-I o-4
Volume, cm 3/mol
P,GPa 1·104 2 5 10
T,K
298.15 42.020 41.812 41.611 41.032 40.148

500 42.257 42.019 41.789 41.133 40.177
1000 43.353 43.044 42.746 41.917 40.710
1500 44.835 44.457 44.098 43.121 41.750
2000 46.559 46.112 45.695 44.590 43.093
Thermal expansion, a10 6, K 1
P,GPa 1·104 2 5 10
T,K
298.15 17.80 14.05 10.98 2.01 6.17
500 37.10 33.84 30.55 21.90 8.43
1000 61.33 58.53 55.96 49.47 41.10
1500 72.03 69.55 67.44 62.59 58.06
2000 78.40 76.21 74.40 70.93 67.82
Bulk modulus, GPa
P,GPa 1·104 2 5 10
T,K
298.15 200.200 204.200 208.200 220.200 240.200
500 175.385 179.385 183.385 195.385 215.385
1000 137.168 141.168 145.168 157.168 177.168
1500 115.103 119.103 123.103 135.103 155.103
2000 100.438 104.438 108.438 120.438 140.438
(i1Krf(j1)p
P,GPa 1·104 P,GPa 1·104

T,K T,K
298.15 -0.1455 1000 -0.0558

500 -0.1049 1500 -0.0350
2000 -0.0247
Vr= 7.77, Vs= 3.93

Table 3.8.6.1. Thermophysical and thermochemical data for y-spinel (Mg2 Si04);
for [y-spinel s.s.].
y-spinel (MgzSi04): stable at 20-25 GPa; metastable at 1 bar

T Cp s !!.~ 98 W jT -(Gr-H298)/T AtW ArG 0

298.15 106.597 90.600 0.000 90.600 -2132.100 -2011.685

300.00 107.126 91.261 0.672 90.602 -2132.136 -2010.937
350.00 119.838 108.768 16.824 91.944 -2132.957 -1990.666
400.00 129.703 125.443 30.344 95.099 -2133.368 -1970.306
450.00 137.326 141.179 41.826 99.353 -2133.486 -1949.914
500.00 143.289 155.969 51.686 104.283 -2133.400 -1919.520
550.00 148.033 169.856 60.237 109.620 -2133.173 -1909.142
600.00 151.879 182.907 67.719 115.189 -2132.852 -1888.790
650.00 155.053 195.193 74.318 120.875 -2132.473 -1868.466
700.00 157.719 206.784 80.183 126.601 -2132.061 -1848.173
750.00 159.996 217.745 85.430 132.316 -2131.639 -1827.910
800.00 161.969 228.136 90.153 137.983 -2131.221 -1807.675
850.00 163.705 238.008 94.430 143.578 -2130.822 -1787.466
900.00 165.252 247.410 98.322 149.088 -2130.452 -1767.280
950.00 166.647 256.383 101.882 154.501 -2147.177 -1746.615
1000.00 167.919 264.963 105.153 159.811 -2147.023 -1725.537
1100.00 170.179 281.076 110.964 170.112 -2146.642 -1683.406
1200.00 172.162 295.971 115.983 179.988 -2146.179 -1641.313
1300.00 173.951 309.823 120.374 189.449 -2145.646 -1599.262
1400.00 175.601 322.775 124.261 198.514 -2399.872 -1551.202
1500.00 177.149 334.943 127.735 207.208 -2396.510 -1490.700
1600.00 178.621 346.424 130.870 215.554 -2393.092 -1430.424
1700.00 180.036 357.295 133.721 223.574 -2439.803 -1369.976
1800.00 181.408 367.622 136.332 231.293 -2436.052 -1307.153
!!.z;sw = Molar volume= 3.965 ±0.003 J/(bar·mol)

Equation:
Cp= 158.56 + 1.22·10"2·T-1.2297·107·T-2 + 1.4841·109·T"3 + 7.9719·103-r- 1
(Valid range 298-1800 K) [J/(K·mol)]
Table 3.8.6.2. Equation of state for y-spinel (Mg2Si04); for [y-spinel s.s.].
a= 1.225·10-5 + 1.104·10-8-T+ 2.496·10-3 -r- 1 - 0.511 T 2
Vo.298 = 39.65
fl= 5.07778·10- 12 + 1.3371·10- 15 • T- 2.9854·10- 19 · T 2 + 2.7822·10-22 ·T 3
K'=4.3 K'n = 6.0·10-4
Volume, cm 3/mol
P,GPa 1·1 0-4 2 5 10 20

T,K
298.15 39.650 39.435 39.229 38.640 37.750 36.240

500 39.807 39.582 39.366 38.751 37.826 36.268
1000 40.267 40.014 39.770 39.086 38.078 36.421
1500 40.829 40.536 40.256 39.483 38.373 36.607
2000 41.505 41.152 40.819 39.921 38.678 36.780
Thermal expansion, m106, K 1
P,GPa 1·1 0-4 2 5 10 20

T,K
298.15 18.16 17.74 16.87 14.50 11.15 6.21

500 20.72 19.48 18.41 15.62 11.90 6.83
1000 25.28 23.77 22.22 18.37 13.77 8.34
1500 30.25 28.06 26.04 21.13 15.65 9.86
2000 35.45 32.35 29.86 23.89 17.52 11.37
Bulk modulus, GPa
P,GPa 1·1 0-4 2 5 10 20

T,K
298.15 183.242 187.542 191.842 204.742 226.242 269.242

500 175.240 179.540 183.840 196.740 218.240 261.240
1000 156.383 160.683 164.983 177.883 199.383 242.383
1500 136.041 140.341 144.641 157.541 179.041 222.041
2000 113.849 118.149 122.449 135.349 156.849 199.849
(aKrfilT)p
P,GPa 1·1 0-4 P,GPa J.l0-4 P,GPa 1·1 0-4

T,K T,K T,K
298.15 -0.0414 1000 -0.0385 2000 -0.0451

500 -0.0383 1500 -0.0429
Vp= 9.79, Vs= 5.77

Table 3.9.1.1. Thermophysical and thermochemical data for hpclinoferrosilite (FeSi03);

for [hpclinopyroxene s.s.].
Hpclinoferrosilite (FeSi0 3): metastable at I bar Molar mass: 143.693 glmol
T Cp s !J.;98 H' /T -(GrH29s)IT tlrH 0 !J.rGO
298.15 86.951 96.604 0.000 96.604 -1192.645 -1116.004

300.00 87.302 97.143 0.547 96.604 -1192.649 -1115.528
350.00 95.603 111.253 13.560 97.693 -1192.594 -1102.675
400.00 101.908 124.450 24.228 100.222 -1192.312 -1089.847
450.00 106.737 136.744 33.137 103.605 -1191.883 -1077.063
500.00 I 10.510 148.193 40.694 107.498 -1191.366 -1064.332
550.00 113.529 158.872 47.183 111.698 -1190.802 -1051.656
600.00 116.005 168.860 52.819 116.041 -1190.222 -1039.032
650.00 118.084 178.230 57.761 120.468 -1189.652 -1026.456
700.00 119.867 187.047 62.135 124.912 -1189.112 -1013.923
750.00 121.428 195.372 66.037 129.335 -1188.622 -1001.427
800.00 122.819 203.254 69.543 133.710 -1188.201 -988.962
850.00 124.080 210.738 72.715 138.023 -1187.871 -976.520
900.00 125.239 217.863 75.601 142.262 -1187.659 -964.095
950.00 126.318 224.664 78.242 146.422 -1187.602 -951.677
1000.00 127.333 231.169 80.672 150.498 -1187.752 -939.257
1100.00 129.221 243.395 85.001 158.395 -1188.063 -914.380
1200.00 130.974 254.715 88.759 165.955 -1188.286 -889.506
1300.00 132.638 265.264 92.071 173.193 -1186.707 -864.672
1400.00 134.241 275. !53 95.026 180.127 -1185.112 -839.960
1500.00 135.801 284.468 97.693 186.775 -1183.496 -815.362
1600.00 137.333 293.281 100.123 193.159 -1181.852 -790.873
1700.00 138.845 301.653 102.356 199.297 -1231.527 -766.077
1800.00 140.342 309.631 104.425 205.206 -1229.975 -738.743
!J.~8H' = Molar volume= 3.5328 J/(bar·mol)

Trus = 1809 K
Equation:
Cp= 110.148 + 0.015219-T- 8.34 16·106 · T" 2 + 9.17225·10 8·T"3+ 9390.4· r- 1
Table 3.9.1.2. Equation of state for hpclinferrosilite (FeSi0 3); for [hpclinopyroxene s.s.].
a= 5.83628·10-5 + 7.97088·10-9 -T- 0.016239T 1 + 2.11268-T-2

Vo.298 = 32.95
fJ= 9.27088·10- 12 + 3.7382·10- 15 · r- L05327·10- 18 -T 2 + 3.097623·10-22 -T 3
K'=4.2
Volume, cm3/mol
P,GPa 1·10-4 2 5 10
T,K
298.15 32.950 32.619 32.305 31.447 30.236
500 33.178 32.825 32.492 31.584 30.314
1000 33.951 33.547 33.167 32.144 30.736
1500 34.924 34.467 34.039 32.898 31.350
2000 36.054 35.533 35.049 33.771 32.064
Thermal expansion, a-106, K 1
P,GPa 1·1 04 2 5 10
T,K
298.15 30.04 27.06 24.97 18.14 9.76
500 38.32 35.49 32.83 26.06 17.52
1000 52.21 49.80 47.60 42.10 35.23
1500 60.43 57.86 55.59 49.88 42.91
2000 66.71 63.74 61.12 54.57 46.75
Bulk modulus, GPa
P,GPa 1·10-4 2 5 10
T,K
298.15 97.090 101.290 105.490 118.090 139.090
500 91.614 95.814 100.014 112.614 133.614
1000 81.529 85.729 89.929 102.529 123.529
1500 73.780 77.980 82.180 94.780 115.780
2000 66.612 70.812 75.012 87.612 108.612
(iJKrliJ1)p
P,GPa 1·1 04 P,GPa 1·104 P,GPa 1·10-4

T,K T,K T,K
298.15 -0.0301 1000 -0.0170 2000 -0.0144
500 -0.0245 1500 -0.0145
Vp= 6.54, Vs = 3.62

Table. 3.9.2.1. Thermophysical and thermochemical data for hpclinoenstatite (MgSi03);

for [hpclinopyroxene s.s.].
Hpclinoenstatite (MgSi03): metastable at 1 bar; stable at pressures 7-20 GPa

T Cp s !!..~ 98 H' jT -(GrH29s)IT !!..rHO !!..{Io

298.15 82.100 65.300 0.000 65.300 -1544.823 -1457.192

300.00 82.373 65.809 0.516 65.302 -1544.836 -1456.648
350.00 89.388 79.044 12.721 66.323 -1545.047 -1441.931
400.00 95.457 91.387 22.694 68.693 -1545.042 -1427.198
450.00 100.572 102.934 31.071 71.863 -1544.860 -1412.477
500.00 104.876 113.760 38.243 75.518 -1544.537 -1397.783
550.00 108.518 123.931 44.470 79.461 -1544.105 -1383.128
600.00 111.628 133.510 49.940 83.570 -1543.586 -1368.516
650.00 114.308 142.554 54.791 87.762 -1543.001 -1353.950
700.00 116.638 151.112 59.127 91.985 -1542.367 -1339.432
750.00 118.682 159.230 63.031 96.199 -1541.697 -1324.959
800.00 120.490 166.949 66.567 100.382 -1541.001 -1310.533
850.00 122.100 174.303 69.787 104.516 -1540.291 -1296.150
900.00 123.545 181.323 72.734 108.589 -1539.574 -1281.810
950.00 124.848 188.039 75.443 112.595 -1547.385 -1267.260
1000.00 126.031 194.473 77.944 116.529 -1546.741 -1252.533
1100.00 128.100 206.585 82.412 124.173 -1545.374 -1223.178
1200.00 129.855 217.808 86.294 131.514 -1543.925 -1193.951
1300.00 131.366 228.263 89.705 138.559 -1542.413 -1164.847
1400.00 132.687 238.048 92.729 145.319 -1668.263 -1132.836
1500.00 133.854 247.243 95.432 151.811 -1665.309 -1094.694
1600.00 134.898 255.916 97.867 158.049 -1662.328 -1056.750
1700.00 135.840 264.122 100.073 164.049 -1709.507 -1018.606
1800.00 136.696 271.911 102.084 169.827 -1706.263 -978.059
/).~8H' = Molar volume= 3.0918 ±0.003 J/(bar·mol)

Equation:
Cp = 110.148 + o.o15219-T- 8.3416·106-T"2 + 9.17225·108-r-3 + 9.3904-10 3-r-1
(Valid range 298.15-1800 K) [J/(K-mo1)]
Table 30902020 Equation of state for hpclinoenstatite (MgSi0 3); for [hpclinopy-roxene soso].
a= 00387701887°10 4 + Oo450015778°10-8oT+ Oo343917089ol0- 3T 1- 1.72362114T2

Vo,z9s = 3009177
fJ= 00889581038°10- 11 + 0.135473202°10- 140 T + 0.317162053°10- 180 T 2+ 0.115235914°10-21 -T 3
K'=3o6 K'PT= 1.5°10-4
Volume, cm3/mol
P,GPa 1°10-4 2 5 10 20
T,K
298.15 300918 300634 30.364 290611 280520 260766

500 31.105 300809 300529 290748 280621 260822
1000 31.720 31.389 31.074 30o210 280981 270057
1500 32.418 320039 31.681 300710 290357 270291
2000 330177 320734 32.320 31.216 290717 27.496
Thermal expansion, ao106, K 1
P,GPa 1°104 2 5 10 20
T,K
298.15 21.86 20.14 19067 30051 23095 15083

500 34081 33.14 31.37 30051 23o95 15083
1000 41.89 39073 37068 30.51 23o95 15083
1500 44o98 42006 39.45 30051 23095 15083
2000 47051 43074 40.34 30051 23095 15083
Bulk modulus, GPa
P,GPa 1°10-4 2 5 10 20
T,K
298015 1070173 1100773 114.373 125.173 1430173 1790173

500 103.446 1070046 1100646 121.446 139.446 175.446
1000 930607 970207 1000807 111.607 1290607 1650607
1500 830122 860722 90.322 101.122 1190122 1550122
2000 72.486 760086 790686 90.486 108.486 144.486
(aKrta1)p
P,GPa 1°104 P,GPa 1°10-4 P,GPa 1°104

T,K T,K T,K
298o15 -000181 1000 -000205 2000 -000210

500 -000188 1500 -000213
Table 3.9.3.1. Thermophysical and thermochemical data for protoferrosilite (FeSi03);

for [protopyroxene s.s.].
Protoferrosilite (FeSi03): a fictive end-member Molar mass: 143.693 g/mol
T Cp s !1~ 98 W /T -(GrH29s)IT 11rH 0 f'1rGO

K J/(mol-K) J/(mol-K) J/(moi·K) J/(moi·K) kJ/mol kJ/mol
298.15 86.951 96.604 0.000 96.604 -1192.645 -1116.004

300.00 87.302 97.143 0.547 96.604 -1192.649 -1115.528
350.00 95.603 111.253 13.560 97.693 -1192.594 -1102.675
400.00 101.908 124.450 24.228 100.222 -1192.312 -1089.847
450.00 106.737 136.744 33.137 103.605 -1191.883 -1077.063
500.00 I 10.510 148.193 40.694 107.498 -1191.366 -1064.332
550.00 113.529 158.872 47.183 111.698 -1190.802 -1051.656
600.00 116.005 168.860 52.819 I 16.041 -1190.222 -1039.032
650.00 118.084 178.230 57.761 120.468 -1189.652 -1026.456
700.00 119.867 187.047 62.135 124.912 -1189.112 -1013.923
750.00 121.428 195.372 66.037 129.335 -I 188.622 -1001.427
800.00 122.819 203.254 69.543 133.710 -1188.201 -988.962
850.00 124.080 210.738 72.715 138.023 -1187.871 -976.520
900.00 125.239 217.863 75.601 142.262 -1187.659 -964.095
950.00 126.318 224.664 78.242 146.422 -1187.602 -951.677
1000.00 127.333 231.169 80.672 150.498 -1187.752 -939.257
1100.00 129.221 243.395 85.001 158.395 -1188.063 -914.380
1200.00 130.974 254.715 88.759 165.955 -1188.286 -889.506
1300.00 132.638 265.264 92.071 173.193 -1186.707 -864.672
1400.00 134.241 275.153 95.026 180.127 -1185.112 -839.960
1500.00 135.801 284.468 97.693 186.775 -1183.496 -815.362
1600.00 137.333 293.281 100.123 193.159 -1181.852 -790.873
1700.00 138.845 301.653 102.356 199.297 -1231.527 -766.077
1800.00 140.342 309.631 104.425 205.206 -1229.975 -738.743
!1~sw = Molar volume= 3.295 J/(bar·mol)

Iron: Tphase = 1184 K. T~hase = 1665 K,
Trus = 1809 K
Equation:
Cp= 110.148 + 0.015219-T- 8.3416·106 · r- 2 + 9.17225·108 -T-3 + 9390.4· r- 1
(Valid range 298.15-1800 K) [J/(Kmo1)]
Table 3.9.3.2. Equation of state for protoferrosilite (FeSi03); for [protopyroxene s.s.]
a= 5.83628·10'5 + 7.97088·10·9 -r- 0.016239-T" 1+2.ll268·T"2

Vo,298 = 35.328
j3= 9.27088·10. 12 + 3.7382·10. 15 ·T- l.05327·10. 18 -T2 + 3.097623·10-22 1 3
K'=4.2
Volume, cm3/mol
P,GPa 1·1 04 2 5 10
T,K
298.15 35.328 34.974 34.637 33.717 32.418

500 35.572 35.195 34.837 33.864 32.502
1000 36.401 35.968 35.560 34.464 32.954
1500 37.445 36.955 36.496 35.273 33.612
2000 38.656 38.098 37.578 36.209 34.378
P,GPa 1·104 2 5 10
T,K
298.15 30.04 27.49 25.21 18.39 9.93

500 38.32 35.38 32.66 25.99 17.54
1000 52.21 49.82 47.65 42.13 35.21
1500 60.43 57.90 55.61 49.91 42.92
2000 66.71 63.71 60.97 54.53 46.81
Bulk modulus, GPa
P,GPa 1·10-4 2 5 10
T,K
298.15 97.090 101.290 105.490 118.090 139.090
500 91.614 95.814 100.014 112.614 133.614
1000 81.529 85.729 89.929 102.529 123.529
1500 73.780 77.980 82.180 94.780 115.780
2000 66.612 70.812 75.012 87.612 108.612
(fJK'['IfJT)p
P,GPa 1·104 P,GPa 1·10-4 P,GPa 1·104

T,K T,K T,K
298.15 -0.0301 1000 -0.0170 2000 -0.0144
500 -0.0245 1500 -0.0145
Vp = 6.54, Vs = 3.62
Table 3.9.4.1. Thennophysical and thennochemical data for protoenstatite (MgSi0 3);
for [protopyroxene s.s.].
Protoenstatite (MgSi03): stable at 1298 K to melting point 1834 K

Molar mass: I 00.389 g/mol
T Cp s !J.~98 W jT -(Gr-Hz9s)IT !J.rH 0 tJ.rGO

K J/(mol-K) J/(mol-K) J/(mol·K) J/(mol-K) kJ/mol kJ/mol
298.15 80.569 66.960 0.000 66.962 -1545.790 -1458.655

300.00 80.862 67.459 0.496 66.964 -1545.806 -1458.114
350.00 88.322 80.497 12.521 67.976 -1546.081 -1445.473
400.00 94.718 92.721 22.407 70.313 -1546.120 -1428.810
450.00 100.084 104.196 30.749 73.447 -1545.969 -1414.153
500.00 104.586 114.981 37.914 77.067 -1547.303 -1399.522
550.00 108.389 125.132 44.153 80.980 -1545.243 -1384.927
600.00 111.631 134.706 49.644 85.062 -1544.728 -1370.375
650.00 114.423 143.754 54.522 89.232 -1544.140 -1355.869
700.00 116.849 152.324 58.890 93.435 -1543.498 -1341.411
750.00 118.975 160.460 62.826 97.634 -1542.814 -1327.000
800.00 120.855 168.200 66.395 101.805 -1542.103 -1312.635
850.00 122.529 175.578 69.649 105.929 -1541.372 -1298.316
900.00 124.030 189.368 75.371 113.997 -1548.418 -1269.556
1000.00 126.612 195.831 77.902 117.928 -1547.746 -1254.896
1100.00 128.759 208.002 82.431 125.571 -1546.317 -1225.680
1200.00 130.579 219.285 86.369 132.916 -1544.799 -1196.597
1300.00 132.145 229.800 89.832 139.969 -1543.212 -1167.644
1400.00 133.514 239.645 92.904 146.741 -1668.981 -1135.789
1500.00 134.723 248.898 95.653 153.246 -1665.943 -1097.810
1600.00 135.803 257.628 98.129 159.499 -1662.873 -1060.035
1700.00 136.776 265.891 100.374 165.517 -1709.960 -1022.065
1800.00 137.662 273.734 102.421 171.313 -1706.662 -981.697
!J.~sw = Molar volume= 3.2458 ±0.003 J/(bar·mol)

hs = 1834K Silicon: Tfus = 1690 K
l:!ruslr = 73.7 kJ/mol Magnesium: Trus = 923 K, Tvap = 1366 K
Equation:
Cp = 145.79 + 1.8986·10.3 -T- 1.374258-106 T 2 + 4.58429-108 -r-3 - 2.01626-104 -T- 1
Table 3.9.4.2. Equation of state for protoenstatite (MgSi03); for [protopyroxene s.s.].
a= 6.40239-1 o- 5 + 1.4439·1 o-8 -T- 0.0632425· r-' r-

+ 7.86955· 2
Vo 298 = 32.458
i= 9.11066·10- 12 + 7.612·10- 17 -T- 7.3162·10-' 8-T 2 + 5.311578-10-2'· T 3
K' = 6.6 K'pr = 1.5·104
Volume, cm3/mol
P,GPa 2
T,K
1500 32.834 32.497 32.185

2000 33.758 33.061 32.461
P,GPa 1-104 2
T,K
1500 47.02 31.45 20.92

2000 63.25 31.45 20.92
Bulk modulus, GPa
P,GPa 2
T,K
1500 93.550 100.150 106.750

2000 44.463 51.063 57.663
(iJKrfCJ1)p
P,GPa
T,K
1500 -0.1223
2000 -0.0683
Table 3.10.1.1. Thermophysical and thermochemical data for orthocorundum (Ah03);

for [orthopyroxene s.s. ].
Orthocorundum: fictive end-member 298.15 to 1800 K Molar mass: 101.961 g/mol
T Cp s !1~98 H' jT -(GrH29s)IT f1cfl 0 f1rGO
298.15 78.681 55.002 0.000 55.002 -1649.465 -1557.240

300.00 79.100 55.490 0.495 55.003 -1649.490 -1556.668
350.00 88.756 68.447 12.450 56.004 -1649.966 -1541.154
400.00 95.901 80.798 22.456 58.338 -1650.126 -1525.596
450.00 101.314 92.410 30.931 61.485 -1650.077 -1510.031
500.00 105.521 103.311 38.188 65.129 -1649.888 -1494.479
550.00 108.870 113.531 44.467 69.069 -1649.607 -1478.951
600.00 111.596 123.125 49.951 73.178 -1649.269 -1463.452
650.00 113.859 132.149 54.782 77.371 -1648.898 -1447.982
700.00 115.772 140.659 59.072 81.590 -1648.513 -1432.541
750.00 117.415 148.704 62.908 85.800 -1648.132 -1417.128
800.00 118.848 156.328 66.361 89.971 -1647.778 -1401.739
850.00 120.115 163.572 69.486 94.089 -1647.476 -1386.371
900.00 121.247 170.470 72.331 98.142 -1647.247 -1371.019
950.00 122.270 177.054 74.933 102.124 -1668.455 -1355.299
1000.00 123.205 183.349 77.323 106.029 -1668.095 -1338.826
1100.00 124.863 195.172 81.572 113.603 -1667.296 -1305.937
1200.00 126.312 206.100 85.241 120.861 -1666.407 -1273.125
1300.00 127.609 216.262 88.451 127.813 -1665.437 -1240.390
1400.00 128.793 225.763 91.291 134.474 -1664.393 -1207.733
1500.00 129.892 234.687 93.828 140.860 -1663.281 -1175.153
1600.00 130.924 243.103 96.115 146.990 -1662.103 -1142.649
1700.00 131.905 251.070 98.191 152.880 -1660.863 -1110.221
1800.00 132.845 258.636 100.091 158.547 -1659.560 -1077.867
11~8H' = Molar volume= 2.74 J/(mol·bar)

Aluminum: Tru. = 933.47 K
Equation:
Cp= 122.6 + 0.007031-T- 5.583·106-r-2 + 5.707-108-T 2 - 1414-r-1
Table 3.1 0.1.2. Equation of state for orthocorundum (Alz0 3); for [orthopyroxene s.s.).
a= 2.66·10·5 + 0.72-10-8-T
Vo29s= 27.40
p'= 9.3·10- 12 + 1.35844·10- 15 -T+ 3.1613·I0-19·T 2 + 1.14126·I0-22 -T 3
K'= 10.2 K'pT= 1.5·10-4
Volume, cm3/mol
P,GPa 1·10-4 2 5 10 20
T,K
298.15 27.400 27.147 26.916 26.327 25.562 24.458
500 27.563 27.300 27.062 26.454 25.669 24.542
1000 28.008 27.715 27.453 26.791 25.951 24.761
1500 28.511 28.179 27.886 27.158 26.098 24.988
2000 29.075 28.693 28.360 27.550 26.564 25.217
P,GPa 1·10-4 2 5 10 20
T,K
298.15 28.75 27.37 26.37 23.69 15.27 17.87
500 30.20 28.60 27.40 24.40 16.85 17.87
1000 33.80 31.64 29.95 26.17 20.75 17.87
1500 37.40 34.68 32.50 27.93 24.65 17.87
2000 41.00 37.73 35.05 29.69 28.55 17.87
Bulk modulus, GPa
P,GPa 1-10-4 2 5 10 20
T,K
298.15 102.713 112.913 123.113 153.713 204.713 306.713
500 99.280 109.480 119.680 150.280 201.280 303.280
1000 90.182 100.382 110.582 141.182 192.182 294.182
1500 80.424 90.624 100.824 131.424 182.424 284.424
2000 70.450 80.650 90.850 121.450 172.450 274.450
(CJKrtanp
P,GPa 1·10-4 P,GPa 1·10·4

T,K T,K
298.15 -0.0166 1000 -0.0190
500 -0.0173 1500 -0.0199
2000 -0.0198
86 Thennodynamic Data for Stoichiometric Phases 000
Table 3.10o2ol. Thennophysical and thennochemical data for orthoferrosilite (FeSi03);

for [orthopyroxene SoSo]o
Orthoferrosilite (FeSi0 3): stable at pressures 1-9 GPa; metastable at I bar

Molar mass 1430693 g/mol
T Cp s tl~ 98 H' jT -(GrH298)/T tlrlfo fltGO

K J/(moloK) J/(moloK) J/(moloK) J/(moloK) kJ/mol kJ/mol
298.15 860951 960604 OoOOO 960604 -11920645 -11160004

300000 87.302 97.143 00547 960604 -11920649 -1115.528
350000 950603 111.253 130560 970693 -1192.594 -11020675
400000 101.908 124.450 240228 1000222 -1192o3l2 -10890847
450o00 106o737 1360744 33.137 1030605 -1191.883 -1077.063
500o00 110.510 148.193 400694 107.498 -1191.366 -1064o332
550000 113.529 1580872 47.183 111.698 -1190o802 -1051.656
600000 1160005 1680860 520819 116o041 -11900222 -10390032
650000 118o084 178o230 570761 120.468 -11890652 -1026.456
700o00 119o867 187o047 620135 1240912 -11890112 -10130923
750000 121.428 1950372 66o037 1290335 -11880622 -1001.427
800000 1220819 2030254 690543 1330710 -11880201 -988o962
850000 1240080 2100738 72o715 138o023 -11870871 -9760520
900000 1250239 2170863 750601 1420262 -11870659 -964o095
950o00 126.318 224o664 780242 146o422 -1187o602 -951.677
1000000 127.333 231.169 800672 150.498 -11870752 -9390257
1100000 1290221 243.395 850001 158.395 -1188o063 -914.380
1200000 1300974 2540715 88o759 1650955 -11880286 -8890506
1300000 132o638 2650264 920071 173.193 -11860707 -864o672
1400000 1340241 2750153 950026 180.127 -1185.112 -8390960
1500000 135o801 284.468 97o693 1860775 -1183.496 -815.362
1600o00 137.333 2930281 1000123 193.159 -1181.852 -7900873
1700o00 1380845 301.653 102.356 1990297 -1231.527 -7660077
1800o00 140.342 3090631 104.425 2050206 -12290975 -738o743
~;sw = Molar volume= 30295 J/(baromol)

Iron: Tpbase = 1184 K, r;base = 1665 K,
Trus = 1809 K
Equation
Cp= 110.148 + Oo015219oT- 8.34l6o106 oT"2 + 9.17225o108 oT"3 + 9390.4oT" 1
(Valid range 298015-1800 K) [J/(Komol)]
Table 3.1 0.2.2. Equation of state for orthoferrosilite (FeSi03); for [orthopyroxene ss.].
a= 5.83628·10·5 + 7.97088-10-9 -T- 0.016239-r- 1 + 2.11268-r-2

V0,2 9s = 32.95
P= 9.27088·10- 12 + 3.7382-Io- 15 -T- L05327·10- 18 -T 2 + 3.097623-10-22 -T 3
K'=4.2
Volume, cm3/mol
P,GPa 1-104 2 5 10
T,K
298.15 32.950 32.619 32.305 31.447 30.236
500 33.178 32.825 32.492 31.584 30.314
1000 33.951 33.547 33.167 32.144 30.736
1500 34.924 34.467 34.039 32.898 31.350
2000 36.054 35.533 35.049 33.771 32.064
Thermal expansion, aot06, K 1
P,GPa 1-104 2 5 10
T,K
298.15 30.04 27.06 24.97 18.14 9.76
500 38.32 35.49 32.83 26.06 17.52
1000 52.21 49.80 47.60 42.10 35.23
1500 60.43 57.86 55.59 49.88 42.91
2000 66.71 63.74 61.12 54.57 46.75
Bulk modulus, GPa
P,GPa 1-10"4 2 5 10
T,K
298.15 97.090 101.290 105.490 118.090 139.090
500 91.614 95.814 100.014 112.614 133.614
1000 81.529 85.729 89.929 102.529 123.529
1500 73.780 77.980 82.180 94.780 115.780
2000 66.612 70.812 75.012 87.612 108.612
(axrtanP
P,Gpa 1·10"4 P,GPa 1·10"4 P,GPa 1·10"4
T,K T,K T,K
298.15 -0.0301 1000 -0.0170 2000 -0.0144
500 -0.0245 1500 -0.0145
Vp= 6.54, Vs= 3.62

Table 3.1 0.3.1. Thermophysical and thermochemical data for orthoenstatite (MgSi03);
for [orthopyroxene s.s.].
Orthoenstatite (MgSi03): stable at 903 -1282 K; Trus = 1828 K

T Cp s t1~98 W jT -(GrH298)/T f1rflo f1rGO
K J/(mo1-K) J/(mol-K) J/(mo1-K) J/(mol·K) kJ/mol kJ/mol
298.15 82.225 66.270 0.000 66.27 -1546.290 -1458.945

300.00 82.496 66.779 0.518 66.272 -1546.299 -1458.403
350.00 89.474 80.030 12.737 67.293 -1546.505 -1443.734
400.00 95.522 92.384 22.718 69.666 -1546.496 -1429.051
450.00 100.625 103.938 31.099 72.839 -1546.311 -1414.380
500.00 104.921 114.768 38.272 76.496 -1545.987 -1399.737
550.00 108.558 124.944 44.501 80.443 -1545.552 -1385.132
600.00 111.664 134.526 49.972 84.554 -1545.031 -1370.571
650.00 114.342 143.572 54.823 88.750 -1544.445 -1356.056
700.00 116.671 152.133 59.159 92.974 -1543.809 -1341.588
750.00 118.715 160.254 63.063 97.191 -1543.137 -1327.167
800.00 120.522 167.974 66.599 101.376 -1542.440 -1312.792
850.00 122.132 175.330 69.819 105.511 -1541.728 -1298.461
900.00 123.576 182.353 72.766 109.587 -1541.009 -1284.171
950.00 124.880 189.070 75.475 113.594 -1548.819 -1269.674
1000.00 126.063 195.506 77.975 117.530 -1548.173 -1254.998
1100.00 128.133 207.621 82.444 125.177 -1546.803 -1225.746
1200.00 129.888 218.847 86.326 132.521 -1545.351 -1196.623
1300.00 131.400 229.305 89.737 139.568 -1543.835 -1167.623
1400.00 132.721 239.092 92.761 146.331 -1669.682 -1135.716
1500.00 133.890 248.282 95.465 152.825 -1666.725 -1097.679
1600.00 134.934 256.964 97.899 159.065 -1663.740 -1059.840
1700.00 135.876 265.173 100.106 165.067 -1710.915 -1021.801
1800.00 136.733 272.964 102.117 170.847 -1707.667 -981.358
f1~ 8 w =11.989±0.025 kJ/mo1 Molar volume= 3.1346 ±0.003 J/(bar·mol)

Trus = 1828 K Silicon: Trus = 1690 K
t1ru,lf0 =74.8 kJ/mol Magnesium: Trus = 923 K, Tvap = 1366 K
Equation:
Cp = 144.45 + 1.8821·10-3 -T- 1.35000·106 -r-2 + 4.612· 108 -T-3 - 1.9380·104 -r- 1
(Valid range 298.15-1800 K) [J/(K-mo1)]
Table 3.! 0.3.2. Equation of state for orthoenstatite (MgSi0 3); for [orthopyroxene s.s.].
a= 2.66·10-5 + 7.2·10-9-T
V0,298 = 31.346
P= 9.3·10- 12 + 1.3584·10- 15 ·T+ 3.1613·10- 191 2 + l.l4l3·10-22 ·T 3
K'= 10.2 K'PT = 1.5·104
Volume, cm3/mol
P,GPa 1·1 04 2 5 10 20
T,K
298.!5 31.346 31.056 30.793 30.119 29.243 27.981
500 31.533 31.232 30.959 30.264 29.366 28.076
1000 32.042 31.707 31.406 30.650 29.688 28.327
1500 32.617 32.238 31.902 31.069 30.031 28.586
2000 33.263 32.825 32.444 31.518 30.389 28.849
Thermal expansion, ~ 106, K 1
P,GPa 1·10'4 2 5 10 20
T,K
298.15 28.75 27.47 26.29 23.68 20.81 17.21
500 30.20 28.68 27.34 24.39 21.24 17.39
1000 33.80 31.67 29.93 26.16 22.28 17.84
1500 37.40 34.66 32.52 27.93 23.33 18.28
2000 41.00 37.64 35.10 29.70 24.37 18.72
Bulk modulus, GPa
P,GPa 1·10'4 2 5 10 20
T,K
298.15 102.710 112.910 123.110 153.710 204.410 306.710
500 99.280 109.480 119.680 150.280 201.280 303.280
1000 90.182 100.382 110.582 141.182 192.182 294.!82
1500 80.424 90.624 100.824 131.424 182.424 284.424
2000 70.450 80.650 90.850 121.450 172.450 274.450
(i1Krti11)p
P,GPa 1·10'4 P,GPa 1·104 P,GPa 1·104

T,K T,K T,K
298.!5 -0.0166 1000 -0.0190 2000 -0.0198
500 -0.0173 1500 -0.0199
Vp= 8.03, Vs =4.82

Table 3.11.1.1. Thermophysical and thermochemical data for garnet (FeSi03);

for [garnet s.s.].
Gamet (FeSi03): metastable end-member Molar mass 143.693 g/mol
T Cp s ,1~ 98 H' jT -(GrH298)/T !!.rHo !!.rGO

K J/(mol-K) J/(mol-K) J/(mol-K) J/(mol·K) kJ/mol kJ/mol
298.15 85.887 88.171 0.000 88.171 -1170.352 -1091.193

300.00 86.286 88.704 0.540 88.163 -1170.354 -1090.701
350.00 95.500 102.735 13.483 89.252 -1170.324 -1077.424
400.00 102.108 115.943 24.171 91.772 -1170.038 -1064.170
450.00 106.841 128.258 33.108 95.150 -1169.600 -1050.961
500.00 110.277 139.702 40.662 99.040 -1169.085 -1037.806
550.00 112.820 150.338 47.112 103.226 -1168.544 -1024.705
600.00 114.745 160.240 52.671 107.569 -ll68.013 -1011.652
650.00 116.238 169.486 57.506 111.980 -1167.520 -998.642
700.00 117.424 178.145 61.745 116.400 -1167.088 -985.668
750.00 118.394 186.281 65.490 120.791 -1166.735 -972.723
800.00 119.208 193.949 68.823 125.126 -1166.480 -959.797
850.00 119.910 201.197 71.808 129.389 -1166.354 -946.884
900.00 120.532 208.069 74.498 133.571 -1166.355 -933.976
950.00 121.096 214.601 76.936 137.665 -1166.546 -921.061
1000.00 121.620 220.826 79.157 141.669 -1166.970 -908.131
1100.00 122.592 232.464 83.062 149.402 -1167.898 -882.191
1200.00 123.512 243.170 86.395 156.776 -1168.827 -856.194
1300.00 124.417 253.092 89.285 163.808 -1168.033 -830.173
1400.00 125.328 262.346 91.827 170.519 -1167.295 -804.212
1500.00 126.254 271.024 94.091 176.933 -1166.602 -778.302
1600.00 127.202 279.202 96.130 183.072 -1165.943 -752.437
1700.00 128.174 286.943 97.987 188.956 -1216.658 -726.202
1800.00 129.171 294.297 99.691 194.606 -1216.199 -697.365
,12~8H' = Molar volume= 2.9425 J/(bar·mol)

Trus = 1809 K
Equation:
Cp = 91.898 + 0.0143297·T- 1.40924· J07.r-2 + 1.43573·109 ·r-3 + 2.80489· 104 · r- 1
(Valid range 298.15-1800 K) [J/(K·mol)]
Table 3.11.1.2. Equation of state for garnet (FeSi03); for [garnet s.s.].
a= 3.0836·10'5 + 6.659·10-9-T- 6.106·10-3-r- 1 + 0.6453-r-2

Vo,298 = 29.425
fl= 5.4854-I0- 12 + 8.06-I0- 16 -T- 4.6·10-20 -T 2 + 1.5674-10'22 -T 3
K'=5.6 K'n = 2.0·1 0'3
Volume, cm3/mol
P,GPa 1-10'4 2 5 10 20
T,K
298.15 29.43 29.26 29.10 28.65 28.00 26.91

500 29.56 29.39 29.22 28.76 28.09 26.99
1000 29.98 29.80 29.62 29.13 28.44 27.35
1500 30.51 30.30 30.10 29.58 28.87 27.79
2000 31.11 30.87 30.65 30.08 29.34 28.26
Thermal expansion, a;106, K 1
P,GPa 1·10'4 2 5 10 20
T,K
298.15 19.60 19.03 15.61 15.52 11.26 27.52

500 24.53 23.85 23.53 21.40 19.69 27.52
1000 32.03 30.90 29.97 28.71 28.21 27.52
1500 37.04 35.43 34.23 32.30 31.41 27.52
2000 41.26 39.03 38.17 34.63 33.03 27.52
Bulk modulus, GPa
P,GPa 1-10'4 2 5 10 20
T,K
298.15 174.649 180.249 185.849 202.649 230.649 286.649

500 169.592 175.192 180.792 197.592 225.592 281.592
1000 156.198 161.798 167.398 184.198 212.198 268.198
1500 140.451 146.051 151.651 168.451 196.451 252.451
2000 122.439 128.039 133.639 150.439 178.439 234.439
(iJKrtanp
P,GPa 1·10'4 P,GPa 1·10'4

T,K T,K
298.15 -0.0250 1000 -0.0289

500 -0.0252 1500 -0.0340
2000 -0.0375
Table 3.11.2.1. Thermophysical and thermochemical data for garnet (MgSi0 3);
for [garnet s.s.].
Gamet (MgSi03): metastable at I bar, stable at 15-22 GPa

T Cp s !J.~ 98 W jT -(GrH298)/T l!.rH 0 !J.rGO

K J/(mol-K) J/(moi-K) J/(mol·K) J/(mol·K) kJ/mol kJ/mol
298.15 79.206 60.300 0.0 60.300 -1513.000 -1423.875

300.00 79.536 60.791 0.499 60.302 -1513.015 -1423.322
350.00 87.396 73.666 12.374 61.292 -1513.342 -1408.344
400.00 93.655 85.760 22.157 63.603 -1513.431 -1393.336
450.00 98.777 97.096 30.395 66.701 -1513.338 -1378.328
500.00 103.063 107.731 37.453 70.278 -1513.106 -1363.338
550.00 106.715 117.730 43.588 74.142 -1512.764 -1348.377
600.00 109.874 127.154 48.983 78.171 -1512.334 -1333.451
650.00 112.641 136.060 53.776 82.284 -1511.835 -1318.564
700.00 115.090 144.499 58.070 86.430 -1511.282 -1303.717
750.00 117.278 152.515 61.945 90.570 -1510.685 -1288.912
800.00 I 19.248 160.148 65.466 94.682 -1510.056 -1274.147
850.00 121.034 167.432 68.683 98.749 -1509.403 -1259.423
900.00 122.662 174.397 71.637 102.760 -1508.735 -1244.737
950.00 124.155 181.069 74.363 106.707 -1516.586 -1229.840
1000.00 125.531 187.473 76.887 110.586 -1515.971 -1214.764
1100.00 127.985 199.556 81.424 118.132 -1514.636 -I 184.707
1200.00 130.116 210.785 85.395 125.391 -1513.179 -1154.777
1300.00 131.990 221.276 88.908 132.367 -1511.622 -1124.973
1400.00 133.653 23 I.I 19 92.046 139.073 -1637.393 -1092.265
1500.00 135.144 240.392 94.870 145.522 -1634.326 -1053.434
1600.00 136.489 249.158 97.430 151.727 -1631.200 -1014.810
1700.00 137.712 257.470 99.764 157.705 -1678.206 -975.995
1800.00 138.829 265.373 101.904 163.469 -1674.761 -934.788
!J.~sw = Molar volume = 2.85 ±0.003 J/(bar·mol)

Transition in Phase Transition in reference state elements
Equation:
Cp= 176.8- 6.44·10 5·r-2 + 6.59·10 7·r-3 - 1.603·103.r-0 .s
Table 3.11.2.2. Equation of state for garnet (MgSi03); for [garnet s.s.].
a= 1.1019·10.5 + 7.5075·10.9 T+ 0.0060403-T" 1 -l.0267-T"2

Vo.298 = 28.5
P= 5.8168-10- 12 + 2.521-10- 15 -T-l.l·I0- 18 -T 2 + 5.58636·10-22 -T 3
K'=4.0 K'n = 1.0·10·3
Volume, cm 3/mol
P,GPa 1·1 04 2 5 10 20
T,K
298.15 28.500 28.317 28.142 27.644 26.900 25.657

500 28.630 28.436 28.250 27.724 26.945 25.691
1000 28.961 28.740 28.529 27.944 27.102 25.757
1500 29.320 29.063 28.822 28.170 27.265 25.884
2000 29.723 29.411 29.125 28.378 27.390 25.956
Thermal expansion, a<l06, K- 1
P,GPa 1·104 2 5 10 20
T,K
298.15 21.97 20.38 19.03 15.47 10.77 6.84
500 22.75 20.93 19.11 15.47 10.77 6.84
1000 23.54 21.72 20.12 15.47 10.77 6.84
1500 25.85 23.04 20.71 15.47 10.77 6.84
2000 28.80 24.59 21.11 15.47 10.77 6.84
Bulk modulus, GPa
P,GPa 1-104 2 5 10 20
T,K
298.15 154.191 158.191 162.191 174.191 194.191 234.191
500 145.515 149.515 153.515 165.515 185.515 225.515
1000 128.264 132.264 136.264 148.264 168.264 208.264
1500 111.004 115.004 119.004 131.004 151.004 191.004
2000 91.509 95.509 99.509 111.509 131.509 171.509
(iJKrfi11)p
P,GPa 1·1 04 P,GPa 1·104

T,K T,K
298.15 -0.0479 1000 -0.0329

500 -0.0390 1500 -0.0369
2000 -0.0404
Vp= 8.91, Vs = 5.05

Table 3.11.3.1. Thermophysical and thermochemical data

for almandine (Fe3AI 2 Si30 12 );
for [garnet s.s.].
Almandine (Fe3AI2 Si3 0 12 ): cubic crystals at 298.15 -1800 K, Tfus = 1683 K

Molar mass: 497.753 g/mo1
T Cp s 1'1.~ 98 H' /T -(GrH298)/T 1'1.rH 0 1'1.rGO

K J/(mol-K) J/(mol-K) J/(mol·K) J/(moi·K) kJ/mol kJ/mol
298.15 343.358 342.600 0.000 342.600 -5271.940 -4949.130

300.00 344.557 344.727 2.114 342.613 -5271.970 -4947.127
350.00 373.420 400.092 53.173 346.919 -5272.260 -4892.951
400.00 396.667 451.526 94.707 356.818 -5271.762 -4838.790
450.00 415.675 499.381 129.349 370.032 -5270.702 -4784.728
500.00 431.407 544.016 158.792 385.224 -5269.251 -4730.805
550.00 444.556 585.769 184.190 401.578 -5267.542 -4677.042
600.00 455.626 624.938 206.362 418.577 -5265.687 -4623.441
650.00 464.999 661.788 225.906 435.882 -5263.782 -4569.998
700.00 472.964 696.548 243.276 453.271 -5261.915 -4516.700
750.00 479.747 729.416 258.821 470.595 -5260.171 -4463.533
800.00 485.528 760.568 272.814 487.754 -5258.647 -4410.474
850.00 490.450 790.155 285.476 504.679 -5257.445 -4357.502
900.00 494.628 818.310 296.982 521.327 -5256.686 -4304.589
950.00 498.160 845.150 307.480 537.670 -5277.856 -4251.324
1000.00 501.123 870.780 317.091 553.689 -5278.125 -4197.292
1100.00 505.601 918.766 334.038 548.728 -5278.800 -4089.142
1200.00 508.481 962.893 348.465 614.428 -5276.760 -3981.072
1300.00 510.069 1003.660 360.842 642.822 -5274.062 -3873.206
1400.00 510.597 1041.490 371.526 669.963 -5271.326 -3765.551
1500.00 510.240 1076.710 380.790 695.919 -5268.853 -3658.084
1600.00 509.137 1109.610 388.850 720.758 -5266.827 -3550.768
1700.00 507.398 1140.420 395.877 744.548 -5265.371 -3443.562
1800.00 505.111 1169.360 402.011 767.353 -5264.328 -3336.429
/',2; 8 H' = 52.74 kJ Molar volume 11.532 J/(mo1·bar)

Tfus = 1683 K Aluminium: Trus = 933.47 K
Tfus = 1809 K
Equation:
Cp= 862.94 4- 0.082878-T- 8874.6·T" 05 + 1.6967·106.r-2
(Valid range 298.15-1200 K) [J/(Km ol)]
Table 3.11.3.2. Equation of state for almandine (Fe3AhSi30n); for [garnet s.s.].
a= 3.0836·10'5+ 0.6659·10-8 -T- 6.106·10-3·T- 1+ 0.64531-2

Vo,29s= 115.284
f3= 4.8076·10- 12 + 3.0405·10- 15 1+ 0.1635·10- 191 2+ 3.9961-10-22 1 3
K'=5.6 K'PT=0.002
Volume, cm 3/mol
P,GPa 1·104 2 5 10 20
T,K
298.15 115.284 114.636 114.011 112.260 109.210 104.264
500 115.801 115.078 114.384 112.457 109.660 104.511
1000 117.472 116.533 115.652 113.292 110.043 105.115
1500 119.525 118.306 117.203 114.392 110.769 105.594
2000 121.890 120.305 118.940 115.666 111.710 106.336
P,GPa 1·104 2 5 10 20
T,K
298.15 19.60 16.77 13.87 5.80 12.67 11.27
500 24.53 21.27 18.38 11.13 12.67 11.27
1000 32.03 28.13 24.84 17.53 12.67 11.27
1500 37.04 32.01 28.20 20.89 12.67 11.27
2000 41.26 34.91 30.55 23.33 12.67 11.27
Bulk modulus, GPa
P,GPa 1·1 o4 2 5 10 20
T,K
298.15 174.651 180.251 185.851 202.651 230.651 286.651
500 156.693 162.293 167.893 184.693 212.693 268.693
1000 121.006 126.606 132.206 149.006 177.006 233.006
1500 92.990 98.590 104.190 120.990 148.990 204.990
2000 70.667 76.267 81.867 98.667 126.667 182.667
(iJKrf(J1)p
P,GPa 1·1 04 P,GPa 1·1 04

T,K T,K
298.15 -0.0166 1000 -0.0190

500 -0.0173 1500 -0.0199
2000 -0.198
Vp= 8.03, Vs =4.82

Table 3o11.4olo Thermophysical and themochemical data for pyrope (Mg3AizSi30u);

for [garnet so so).
Pyrope (Mg3AizSh0u): cubic crystals at 298ol5-1800 K, melting at 1570 K

Molar mass: 403.127 g!mol
T Cp s ll~98 WjT -(GrH298)/T llcH 0 !!eGO

K J/(moloK) J/(moloK) J/(moloK) J/(moloK) kJ/mol kJ/mol
298.15 3250630 2660270 00000 2660270 -6287ol50 -59360613

300000 327.141 268o289 2o0l9 266o280 -62870210 -5934.437
350000 3620046 321.477 51.086 270o391 -6288.146 -5875o550
400000 3870918 371.593 91.651 2790943 -62880011 -58160606
450000 4070552 4180468 1250708 2920760 -6287.157 -57570726
500000 4220839 4620231 1540687 3070544 -62850819 -56980968
550o00 435o039 503.124 179o638 323o486 -62840157 -5640o362
600000 4450000 541.419 201.350 3400068 -62820285 -5581.916
650000 453.302 577.375 220.421 3560954 -62800285 -55230633
700o00 460.353 611.233 237.314 3730919 -62780218 -5465o506
750000 466.443 6430207 252.391 390o816 -62760134 -54070528
800o00 471.783 673.484 2650939 4070545 -62740084 -53490688
850000 476.531 702o231 278.190 4240041 -6272.112 -5291.974
900000 4800804 729.592 289.329 440o262 -62700257 -5234.373
950000 484o693 755o693 299o5ll 456.182 -6315.480 -51750746
1000o00 4880268 7800647 3080861 471.786 -6313o815 -51150803
1100000 4940681 827.491 325.468 502o023 -6310o297 -49960170
1200000 500.361 8700782 339o810 5300972 -63060564 -48760867
1300000 505o513 911.039 3520362 558o677 -63020645 -47570884
1400000 5100276 948o678 363.473 5850205 -6298o558 -46390208
1500000 5140745 9840037 373.410 6100627 -6294.315 -45200830
1600000 5l8o989 1017039 382.377 6350017 -62890925 -44020740
1700000 5230056 1048098 390.534 658.447 -62850387 -42840929
1800000 5260984 1078o99 3980006 6800984 -62800458 -4167.395
!!.~ 8 H'= 50009 kJ Molar volume= 11.328 J/(molobar)

Teu. = 1570 K Aluminium: Trus = 933.47 K
Silicon: Teu. = 1690 K
Equation:
Cp = 476o8- 0003167-T- 2.12o10 7oT02 + 2ol68°109oT"3 - 1170oT1
(Valid range 298ol5-1570 K) [J/(Kmo1)]
Table 3.11.4.2. Equation of state for pyrope (Mg3AlzSi 30 12); for [garnet s.s.].
a= 0.991·10- 5 + l.l65·10. 8-T+ 0.010624-r- 1- 2.500-r-2

Vo.29s = 113.28
fJ= 5.546·10- 12 + 8.06·10- 16 -T- 4.6·10-20 -T 2 + 1.567-l0"22 -T 3
K'=4.8
Volume, cm3 /mol
P,GPa 1·1 04 2 5 10 20
T,K
298.15 113.280 112.630 112.011 110.250 107.630 103.260
500 113.853 113.181 112.541 110.725 108.029 103.552
1000 115.480 114.747 114.041 112.060 109.144 104.355
1500 117.309 116.483 115.690 113.483 110.270 105.072
2000 119.414 118.454 117.537 115.009 111.386 105.644
P,GPa 1·1 04 2 5 10 20
T,K
298.15 20.89 19.89 19.51 17.98 20.12 13.89
500 26.98 26.22 25.27 22.98 20.12 13.89
1000 29.68 28.59 27.47 24.61 20.12 13.89
1500 33.36 31.67 30.09 25.93 20.12 13.89
2000 37.90 35.56 33.34 27.55 20.12 13.89
Bulk modulus, GPa
P,GPa 1·1 o4 2 5 10 20
T,K
298.15 172.820 177.620 182.420 196.820 220.820 268.820
500 167.867 172.667 177.467 191.867 215.867 263.867
1000 154.734 159.534 164.334 178.734 202.734 250.734
1500 139.269 144.069 148.869 163.269 187.269 235.269
2000 121.542 126.342 131.142 145.542 169.542 217.542
(iJKrfC}1)p
P,GPa 1·104 P,GPa 1·104

T,K T,K
298.15 -0.0245 1000 -0.0284

500 -0.0247 1500 -0.0335
2000 -0.0370
Vr= 9.11, Vs = 5.07

Table 3.12.1.1. Thermophysical and thermochemical data for corundum (Al20 3 );

for [ilmenite s.s.).
Corundum (Al20 3): stable at 298.15-2345 K, Trus = 2345 K

T Cp s I1~98 H' jT -(GrH29s)IT f1tlf0 11/]0
298.15 78.681 50.920 0.000 50.920 -1675.708 -1582.266

300.00 79.100 51.405 0.495 50.920 -1675.734 -1581.686
35o.oo· 88.756 64.362 12.450 51.912 -1676.210 -1565.968
400.00 95.901 76.703 22.456 54.247 -1676.370 -1550.206
450.00 101.314 88.325 30.931 57.395 -1676.321 -1534.436
500.00 105.521 99.226 38.188 61.039 -1676.132 -1518.680
550.00 108.870 109.446 44.467 64.980 -1675.851 -1502.948
600.00 111.596 119.040 49.951 69.089 -1675.513 -1487.244
650.00 113.859 128.064 54.782 73.282 -1675.142 -1471.570
700.00 115.772 136.574 59.072 77.502 -1674.757 -1455.250
750.00 117.415 144.619 62.908 81.711 -1674.376 -1440.308
800.00 118.848 152.243 66.361 85.883 -1674.022 -1424.715
850.00 120.115 159.487 69.486 90.001 -1673.719 -1409.143
900.00 121.247 166.386 72.331 94.055 -1673.491 -1393.587
950.00 122.270 172.969 74.933 98.036 -1694.699 -1377.662
1000.00 123.205 179.265 77.323 101.941 -1694.339 -1360.985
1100.00 124.863 191.087 81.572 109.515 -1693.540 -1327.687
1200.00 126.312 202.015 85.241 116.774 -1691.651 -1294.467
1300.00 127.609 212.177 88.451 123.726 -1691.681 -1261.324
1400.00 128.793 221.678 91.291 130.387 -1690.637 -1228.258
1500.00 129.892 230.602 93.828 136.774 -1689.525 -1195.269
1600.00 130.924 239.018 96.115 142.904 -1688.347 -1162.357
1700.00 131.905 246.985 98.191 148.794 -1687.106 -1129.520
1800.00 132.845 254.551 100.091 154.461 -1685.804 -1096.758
/),.~ 8 H' = 10.016 kJ Molar volume= 2.5575 J/(mol·bar)

Aluminium: Trus = 933.47 K
Equation:
Cp = 122.6 + 0.007031·T- 5.583·106·T"2 + 5.707·1081 2- 1414-T"1
(Valid range 298.15-1800) [J/(Kmol)]
Table 3.12.1.2. Equation of state for corundum (Al20 3); for [ilmenite s.s.].
a= 4.196·10· 5 - 0.08·10· 8-T- 11.406·10·3 -r- 1 + 1.0623-r-2

Vo,29S = 25.575
fJ= 3.8469·10- 12 + 0.368725-10- 15 -T + l.2898-10- 19 -T 2 + 0.235·10-22 -T 3
K'=4.2
Volume, cm 3/mol
P,GPa 1·104 2 5 10 20
T,K
298.15 25.575 25.474 25.376 25.092 24.652 23.877

500 25.676 25.572 25.472 25.180 24.729 23.936
1000 26.034 25.921 25.811 25.495 25.009 24.161
1500 26.459 26.334 26.213 25.865 25.332 24.412
2000 26.918 26.776 26.641 26.251 25.661 24.652
Thermal expansion, CJ'l06, K 1
P,GPa 1·104 2 5 10 20
T,K
298.15 15.42 11.14 10.98 9.45 7.75 4.50

500 23.00 23.38 22.89 21.54 19.53 16.22
1000 30.82 29.87 29.17 27.35 24.60 20.22
1500 33.63 32.47 31.65 29.22 25.75 20.13
2000 34.92 34.49 33.58 30.52 26.3 19.44
Bulk modulus, GPa
P,GPa 1·1 o4 2 5 10 20
T,K
298.15 251.96 256.162 260.362 272.962 293.962 335.962
500 245.92 250.115 254.315 266.915 287.915 329.915
1000 228.93 233.132 237.332 249.932 270.932 312.932
1500 209.67 213.865 218.065 230.665 251.665 293.665
2000 189.10 193.298 197.498 210.098 231.098 273.098
(iJKrf(J1) p
P,GPa 1·104 P,GPa 1·1 04

T,K T,K
298.15 -0.0287 1000 -0.0365

500 -0.0312 1500 -0.0402
2000 -0.0417
Vp= 10.88, Vs = 6.401

Table 3.12.2.1. Thermophysical and thermochemical data for ilmenite (FeSi03);

for [ilmenite s.s.].
Ilmenite (FeSi03): metastable end-member Mo1armass: 143.693 g/mol
T Cp s !i~98 H' jT -(GrHzgs)IT l!.rH 0 !!.rOO

K J/(mol·K) J/(mol·K) J/(mol-K) J/(mol·K) k:J/mol k:J/mol
298.15 79.903 90.128 0.000 90.128 -I 139.570 -1060.994

300.00 80.385 90.624 0.535 90.128 -1139.583 -1060.507
350.00 91.299 103.884 12.740 9I.l44 -1139.802 -1047.304
400.00 98.981 116.606 23.068 93.538 -1139.697 -1034.094
450.00 104.460 128.599 31.824 96.775 -1139.396 -1020.911
500.00 108.455 139.822 39.297 100.525 -1138.986 -1007.767
550.00 111.442 150.305 45.726 104.579 -1138.524 -994.667
600.00 113.738 160.105 51.302 108.802 -1138.053 -981.610
650.00 115.550 169.283 56.177 113.106 -1137.602 -968.592
700.00 117.022 177.902 60.472 117.429 -1137.197 -955.606
750.00 118.250 186.018 64.285 121.734 -1136.857 -942.648
800.00 119.305 193.685 67.691 125.993 -1136.603 -929.709
850.00 120.233 200.946 70.755 130.191 -1136.458 -916.784
900.00 121.069 207.842 73.527 134.315 -1136.446 -903.863
950.00 121.839 214.409 76.050 138.359 -1136.605 -890.938
1000.00 122.561 220.677 78.358 142.319 -1136.987 -878.000
1100.00 123.913 232.422 82.438 149.984 -1137.802 -852.050
1200.00 125.197 243.260 85.948 157.311 -1138.581 -826.054
1300.00 126.453 253.330 89.016 164.314 -1137.600 -800.050
1400.00 127.706 262.747 91.735 171.013 -1136.642 -774.121
1500.00 128.968 271.601 94.175 177.426 -1135.694 -748.260
1600.00 130.246 279.965 96.389 183.576 -1134.747 -722.462
1700.00 131.544 287.900 98.419 189.481 -1185.141 -696.312
1800.00 132.863 295.456 100.296 195.161 -1184.329 -667.581
~298Fr = Molar volume= 2. 760 J/(bar·mol)

Iron: Tphase = I I 84 K, T~hase = 1665 K,
Tfus = 1809 K
Equation:
Cp = 90.65 + 0.017301-T- l.4048·10 7·r-2 + 1.3383·109· r- 3 + 2.732·104.r- 1
Table 3.12.2.2. Equation of state for ilmenite (FeSi03); for [ilmenite s.s.].
a= 2.2704·10· 5 + 6.8209·10-9 -T- l.809·10-3·T" 1 + 0.3851T"2

V0 ,298 = 27.6
P= 4.7528·10- 12 + 8.2987-I0- 16·T- 3.8777-10-20 1 2 + l.2095·10- 22 ·T 3
K'=4.0 K'PT= 3.0·104
Volume, cm3/mol
P,GPa 1·104 2 5 10 20
T,K
298.15 27.600 27.463 27.331 26.950 26.369 25.365
500 27.731 27.588 27.451 27.056 26.456 25.424
1000 28.095 27.937 27.785 27.353 26.702 25.601
1500 28.519 28.342 28.171 27.690 26.977 25.797
2000 29.004 28.799 28.602 28.056 27.263 25.986
P,GPa 1·1 04 2 5 10 20
T,K
298.15 23.00 22.23 21.76 19.35 16.67 12.72
500 24.04 23.12 22.21 20.03 16.77 13.09
1000 28.10 27.06 26.03 23.38 19.83 14.01
1500 31.90 30.43 29.05 25.47 20.93 14.92
2000 35.54 33.51 31.64 27.00 21.15 15.83
Bulk modulus, GPa
P,GPa 1·10-4 2 5 10 20
T,K
298.15 200.005 204.005 208.005 220.005 240.005 280.005
500 193.305 197.305 201.305 213.305 233.305 273.305
1000 176.527 180.527 184.527 196.527 216.527 256.527
1500 158.263 162.263 166.263 178.263 198.263 238.263
2000 138.407 142.407 146.407 158.407 178.407 218.407
(iJKr/iJT)p
P,GPa 1·10-4 P,GPa 1·10-4

T,K T,K
298.15 -0.0336 1000 -0.0348

500 -0.0330 1500 -0.0383
2000 -0.0407
Table 3.12.3.1. Thermophysical and thermochemical data for ilmenite (MgSi03);

for [ilmenite s.s.].
Ilmenite (MgSi03): metastable at 1 bar, stable at pressures 18-25 GPa

T Cp s b.~ 98 W jT -(GrH298)/T b.rflo tJ.tGO

K J/(mol-K) J/(mol·K) J/(mol·K) J/(mol·K) k.J/mol k.J/mol
298.15 75.137 58.300 0.000 58.300 -1494.100 -1404.380

300.00 75.547 58.766 0.473 58.302 -1494.123 -1403.823
350.00 85.266 71.174 11.923 59.251 -1494.600 -1388.730
400.00 92.735 83.069 21.578 61.491 -1494.762 -1373.591
450.00 98.520 94.340 29.819 64.52 -1494.697 -1358.447
500.00 103.075 104.965 36.925 68.039 -1494.470 -1343.318
550.00 106.729 114.966 43.111 71.856 -1494.126 -1328.219
600.00 109.714 124.385 48.541 75.844 -1493.700 -1313.155
650.00 112.192 133.268 53.345 79.923 -1493.216 -1298.129
700.00 114.284 141.661 57.625 84.036 -1492.693 -1283.142
750.00 116.073 149.608 61.463 88.145 -1492.146 -1268.193'
800.00 117.624 157.150 64.926 92.224 -1491.588 -1253.281
850.00 118.984 164.323 68.067 96.256 -1491.027 -1238.404
900.00 120.191 171.158 70.930 100.229 -1490.472 -1223.559
950.00 121.271 177.686 73.551 104.135 -1498.457 -1208.497
1000.00 122.247 183.932 75.962 107.970 -1497.996 -1193.248
1100.00 123.954 195.666 80.249 115.416 -1497.027 -1162.819
1200.00 125.411 206.515 83.954 122.561 -1496.008 -1132.482
1300.00 126.687 216.605 87.193 129.412 -1494.952 -1102.230
1400.00 127.827 226.036 90.055 135.980 -1621.280 -1069.035
1500.00 128.863 234.891 92.608 142.282 -1618.819 -1029.675
1600.00 129.818 243.238 94.905 148.334 -1616.341 -990.479
1700.00 130.709 251.135 96.985 154.151 -1664.031 -951.053
1800.00 131.549 258.630 98.882 159.749 -1661.301 -909.191
CJ.2tsw = Molar volume= 2.635 ±0.003 J/(bar·mol)

Equation:
Cp = 125.5 + 5.303·10-3 -T- 6.282·10 6-T-2 + 7.665-108 T 3- 3.04-103 T 1
Table 3.12.3.2. Equation of state for ilmenite (MgSi0 3); for [ilmenite s.s.].
a= 2.2704·10· 5 + 6.8209·10-9 -T- 0.001809-r- 1 + 0.3851-T-2

Vo.298 = 26.35
~ = 4.504·10- 12 + 8.2987·10. 16 -T- 3.8777·10-20 · T 2 + 1.2095·10-22 -T 3
K=4.0 K'PT= 3.0·10-4
Volume, cm3/mol
P,GPa 1·1 0-4 2 5 10 20

T,K
298.15 26.35 26.226 26.105 25.758 25.227 24.304
500 26.475 26.345 26.220 25.860 25.310 24.360
1000 26.822 26.678 26.540 26.143 25.544 24.526
1500 27.228 27.064 26.908 26.465 25.805 24.708
P,GPa 1·1 0-4 2 5 10 20

T,K
298.15 23.00 21.74 21.42 20.02 16.65 11.83
500 24.04 23.18 22.40 19.95 16.70 11.90
1000 28.10 26.98 26.00 23.36 19.69 14.64
1500 31.90 30.44 29.01 25.45 20.75 14.64
Bulk modulus, GPa
P,GPa 1·10"4 2 5 10 20
T,K
298.15 210.474 214.474 218.474 230.474 250.474 290.474
500 203.072 207.Q72 211.072 223.Q72 243.Q72 283.072
1000 184.637 188.637 192.637 204.637 224.637 264.637
1500 164.751 168.751 172.751 184.751 204.751 244.751
(CJK]'Ii)T)p
P,GPa 1·10-4 P,GPa 1·10"4

T,K T,K
298.15 -0.0372 1000 -0.0380
500 -0.0364 1500 -0.0415
Vp= 11.04, Vs = 6.57

Table 3.13.1.1. Thermophysical and thermochemical data for perovskite (A120 3);
for [perovskite s.s.].
Perovskite (Ah03): a fictive end-member 298.15 to 1800 K

T Cp s ll.~98 H' jT -(GrH29s)IT fl.cH 0 fl.cGO

298.15 78.681 84.717 0.000 84.717 -1554.581 -1471.216

300.00 79.100 85.205 0.495 84.719 -1554.607 -1470.700
350.00 88.756 98.162 12.450 85.720 -1555.082 -1456.671
400.00 95.901 110.503 22.456 88.053 -1555.243 -1442.598
450.00 101.314 122.125 30.931 91.200 -1555.193 -1428.519
500.00 105.521 133.026 38.188 94.844 -1555.004 -1414.453
550.00 108.870 143.246 44.467 98.784 -1554.724 -1400.411
600.00 111.596 152.840 49.951 102.893 -1554.386 -1386.397
650.00 113.859 161.864 54.782 107.086 -1554.015 -1372.413
700.00 115.772 170.374 59.072 111.306 -1553.630 -1358.458
750.00 117.415 178.419 62.908 115.514 -1553.249 -1344.531
800.00 118.848 186.043 66.361 119.686 -1552.895 -1330.628
850.00 120.115 193.287 69.486 123.804 -1552.592 -1316.746
900.00 121.247 200.185 72.331 127.857 -1552.364 -1302.880
950.00 122.270 206.769 74.933 131.839 -1573.572 -1288.645
1000.00 123.205 213.065 77.323 135.744 -1573.212 -1273.658
1100.00 124.863 224.887 . 81.572 143.318 -1572.413 -1243.740
1200.00 126.312 235.815 85.241 150.576 -1571.523 -1213.900
1300.00 127.609 245.977 88.451 157.528 -1570.553 -1184.136
1400.00 128.793 255.478 91.291 164.189 -1569.510 -1154.451
1500.00 129.892 264.402 93.828 170.576 -1568.397 -1124.842
1600.00 130.924 272.818 96.115 176.705 -1567.220 -1095.310
1700.00 131.905 280.785 98.191 182.595 -1565.979 -1065.853
1800.00 132.845 288.351 100.091 188.262 -1564.677 -1036.471
fl.~Sfl'= Molar volume= 2.4 J/(mol·bar)

Aluminium: Tfus = 933.47 K
Equation:
Cp= 122.6 + 0.007031·T- 5.583·106·T"2 + 5.707-I08·T 2 -1414T 1
Table 3.13.1.2. Equation of state for fictive end member ofperovskite (Al20 3);
a= 4.802·10-5 + 0.45677-10-8 -T- 8.5134·10-3 -r-1 + 1.1908·10- 1-r-2

Vo,298 = 24.0
j3= 3.7184·10- 12 + 0.23496·10- 15 -T + 2.2508·10- 191 2
K'=4.1 K'pr= 0
Volume, cm3/mol
P,GPa 1·104 2 5 10 20
T,K
298.15 24.000 23.909 23.821 23.564 23.165 22.457
500 24.140 24.047 23.956 23.692 23.283 22.559
1000 24.626 24.524 24.425 24.137 23.694 22.914
1500 25.211 25.096 24.985 24.665 24.174 23.319
2000 25.864 25.733 25.607 25.245 24.694 23.747
Thermal expansion, m106, K 1
P,GPa 1-10-4 2 5 10 20
T,K
298.15 22.15 22.09 21.19 2Q.42 18.50 15.98
500 33.75 33.27 32.89 31.53 29.83 26.83
1000 44.19 43.50 42.85 41.07 38.33 33.87
1500 49.25 48.35 47.47 45.11 41.54 35.90
2000 52.93 51.78 50.77 47.72 43.47 36.75
Bulk modulus, GPa
P,GPa 1·1 04 2 5 10 20
T,K
298.15 262.577 266.677 270.777 283.077 303.577 344.577
500 256.927 261.027 265.127 277.427 297.927 338.927
1000 239.324 243.424 247.524 259.824 280.324 321.324
1500 218.471 222.571 226.671 238.971 259.471 300.471
2000 196.516 200.616 204.716 217.016 237.516 278.516
(dKpd1)p
P,GPa 1-10-4 P,GPa 1·10-4

T,K T,K
298.15 -0.0254 1000 -0.0392
500 -0.0304 1500 -0.0434
2000 -0.0438
Table 3.13.2.1. Thermophysical and thermochemical data for perovskite (FeSi03);

Perovskite (FeSi0 3): metastable end-member Molar mass: 143.693 g/mol
T Cp s !1~ 98 H' jT -(GrH298)/T f1rHo 11rGO

K J/(mol-K) J/(mol·K) J/(mol-K) J/(mol-K) kJ/mol kJ/mol
298.15 90.914 91.070 0.000 91.070 -1096.780 -1018.485

300.00 91.191 91.634 0.572 91.070 -1096.773 -1018.000
350.00 97.926 106.215 14.016 92.199 -1096.566 -1004.884
400.00 103.352 119.658 24.856 94.802 -1096.192 -991.810
450.00 107.748 132.094 33.830 98.264 -1095.703 -978.791
500.00 111.352 143.639 41.408 102.231 -1095.140 -965.830
550.00 114.350 154.397 47.907 106.490 -1094.535 -952.928
600.00 116.877 164.458 53.552 110.906 -1093.913 -940.082
650.00 119.035 173.901 58.508 115.392 -1093.297 -927.288
700.00 120.897 182.792 62.900 119.892 -1092.708 -914.540
750.00 122.521 191.189 66.822 124.368 -1092.164 -901.833
800.00 123.951 199.143 70.348 128.795 -1091.688 -889.161
850.00 125.219 206.697 73.539 133.157 -1091.301 -876.515
900.00 126.354 213.887 76.443 137.444 -1091.032 -863.889
950.00 127.375 220.746 79.097 141.649 -1090.921 -851.274
1000.00 128.300 227.303 81.534 145.769 -1091.021 -838.659
1100.00 129.913 239.610 85.861 153.749 -1091.247 -813.400
1200.00 131.278 250.974 89.591 161.383 -1089.420 -788.151
1300.00 132.452 261.529 92.844 168.686 -1089.830 -762.943
1400.00 133.477 271.383 95.710 175.673 -1088.286 -737.856
1500.00 134.383 280.624 98.259 182.365 -1086.778 -712.878
1600.00 135.192 289.323 100.542 188.781 -1085.312 -688.000
1700.00 135.922 297.541 102.602 194.939 -1135.239 -662.800
1800.00 136.587 305.329 104.472 200.857 -1134.021 -635.045
11~8H' = Molar volume= 2.559 J/(bar·mol)

Trus = 1809 K
Equation:
Cp= 142.22 + 0.01537-T- 1.1788-106 · r- 2 + 2.733·10 8 -r- 3 - 14556-r- 1
Table 3.13.2.2. Equation of state for metastable end member of perovskite (FeSi03);
for [perovskite s.s.).
a= 2.627·10" 5 + 1.5198·10-8 -T- 4.29·10- 2 -T-2

Vo,298 = 25.59
fJ= 3.367-I0- 12 + 1.01·10- 15 -T
K'=4.0
Volume, cm 3/mol
P,GPa 1·1 04 2 5 10 20
T,K
298.15 25.590 25.497 25.404 25.141 24.728 23.992
500 25.756 25.657 25.560 25.280 24.845 24.072
1000 26.245 26.131 26.020 25.700 25.206 24.341
1500 26.845 26.715 26.589 26.227 25.673 24.713
2000 27.564 27.417 27.275 26.867 26.250 25.192
Thermal expansion, tl'106 , K 1
P,GPa 1·1 0 4 2 5 10 20
T,K
298.15 30.32 29.23 28.82 25.48 21.69 14.75
500 33.70 32.68 31.85 29.02 24.95 18.16
1000 41.43 40.44 39.47 36.80 32.78 26.29
1500 49.05 48.06 47.11 44.42 40.57 34.37
2000 56.66 55.67 54.76 52.01 48.36 42.44
Bulk modulus, GPa
P,GPa 1·10-4 2 5 10 20
T,K
298.15 272.630 276.630 280.630 292.630 312.630 352.630
500 258.264 262.264 266.264 278.264 298.264 338.264
1000 228.467 232.467 236.467 248.467 268.467 308.467
1500 204.834 208.834 212.834 224.834 244.834 284.834
2000 185.632 189.632 193.632 205.632 225.632 265.632
(i1Kz{a1)p
P,GPa 1·104 P,GPa 1-104

T,K T,K
298.15 -0.0751 1000 -0.0527

500 -0.0674 1500 -0.0424
2000 -0.0348
Table 301303.1 Thermophysical and thermochemical data for perovskite (MgSi03);

for [perovskite soso]o
Perovskite (MgSi0 3): metastable at I bar, stable at pressures above 23 GPa

Molar mass: 1000389 g/mol
T Cp s !1;9swfr -( GrHzgs)IT !'!rHo !'!rGO

K J/(mol-K) J/(moloK) J/(mol-K) J/(moloK) kJ/mol kJ/mol
298.15 800670 630600 OoOOO 630600 -14490500 -1361.360

300000 800917 64.100 00506 630602 -14490513 -13600813
350000 87.487 77.072 12.468 640604 -14490810 -13460003
400000 93.344 890146 22.221 660926 -14490905 -1331.165
450000 98.316 100.436 30.408 700029 -14490832 -13160325
500000 102.492 111.017 37.413 730604 -14490626 -1301.501
550000 1060007 1200955 43.494 77.462 -14490316 -12860703
600000 1080987 1300311 480831 81.480 -14480926 -1271.936
650000 111.537 139.137 530559 850579 -1448.477 -12570205
700000 1130736 147.486 570780 890705 -14470984 -12420510
750000 1150652 1550399 61.576 930823 -1447.462 -12270851
800000 1170332 162o918 650009 970909 -14460921 -12130228
850000 1180819 1700077 68.132 101.945 -14460372 -11980639
900000 120.144 1760907 700985 1050921 -14450822 -11840083
950000 121.331 183.435 730604 1090831 -1453o806 -11690308
1000000 122.402 1890686 760018 1130668 -1453.340 -1154.346
1100000 1240260 201.442 80.322 121.120 -1452.348 -1124.494
1200000 1250819 2120323 840050 1280273 -1451.293 -10940735
1300000 1270149 222.448 87.315 135.132 -14500193 -10650067
1400000 1280302 231.913 900203 141.711 -1576.473 -1032.458
1500000 1290314 2400801 920777 1480023 -15730966 -9930687
1600000 130.213 2490176 950089 1540086 -1571.446 -9550084
1700000 131.019 2570094 970180 1590915 -16190100 -9160252
1800000 131.748 2640604 990080 1650524 -16160344 -8740987
!12:sw = Molar volume= 20559 ±00003 J/(baromol)

Transition in Phase Transitions in reference state elements
Equation:
Cp = 13709 + 1.564o10-3 oT- 3.191°106 -T-2 + 7.192°108 -T-3 - 1.459°1040 r- 1
Table 3.13.3.2. Equation of state for perovskite (MgSi03); for [perovskite s.s.].
a= 4.903·10· 5 - 2.307·10·9 -T- 0.01812T 1 + 2.543-T -2

Vo.298 = 24.44 7
P= 3.7184-10- 12 + 2.3496·10-' 6T + 2.2508-1o-' 9 -T2
K'=4.1 K'PT= 1.0-104
Volume, cm3/mol
P,GPa 1·1 04 2 5 10 20
T,K
298.15 24.447 24.354 24.264 24.003 23.596 22.875

500 24.540 24.445 24.352 24.084 23.669 22.933
1000 24.877 24.773 24.673 24.383 23.936 23.151
1500 25.292 25.177 25.066 24.746 24.256 23.406
2000 25.744 25.614 25.489 25.131 24.588 23.660
Thermal expansion, Cf106 , K 1
P,GPa 1-10-4 2 5 10 20
T,K
298.15 16.17 16.24 15.21 13.93 13.10 10.25
500 21.81 21.34 20.96 19.69 17.92 15.07
1000 31.15 30.44 29.82 28.05 25.40 21.29
1500 34.62 33.73 32.86 30.54 27.20 22.06
2000 35.99 34.89 33.85 31.00 26.97 20.91
Bulk modulus, GPa
P,GPa 1-10-4 2 5 10 20
T,K
298.15 262.573 266.673 270.773 283.073 303.573 344.573
500 256.927 261.027 265.127 277.427 297.927 338.927
1000 239.324 243.424 247.524 259.824 280.324 321.324
1500 218.471 222.571 226.671 238.971 259.471 300.471
2000 196.516 200.616 204.716 217.016 237.516 278.516
(i)K Tli)1)p
P,GPa 1-10-4 P,GPa 1·10-4

T,K T,K
298.15 -0.0254 1000 -0.0392

500 -0.0304 1500 -0.0434
2000 -0.0438
Vp= 11.04, Vs = 6.57

Footnote A: (Re Tables 3.2.1.1 and 3.2.2.1., Iron-bee, Fe and Iron-fcc, Fe)
Tcurie = 1042 K
Tbc}cc= 1176K, N!H = 1.07kJ
Treebee'= 1662 K, I!!.!H = 1.03 kJ
Magnetic contribution to Gibbs energy for Iron-bee: Chi= R.P(t)·T·1n(I3M+ 1)
t = TITcurie, ~M = 2.22
298.15-1042 F(t)= l-0.90529938·t" 1-0.15300835·e -0.00680037l·t9-0.00 15300835·t15
1042-3000 F(t)=-0.06417312l·r 5-0.0020372419·r 15-4.2782081·10 4 ·r25
3.3
Comments on Equation of State Tables
Table 3.1.1.2. a-Quartz (Si02): The thermal expansion was determined by Skin-
ner [66SKI]. The bulk modulus determined by different techniques (ultrasonic and
static compression) is in the pressure range of 36.4-40.4 GPa. The value of K' is in
the range of 5.3-6.4 ([65MCS/AND], [68SOG], [69CHU/SIM], [760LII
HAL], [80LEV/PRE], [81CAR/JOR]). The recommended values of thermal ex-
pansion, compressibility and K' are from Saxena et al. [93SAX/CHA]. The sound
wave velocities are from Chung [74CHU].
Table 3.1.2.2. P-Quartz (Si02): Thermal expansion was studied by Ackermann

and Sorrell [74ACK/SOR] and Bourova and Richet [98BOUIRIC], it was found
that thermal expansion is almost zero at 853-1400 K and becomes negative at tem-
peratures above 1400 K. Recommended values of thermal expansion, compressi-
bility and K' are from Saxena et al. [93SAX/CHA].
Table 3.1.3.2. Tridymite (Si02): The thermal expansion was obtained by Taylor
[84TAY]. Experimental data on compressibility are not available. The recom-
mended data are from Swamy et al. [94SWNSAX].
Table 3.1.4.2. Cristobalite (Si02): The thermal expansion was obtained by Tay-
lor [84TAY]. The experimental data on compressibility are from Yeganeh-Haeri et
al. [92YEG/WEI] and from Palmer and Downs [91PAL/DOW]. The recom-
mended data are from Swamy et al. [94SWNSAX]. Sound wave velocities are
from Yeganeh-Haeri et al. [92YEG/WEI].
Table 3.1.5.2. Coesite (Si02): The thermal expansion of coesite was determined
by Skinner [62SKI]. The bulk modulus was measured by different techniques:
static compression as 96 GPa by Levien and Prewitt [81LEV/PRE], ultrasonic as
97.2 GPa by Akimoto [72AKI] and Brillouin scattering as 113.7 GPa by Weidner
and Carleton [77WEIICAR]. The value obtained by ultrasonic measurement is in
good agreement with that by static compression; the value obtained by Brillouin
spectroscopy is higher. The K' was determined by Levien and Prewitt [81LEV/
Comments on Equation of State Tables 111
PRE]. The recommended values of thermal expansion, compressibility and K' are
from Swamy eta!. [94SWA/SAX]. The sound wave velocities are from Weidner
and Carleton [77WEI/CAR].
Table 3.1.6.2. Stishovite (Si0 2). The thermal expansion of stishovite was deter-
mined in several studies ([74ITO/KAW] a= (13.5±0.6)·10-6 K 1, [79WEA/CHI]
a= 8.9·10-6 K 1, [88DOR/GAL] a= 10.8·10-6 K 1). The bulk modulus was meas-
ured by different techniques: shock wave 300 GPa ([70AHR/TAK]), static com-
pression 313 GPa ([87SUG/END], [90ROS]), ultrasonic 305 GPa ([96LIIRIG])
and Brillouin scattering 316 GPa ([82WEI/BAS]). Those values are in good
agreement; the measurement of Mizutani et a/. [72MIZIHAM] gave a higher
value, other measurements ([76LIEIRIN], [760LI], [77aSAT]) gave lower values.
The value of K' equal to 5.3 was determined by Li eta/. [96LIIRIG]. The value of
K' equal to 6 was obtained by Olinger [760LI] and Sugiyama eta/. [87SUG/END]
and a value of K' equal to 7 was obtained by Ahrens et a/. [70AHR/TAK]. Rec-
ommended values of thermal expansion, compressibility and K' are from Swamy
et al. [94SWA/SAX]. Sound wave velocities are from Li et a!. [96LIIRIG]; they
are in good agreement with data obtained by Weidner eta!. [82WEI/BAS].
Table 3.2.1.2. Iron-bee (Fe). The compressibility for Iron-bee was studied by
Huang et a!. [87HUA/BAS] in static compression experiments, they obtained val-
ues K = 166 GPa and K' = 5. The recommended values are from are from Fabrich-
naya and Sundman [97FAB/SUN] (according to the assessment of Saxena).
Table 3.2.2.2. Iron-fcc (Fe). The P-V-T relation in iron-fcc was recently studied
by Dubrovinsky and Saxena [99DUB/SAX] and they determined K = 142 GPa, K'
= 5.2 and thermal expansion a= 6.36·10- 5 K 1 at 298 K. Previous data of Boehler
et al. [90BOE/BAR] and Funamori et al. [96FUNIUSH] present lower values for
bulk modulus K = 120 GPa. Recommended values are from are from Fabrichnaya
and Sundman [97FAB/SUN] (according to the assessment of Saxena).
Table 3.3.1.2. Andalusite (AhSi0 5). The thermal expansion was determined by
Winter and Ghose [79WIN/GHO] and gave a= 25·10-6 at 298 K. The bulk
modulus was determined in the static compression experiments of Brace et a/.
[69BRAISCH] to be 130 GPa for all three polymorphs. Later it was determined by
Vaugham and Weidner [78 VAU/WEI] (Brillouin Scattering) and by Ralph eta!.
[84RAL/FIN] (static compression). Yang et a!. [97YAN/HAZ] refitted data of
Ralph et al. [84RAL/FIN] and obtained value K = 151 GPa. The recommended
values are from Saxena eta!. [93SAX/CHA].
Table 3.3.2.2. Sillimanite (AhSi0 5). The thermal expansion of sillimanite was
determined by Skinner [66SKI] (a= 15.8·10-6 K 1) and Winter and Ghose
[79WIN/GHO] (a= 14.5-10-6 K 1). The bulk modulus was determined in the static
compression experiments of Brace et a/. [69BRA/SCH] (K = 130 GPa for all three
polymorphs); later static compression experiments provided a higher value for the
bulk modulus of sillimanite, 171 GPa ([97YANIHAZ]) at K' = 40 Brillouin scatter-
ing gives value 171 GPa ([78VAU/WEI])o The recommended values of thermal
expansion, compressibility and K' are from Saxena et alo [93SAX/CHA]o The
sound velocities are those of Vaughan and Weidner [78VAU/WEI]o
Table 3.3.3.2. Kyanite (AhSi05). The thermal expansion was determined by

Skinner et al. [61SKI/CLA] (a= 27°10-6 K 1) and by Winter and Ghose
[79WIN/GHO] (a= 2607°10-6 K 1)o The bulk modulus was determined in the static
compression experiments of Brace et al. [69BRA/SCH] to be 130 GPa for all three
polymorphs; later static compression experiments provided a higher value for bulk
modulus of kyanite 193 GPa ([97YAN/DOW]), 160 GPa ([97COM/ZAN]) at K' =
4. The recommended values of thermal expansion, compressibility and K' are from
Saxena et alo [93SAX/CHA].
Table 3.4.1.2. Hematite (Fe20 3). The elastic constants measured in ultrasonic and
static compression experiments are in poor agreement, values of Ks were obtained
in the range 206.6-241.7 GPa, the value of K' was obtained close to 4.5. Elastic
properties were measured by different techniques ([68AND/SCH], [68LIE/SCH],
[74CHU], [86LIEIMAA])o The thermal expansion was determined by Skinner
[66SKI]. The recommended values are from Fabrichnaya and Sundman
[97FAB/SUN]o
Magnesioferrite S.S. - end members: magnetite (FeFe20 4) and magne-

sioferrite (MgFe204).
Table 3.5.1.2. Magnetite (FeFe20 4). The elastic constants measured in ultrasonic
and static compression experimentas are in poor agreement. Values of Ks were
obtained in the range 155.0-183.0 GPa, value of K' was obtained close to 40 The
elastic properties were measured by different techniques ([74CHU], [74MAO/
BAS], [78WIL/BAS])o The thermal expansion was obtained by Skinner [66SKI]o
The recommended parameters are from Fabrichnaya and Sundman [97FAB/SUN].
Table 3.5.2.2. Magnesioferrite (MgFe20 4). The thermal expansion was obtained
by Skinner [66SKI]. Recommended parameters are from Fabrichnaya and Sund-
man [97FAB/SUN].
Spinel S.S. - end members: hercynite (FeAI20 4) and spinel (MgAh0 4).
Table 3.6.1.2. Hercynite (FeAh04). The elastic constants were meassured in ul-
trasonic experiments by Wang and Simmons [72WAN/SIM]o The thermal expan-
sion is available in Skinner [66SKI]. The sound wave velocities are from Chung
[74CHU]. The recommended data are from Saxena et alo [93SAXICHA].
Table 3.6.2.2. Spinel (MgAh04). The thermal expansion was measured by Skin-
ner [66SKI]. The bulk modulus was determined in ultrasonic experiments by
Comments on Equation of State Tables ll3
Chang and Barsch [73CHA/BAR] (K = 197.43 GPa, K' = 4.89), by light-sound

scattering [75LIU/SCH] (K = 196.9 GPa) and in static compression experiments
[86FIN/HAZ] (K = 194 GPa, K' = 4). They are in good agreement. The recom-
mended values are from Saxena et al. [93SAX/CHA]. The sound wave velocities
are from Chung [74CHU].
Magnesiowustite S.S. - end members: wustite (FeO); charged wustite

(FeO+) and periclase (MgO).
Table 3.7.1.2. Wustite (FeO). The thermal expansion was accepted from the
handbook of Haas [88HAA]. The compressibility ofFeO was studied in ultrasonic
experiments ([78JACILIE], [82BON/GRA], [85JAC/WEB], [90JACIKHA]), in
static compression experiments ([81HAZ], [85YAG/SUZ], [86JEA/SAT], [87LIU/
LIU], [93MAO/SHU], [96FEI]), in shock wave experiments ([80JEA/AHR]); by
resonance techniques [80SUM]. According to the following studies ([80SUM/
KUM], [80JEA/AHR] and [78JACILIE]) the bulk modulus is 180 ± 2 GPa. Ac-
cording to Hazen [81HAZ] it is 154 GPa. Jackson et al. [90JACIKHA] determined
the bulk modulus to be 153 (K' = 3.1). Fei [96FEI] obtained a value of K equal
to146 at K' = 4.
Table 3.7.2.2. Charged wustite (FeO). Equation of state parameters for fictive
end-member are the same as those for wustite.
Table 3.7.3.2. Periclase (MgO). The thermal expansion was experimentally stud-
ied by Suzuki [75SUZ] and Hazen [76HAZ] at 300-1400 K and by [97SAX/DUB]
at 300-3100 K. The elastic constants of periclase were measured in ultrasonic,
static compression and shock wave experiments. Values for bulk modulus and its
pressure derivative K = 162.3 GPa and K' = 4 obtained in ultrasonic studies
([69CHAIBAR], [70SPE], [73CHU], [79SON/SCH], [82BON/GRA], [82JAC/
NIE]) are in a good agreement with data obtained in the shock wave study ofVas-
siliou and Ahrens [81VAS/AHR] K = 162.7 GPa and K' = 4.27 and in the rectan-
gular parallelepiped resonance study of Sumino and Anderson [83SUM/AND] K =
162.8 GPa. Data obtained in static compression experiments are not in very good
agreement with data mentioned above ([76SAT] K = 166.0 K' = 4.2; [79MAO/
BEL] K = 160.0 K' = 4.56). The recommended values for thermal expansion,
compressibility and K' are from a book of Saxena et al. [93SAX/CHA]. The sound
wave velocities are from ultrasonic measurements of Sumino and Ohno [76SUM/
OHN].
Olivine S.S. -end members: fayalite (Fe2Si04) and forsterite

(Mg2Si04).
Table 3.8.1.2. Fayalite (Fe2Si04). The thermal expansion is determined by Su-

zuki et al. [81 SUZ/SEY) at 298-1273 K, a(298) = 26·1 o-6 K 1• According to Ply-
mate and Stout [90PL Y/STO) the thermal expansion is equal to 21.4·10-6 K 1• The
compressibility of fayalite was studied in ultrasonic experiments ([71CHU],
[79SUM], [88GRNSCH]) and in static compression experiments ([75YAGIIDA],
[90PLY/STO]). According to Graham and Schwab [88GRNSCH] the bulk
modulus is 127±0.6 GPa at K' = 5.25 which is in reasonable agreement with the
data of Yagi et al. [75YAGIIDA] K = 124±2 GPa, K' = 5), other data ([71CHU]
and [90PLY/STO]) give a lower value of the bulk modulus 121±2 GPa, K' =
6±0.5. According to Sumino [79SUM] the value of Kr is higher and equal to
136.6 GPa. The recommended data are from Fabrichnaya and Sundman
[97FAB/SUN]. The sound wave velo_cities are from Sumino [79SUM].
Table 3.8.2.2. Forsterite (M~Si04). The thermal expansion is determined in sev-

eral studies ([75SUZ], [85MATIMAN], [85WHI/ROB], [84SUZ/TAK]) at 298-
1273 K, a.(298) = (27 .2±2) ·1 o-6 K 1• Recently thermal expansion was measured at
400-2160 K (see [96BOU/AND]), it increased smoothly from 28·10-6 to 45·10-6
K 1• The compressibility of forsterite was studied by a resonance method
([77SUM/NIS], [891SA/AND]), in ultrasonic experiments ([69GRAIBAR],
[69KUM/AND] and [81MAT/MAN]). Experimental values are in fair agreement.
The adiabatic bulk modulus was obtained as 128.6±0.5 GPa. The pressure deriva-
tive K' was 5.6 according to Matsui and Manghnani [81MAT/MAN], 4.97 accord-
ing to Graham and Barsch [69GRAIBAR] and 5.37 according to Kumazawa and
Anderson [69KUM/AND]. The recommended data are from Saxena [96SAX].
The sound velocities are from measurements of Kumazawa and Anderson
[69KUM/AND].
fi-Spinel S.S. - end members: fi-spinel (Fe2Si04) and fi-spinel

(M~Si04).
Table 3.8.3.2. (}-Spinel (Fe2Si04). The equation of state parameters for fictive
end-member ~-Fe2 Si04 were assessed by Saxena et al. [93SAX/CHA] from struc-
tural analogies.
Table 3.8.4.2. P-Spinel (Mg2Si04). The thermal expansion was determined by

Suzuki et al. [80SUZ/OHT], a.(293) = (20.6±2)·1 o-6 K 1• The compressibility of
forsterite was studied by Brillouin scattering by Sawamoto et al. [84SA W/WEI]
and in static compression experiments ([75MIZ/OHT], [92FEI/MAO]). The ex-
perimental values are in fair agreement. The bulk modulus obtained by Sawamoto
et al. [84SAW/WEI] 174±6 is in good agreement with data of Fei et al. [92FEII
MAO]. The pressure derivative is 4.8 according to Gwanmesia et al. [90GWAI
RIG] and 4.74 according to Rigden eta/. [92RIG/GWA]. The recommended data
are from Saxena [96SAX]. The sound wave velocities are from the study of Sa-
wamoto et al. [84SAW/WEI].
y-Spinel S.S. - end members: y-spinel (Fe2Si04) andy-spinel (Mg2Si04)

(or ringwoodite).
Table 3.8.5.2. y-Spinel (F~Si0 4). The thermal expansion is determined by Su-
zuki et al. [79SUZ/OHT] a(293) = (21.3±2) ·10-6 K 1• The compressibility of y-
fayalite was studied in ultrasonic studies by Liebermann [75LIE] and the value for
bulk modulus was obtained K = 193 GPa. In static compression experiments the
value was ranging from 189 to 207 GPa [77bSAT], [76WIL/BAS], [93HAZ]).
Bulk moduli obtained by different methods are in fair agreement (ca. 200±10
GPa). The pressure derivative was constrained during regression as 4 according to
Sato ([77bSAT] and to Wilburn and Bassett [76WIL/BAS]. According to Hazen
[93HAZ] K' is equal to 4.8. According to Plymate and Stout [94PLY/STO] the
bulk modulus at 400 °C is 177.3±17 GPa and K' is 5.4±2.5. The recommended
data are from a study of Fabrichnaya and Sundman [97FAB/SUN]. The sound
wave velocities are from work of Liebermann [75LIE].
Table 3.8.6.2. y-Spinel (Mg2 Si04), (or ringwoodite). The thermal expansion is
determined by [79SUZ/OHT], a(293) = (19±2) ·10-6 K 1• The compressibility of
forsterite was studied by Brillouin scattering ([84WEIISAW), in static compres-
sion experiments ([75MIZ/OHT], [94MEN/FEI]). The bulk modulus obtained by
Sawamoto et a/. [84SAW!WEI] K = 184±6 GPa is in good agreement with data of
Meng et al. [94MEN/FEI] K = 182±3 GPa. The measurement of Mizukami et al.
[75MIZ/OHT] gave a higher value of208±8 GPa. The pressure derivative is equal
to 4.3 according to Meng et al. [94MEN/FEI] and 4.84 according to Rigden et al.
[92RIG/GWA]. The recommended data are from [96SAX]. Sound wave velocities
are from Weidner and Sawamoto [84WEIISAW].
Hpclinopyroxene S.S. - end-members: hpclinoferrosilite (FeSi03 ) and hpcli-

noenstatite (MgSi03). {Note A. The equation of state parameters for polymorphic
modification of enstatite are from Shi et al. [94SHIISAX]. The data for ferrosilite
end-members are the same as for orthoferrosilite except for the volume of proto-
ferrosilite, which was fitted to phase equilibria (see [98FAB]).}
Table 3.9.1.2. Hpclinoferrosilite (FeSi03).
Table 3.9.2.2. Hpclinoenstatite (MgSi03).
Protopyroxene S.S. - end members: protoferrosilite (FeSi03) and pro-

toenstatite (MgSi03) {see Note A (above)}.
Table 3.9.3.2. Protoferrosilite (FeSi03).
Table 3.9.4.2. Protoenstatite (MgSi03).

Orthopyroxene S.S. - end members: orthocorundum (Ah03), ortho-

ferrosilite, (FeSi03) and orthoenstatite (MgSi03).
Table 3.10.1.2. Ortbocorundum (Alz03). The equation of state parameters of this

fictive end-member are assessed by Fabrichnaya [99FAB] from structural analo-
gies and phase equilibria.
Table 3.10.2.2. Orthoferrosilite (FeSi03). The thermal expansion and com-

pressibility have been recently studied by Yang and Ghose [94YAN/GHO] and by
Hugh-Jones [97HUG]. The values obtained in those studies are in good agreement
(27.5·10-6 K 1 according to [97HUG] and 29·10"6 K 1 by [94YAN/GHO]). The data
for bulk modulus was obtained by various Brillouin spectroscopic techniques
(84BAS/WEI]) and ultrasonic measurements ([74CHU]). The obtained value of
adiabatic bulk modulus is I 01 GPa. The value of K' was not experimentally de-
termined. The recommended values for thermal expansion, compressibility and K'
are from assessment of Fabrichnaya and Sundman [97F AB/SUN]. The sound ve-
locities are from the study of Bass and Weidner [84BASIWEI]; according to
Chung [74CHU] they are Vp = 6.794 and Vs = 3.917.
Table 3.10.3.2. Orthoenstatite (MgSi03). The thermal expansion and compressi-

bility have been recently studied by Yang and Ghose [94YAN/GHO] and by
Hugh-Jones [97HUG]. There is quite a large difference between values obtained
in those studies: 32.2·10-6 K 1 according to Hugh-Jones [97HUG] and 23.5·10-6 K 1
by Yang and Ghose [94YAN/GHO], and opposite influence of Fe on thermal ex-
pansion has been found in those studies. The values presented in previous studies
(see [82DIE/ARN], [66SKI], [62SARIHUM] and [72FRI/BUL]) change over the
range 20·10-6-48·10-6 K 1• The data for bulk modulus were obtained by different
techniques: static compression ([94ANG/HUG]), Brillouin spectroscopy ([78WEII
WAN], [88DUFNAU]) and ultrasonic interferometry ([93WEB/JAC], [98FLE/
LI]). The obtained range of values of bulk modulus are 100-110 GPa, K' = 9-11.
Angel and Hugh-Jones [94ANG/HUG] suggested two sets of parameters to de-
scribe compressibility of orthoenstatite below 4 GPa (K = 95.8, K' = 14.8) and
above 4 GPa (K = 122.8, K' = 5.6). The recommended values for thermal expan-
sion, compressibility and K' are from a study of Saxena [96SAX]. The sound ve-
locities are accepted from the following studies: [78WEI/WAN] and [98FLEILI];
according to Duffy and Vaughan [88DUFNAU] they are Vp = 7.834, Vs = 4.752.
[See Note A above.]
Garnet S.S. - end-members: garnet (FeSi03); garnet (MgSi03) (or ma-

jorite); garnet (FeJAlzSi3012) (or almandine); and pyrope
(M~Al2Sh012).
Table 3.11.1.2. Garnet (FeSi03). The equation of state parameters for the fictive
end-member were assessed by Fabrichnaya [95FAB] from structural analogies.
Table 3.11.2.2. Garnet (MgSi0 3), (or majorite). The P-V-T relations in garnet
Py62En38 composition were studied by Wang et al. [98WAN/WEI] at pressure
and temperature conditions up to 11 GPa and 1163 K. They determined the ther-
mal expansion to be 25·10-6 K 1 for cubic garnet. They determined K8 to be 160
GPa and K' to be 4.9. The data for bulk modulus were obtained by Brillouin scat-
tering measurements ([90BAS/KAN], [90YEAIWEI], [97P AC/WEI] and [97SIN/
BAS]), in static compression experiments ([87YAG/AKA] and [92YAGIUCH])
and in ultrasonic experiments [94RIG/GWA]. The obtained values are in reason-
able agreement. For pure MgSi0 3 the value of the bulk modulus is in the range
151-166 GPa, for composition of garnet Py40En60 160-172 GPa and for
Py60En40 158-170 GPa. Values of Vp and Vs are from Brillouin scattering meas-
urements ([97PAC/WEI]); they are in agreement with data of Rigden et al.
[94RIG/GWA] (Vp = 9.0, Vs = 5.01) and Sinogeikin et al. [97SIN/BAS] (Vp =
8.92, Vs = 4.97). The recommended values for thermal expansion, compressibility
and IC are from [96SAX].
Table 3.11.3.2. Garnet (Fe3Al2Si30 4), (or almandine). The thermal expansion
was determined by Skinner [56SKI] a= 15.7-10-6 K 1 and Thiebolt et al.
[98THIIROU] (a= 20.1·10-6 K 1); according to the calculation of Ottonello et al.
[960TT /BOK] it is 19·1 o- 6 K 1• The data for bulk modulus were obtained by Bril-
louin scattering measurements [80LEIIWEI], in static compression experiments
([78SAT/AKA], [87YAG/AKA] and [74BAS/TAK]) and in ultrasonic experi-
ments ([761SA/GRA], [78SUMINIS], [78BAB/FIA] and [97CHE/MIL]). The ob-
tained values are in reasonable agreement with each other 175-180 GPa. The value
of K' was measured by Anderson et al. [68AND/SCH] and Isaak and Graham
[76ISA/GRA]. The Vp and Vs are from ultrasonic data of Babuska et al.
[78BAB/FIA]. They are in agreement with other ultrasonic measurement of Su-
mino and Nishizawa [78SUM/NIS] Vp = 8_43, Vs = 4.73; Chen et al.
[97CHE/MIL] Vp = 8_42, Vs = 4.68. The recommended values for thermal expan-
sion, compressibility and K' are from a book of Saxena et al. [93SAX/CHA].
Table 3.11.4.2. Pyrope (M~AhShOu). The thermal expansion was determined

by Skinner (56SKI] (a= 19.8·10-6 K 1), Sumino et al. [83SUM/AND] (a=
23.6·10-6 K 1) and by Thiebolt et al. [98THI/ROU] (a= 20.2-10-6 K 1). Data for the
bulk modulus were obtained by Brillouin scattering measurements ([80LEI/WEI],
[910NE/BAS]), in static compression experiments ([78SAT/AKA], [78LEV/PRE]
and [89HAZ/FIN]) and in ultrasonic experiments ([76ISA/GRA], [77BON/GRA],
[78SUM/NIS], [78BAB/FIA] and [97CHE/MIL]). The obtained values are in rea-
sonable agreement with each other 166-179 GPa. K' was measured by Levien and
Prewitt [78LEV/PRE] K/= 4.5 and by Rigden et al. [94RIG/GWA] K' = 5.3. Val-
ues of Vp and Vs are from Brillouin scattering measurements [910NE/BAS]; they
are in agreement with the data of Leitner et al. [80LEI/WEI] (Vp = 9.10, Vs =
5.03) and ultrasonic data of Babuska et al. [78BAB/FIA] (Vp = 9.13, Vs = 5.09)
and Chen et al. [97CHE/MIL] (Vp = 9.08, Vs = 5.08). The recommended values for
thermal expansion, compressibility and K' are from Saxena eta!. [93SAX/CHA].
Ilmenite S.S. -end members: corundum (Al20 3), ilmenite (FeSi03),

and ilmenite (MgSi03).
Table 3.12.1.2. Corundum (Ah03). Thermal expansion was determined by

Wachtman eta!. [62WAC/TEF] and White and Roberts [83WHIIROB]. The bulk
modulus was determined in ultrasonic experiments to be in the range 250-255
GPa; the values of K' are in the range 3.97-4.27 ([60WACITEF], [66AND],
[68AND/SCH], [68GIE/BAR], [68CHU/SIM], [89GOT/AND]). In the static com-
pression experiments of Sato and Akimoto [79SAT/AKI] a much lower value of
Kr was obtained than in ultrasonic measurements; in experiments of Finger and
Hazen [78FIN/HAS] a higher value of Kr was obtained. The shock wave data of
Gupta [83GUP] gave a value of adiabatic modulus lower than that obtained in ul-
trasonic measurements. The recommended values of thermal expansion, com-
pressibility and K' are from a book of Saxena [93SAX/CHA]. The sound velocity
data are from study of Goto et al. [89GOTNAM]; they are in good agreement
with the data of Chung [74CHU].
Table 3.12.2.2. Ilmenite (FeSi03). Equation of state parameteers for fictive end-
member were assessed by Fabrichnaya [95FAB] from structural analogies.
Table 3.12.3.2. Ilmenite (MgSi03). Thermal expansion and compressibility were

experimentally studied by Ashida et al. [88ASHIKUM]. They determined a to be
24.4·10-6 K 1 in the range 298-876 K. Data for the bulk modulus were obtained
from Brillouin scattering measurements by Weidner and Ito [85WEIIITO] Ks =
212 GPa. The value of K' was not determined experimentally. The values of Vp
and Vs are from Brillouin scattering measurements of Weidner and Ito
[85WEIIITO]. The recommended values for thermal expansion, compressibility
'
and K are from a study of Saxena [96SAX].
Perovskite S.S. -end-members: perovskite (Al2 0 3), perovskite

(FeSi03) and perovskite (MgSi03).
Table 3.13.1.2. Perovskite (Al2 0 3). The equation of state parameters for this fic-
tive end-member were assessed by Fabrichnaya [99FAB] from structural analogies
and phase equilibria.
Table 3.13.2.2. Perovskite (FeSi03). The equation of state parameters for this
fictive end-member were assessed by Fabrichnaya [98FAB] from structural analo-
gies.
Comments on Thermodynamic Tables 119
Table 3.13.3.2. Perovskite (MgSi03). The thermal expansion and compressibility

were recently experimentally studied by Saxena et al. [98SAX/DUB]. They de-
termined Kr, K' and a from in-situ X-ray studies to be at 261 Gpa, 4 and 11-
12·10-6 respectively K 1 • The data for bulk modulus obtained by different tech-
niques are in the range 246-272 ([89YEG/WEI], [87KUDIITO], [82YAG/MAO],
[91MAO/HEM], [91ROSIHAZ], [94YEG], [96FUNNAG]). The data on thermal
expansion are in the range 8-25·10-6 K 1 ([94MOR/OHT], [96FUNNAG],
[95UTS/FUN], [90PAR/W AN], [94WAN/WEI], [89ROSIHAZ], [98FIQ/AND]).
The Vp and Vs are from Brillouin scattering measurements by Yeganeh-Haeri
[94YEG]. The recommended values for thermal expansion, compressibility and K'
are from the study of Saxena [96SAX].
3.4
Comments on Thermodynamic Tables
Table 3.1.1.1. a-Quartz (Si02). All thermodynamic values were determined by
calorimetry. The heat capacity of a-quartz is described by two different equations
over temperature ranges (298-848 K and 848-1800 K). The recommended expres-
sions are from Saxena et al. [93SAX/CHA] and Robie and Hemingway [78ROB/
HEM]. The experimental data on heat capacities are based on DSC measurements
of Hemingway (87HEM] and of Ghiorso et al. [79GHIICAR] in the temperature
range of 298.15 to 1000 K and on drop calorimetric measurements for tempera-
tures above 1000 K by Richet et al. [82RIC/BOT]. Thermodynamic values at 298
K for a-quartz (enthalpy of formation from elements and entropy) are CODATA
key values [89COX/WAG] and they are the same as in Robie et al. [78ROB/
HEM].
Table 3.1.2.1. P-Quartz (Si02). For heat capacities the same expressions are used
for ~-quartz as for a-quartz. The enthalpy and entropy of ~-quartz are assessed
from phase equilibria of Saxena et al. [93SAX/CHA]. Experimental data on the
a=~ transition are from Cohen and Klement [67COH!KLE] and by Mirwald and
Massonne [80MIRIMAS].
Table 3.1.3.1. Tridymite (Si02). The heat capacity between temperatures 272 to
839 K was measured in several studies ([36AND], [79THO/WEN], [41MOS/
PIT]). The entropy is as in Anderson [36AND]. The recommended Cp expression
is from Swamy et al. [94SWA/SAX] similar to CODATA data [93KHO/WES].
The enthalpy of solution was measured in several studies ([32ROT/TRO],
[32ROT/BEC], [59HUM/SCH]). The recommended values for entropy and en-
thalpy data are assessed by Swamy et al. [94SWA/SAX].
Table 3.1.4.1. Cristobalite (Si02). The entropy was measured by Westrum (un-
published data on low-temperature adiabatic calorimetry, see [95ROB/HEM]).
The heat capacity at high temperatures by Richet et al. [82RIC/BOT] fitted the
data obtained in following studies ([ 19WHI], [21 WIE], [72SMIIHEM] and

[82RIC/BOT]). The enthalpy of a-quartz and cristobalite in aqueous HF solution
is (2.64±0.2) kJ/mol measured by Kracek et al. [53KRAINEU], and in lead cad-
mium borate melt it is (2.68 ±0.68) kJ/mol measured by Holm et al. [67HOLI
KLE]. The recommended Cp expression is from fitting of CODATA data
[93KHOIWES] given in Swamy et al. [94SWA/SAX]. The recommended values
for entropy and enthalpy data are from Swamy et al. [94SWA/SAX].
Table 3.1.5.1. Coesite (Si02). The heat capacity of coesite was studied by Holm
et al. [67HOL/KLE] using adiabatic calorimetry 11-350 K and enthalpy increment
measurements at 570-1070 K [67HOLIKLE] and also DSC measurements (at 350-
660 K [82WAT], at 183-703 K [95AKANUS]). The recommended Cp data are
from Akaogi et al. [95AKANUS], which are in agreement with [67HOL/KLE]
within 3-4 per cent. The entropy of coesite at 298 K calculated from IR and Ra-
man spectra is 40.7±1.0 J/(K·mol) by Akaogi et al. [95AKANUS] and it agrees
with values obtained by adiabatic calorimetry 40.4 J/(Kmol) from Holm et al.
[67HOL/KLE] and 40.38±0.12 J/(Kmol) from Hemingway eta/. [98HEM/BOH].
The new data obtained by adiabatic calorimetry by Atake et al. [OOATAIINO]
S~ 948 is equal to 39.28±0.27 J/(Kmol) but this value is obtained on a synthetic
sample too small for the mass of the calorimeter and it is rejected. The recom-
mended value is 40.6 J/(Kmol). The enthalpy of the transition ~-quartz=coesite as
measured in lead borate melt; the data are: 1.34±0.29 kJ/mol at 975 K
[84AKA/NAV], 1.67±0.42 kJ/mol at 973 K [88ZID/SEM] and 1.268 kJ/mol at
979 K [95AKANUS]. The enthalpy of the a-quartz=coesite transition at 298 K is
3.4 kJ/mol (differential drop-solution calorimetry) [95AKANUS]. The recom-
mended value of the enthalpy of formation from elements -906.4 kJ/mol is from
study of Saxena [96 SAX]. The calculated enthalpy of a-quartz=coesite transition
is 1.287 kJ/mol at 975 K and enthalpy of the a-quartz=coesite transition is
4.3 kJ/mol at 298 K.
Table 3.1.6.1. Stisbovite (Si02). The heat capacity at 6-350 K was measured by
Holm et al. ([67HOL/KLE], adiabatic calorimetry). The heat capacity was deter-
mined using differential scanning calorimetry in the temperature range (350-700
K) by Watanabe [82WAT] and in the range (183-703 K) by [95AKANUS]. The
recommended data are from [95AKANUS]. The entropy at 298 K calculated from
IR and Raman spectra by Akaogi et al. [95AKANUS] is 27.3±1.0 J/(Kmol), this
value is consistent with data of Holm et al. [67HOL/KLE] 27.8 J/(Kmol). The
entropy of the coesite=stishovite transition calculated by Liu et al. [96LIU/TOP]
from phase equilibria is -16.73 J/(Kmol). This yields an entropy measurement of
24 J/(Kmol). The value recommended in this work is 24.6 J/(Kmol). The en-
thalpy of the coesite=stishovite transition at 298 K determined by drop-solution
calorimetry is: 44.27±1.42 kJ/mol [67HOL/KLE], 48.95±1.72 kJ/mol [84AKA/
NAV], 33.81±1.06 kJ/mol [95AKANUS] and 29.85±0.78 kJ/mo1 [96LIU/TOP].
The value for enthalpy of the coesite=stishovite transition at 298 K recommended
in this work 32.4 kJ/mol is in agreement with the calorimetric data of [95AKA/
YUS] and [96LIU/TOP].
Table 3.2.1.1 and Table 3.2.2.1. Iron, bee and fcc (Fe). Recommended data for
modifications of iron are from the assessment of Sundman [91SUN]. They are in
good agreement with the CODATA values [93KHO/WES] and the data of Robie
and Hemingway [95ROBIHEM].
Table 3.3.1.1. Andalusite (AhSi0 5). The heat capacity at temperatures between
250 and 1600 K was determined by Pankratz and Kelley [64PANIKEL]. Low tem-
perature heat capacity between 10 and 380 K was determined by adiabatic calo-
rimetry by Robie and Hemingway [84ROBIHEM]. The enthalpy of solution in
2PbO·B 20 3 solvent at 973 K was measured by Anderson and Newton [77AND/
NEW]; the enthalpy of andalusite=sillimanite transition is calculated to be
-2.80±1.0 kJ/mol using data of Anderson and Kleppa [69ANDIKLE]. The ac-
cepted data are from Saxena et al. [93SAX/CHA]. The calculated enthalpy of an-
dalusite=sillimanite transition at 973 K is -3.31 kJ/mol.
Table 3.3.2.1. Sillimanite (AhSi0 5). The heat capacity at temperatures between
250 and 1600 K was determined by Pankratz and Kelley [64PANIKEL]. The low
temperature heat capacity between 10 and 380 K was determined using adiabatic
calorimetry by Robie and Hemingway [84ROBIHEM]. The enthalpy of solution in
2PbO·B 20 3 solvent at 970 K was measured by Charlu et al. [75CHAINEW] and
the enthalpy of formation from oxides is calculated to be -2.39±0.6 kJ/mol. The
enthalpy of formation from elements at 298 K calculated from the data of Charlu
eta!. [75CHA/NEW] is -2585.94 kJ/mol. The enthalpy of solution in 2PbO·B20 3
solvent at 973 K was determined by Anderson and Kleppa [69ANDIKLE] and
Navrotsky et al. [73NAV/NEW]. These values are in agreement with that of
Charlu et al. [75CHA/NEW]. The accepted data are from Saxena et al.
[93SAX/CHA].
Table 3.3.3.1. Kyanite (AhSi0 5). The heat capacity at temperatures between 250
and 1600 K was determined by Pankratz and Kleppa [64PANIKEL]. The low tem-
perature heat capacity between 10 and 380 K was determined using adiabatic calo-
rimetry method by Robie and Hemingway [84ROBIHEM]. The enthalpy of solu-
tion in 2PbO·B 20 3 solvent at 973 K was measured by Anderson and Newton
[69AND/NEW]. The enthalpy of the sillimanite=kyanite transition is calculated to
be -5.94±0.75 kJ/mol. The accepted data are from Saxena et al. [93SAX/CHA];
the calculated enthalpy of sillimanite=kyanite transition at 970 K is -7.15 kJ/mol.
Table 3.4.1.1. Hematite (Fe20 3). The heat capacity was measured by Coughlin et
a!. [51COUIKIN] between 375 and 1757 K using drop calorimetry and between
300 and 1050 K by Gr0nvold and Samuelsen [75GR0/SAM] using quasi-
adiabatic calorimetry. The low-temperature heat capacity and entropy were deter-
mined from adiabatic calorimetry by Gr0nvold and Westrum [59GR0/WES]. The

recommended heat capacity Cp(1), entropy and enthalpy of formation at 298 K are
from Saxena et al. [93SAX/CHA].
Magnesioferrite S.S. - end members: magnetite (FeFe20 4) and magnesiofer-

rite (MgFez04).
Table 3.5.1.1. Magnetite (FeFe2 0 4). The heat capacity was determined by the
method of drop calorimetry between 352 and 1825 K by Coughlin et a!.
[51 COUIKIN], by method of quasi-adiabatic calorimetry between 300 and 1050 K
by Gr0nvold and Sveen [74GR0/SVE] and by adiabatic calorimetry at 5-350 K
by Westrum and Gr0nvold [69WES/GR0]. The recommended data on heat ca-
pacity Cp(1), entropy and enthalpy of formation from elements are fitted data of
Sundman [91SUN].
Table 3.5.2.1. Magnesioferrite (MgFe20 4). The heat capacity was measured by
Bonnickson [54BON]. The recommended thermodynamic data are from Robie and
Hemingway [95ROB/HEM], refitted by Fabrichnaya [98FAB].
Spinel S.S. - end members: hercynite (FeAh04) and spinel (MgAh04).
Table 3.6.1.1. Hercynite (FeA1z04). The thermodynamic data of hercynite was

assessed in different studies ([93SAX/CHA], [90HOL/POW]). The heat capacity
is accepted from Saxena et al. [93SAX/CHA]; entropy and enthalpy of formation
are accepted from the assessement ofFabrichnaya [99FAB].
Table 3.6.2.1. Spinel (MgA120 4). The heat capacity was determined by drop calo-
rimetry in the study ofRichet and Fiquet [91RIC/FIQ]. The low-temperature heat-
capacity data was measured in the study ofBonnickson [55BON] and of King [55
KIN]. The enthalpy of solution (calorimetry in 2PbO·B 20 3 solvent at 970 K) was
determined by Charlu eta!. [75CHA/NEW]; the enthalpy of formation from ox-
ides is calculated to be -22.52±0.8 kJ/mol. The enthalpy of formation from the
elements at 298 K as calculated from the data of Charlu et a!. [75CHAINEW] is
-2301.94 kJ/mol. The recommended heat capacity Cp{1) is from the study of
Richet and Fiquet [91RIC/FIQ] refitted by Fabrichnaya [99FAB] with entropy
from low-temperature calorimetric data and enthalpy of formation assessed by
Fabrichnaya [99FAB].
Magnesiowustite S.S. -end members: wustite (FeO), charged wustite

(FeO} and periclase (MgO).
Table 3.7.1.1. Wustite (FeO). The heat capacity was measured by the method of
drop calorimetry in the temperature range 340-1800 K by Coughlin et a!.
[51COUIKIN] and by adiabatic calorimetry in the range 52-298 Kin the study of
Todd and Bonnickson [51TOD/BON] and in the range 13-450 Kin the study of
Stolen et al. [96STO/GLO]. The recommended value for the entropy and enthalpy
of formation from elements at 298 K are from the assessment of Sundman
[91SUN].
Table 3.7.2.1. Charged Wustite (FeO+). Fictive end-member. The thermody-

namic data were assessed by Sundman [91SUN].
Table 3.7.3.1. Periclase (MgO). The heat capacity was determined by drop calo-
rimetry by Victor and Douglas [63VIC/DOU] up to 1173 K, by Pankratz and Kel-
ley [63PAN/KEL] up to 1800 K and by Richet and Fiquet [91RIC/FIQ] from 800
to 1800 K. The heat capacity (350-650 K) was measured also by differential scan-
ning calorimetry by Watanabe [82WAT] and by Krupka et al. [79KRU/ROB]. The
data are in good agreement. The low-temperature heat capacity was measured by
method of adiabatic calorimetry ([59BARIBER], [69GME]). The entropy of peri-
clase was calculated from adiabatic calorimetry measurements. The enthalpy of
formation from the elements are from CODATA [89COX/WAG].
Olivine S.S. - end members: fayalite (Fe2Si04 )

and forsterite (Mg2Si04).
Table 3.8.1.1. Fayalite (Fe2Si04). The entropy is accepted from a study of Robie
et al. [82ROB/FIN] which was based on the low-temperature heat capacity from 5
to 380 K. The heat capacity equation at higher temperature is accepted from the
same study [82ROB/FIN]. They combined their Cp measurements at temperatures
higher than 298 K with the enthalpy increment data of Orr [530RR]. The heat ca-
pacity measured by Watanabe [82WAT] is in a good agreement with data of Robie
et al. [82ROB/FIN]. The enthalpy of formation is from the study of King
([52KIN], aqueous HF calorimetry) and with a correction to quartz solution en-
thalpy Hemingway et al. [77HEM/ROB], the calorimetric value becomes
-1479.36±2.4 kJ/mol. The recommended value -1477.35 kJ/mol is assessed by
Fabrichnaya and Sundman [97F AB/SUN] from phase equilibria and emf studies
on Si02+fayalite+iron and Si02+fayalite+magnetite buffer reactions. The consis-
tency with high-pressure phase equilibria Ohtani [790HT] is achieved in the study
ofFabrichnaya and Sundman [97FAB/SUN].
Table 3.8.2.1. Forsterite (Mg2Si04). The entropy of forsterite is accepted from

the assessment of Saxena [96SAX], which is 1.5 J/( K-mol) higher than low-
temperature adiabatic calorimetric data of Robie et al. [82ROB/HEM] and 0.6
J/(K-mol) higher than value of Kelley [43KEL]. The recommended heat-capacity
expression is accepted from Saxena et al. [93SAX/CHA] and it is closely similar
to the data obtained by Robie et al. [82ROB/HEM], in the temperature range
298.15-380 K and to the data of Orr [530RR] on the enthalpy increment. The heat
capacities of Watanabe [82WAT] are about 1.3% higher. The data on the enthalpy
of formation of forsterite at 298.15 K, calculated from solution calorimetry are:
-2177.2±2.2 kJ/mol [48TOR/SAH], -2170.4±1.3 [67KIN/BAR], corrected by

[77HEM/ROB], -2175.1 [75CHAINEW], -2171.9 [79KIS/OGO] and -2172.25
[84BRO/NEW]. The recommended value -2174.14 kJ/mol is from Saxena
[96SAX].
P-Spinel S.S. - end members: P-spinel (Fe2Si04)

and P-spinel (M~Si04).
Table 3.8.3.1. (3-spinel (Fe2Si04). This phase is a fictive one; thermodynamic data
were assessed by Saxena et al. [93SAX/CHA].
Table 3.8.4.1. (3-spinel (MgzSi04). The heat capacity of P-spinel was measured in
temperature range of350-700 K by Watanabe [82WAT], by differential scanning
calorimetry. The enthalpy of solution was measured by Akaogi et al. [84AKA/
ROS] by calorimetry in 2PbO·B 20 3 solvent at 975 K and by Akaogi et al.
[89AKAIITO]. The calorimetric value for enthalpy of the forsterite=P-spinel tran-
sition is 29970±2840 J/mol at 975 K. The heat-capacity data recommended here
are the data of Watanabe [82WAT] refitted by Saxena et al. [93SAX/CHA]. The
enthalpy and entropy of the forsterite=P-spinel transition is assessed from phase
equilibria by Saxena [96SAX]. The recommended value of enthalpy for the for-
sterite=P-spinel transition at 975 K is equal to 30160 J/mol in good agreement
with calorimetric data.
y-Spinel S.S. -end members: y-spinel (Fe2Si04) andy-spinel (Mg2Si04)

(or ringwoodite).
Table 3.8.5.1. y-Spinel (Fe2Si04). The heat capacity (350-700 K) is accepted

from the study of Watanabe [82WAT], by differential scanning calorimetry. The
enthalpy of solution at 986 K given by calorimetry (2PbO·B20 3 solvent) was
measured by Navrotsky et al. [79NAV/PIN]; the enthalpy of transition is calcu-
lated to be 2940±830 J/mol. Enthalpies of fayalite and y-spinel are measured by
transposed temperature drop calorimetry in a study of Akaogi et al. [89AKAIITO].
The difference in observed enthalpy effect corresponds to an enthalpy for the faya-
lite=y-spinel transition at 298 K equal to 6610±2430 J/mol. The heat-capacity data
recommended here are refitted by Saxena et al. [93SAX/CHA] using data of Wa-
tanabe [82WAT]. The enthalpy and entropy increment of the fayalite=y-spinel
transition is assessed by Fabrichnaya and Sundman [97FAB/SUN] from phase
equilibria. The calculated value of the enthalpy increment of the fayalite=y-spinel
transition at 975 K is equal to 10900 J/mol and at 298.15 K is equal to 12270. This
value disagrees with calorimetric data.
Table 3.8.6.1. y-Spinel (MgzSi04) (or ringwoodite). The heat capacity was
measured in the temperature range 350-700 K by Watanabe [82WAT] using a dif-
ferential scanning calorimetry. The enthalpy of solution calorimetry (in
2PbO·B 20 3 solvent at 975 K) was measured in studies of Akaogi et al.

[84AKA/ROS] and [89AKAIITO]. The calorimetric values for the enthalpy of the
~-spinel=y-spinel transition at 975 K are 6823±3767 J/mol [84AKA/ROS] and
9080±2120 J/mol [89AKAIITO]. The heat-capacity data recommended here are
those of Watanabe [82WAT] refitted by Saxena et al. [93SAX/CHA]. The en-
thalpy and entropy of ~-spinel=y-spinel transition are assessed in Saxena [96SAX]
from phase equilibria. The calculated value of enthalpy of ~-spinel=y-spinel transi-
tion at 975 K is equal to 7060 J/mol and is in a good agreement with calorimetric
data.
Hpclinopyroxene S.S. - end-members: hpclinoferrosilite (FeSi03) and hpcli-

noenstatite (MgSi03). {Note B. The thermodynamic data for hpclino- and proto-
modifications of enstatite are from Shi et al. [94SHI/SAX]. Thermodynamic data
for all modifications of ferrosilite are the same as those for orthoferrosilite.}
Table 3.9.1.1. Hpclinoferrosilite (FeSi03).
Table 3.9.2.1. Hpclinoenstatite (MgSi03).
Protopyroxene S.S. - end members: protoferrosilite (FeSi03)

and protoenstatite (MgSi0 3). [See Note B (above).]
Table 3.9.3.1. Protoferrosilite (FeSi0 3).
Table 3.9.4.1. Protoenstatite (MgSi03).
Orthopyroxene S.S. - end members: orthocorundum (Alz0 3),

orthoferrosilite (FeSi0 3) and orthoenstatite (MgSi0 3).
Table 3.10.1.1. Orthocorundum (Ah0 3). The data for the fictive end-member
Alz0 3 with the structure of orthopyroxene were assessed by Fabrichnaya [99F AB].
Table 3.10.2.1. Orthoferrosilite (FeSi03). The heat capacity of ferrosilite was

measured in the temperature range of 350-610 K by Watanabe [82W AT] using the
method of differential scanning calorimetry. The entropy, S, is the calorimetric
value 94.6±0.1 J/(Kmol) obtained indirectly in study of Bohlen et al. [83BOH/
MET]. The recommended Cp(T) is refitted data of Watanabe [82WAT]; the rec-
ommended entropy of 96.6 J/(Kmol) is calculated from phase equilibrium Fa +
quartz= 2Fs experimentally studied by Bohlen and Boettcher [81BOH/BOE].
Table 3.10.3.1. Orthoenstatite (MgSi0 3). The entropy of (clino)enstatite at

298.15 K is taken from Krupka et al. [85KRU/ROB] who measured the heat ca-
pacity of enstatite in the range 5-380 K using low-temperature adiabatic calo-
rimetry. The heat-capacity expression recommended in Saxena [96SAX] based on
measurements of Haselton [79HAS] is in a good agreement with data of Krupka et
al. [85KRU/HEM]. The enthalpy of enstatite formation as determined by using

aqueous HF calorimetry is given in [48TOR/SAH]. That value was adjusted in
[77bHEM/ROB] where the value of -1547.75 ±1.22 kJ/mol was recommended.
The enthalpy of formation from oxides was measured in the study of Charlu et al.
[75CHA/NEW] by lead borate melt calorimetry (-36.88 kJ/mol). The calculated
enthalpy offormation from elements is -1548.24±2.5 kJ/mol. The enthalpy of cli-
noenstatite formation from oxides at 965 and 1173 K was determined in the study
of Shairer and Kleppa [73SHEIKLE] using lead borate melt calorimetry. The val-
ues are equal to -36.3 kJ/mol and -34.1 respectively; the calculated values of en-
thalpy offormation from the elements are -1547.66 and -1546.67±2.5 kJ/mol. The
emf measurements of Rog et al. [74ROGILAN] yielded the Gibbs energy of for-
mation from oxides in the temperature range from 1373 to1573 K. The calculated
value of the enthalpy offormation from the elements is -1549.24±2.5 kJ/mol. The
enthalpy of clinoenstatite formation from oxides was determined by Kiseleva et a!.
[79KIS/OGO] using Pb2 B2 0 5 solution calorimetry at 1170 K to be -34.8 kJ/mol.
The calculated value of LlrH 0 from elements at 298.15 K is -1547.36±2.5 kJ/mol.
Measurements by (Na,Li)B0 2 solution calorimetry at 1023 K by Chatillon-Colinet
et al. [83CHA/NEW] gave enthalpy of orthoenstatite formation from oxides equal
to -35.9 kJ/mol. The calculated value of LlrH 0 from elements at 298.15 K is
-1547.62±2.5 kJ/mol. The enthalpy of orthoenstatite formation from oxides at
1073 K (-33.9 kJ/mol) was determined by Brousse eta!. [84BRO/NEW], based on
(Na,Li)B02 solution calorimetry. The calculated value of LlrH 0 at 298.15 K is
-1545.88 kJ/mol. [See Note B.]
Garnet S.S. - end-members: garnet (FeSi03), garnet (MgSi03)

(or majorite), garnet (Fe3AhSi012) (or almandine), and pyrope
(Mg3AhSh012).
Table 3.11.1.1. Garnet (FeSi0 3). The thermodynamic data for this fictive end-
member is assessed by Fabrichnaya [95FAB] from structural analogies and phase
equilibria
Table 3.11.2.1. Garnet (MgSi03) (or majorite). The heat capacity of tetragonal
garnet (170-700 K) was measured by Yusa et al. [93YUS/AKA] (differential-
scanning calorimetry). The enthalpy of the pyroxene=garnet transition as deter-
mined in study of Yusa et al. [93YUS/AKA] by solution calorimetry at 983 Kin
Pb 2B20 5 melt was 30.8 kJ/mol. The calorimetric study of cubic garnet-pyrope
solid solutions in the system M~Si4 0 12 -Mg3 Al2 Si 3 0 12 with concentration of
Mg4 Si4 0 12 component between 0 and 58 mol per cent was done by Akaogi et al.
[87 AKA/NAV]. The enthalpy of pyroxene=cubic garnet transition was determined
as 146 kJ/mol for M~Si4 0 12 at 987 K. The calculated values of garnet MgSi0 3
formation from elements at 298 K are -1514.41 and -1508.71 kJ/mol using data of
Yusa et al. [93YUS/AKA] and Akaogi et al. [87AKA/NAV], respectivly. The rec-
ommended value in this work is -1513 kJ/mol from assessment of Saxena
[96SAX].
Table 3.11.3.1. Garnet (Fe3Al2Si30 12), (or almandine). The heat capacity was
measured by Anovitz et al. [93ANO/ESS] (adiabatic calorimetry, 6-350 K) and by
Watanabe [82WAT] (differential scanning calorimetry, 420-1000 K). The differ-
ence between the data of Watanabe [82WAT] and that of Anovitz et al.
[93ANO/ESS] is 2 per cent. The entropy of 342.6 J/(mol · K) at 298 K is calcu-
lated from low-temperature heat-capacity data of Anovitz et al. [93ANO/ESS].
The enthalpy of formation from the elements is accepted from an assessment of
Fabrichnaya [99FAB] based on experimental phase equilibrium data (-5271.94
kJ/mol).
Table 3.11.4.1. Garnet (M~AhSh0 12), (or pyrope). The heat capacity was
measured by Tequi et al. [91TEQ/ROB] (drop-calorimetry, 820-1300 K) and by
Watanabe [82WAT] (differential scanning calorimetry, 350-650 K). Low-
temperature heat capacity (10-350 K) was measured in [80HAS/WES] (adiabatic
calorimetry). The value of Cp at 298 K was measured to be 325.31 (J/mol·K). The
value of entropy at 298 K was calculated as 266.27 (J/mol·K). Those values for
entropy and heat capacity at 298 K are recommended in this work. The recom-
mended Cp (1) is accepted from Saxena et al. [93SAX/CHA] and it is in very
good agreement with data of Tequi et al. [91 TEQ/ROB]. The values obtained by
Watanabe [82WAT] are 3 per cent lower than recommended data. The enthalpy of
formation from the elements is accepted from assessment ofFabrichnaya [99FAB]
based on experimental phase equilibria (-6287.15 kJ/mol). The enthalpy of solu-
tion in 2PbO·B20 3 solvent at 970 K was measured by Charlu et al.
[75CHAINEW]; the enthalpy of formation from oxides is calculated to be
-84.6±1.6 kJ/mol. The enthalpy of formation from the elements at 298 K calcu-
lated from the data ofCharlu et al. [75CHA/NEW] is -6292.4 kJ/mol.
Ilmenite S.S. - end members: corundum (Ah03), ilmenite (FeSi03)

and ilmenite (MgSi03).
Table 3.12.1.1. Corundum (Al2 0 3). The heat capacity in the temperature ranges
of (273-1173 K) and (10-2250 K) are measured respectively by Ditmars et al.
[71DIT/DOU] and by [82DITIISH]. Heat capacity measured by drop-calorimetry
by Richet eta/. [82RIC/BOT] agrees with the data of Ditmars et al. (82DITIISH]
(0.2 per cent difference). Data of Krupka et al. [79KRU/ROB] obtained by differ-
ential scanning calorimetry are 1.5 per cent lower than data of Ditmars et a/.
[82DITIISH]. The entropy at 298 K is accepted from low-temperature measure-
ments of heat capacity of Ditmars et al. [82DITIISH]. The enthalpy of formation
from oxides is accepted from the Handbook of Robie and Hemingway
[95ROB/HEM]
Table 3.12.2.1. Ilmenite (FeSi03). The thermodynamic properties for the fictive
end-member was assessed by Fabrichnaya [98FAB] from phase equilibria.
Table 3.12.3.1. Ilmenite (MgSi03). The heat capacity (350-500 K) was measured
by Watanabe [82WAT] by the method of differential scanning calorimetry. The
data between 170 and 700 K were obtained by Ashida et a!. [88ASH/KUM].
Those determinations are in a close agreement. The enthalpy of transition pyrox-
ene=ilmenite at 298 K was determined by drop-solution calorimetry to be
59.03±4.26 kJ/mol in the study of Ashida eta/. [88ASH/KUM]. This value is sub-
stantially less than 71.8 kJ/mol determined by combination of solution drop calo-
rimetry in the study of Ito and Navrotsky [85ITO/NAV]. The recommended value
for the enthalpy of the pyroxene=ilmenite transition is 52.19 kJ/mol and the value
for the enthalpy of formation from the elements at 298.15 K is -1494.1 kJ/mol.
These data are from a study of Saxena [96SAX].
Perovskite S.S. - end-members: perovskite (Al20 3),

perovskite (FeSi03) and perovskite (MgSi03).
Table 3.13.1.1. Perovskite (AI20 3). Data for this fictive end-member were as-
sessed by Fabrichnaya [99FAB].
Table 3.13.2.1. Perovskite (FeSi03). The thermodynamic properties of this fic-

tive end-member were assessed by Fabrichnaya [98F AB].
Table 3.13.3.1. Perovskite (MgSi03). The heat capacity was measured in the
study of Akaogi and Ito [93aAKAIITO]. The data on the enthalpy of transition
pyroxene=perovskite at 298 K as determined by drop-solution calorimetry were:
110.1±4.1 kJ/mol [90ITO/AKA] and 102.2±2.5 kJ/mol [93bAKAIITO]. The rec-
ommended values are 96.79 kJ/mol for the enthalpy of pyroxene=perovskite tran-
sition and -1449.5 kJ/mol for the enthalpy of formation from the elements at
298.15 K. They are from the study of Saxena [96SAX].
Chapter4
Solid Solution Models and Data
4.1
Olivine/fi-, y-Spinels
An ionic model with mixing occurring in the first sublattice is applied to olivine,
P- andy-spinel phases, described by the formula (Fe+2,Mg+2) 2(Si+4)(0-2) 4. The end-
members are Fe2Si04 and MgzSi04.
Olivine (Mg,Fe)2Si04 has been described by a symmetric regular solution
model with a mixing parameter equal to 9000 J/mol (Saxena et al. [93SAX/
CHA]), this value is in good agreement with other estimates. Activity-composition
relations were derived from data on phase equilibrium by Nafziger and Muan
[67NAF!MUA] and Kitayama and Katsura [68KITIKAT]. The first calorimetric
study of Sahama and Torgesson [49SAH/TOR] found positive deviation from
ideality in olivine solid solutions. The calorimetric study of Wood and Kleppa
[81 WOOIKLE] indicated positive deviations from ideality in olivines too. They
used symmetric (W = 8.4 kJ/mol) and an asymmetric model (WMg-Fe = 16.8 kJ/mol
and WFe-Mg = 8.4 kJ/mol) to describe their experimental data. New calorimetric
measurements of Kojitani and Akaogi [94KOJ/AKA] showed that the regular
symmetric model fitted experimental data well with a mixing parameter WH =
10.6±1.7 kJ/mol. The mixing parameter for olivine derived from the Fe-Mg
partitioning data of Wiser and Wood
[91WIS/WOO] and von Seckendorff and
O'Neill [93SEC/ONE] was equal to WH = 7.4 ±1.6 J/mol, assuming ideal mixing
in pyroxene. The mixing parameters of P- and y-spinel have been assessed by
Fabrichnaya [98F AB] from phase equilibria in the Fe0-Mg0-Si02 system. Mixing
Table 4.1. Mixing parameters for the Fe2 Si04-Mg2Si04 solid solutions.
Interactions in phase Mixing parameter
Olivine
(Fe+2 ,Mg+2) 2 Si04 Lo= 9000
P-spinel
(Fe+z ,Mg+2) 2Si04 L 0 = 10401- 14.473·T
L 1 = 972
y-spinel
(Fe+2,Mg+2) zSi04 L0 = 33873 - 32.5- T
130 Solid solution models and data
properties of olivine, ~- andy-spinel are described in the form of Redlich-Kister

polynomial and corresponding parameters are presented in Table 4.1.
4.2
Pyroxenes
Orthopyroxene solid solutions are described by a molecular model. The end-

members are MgSi03, FeSi03 and Ah03. Mixing between MgSi03 and FeSi03
was assumed to be ideal following Saxena et al. [93SAX/CHA]. Calculations of
[99FAB] shows that using a regular solution model for the MgSiOrAh03
orthopyroxene did not give an essentially better fit with experimental data in
comparison with an ideal model. Therefore, ideal mixing between MgSi03 and
Ah0 3 was accepted. Mixing between FeSi03 and Al20 3 and ternary interaction
between MgSi03, FeSi03 and Ah03 was assessed in [99FAB] from phase
equilibria determined by Aranovich and Berman [97ARA/BER], Kawasaki and
Matsui [83KAWIMAT], Lee and Ganguly [88LEE/GAN] and Eckert and Bohnen
[92ECK/BOH].
The high pressure phase clinopyroxene (Hpcpx) contains almost no alumina.
Experiments show that the A}z03 content inCa-free clinopyroxene was very low
(0.3-0.5 mol. per cent) at high pressures. Hpclinopyroxene and protopyroxene in
the FMS and FMAS systems are described by the formula (Fe+2,Mg+2)(Si+4)(0-2) 3.
The end-members are FeSi03 and MgSi0 3.
Hpclinopyroxene is described as an ideal solution; protopyroxene is considered
as a regular solution to reproduce data of Bowen and Schairer [35BOW/SCH] and
of Nafziger and Muan [67NAF/MUA] for maximum content of FeSi03 in
pyroxene of 56 mol. per cent in equilibrium with olivine and silica. The
recommended mixing parameters for pyroxenes are presented in Table 4.2.
Table 4.2. Mixing parameters for pyroxene solid solutions.
Orthopyroxene
A}z03-FeSi03 Lo=- 1510- 3.653·T- 7.408·10-6 -P
A}z0 3-FeSi03-MgSi03 Lo=- 6934
Protopyroxene
(Fe+2,Mg+2)Si03 L 0 = 14754.1-11.7685-T
Hpclinopyroxene
(Fe+2,Mg+2)Si03 Lo=O
Magnesiowustite 131
4.3
Magnesiowustite
Magnesiowustite solid solutions are described by the formula (Fe+2 ,Fe+3, Mg+2 ,
Va)(0-2). The end-members are FeO, MgO, Fe0+ 1 and vao· 2 (Va =vacancy).
Wustite is stable from about 830 to 1700 K and has a considerable field of
solid solubility. When in equilibrium with metallic iron, the wustite composition is
almost independent of temperature X(O) = 0.5136. At higher oxygen potential and
temperatures wustite remains stable up to X(O) = 0.55 due to increase of the Fe+3
fraction. With increasing Mg+2 content the amount ofFe+3 decreases according to
Srecec et al. [87SRE/END). With an MgO content of 40 mol. per cent, the content
of Fe+J is close to zero. The model applied to wustite takes into account two
sublattices. Oxygen ions form an fcc lattice and Mg+2 , Fe+2 , Fe+3 , and vacancies fill
the octahedral sites.
This model implies four end-members: stoichiometric "FeO", MgO and two
hypothetical charged compounds Fe0+ 1 and Va0"2 • Only neutral combinations of
Fe+3 and vacancies have physical significance, where the site fraction of vacancies
is half that ofFe+3 • For use in other oxide systems, it is convenient to set the Gibbs
energy ofVao·2 to zero so as not to relate this parameter to the Fe-0 system. No
calorimetric studies of magnesiowustite solid solutions are known. Experimental
studies of magnesiowustite + iron equilibrium indicated pronounced positive
deviations from ideality in magnesiowustite. Several studies on this equilibrium by
Hahn and Muan [62HAHIMUA], Engell [62ENG], Katsura and Kimura [65KAT/
KIM], Srecec et a!. [87SRE/END], where activity-composition relations for
magnesiowustite solid solutions were derived. Data sets differ in the extent of
deviations from ideality. Srecec et al. [87SRE/END] exist, found less pronounced
positive deviations from ideality than those in a majority of previously published
models. Recommended mixing parameters for magnesiowustite are presented in
Table 4.3.
Table 4.3. Mixing parameters for magnesiowustite.
Magnesiowustite
L 0 = -12324.4
L 1 = 20070
L 0 = 17681.09- 5.80263-T
L 1 = 12116.7 -12.86827-T
L0 = 34899.17 + 1.09273-T
L 1= 198447.3- 148.0592-T
4.4
Spinel
Spinel solid solutions are described by the formula (Fe+2,Mg+2)(Fe+3, Al+3)2(0-2)4.

The end-members are Fe304, MgFe204, MgAh04 and FeAlz04. For lack of data
only interactions between Fe304 and MgFe204 and between MgAh04 and FeAh04
have been considered. Solid solution between Fe30 4 and MgFe20 4 are called
magnesioferrite. In the FMAS system we limited ourselves by considering phase
relations at low oxygen fugacity and the presence ofFe+3 in the second sublattice
was ignored. Mixing parameters in spinel were assessed by Fabrichnaya [98FAB]
and [99FAB] and are presented in Table 4.4.
4.5
Garnet
The FMAS garnet solid solutions are presented by the formula (Fe+2,
Mg+2)3(Al+3, Fe+2, Mg+2)(Al+3, St4)(St4) 30 12 . This corresponds to a reciprocal
solutions with twelve end-members: Mg3MgSiSh012, Mg3AlAlSh0 12 ,
Fe3AlAlSh012, Fe3FeSiSi3012, (Fe3AlSiSh012t\ (Fe3FeAlSi3012r 1,
(Mg3AlSiSh0!2)+1, (Mg3MgAlSi3012r 1, Fe3MgSiSi3012, Mg3FeSiSi3012,
(Fe3MgAlSh0 12r 1 and (Mg3FeAlSi3012r 1. Only the first three of these are real;
the others are fictive species and only combination of charged species has
physical meaning. Garnets are usually described by a completely disordered
model, which is based on a suggestion that heterovalent substitution AlAl-MgSi
takes place in octahedral sites consisting of two sublattices (Akaogi et a!.
[87AKA/NAV]). At3 cations are disordered in both sublattices. Dodecahedral
sites are occupied by Mg+2, tetrahedral sites by Si+4 • This corresponds to the
model of ideal mixing of Py and Mg4 Si40 12 components with the number of
positions equal to 2. The sublattice model is equivalent to the ideal model, if the
Gibbs energies of charged particles compensate each other.
Table 4.4. Mixing parameters for spinel.
Magnesioferrite
Lo= 1878.56- 5.5056·T

L 1=-1712.94-10.039·T
Spinel
Lo= 10187- 9.195·10-6-P

L1= 8724- 3.492·10-6 -P
Gamet 133
Fabrichnaya [95F AB] evaluated thermodynamic data for the fictive end-
member FeSi03-garnet from structural analogies and assessed mixing properties of
FeSiOrMgSi03garnet from experimental data ofKato [86KAT] and ofOhtani et
al. [910HTIKAG]. The Gibbs energies of other fictive end-members are linear
combinations of the first four end-members. The Gibbs energies for garnet end-
members are presented in Table 4.5.
The mixing parameters of almandine-pyrope garnet solid solutions were
obtained in many studies from experimental data on phase equilibrium oli-
vine+garnet and other equilibria by Hackler and Wood [89HAC/WOO], Berman
[90BER], Koziol and Bohlen [92KOZ/BOH] and Berman and Aranovich [96BER/
ARA]. Those data indicate small positive deviation from ideality in pyrope-alman-
dine solid solutions. The only direct measurements of excess enthalpy of mixing
for almandine-pyrope garnet was made by Geiger and Newton [87GEI/NEW].
They found that mixing is substantially non-ideal with large positive deviations
near almandine composition (WFe-Mg = 36.17 and WMg-Fe = -15.76 kJ/mol). This
result is in a good agreement with data of Ganguly and Saxena [84GAN/SAX],
which indicated asymmetric positive deviation from ideality towards the Fe-end.
The data presented here are from [99F AB], where mixing properties of almandine-
pyrope were derived from olivine + garnet and pyroxene + garnet equilibria.
Mixing between AI and Mg on octahedral sites was assessed by Gasparik: [90GAS]
and by Fabrichnaya [99FAB]. Mixing parameters in the (Fe,Mg)Si03 garnet was
reassessed by [98FAB]. Fabrichnaya [99FAB] concluded that mixing between AI
and Fe in octahedral site is close to ideal based on comparison of calculated phase
diagram and data of Akaogi and Akimoto [77AKA/AK1]. Other mixing parameters
Table 4.5. The Gibbs energies for garnet phase end-members.
End-member Gibbs energy
Mg3AlAISi30,2 Gpyrope
Fe3AlAlSh012 Galmandine
Mg3MgSiSh012 4· GMgSi03-gamet
Fe3FeSiSh012 4· GFeSi03-garnet
(Mg3AlSiSh012t' Gpyrope
(Fe3AlSiSh012t' Galmandine
(Mg3MgAlSi3012r' 4·GMgSio3-gamet
(Fe3FeAISi3012r' 4· GFeSi03-gamet
Mg3FeSiSh012 3·GMgSio3-gamet + GFeSi03-gamet
Fe3MgSiSh012 3 GFeSi03-garnet + GMgSi03-gamet
(Mg3FeAlSh012r' 3·GMgSi03-gamet + GFeSi03-gamet
(Fe3MgAlSi3012r' 3·GFeSi03-gamet + GMgSi03-gamet
Table 4.6. Mixing parameters for garnet.
Garnet
(Mg)J(Al,Mg)(Si)Si3012 Lo=A A= -35872 + 15.052-T
(Mg)J(Al,Mg)(Al)Sh012 Lo=A
(Fe )J(Al,Mg)(Si)Si3012 Lo=A
(Fe)J(Al,Mg)(Al)ShO,z Lo=A
(Fe,Mg)3(Mg)(Si)ShO,z Lo=3-B B= -20000
(Fe,Mg)J(Mg)(Al)Si3012 Lo=3·B
(Fe,Mg)J(Fe)(Si)Si3012 Lo=3-B
(Fe,Mg)J(Fe)(Al)Sh012 Lo=3-B
(Fe,Mg)J(Al)(Al)Si3012 Lo=C c= -1936- 3.608-10-6-P
L 1=D D= 11054+3.302·10·6 -P
(Fe,Mg)J(Al)(Si)ShO,z Lo=C
L 1=D
(Mg)J(Fe,Mg)(Si)Si30,z Lo=B
(Mg)J(Fe,Mg)(Al)Si30,2 Lo=B
(Fe )J(Fe,Mg)(Si)Sh012 Lo=B
(Fe )J(Fe,Mg)(Al)Sh012 Lo=B
Units: L-parameters are in J/mol; P is in Pa
Table 4.7. The Gibbs energies for ilmenite and perovskite end-members.
Phase End-member Gibbs energy
llmenite,MgSi03 GMgSi03-ilmenite, perovskite

Perovskite (MgAl03)" 1 GMgSi03-ilmenite, perovskite
FeSi03 GFeSi03-ilmenite, perovskite
(FeAlo3r' GFeSi03-ilmenite, perovskite
AlA10 3 GAl20 3-ilmenite, perovskite
(AlSi03t' GAl20 3-ilmenite, perovskite
for garnet have been assessed by Fabrichnaya [99FAB] and accepted in this work.
Recommended values for interaction parameters in garnet are presented in Table
4.6.
Ilmenite/Perovskite 135
4.6
Ilmenite/Perovskite
Phases with ilmenite and perovskite structures are described as (A1+3, Fe+2 ,
Mg+2)(At3, St4 )(U2 )J. End-members are MgSi03, Ab03, (MgAl03r 1, (A1Sio3r 1,
FeSi03 and (FeAl03r 1• The Gibbs energies for end-members in ilmenite and
perovskite phases are presented in Table 4. 7.
There are two positions in the perovskite structure: dodecahedral (A) and
octahedral (B). Weng et al. [82WEN/MAO] proposed that Al is equally distributed
between A and B positions resulting in a distortion of the cubic structure. Jackson
et al. [87JACIKNI] proposed that Fe+2 could substitute Si+4 in a B position with an
associated vacancy and occupation of A position by Si+4 • More recent measure-
Table 4.8. Mixing parameters for ilmenite and perovskite.
Ilmenite
(Al,Mg)(Si)03 Lo=E E = 1632 + 16·T
L 1=F F= -1490.477
(Al,Mg)(Al)03 Lo=E
LI=F
(Mg)(Al,Si)0 3 Lo=E
LI=F
(Al)(Al,Si)03 L 0=E
L 1=F
(Al,Fe)(Si)03 L0=G G = 116902
L 1=H H= -755
(A1,Fe)(A1)03 L0=G
LI=H
(Fe)(A1,Si)03 L0=G
LI=H
Perovskite
(A1,Mg)(Si)0 3 L0=1 1 = 964 + 6.844·1 o·7 ·P
(A1,Mg)(A1)0 3 L0=1
(Mg)(A1,Si)03 Lo=I
(A1)(A1,Si)0 3 L0=1
(A1,Fe )(Si)03 Lo=J J= -192460 + 20-T+ 5·10·6 -P
L 1=K K= 192460- 20·T- 5·10·6 -P
(A1,Fe)(Al)03 Lo=J
L 1=K
(Fe)(A1,Si)03 Lo=J
LI=K
Units: L-parameters are in J/mo1, Pis in Pa

ments were interpreted as evidence that Si+4 could not occupy an A position
[92HEM/COH]. Fe +z was found not to occupy B position by Kudo et al. [90KUD/
PRE).
Ilmenite has a miscibility gap at pressures of 20-25 GPa. Two different phases
with ilmenite structure in MgSi0 3-rich and AlzOrrich compositions are stable.
Corundum (A}z03), stable at 1 atm., contains at high pressure some MgSi03
forming A}z0 3-rich ilmenite.
Mixing between MgSi03 and A}z0 3 in ilmenite and perovskite structures was
considered by Gasparik [90GAS] and very large negative deviations from ideal
behavior were assumed. The mixing model used by Fabrichnaya [99FAB] gives
values quite different from data of Gasparik [90GAS], since new data appeared
about the miscibility gap in ilmenite solid solution and decomposition of
perovskite with pyrope composition to perovskite with low content of A}z0 3 and
AlzOrrich ilmenite (corundum solid solution). Mixing parameters for ilmenite and
perovskite phases have been assessed by Fabrichnaya [99FAB] and are presented
in Table 4.8.
Chapter 5
Calculation of Phase Diagrams
5.1
The Si02 System
The thermodynamic data accepted in this study are from Swamy et al. [94SWN
SAX] except data for coesite, stishovite and liquid. Thermodynamic parameters
for coesite and stishovite were assessed by Saxena [96SAX] taking into account
new calorimetric measurements and phase equilibrium data. Enthalpy, entropy,
and temperature dependence of heatcapacity for liquid phases were assessed by
Swamy et al. [94SWNSAX], equation of state parameters for the liquid were as-
sessed by Fabrichnaya and Sundman [97F AB/SUN], taking into account new data
of Shen and Lazor [95SHEILAZ] on stishovite melting. In this book data for the
liquid phase are not presented since data at high pressures are fragmentary for
even simple end-member systems, such as the Fe-0, Fe0-Si02 and Mg0-Si0 2
systems. For complex systems, such as FeO-MgO-AlzOrSi02, experimental data
on melting are not available even at 1 atm. However, we present calculated phase
equilibria with liquid to show stability limits for solid phases when possible. A
calculated
P-T phase diagram of the Si02 system at pressures up to 40 GPa is pre-
40
(!]76JAC Melting
¢90KAN X
35 X95SHEILAZ
680MIRIMAS Cua=Coes
30 "'J'82BOHIBOE X
+79AKE
~67COHIKLE a=p.Qua
25 *77YAG/AKJ eoe...St X
111 )(77SUI X
0..
(.!)
.._
20 (!)93ZHAIUE
Cl. *95ZHA/ll
Y95SERIZER
15 )(84KOSIISH
10
5 Uq
C<.Q
0
0 1000 2000 3000 4000 5000
T/K
Fig. 5.1. Phase diagram of the Si02 system. The melting curve of Si02 is calculated using
data of [97F AB/S UN]. Symbols represent experimental data indicated in Chapter 1.
13 8 Calculation of phase diagrams
<!)45DARIGUR
Liq·o+Gas
'i746DARIGUR
1800 ~57ENG
Magn+Gas Z65VAURAC
C) SOTAK/KIM
[2]70CAMJBOU
1600 +69LYKIKUZ
*66ACK!SAN
Y52TOU
~
i=::: 1400
1200
1000
0.52 0.54 0.56 0.58 0.60

X(O)
Fig. 5.2a. Phase diagram ofthe Fe-0 system. Temperature vs. composition in oxide sta-
bility field (wustite, magnetite, hematite).
sented in As mentioned in Chapter 2 experimental data on coesite = stishovite

equilibrium are still controversial. Our calculations are in reasonable agreement
with the data of Zhang et a!. [95ZHAILI], Suito [77SUI], Yagi et a!.
[77YAG/AKI] and Zhang et a!. [93ZHAILIE]. The data of Serghiou et a!.
[95SER/ZER] do not concur with our calculations.
5.2
The Fe-0 System
The thermodynamic data accepted in this study were assessed by Sundman
[91SUN]. The calculated phase diagram of the Fe-0 system (enlarged part for
mole fraction of 0 changing from 0.5 to 0.6), showing the most important equilib-
ria between wustite, magnetite, hematite, iron and liquid is presented in Fig. 5.2a.
The calculated phase diagram is in agreement with experimental data within un-
certainty limits. Available experimental data ([45DAR/GUR], [46DAR/GUR],
[66ACK/SAN], [69LYKIKUZ], [57ENG], [65VALIRAC], [80TAKIKIM],
[70CAM/BOU], [70TOU]) are presented in Fig. 5.2a. The temperature of the
lower three-phase equilibrium (wustite +magnetite+ iron) is 833 K and it is con-
sistent with experimental data. The temperature of the upper three phase equilibria
restricting the stability field of wustite (wustite + iron-fcc + liquid and wustite +
magnetite + liquid) are 1643 K and 1695 K, respectively, and are in good agree-
ment with the data of Darken and Gurry [46DAR/GUR].
The Fe-0 System 139
6BRIZ/GOR. * *z 67SWANVAG. ~ 55MAR. A

73GID/GOR. y X+ 68BRA!HED. )( LEV/WAG. ~ 66ACK!SAN. 'i <;> ICJ
-12 T/K
1273Y ~
1238*
-14 1223~
1173X
*
- -16 1138
X
N
0 1073 'i +
;;:: -18
0
10382':
0> 1023(;>
.Q
975 ICJ
-22
905 A
0.34 - 0.35 0.36 0.37

x(02)
Fig. 5.2b. Phase diagram of the Fe-0 system. Oxygen fugacity vs. composition in wustite
stability field.
73GID/GDR ·ICJ +
45DAR/GAR. )( w ** ~ 67SWA/WAG <:> + '+' ,:', 688RA!HED. y Xv
-6 77K
1673 )(
-7
-8
-£
1523<;>
-9 1473 *X Cl
N
....... -10
0
0> 1373<!>Z?
.Q -11
13481C]
1323A+
-12
-13
-14
0.34 0.35 0.36 0.37 0.38
x(02)
Fig. 5.2c. Phase diagram ofthe Fe-0 system. Oxygen activity vs. composition in wustite
stability field.
140 Calculation of phase diagrams
2000
450ARIGUR:
1900 7+
Gas 460ARIGUR:
Uq l!>.!!l<'>X
1800 880NE:
ClY
82016/GOT
1700
~
*
69BRY/SME:
j:::: 1600 X
Magn
1500
1400
1300
1200
-1 0 2 3 4 5
Fig. 5.2d. Phase diagram ofthe Fe-0 system. Temperature vs. log 10 (Pc 021Pc0 ) in oxide
stability field.
Figs. 5.2b and 5.2c present calculated oxygen fugacity in the wustite stability
field along with available experimental data ([73GID/GOR], [66ACK/SAN],
[67SWA/WAG], [45DAR/GUR], [68BRAIHED]). The calculated and experimen-
tal data are in good agreement. The relation between oxygen fugacity and tem-
perature in the Fe-0 system is shown in Fig. 5.2d together with experimental data
of Darken and Gurry ([45DAR/GUR], [46DAR/GUR]), of Oishi eta/. [82018/
GOT] as well as of Bryan and Smeltzer [69BRY/SME].
5.3
The FeO-Si02-02 System
The thermodynamic data accepted in this study were assessed by Fabrichnaya and
Sundman [97FAB/SUN]. Fig. 5.3a presents log 10 (PcoiPco) vs. temperature phase
diagram of the FeO-SiOz-02 system together with experimental data on solid
phase equilibria ([66SCHIMUA], [81SCHIKUS], [81JAC/ROS], [85JAC],
[870NE], [880NE] and others) and equilibria of liquid and solid phases
([27bGRE], [48DAR], [51SCHIENS], [52MIC/SCH], [82018/GOT]). Taking into
account the uncertainty of experimental measurements, the general agreement be-
tween calculations and experiments is good. Presented values of log 10 (PcoiPco)
are calculated from oxygen fugacity. That fugacity for phase equilibria between
solids {IFQ, IW, WM, QFM and MH buffers) was measured in many experimental
studies. Not all of them are presented in Fig. 5.3a. It should be stated that standard
The Fe0-Si02- 0 2 System 141
6 ~66SCH/MUA
~48DAR
Si02+Hem
-
~52MIC/SCH
5
X51SCHIENS
+82015/GOT
0 4 *32SCHIFRA
-"'
Cl...(.) <0)46CIR
3 X696RY/SME
0 )(78HEW
Cl...(.) 2 YB9JAC
.._ *870NE
0 0880NE
...... +B1SCHIKUS
0)
0 'f27GRE
0 .:reSJAC/ROS
t><]81JAC
-1
-2 lron+Si02
800 1000 1200 1400 1600 1800 2000

T/K
Fig. 5.3a. Phase diagram for the FeO-SiOz-0 2 system. Calculated log10(PcoiPco ) vs.
temperature along with experimental data. Four-phase equilibria are labeled by numbers: 1
-Hem + Magn + Si0 2 + Liq; 2- Si02 + Magn +Fa+ Liq; 3 -Fa+ Wu + Magn + Liq; 4-
Fa+ Wu +Iron+ Liq; 5 -Iron+ Si02 +Fa; 6- Fa+ Iron+ Mag; 8- Iron+ Si02 + Liq +
Liq; I.
20 Fa==Y
i!\67AKI/KOM
18 X X X X X (']77AKI/YAG
Wu+St
~87YAGIAKA
16 C)
Cl Z790HT
Cl Fs=Y+St
14 'i770AKVSYO
Fa+(a.p)O=Fs
Ct1 12 +BOBOHIESS
a..
Q 10 *BOBOHIESS
0.. Y=Wu+St
X790HT
8 (!)79NAV/PIN
6
4
2
Fa+Cr
0
1000 1200 1400 1600 1800 2000 2200
T/K
Fig. 5.3b. Phase diagram for the Fe0-Si02-02 system. Subsolidus phase relations at
pressures up to 25 GPa. The experimental curve of Ohtani [790HT] is shown by dashed
lines.
deviations of experimental data are quite narrow [ ± 0.02 in value of log 10

(PcoiPco)] and the solid phase equilibria calculated in this study agree with ex-
periments quite well. For equilibria including liquid phase, the uncertainty in
measured oxygen fugacity is higher. Fabrichnaya and Sundman [97FAB/SUN]
have calculated equilibria between solid and liquid phases using a two-sublattice
ionic model for the liquid. Their calculations for liquid-solid phase equilibria are
presented in Fig. 5.3a to show stability limits for solid phases.
The calculated subsolidus phase diagram of the Fe-Si-0 system is presented in
Fig. 5.3b. The phase diagram at pressures up to 10 GPa is consistent with experi-
mental data. At pressures below 20 GPa y-spinel decomposes to a wustite and
stishovite mixture. Experimental data on this equilibrium are very poor. According
to the calculation fayalite decomposes to a mixture of wustite and ferrosilite in the
field of melt stability. The experimental curve for fayalite melting is shown by a
dashed line. Thus, phase diagrams calculated from thermodynamic data obtained
in this study are consistent with experimental data at 1 atm. and at pressures up to
20 GPa.
5.4
The MgO-Si02 System
The thermodynamic data accepted in this study were assessed by Saxena
[96SAX]. Phase equlibria data for the system offorsterite composition (Mg2 Si04)
and enstatite composition (MgSi03) along with experimental data are presented in
26 Y=Pv+MgO
,.,,., Pv+ MgO

A891TOITAK
IC]981AI!NIS
24
"' A
01=~
~89KAT~TO
Z94MOAJKAT
22 +77SUI
ICl
XS7AKI
ICl .90GAS
co 20 C)
~=Y
0..
Q 'f89KAT~TO
*77SUI
0.. 18 C)87AKI
"'k.79YAGMAO
16
14
01
12
1000 1500 2000 2500 3000
T/K
Fig. 5.4a. Phase diagram of the Mg0-Si02 system at pressures up to 26 GPa. Phase dia-
gram for Mg2 Si04 composition calculated using values of Saxena [96SAX] together with
experimental data.
The Fe0-Mg0-Si0 2 System 143
Um:a<Pv
<!)891TO.TAK
&95KATIOHT
26~----~------L-----J------+ +910HTIKAG
+B7SAW
Hpcpx==Gar
A910HT/KAG
*87SAW
22 )(90PREIGAS
'(+St=llm
'f'95KATIOHT
\':r87SAW
Gar= lim
CJ9tOHTIKAG
m 18
-
*.B7SAW
a. y90GAS
(!) 16 Hpopx:IJ+St
YBSITO/NAV
Q. 14 M90PREIGAS
Gar-Pv
.87SAW
12 fi90GAS
Gar=I}>St
10 XB7Saw
~90GAS
~="I(+S~
8 Opx <!)B7SAW
+851TOINAV
6~-----,------.-----,------+ !>+St~lim
)..87SAW
1000 1500 2000 2500 3000 ~•7+St:llm
087SAW
T/K Op~Hpopx
QSOPACIGAS
Fig. 5.4b. Phase diagram ofthe Mg0-Si02 system at pressures up to 26 GPa. Phase
diagram for MgSi03 composition calculated using values of Saxena [96SAX] together with
experimental data.
Fig. 5.4a and 5.4b. The comparison with experimental data shows that calculations
are in agreement with available experimental phase equilibria within uncertainty
limit except for new data of Irifune et al. [98IRIINIS], which indicated that the
transition pressure of y-spinel = perovskite + MgO was 2 GPa lower than obtained
in previous studies. Another problem is that the calculated phase boundary is too
flat, which does not quite match the sparse phase equilibrium data.
5.5
The FeO-MgO-Si02 System
Thermodynamic data for phases in the Fe-Mg-Si-0 system accepted in this study
were assessed by Fabrichnaya [98FAB]. Calculated log 1o/{02) and Fe+3 content in
magnesiowustite vs. bulk composition ofmagnesiowustite in equilibrium with me-
tallic iron are presented on Figs. 5.5a and 5.5b, along with experimental data of
Hahn and Muan and others ([62HAH/MUA], [81WIS/WOO], [65KATIKIM],
[87SRE/END], [80SIM], [73GID/GOR]). Experimental data on the Fe+3 content
and calculations are in rather good agreement. Calculated data on oxygen fugacity
vs. magnesiowustite composition agree with the results of Hahn and Muan
[62HAH/MUA] better than with the results of Wiser and Wood [81 WIS/WOO].
-10
-11
-12
-
o"'
~ -13
c::ii
.Q
-14
t>- 1T =1400 K, 91WIS/WOO

-15 [CJ- 2 T =1373 K, 62HAHIMUA
~- 3 T =1573 K, 62HAHIMUA
-16
0 0.2 0.4 0.6 0.8 1.0
Fe/(Fe+Mg) in Mw
Fig. 5.5a. Phase diagram of the FeO-Mg0- 02 system. Equilibrium magnesiowustite +

iron in the system Fe-Mg-02• The dependence of oxygen fugacity vs. magnesiowustite
composition at temperatures of 1373, 1400, and 1573 K and pressure of 1 bar along with
experimental data of Hahn and Muan [62HAHIMUA] and Wiser and Wood
[91WIS/WOOJ_
The maximal difference between calculated and experimental value of

log 10 ./{02) is 0.2. For iron+wustite equilibrium in the Fe-0 system, the difference
between calculated and experimental values of log 1o/{02 ) is +0.06 and -0.15 for
data of Wiser and Wood [91WIS/WOO] and for Hahn and Muan [62HAH/MUA],
respectively. The data accepted in this study for iron+wustite equilibrium are in
agreement with available experimental results (see [97FAB/SUN]). This compari-
son shows, that experimental error in log 1o/{02 ) could be higher than ±0.04, stated
by Wiser and Wood [91WIS/WOO]_ Another source of uncertainty is error in
composition determination. Those uncertainties are sufficient to bring our calcula-
tion and experimental data ([62HAH!MUA], [91 WIS/WOO]) into agreement
The phase relations in the Fe0-Mg0- Fe2 0 3 system have been calculated and
compared with the experimental data ofKatsura and Kimura [65KATIKIM], Spei-
del [67SPE], and Brynestad and Flood [58BRY/FLO]_ The calculated phase dia-
gram at T = 1433 K is presented in Fig. 5.5c along with the data of Katsura and
Kimura [65KATIKIM]_ Results of the calculations deviate significantly from ex-
perimental data, especially at high temperatures. The reason for disagreement
could be that the experimental uncertainties are higher than assumed, or that more
complicated models are needed to describe the magnesiowustite and magnesiofer-
rite solid solutions.
The Fe0-Mg0-Si02 System 145
0.12
T= 1573 K
0.10
-
C')
+
Q)
u..
0.08
,!.. 87SRE/END
[!]·SOSIM
~65KAT/KIM
'ij7· 73GID/GOR
:s:
~
0.06
:2:
>-
0.04
0.02
0
0 0.2 0.4 0.6 0.8 1.0
Fe/(Fe+Mg)in Mw
Fig. 5.5b. Phase diagram of the FeO-Mg0-02 system. Equilibrium magnesiowustite +
iron in the system Fe-Mg-02 • The dependence ofFe+3 content in magnesiowustite vs. bulk
Fe content in magnesiowustite at 1573 K and 1 bar along with experimental data ofSrecec
eta/. [87SRE/END], Simons [80SIM], Katsura and Kimura [65KATIKIM] and Giddings
and Gordon [73GID/GOR].
Calculations made in this work show that it is impossible to describe equally

well data at low oxygen fugacities in the Fe-Mg-0 system, olivine+magne-
siowustite exchange equilibrium and data at higher oxygen fugacities in the Fe-
Mg-0 system using a sublattice model for magnesiowustite. The experimental data
on phase equilibria in the presence of metallic iron have been given higher weight
in the present study, because there are more data at low oxygen fugacities and they
are in good mutual agreement. As a result of such selection, the calculated isobars
in the magnesiowustite stability field deviate from experimental data more than the
stated uncertainty of experiments.
The MgFe20 4 is a quite complex phase (see [920NE/ANN]). There is disor-
dering ofMg+2-Fe+3 between tetrahedral and octahedral sites, MgFe20 4 could form
solid solutions not only with Fe30 4 - as proposed in present study -but also with
MgO and Fe2 0 3 . To reproduce the boundary between the magnesiowustite stabil-
ity field and the magnesiowustite + magnesioferrite two-phase region a more
complicated description of magnesioferrite of solid solution is probably necessary.
65KAT/KIM
T=1433 K
t. log(f02)=-8.9
[!]log(f02)~7.8
Cllog(f02)=·0.6B
<!>log(f02)=-4
.log(f02)=-12
(!>log(f02)~5.9
+ log(I02)=-8.8
0.2 0.4 0.6 0.8 1.0

Fe01.5
x(Fe01.5)
Fig. 5.5c. Phase diagram of the FeO-Mg0-02 system. Phase relations in the Mg0-Fe0-
Fe01.5 system at I433 K and I bar together with experimental data ofKatsura and Kimura
[65KAT/KIM].
1.0 I
0.9 T:1400K
0.8 91W1S.WOO
1:1· with Fe sa!Uration
0.7 1!.- without Fe sa!Uration
0 67NAF/MUA
.s 0.6 0· with Fe satur.ition
'Si
:::E
~ 0.5
'al
u.
0.4
0.3
0.2
0.1
0
0 0.2 0.4 0.6 0.8 1.0
Fe/(Fe + Mg) in Mw
Fig. 5.6a. Phase diagram of the Fe0-Mg0-Si02 system. Equilibrium olivine+ magne-
siowustite +iron. Experimental data of Wiser and Wood [9IWIS/WOO] and Nafziger and
Muan [67NAFIMUA] and calculated Fe-Mg partition between olivine and magnesiowustite
in the system Fe0-Mg0-Si0 2-0 2 at I400 K and I bar.
Table 5.1. Exchange equilibrium olivine+ magnesiowustite Kle(OUMw) calculational and

experimental data ofFei et al. [91FEI/MAO].
Fe/(Fe+Mg) Xsio2 T,K P,GPa Kn (calc.) Kn (exptl.)
0.399 0.222 1473 2 0.0988 0.0612

0.442 0.208 1473 2 0.0972 0.0549
0.475 0.219 1473 2 0.0949 0.0469
0.0469
0.0544
0.184 0.209 1473 2 0.1536 0.2137
0.640 0.210 1473 2 0.0987 0.0523
0.300 0.202 1473 2 0.1341 0.0766
0.184 0.209 1723 2 0.1757 0.2721
0.2553
0.2401
0.2763
0.444 0.220 1723 2 0.1181 0.0824
0.0983
0.278 0.203 1723 2 0.1476 0.1085
0.278 0.203 1723 4 0.1348 0.0998
0.444 0.220 1723 4 0.1102 0.0839
0.1021
0.640 0.210 1723 4 0.1123 0.0859
0.184 0.209 1723 4 0.1591 0.2263
0.444 0.220 1623 2 0.1099 0.0624
0.640 0.210 1473 1 0.0988 0.0630
0.444 0.220 1723 9 0.0871 0.0705
0.475 0.219 1723 9 0.0865 0.0544
0.640 0.210 1723 9 0.0898 0.0667
0.278 0.203 1723 9 0.1059 0.0869
0.0877
0.0839
The calculated Fe-content in olivine vs. Fe-content in magnesiowustite at 1 bar

along with experimental data of Wiser and Wood [91WIS/WOO] and Nafziger
and Muan [67NAFIMUA] are presented in Fig. 5.6a. The calculation agrees with
the data of Wiser and Wood better than with the data ofNafziger and Muan. The
Fe-Mg distribution coefficient for the olivine+magnesiowustite exchange reaction
Kbe (01/Mw) = (x~~. x~; )I( X~~. x~w) calculated for different bulk composi-
tions, temperatures and pressures (up to 9 GPa) together with experimental data of
Fei et al. [91FEI/MAO] are presented in Table 5.1. Calculated and experimental
values agree within uncertainty limits.
1.0
0.9
0.8
0
--
c 0.7
0) 0.6
~
+ 0.5
--
Q)
LL 0.4
Q) 0.3
l.i..
0.2
0.1
0.4 0.6 0.8 1.0
Fe/(Fe + Mg) in Opx
Fig. 5.6b. Phase diagram ofthe Fe0-Mg0-Si02 system. Calculated Fe-Mg partition be-
tween olivine and orthopyroxene at temperatures of 1173, 1273, and 1423 K and pressure
of 1.6 GPa along with experimental data of von Seckendorff and O'Neill [93SEK/ONE].
0.8 -J.--.L_-L-_1.---L_-L_--'---+
92KOCICEM
0.7
T=1173 K, P-=1 GPa
0 0.6 T=1273 K, P-=1 . 3 GPa
c:
:::. 0.5
en
~
<t
u..
0.4
~
u.. 0.3
0.2
0.1
0.1 0.2 0.3 0.4 0.5 0.6 0.7

Fe/(Fe+Mg) in Opx
Fig. 5.6c. Phase diagram of the Fe0-Mg0-Si02 system. Calculated Fe-Mg partition be-
tween olivine and orthopyroxene at 1173 K and I GPa [!]and 1273 K and 1.3 GPa [2]. Tri-
angles and squares are experimental data of Koch-Muller et al. [92KOC/CEM] at given
pressures and temperatures.
The Fe0-Mg0-Si0 2 System 149
1.4
T~1273 K
1.3 l>Fe in OPX 92KOC/CEM

<!>Fe in 01 92KOCICEM
C]Fe in OPX 81BOHIBOE
1.2 OFe in 01 81BOHIBOE
1.t
1U 1.0
CL 66
C)
0.0.9
t,6 6
0.8
Opx
0.7
0.6
0.5
0.30 0.35 0.40 0.45 0.50
x(FeO)
Fig. 5.6d. Phase diagram ofthe Fe0-Mg0-Si01 system. Phase diagram for pyroxene
composition [x5;02=0.5). Calculated olivine+ orthopyroxene+ quartz equilibrium at 1273 K
along with experimental data of Bohlen and Boettcher [81BOH/BOE] and Koch-Muller et
al. [92KOC/KEM].
Calculated data on olivine+orthopyroxene and olivine + orthopyroxene +

quartz phase equilibria are consistent with the experimental data of Nafziger and
Muan [67NAF/MUA], of Matsui and Nishizawa [74MAT/NIS], of Bohlen and
Boettcher [81BOH/BOE], of von Seckendorff and O'Neill [93SEC/ONE] and of
Koch-Muller et al. [92KOC/CEM]. Some examples of calculated and experimen-
tal data on these equilibria are presented in Figs. 5.6bcde. One notices a sys-
tematic shift of 0.07 GPa in pressure for olivine + orthopyroxene + quartz equilib-
rium between the data of Bohlen and Boettcher [81BOH/BOE] and of Koch-
Muller eta!. [92KOC/CEM] in the Fe0-Si0 2 system. Taking into account this dif-
ference in pressure calibration will bring the experimental data on three-phase
equilibrium in the Fe0-Mg0-Si02 system of Koch-Muller et a!. [92KOC/CEM]
into better agreement with the data of Bohlen and Boettcher [81BOH/BOE] and
with calculations made in this study.
The calculated phase diagram of the Fe0-Mg0-Si02 system at 1473 K is pre-
sented in Fig. 5.6e along with data of Nafziger and Muan [67NAF/MUA). The
equilibria of magnesioferrite with olivine, pyroxene, and silica are calculated in
this study. Calculations show that magnesioferrite in Mg-rich compositions con-
tains more Fe than indicated in experiments of Speidel and Osborn [67SPE/OSB]
Si02 T= 1473 K
67NAF/MUA
6· OI+Px+Fe
CJ· OI+SiO,+Fe
0.4
0.3 01
O~,~--~~---M_w~----"----"----~
0 0.2 0.4 0.6 0.8 1.0
MgO x(FeO) FeO
Fig. 5.6e. Phase diagram of the Fe0-Mg0-Si02 system. Phase diagram at 1473 K and
1 bar together with experimental data of Nafziger and Muan [67NAF/MUA].
20
ro
a..
C> Y • Mw+St(PV+MW+St)
Q. 15 • Y(Y+MW+St)
10
5+---~--,---,---,--,---,---r
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
x(FeO)
Fig. 5.6f. Phase diagram ofthe Fe0-Mg0-Si02 system. Phase diagram for olivine com-
position [xsio2= l/3] at 1873 K and pressures up to 30 GPa along with experimental data of
Katsura and Ito [87KAT/ITO], Ito et al. [84ITO/TAK] and Ito and Takahashi
[89ITO/TAK].
and Jamieson and Roeder [84JAM/ROE]. The available set of experimental data is
not adequate to get a better fit for equilibria involving magnesioferrite.
Phase diagrams for olivine and pyroxene systems at pressures up to 30 GPa
have been calculated in this study. Using a more complicated model for magne-
siowustite than a binary solution model of FeO-MgO in the study of Fabrichnaya
[98F AB] resulted in better agreement between calculated phase diagrams and
available experimental data. Examples of calculated phase diagrams are presented
in Figs. 5.6f, 5.6g and 5.6h. A phase diagram of the Fe2Si04-Mg2 Si04 system at
1873 K calculated over the pressure range 10-30 GPa is consistent with the data of
Katsura and Ito [89KAT/ITO] and that of Ito and Takahashi [89ITO/TAK]. It is
presented in Fig. 5.6f.
The phase diagram for the FeSi03-MgSi03 system at 1373 Kover the pressure
range 19-28 GPa along with data of [82ITO/YAM] are presented in Fig. 5.6g. The
calculations agree with experimental data within uncertainty limits. The phase dia-
gram for the FeSiOrMgSi03 system at 2073 K and pressure range of 10-26 GPa
is presented in Fig. 5.6h along with the experimental data of Ohtani et a/.
[910HT/KAG]. The topology of the calculated phase diagram for the FeSi0 3-
MgSi03 system at 2073 K is consistent with the experimental data of Ohtani eta/.
[910HT/KAG]. However, there are still differences in phase compositions be-
28
821TO/YAM
27 ~ T= 1373 K X· Pv(Pv+Mw+St)
~ MW+St(Pv+Mw+St)
26 [!]· Y+SI('Y+Mw+St)
C!>· Mw+SI('Y+MW+St)
25 Mw+St 'f· (Pv)
A·('Y+St)
24 +·(Mw+St)
e- Y+St(llm+ Y+St)
ttl
23 6-llm(llm+Y+St)
a. 'f'·llm(llm+Pv)
(!) 22 ~- Pv(llm+Pv)
Q.
21 r+St
20
19
18
0 0.1 0.2 0.3 0.4 0.5
MgSi0 3 FeSi03
x(FeO)
Fig. 5.6g. Phase diagram of the Fe0-Mg0-Si02 system. Phase diagram for pyroxene
composition [xsio2=0.5] at 1373 K and pressures above 20 GPa along with experimental
data of Ito and Yamada [82ITONAM].
26 I
9t0HTII<AG
+~ Px(Gar+~
24 <!I·GaiGa+"''
*~ Ga: {Gct+7+S1J
22 • · y+st(Gor.y-;.S:
20
t'O
a.. 18
(!)
Q:.
16
14
Hpcpx
12
10
0 0.1 0.2 0.3 0.4 0.5
MgSi03 x(FeO) FeSi03
Fig. 5.6h. Phase diagram of the Fe0-Mg0-Si02 system. Phase diagram for pyroxene
composition [xsio2=0.5] at 2073 K and pressures between 10 and 26 GPa along with ex-
perimental data are ofOhtani et al. [9IOHT/KAG].
tween experimental data and calculations for clinopyroxene+majorite and majorite

+ y-spinel + stishovite assemblages.
The iron partition between perovskite and magnesiowustite was extensively
studied because of its importance for understanding of mineral structure of the
Earth's mantle. Recently new experimental data on phase equilibria involving
perovskite and magnesiowustite have been published ([96KATIITO], [97MAR/
WAN], and [96FEI/WAN]). The experimental data of Fei et al. [96FEIIWAN] on
maximal solubility of the FeSi03 in perovskite at 26 GPa are in good agreement
with calculations made in this study. According to calculations, maximum solubil-
ity of the FeSi03 in perovskite changes from x;; =0.0787 at 1473 K to x;; =
0.113 at 2013 K. According to Fei et al. [96FEIIWAN] this value changed from
0.064-0.076 to 0.119-0.125 at corresponding temperatures. As mentioned in the
Chapter 2, there is disagreement in the K0 {PvfMw) values between new measure-
ments ([96KATIITO] and [97MARIWEN]) and previous studies ([82ITONAM],
[84ITO!fAK], [89ITO!TAK], and [91FEIIMAO]). The value is twice as high as
that obtained before. The calculations made in this study agree with the data of Ito
and Yamada [82ITONAM], Ito et al. [84ITO!fAK], Ito and Takahashi [89ITO/
TAK], and Fei et al. [91FEIIMAO]. The reason for disagreement between the two
groups of experimental data could be attributed to differences in experimental
techniques and influence of minor elements. It was shown by Wood and Rubie
[96WOO/RUB], that even small amounts of the Ah03, for example, had a strong
effect on the K0 value.
The FAS System 153
5.6
The F AS System
The calculated reactions between stoichiometric phases in the F AS system are pre-
sented in Fig. 5.7a together with experimental data of Bohlen et al. [86BOH/
DAL], Shulters and Bohlen [89SHU/BOH], Harlov and Newton [92HARINEW],
and Mukhopadhyay and Holdaway [94MUK/HOL]. To get better agreement with
experimental data, in this study an attempt was made to optimize entropies and en-
thalpies of the AbSi0 5 polymorphs. However, this led to umealistic values for en-
tropies, quite well established in calorimetric studies (Robie and Hemingway
[84ROB/HEM]). Therefore, the data of Saxena et al. [93SAX/CHE] are accepted
for the AhSi0 5 polymorphs. Some inconsistency in slope of Her + Qua = Alm +
Sil and Her+ Sil = Al 20 3 + Aim between calculations and experimental data could
be attributed to order-disorder phenomena in sillimanite and hercynite. Location of
the Qua+ Ky + Fe 30 4 = Fe 20 3 +Aim phase boundary at pressures 0.2 GPa lower
than in experiments of Harlov and Newton [92HAR/NEW] could be partly ex-
plained by Fe+3 entering in almandine and kyanite and At3 in magnetite. Probably,
additional data on thermal expansion and compressibility of the phases involved
are needed. The phase diagram of the FeSiOrAb03 system is presented in Fig.
5. 7b together with the experimental data of Aranovich and Berman [97 ARA/
BER]. The differences between calculated and experimental data are within uncer-
tainty limits.
3.0
l2l 1:Her+p..a=Aim+Sil
08680HIDOL
CJ
2.5 2:Her+Si1=COr+Aim
A89SHUIBOH
3:Fcor=!3-0+Aim+Si1
l2l [C)
¢94MUKIHOL
2.0 4:Ky+Magn+P-0=<
=Hem+Alm
I!]92HARINEW
& 1.5 5:Fcor=J3-0+Her
-- 1.0
(!)
0..
0.5
¢
0
800 1000 1200 1400 1600
7/K
Fig. 5.7a. Phase diagram of the Fe0-Alz0rSi0 2 system. Univariant reactions in the
FeO-Al 20rSi02 system along with experimental data of Bohlen et al. [86BOH/DOL],
Shulters and Bohlen [89SHU/BOH], Harlov and Newton [92HARINEW], and Muk-
hopadhyay and Holdaway [94MUKIHOL].
2.2
!;
97ARA/SE.•
eoox...Fa.,.Alm
OAim+O+Fa
2.0 1.5
90px.Aim+0+Fa
1.8
a!
a.. 1.6
Q
• •
f 1!•14
Q.
1.4
1.2
Aim+O+F'a
1.0 0
0.8
1100 1150 1200 1250 1300 1350 1400
T/K
Fig. 5.7b. Phase diagram of the Fe0-Al20 3-Si02 system. Phase diagram of the FeSi03-
Al203 join along with experimental data of Aranovich and Berman [97ARAIBER]. Lines
are calculated univariant reaction and isopleths. Numbers next to circles are experimental
values of mol% Al20 3 in orthopyroxene.
12
77AKA/AKI
T'=1273 K (!)Hpcpx
Gar+ +St lliY+St

11 eGar
10
al
a..
(.!)
0.. 9
Gar+Y+ Coes
•Gar
•
(!)
8
Gar+ Px
Cl
•
7
•
6
0 0.02 0.04 0.06 0.08 0.10 0.12 0.14
Fe4Si40 12 Fe3AI2Si3012
x(AI 20 3)
Fig. 5.7c. Phase diagram ofthe Fe0-A}z03-Si02 system. Calculated phase diagram of
the Fs-Almjoin along with experimental data of Akaogi and Akimoto [77AKA/AKI].
The MAS System 155
The calculated phase diagram of the Alm-Fs join for an ideal garnet solution is
presented along with experimental data of Akaogi and Akimoto [77 AKNAKI] in
Fig. 5.7c. The calculated and experimental data are in good agreement. According
to present work almandine decomposes to an oxide mixture at pressures ~ 28 to 29
GPa, that is higher than that experimentally determined by Akaogi et al. [98AKN
OHM]. Probably, additional data on the thermal expansion and the compressibility
of almandine are needed.
5.7
The MAS System
The phase diagram of the MAS system is shown in Fig. 5.8a along with the ex-
perimental data of Perkins et al. [81PERIHOL], Gasparik and Newton [84GAS/
NEW], Danckwerth and Newton [78DAN/NEW], Herzberg [83HER], and Seifert
[74SEI]. The orthopyroxene is considered to be an ideal solution, because using
more complicated solution models did not give essentially better fits to experimen-
tal data.
4.5 +--_.L--;..---1,.._--r--'--~-'--~-+ (OI,Opx,Gar)

0B1PER/HOL
40
•
~~~
Q84GAS/NEW
(OI,Opx,Sp,Gar)
3.5 ¢78DANINEW
684GAS/NEW
3.0 (OI,Opx,Sp,Cord)
'i166FAWNOD
ct1 +B3HER
Q_ 2.5 *74SEI
(!)
Ct2.0
1.5
1.0
5 7
0.5
w ~++
0+-----~----.----.-----.-----r
1000 1200 1400 1600 1800 2000
T/K
Fig. 5.8a. Phase diagram of the Mg0-Al20 3-Si02 system. Phase diagram of the MgO-
Al203-Si02 system at pressures up to 4.5 GPa together with experimental data ofDanck-
werth and Newton [78DAN/NEW], Perkins et al. [81PER/HOL], Gasparik and Newton
[84GAS/NEW], Fawcett and Yoder [66FAWNOD], Herzberg [83HER], and Seifert
[74SEI]. Lines are calculated univariant reactions and isopleths. Numbers adjacent next to
squares and circles are experimental values of mol% Al203 in orthopyroxene.
30 87KAN
Pv ¢11m
Pv +111
28 T= 1273 K 011m+St+Gar+
est+r
26 ~llm+Gar
®Gat+St+r
24 •Gar
7Gar+H;:cpx
~
22 C)Hpcpx
~IJ+Sl
ctl 20 OP+St+Gar
a.. *•(Gar)
C) 77A'r(.AJAKI
Q. +x(Gar)
C)Hpcpx
eaar
14 OGar+Hpcpx
12
7
Gar+Hpcpx
*0
10 "'o 7 0 8 +
0 0.05 0.10 0.15
X(AI203)
Fig. 5.8b. Phase diagram of the Mg0-AI20 3-Si02 system. Calculated phase diagram of
the En-Py join at 1273 K and pressures up to 30 GPa along with experimental data of
Akaogi and Akimoto [77AKA/AKI] and Kanzaki [87KAN]. X(Ah03) is the mole fraction
of Al20 3 in the Mg0-Ah03-Si02 system X(Al203)=nAlz03/(nMgO+nSiOz+nAlz03). Solid
solutions of corundum (Ah0rMgSi03) are indicated as Ill.
The decomposition of kyanite to stishovite and corundum is an additional test

for data consistency in the A}zSi05 system. The calculated pressure of kyanite
upper stability limit is 13.2 GPa, almost independent of temperature (dP/dT =
1.3·1 o-4 GPa/K), and agrees with experimental data of Irifune et al. [951RI/KUR],
P(GPa) = 11.9 + 0.0008·T(K). According to Schmidt et al. [97SCHIPOL] kyanite
decomposed to oxides at 14 GPa and 1273 K as well as at 17.5 GPa and 2273 K.
The calculated phase diagram of the En-Py join at pressures up to 20 GPa is
presented in Fig. 5.8b along with experimental data of Akaogi and Akimoto
[77AKA/AKI] and Kanzaki [87KAN]. It was not clear (see [87KAN]) why the
value of maximal solubility of M~S40 12 in garnet was so different in experiments
of Akaogi and Akimoto [77AKA/AKI] (50-60 mol. %) and Kanzaki [87KAN]
(80-90 mol. %). Probably, there were large uncertainties in experimental pressure
(2 GPa) and composition determinations. In the calculations made in this study for
the ideal model of garnet, the maximal solubility of enstatite in garnet is 35 mol.
%, less than in both experiments. Taking into account deviation from ideality in
garnet results in better agreement with the experimental data of Akaogi and Aki-
moto [77AKA/AKI] (the calculated value was 45 mol %). The same maximal
solubility of the M~Si40 12 in garnet was obtained in calculations of Gasparik
[90GAS]. Calculations of Akaogi et al. [87AKA/NAV], based on calorimetric
The MAS System 157
30
T=1773 K
~ '"''""
C)lim-MgSi03
XPv-MQSiOJ
28 Pv • 111 Cl (!)Gar + Pv
Pv Cl ¢Gar+ ~m
26 Gar -+ Pv
e Gar
6 +X(?v)
VX(Gar)
24 0 0 9Sif WKO I
t:<l<ii1 r + nr
22 • Cl ?v + 111
• Gar
I
ell
a.. 20 Gar +Um Gar
C> Pv
*X(Pv )
Q llm+jl+S< <!IX(Gar)
Q. 18
Gar+jl+SI
16
14
12
Ga:+~t
10 I
0 0.05 0.1 0 0.15
X(Ab0 3)
Fig. 5.8c. Phase diagram of the Mg0-Al20 3-Si02 system. Calculated phase diagram of
the En-Py join at 1773 K along with experimental data of Irifune and Ringwood
[87IRJIR1N] and Irifune et al. [961Rl/KOI].
30
Pv 9eiAVKOI
28 Pv + Ill * X(PY)
(l AX(Ga~
26 111 (IX(III)
24
ca 22
0...
(.!)
Q. 20
Gar•ll1
18
16
14
T= 1773 K
12
10
0 0.2 0.4 0.6 0.8 1.0
MgSi0 3 AIP J
x(AI20 3 )
Fig. 5.8d. Phase diagram of the Mg0-AI20 3-Si02 system. Calculated phase diagram of
the En-Ah03 join at 1773 K along with experimental data of Irifune et al. [96IRJ/KOI].
15 8 Calculation of phase diagrams
measurements, were in better agreement with the data of Kanzaki [87KAN]. Ob-
servations ofKanzaki [87KAN], that boundaries ofGar+~+St and Gar+y+-St equi-
libria were almost pressure independent, are in contradiction with experiments of
Akaogi and Akimoto [77AKA/AKI] and calculations of Akaogi et al. [87AKA/
NAV], of Gasparik [90GAS] and of this study. According to present calculations
and those of Gasparik [90GAS], garnet in equilibrium with Mg-ilmenite is en-
riched in the A}z03 more than indicated in experiments of Kanzaki [87KAN]. The
compositions of garnet in equilibrium with~+ St, y+ St, and ilmenite at 1273 K
and 15-24 GPa are the most critical data in the MAS system.
The calculated phase diagrams of the En-Py join at 1773 K along with the ex-
perimental data of Irifune and Ringwood [87aiRIIRIN] and Irifune et al. [86IRI/
SEC] are presented in Fig. 5.8c. The calculated data are in good agreement with
experiments. According to this study, there is no direct transition of garnet to the
perovskite phase at pyrope composition. At pressures above 27 GPa, there is a
wide region of perovskite + corundum (Ill) stability. The A}z0 3 content in the
perovskite phase significantly increases with temperature and more slowly with
pressure, in agreement with experimental data of Irifune et al. [96IRIIKOI] and
Yagi et al. [97YAG/ONE].
The calculated phase diagram of the MgSi03-A}z03 system at 1773 K is pre-
sented in Fig. 5.7d along with experimental data of Irifune and Ringwood
[87aiRIIRIN] and lrifune et al. (961RI/KOI). It shows the existence of ilmenite
solid solution in MgSiOrrich compositions (11m) and A}z03-rich compositions
(Ill).
5.8
The FMAS System at Pressures up to 5 GPa
The calculated Fe-Mg exchange equilibrium data between olivine and garnet are
in good agreement with experiments of Hackler and Wood [89HAC/WOO) and
Kawasaki and Matsui [77KAW/MAT]. They are presented in Figs. 5.9a,b. There
is a good agreement between data calculated in this study and experiments of
Jamieson and Roeder [84JAM/ROE] for the exchange equilibrium olivine+spinel;
the results are presented in Fig. 5.9c.
Thermodynamic data obtained in this study reproduce experimental measure-
ments for orthopyroxene-garnet equilibria within uncertainty limits. The calcu-
lated Fe/(Fe+Mg) ratio in garnet and the A}z0 3 content in orthopyroxene vs. the
Fe/(Fe+Mg) ratio in orthopyroxene along with experimental data of Kawasaki and
Matsui [83KAW/MAT] are shown in Figs. 5.9defg. Calculated phase composi-
tions and experimental data of Harley [84HAR], of Lee and Ganguly [88LEE/
GAN], and of Eckert and Bohlen [92ECKIBOH] for pyroxene + garnet and py-
roxene + garnet + quartz equilibria are presented in Table 5.2. The calculated
phase compositions for orthopyroxene + olivine + spinel equilibrium along with
experimental data of Gasparik [87GAS] are presented in Table 5.3. According to
our calculations, at pressure of 18 GPa and a Fe/(Fe+Mg) ratio greater than 0.17,
the orthopyroxene + olivine + spinel equilibrium is metastable. At pressures
The FMAS System at Pressures up to 5 GPa 159
1.0 1.0
T:=1373 K, ?-=5 GPa
T-.:1273 K, ?s0.91 GPa 0.9
0.9 A"- Ont<AWIMAT <!l
A8-;,HAC'W'OO
0.8
0.8 t."' 6
6 -~
0.7 <!l
0.7
-~ Cii 0.6
~ 0.6 A ::;;;:
A + 0.5 <!>
+ 0.5 Q)
Q) A u.. 0.4 <!l<!l
u..
"ai 0.4
A
"ai
u.. 0.3
<!>
u.. A <!l
0.3 0.2
A <!J{!j!>
0.2 0.1
<!l
0.1 0
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0 0.2 0.4 0.6 0.8 1.0
Fe/(Fe + Mg) in Gar Fe/(Fe + Mg) in Gar
Fig. 5.9 a,b. Phase diagram of the Fe0-Mg0-Al20 3-Si0 2 system at pressures up to 5
GPa. Exchange equilibrium olivine+ garnet along with experimental data.
0.7
84J!\MIROE
0.6 6 T>1573 K, f=101325 GPa
0..
(/)
0.5
.s
o; 0.4 A
6
~
+
Q) 0.3
u..
"a5
u.. 0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6
Fe/(Fe + Mg) in 01
Fig. 5.9c. Phase diagram of the Fe0-Mg0-Al20 3-Si02 system at pressures up to 5

GPa. Exchange equilibrium olivine + spinel along with experimental data of Jamieson and
Roeder [84JAM/ROE].
1-4 GPa, the experimental data and calculations are in reasonable agreement. The
uncertainty of the Ah0 3 content in orthopyroxene in the experiments of Kawasaki
and Matsui [83KA W/MAT] is 50% of the measured value and calculations de-
scribe experimental data within uncertainty limits. However, the decrease in the
Ah0 3 content with increasing iron content in Fe-depleted compositions seems to
be too strong.
Table 5.2. Comparison of calculated and experimental data for the equilibria othopyroxene+garnet and orthopyroxene+ garnet+ quartz. 0\
0
Bulk composition T,K P,GPa Calculation Experiment

XFeO XSiO X Aim XFs XOCor X Aim XFs XOCor n
I"
()
~
Lee and Ganguly [88LEE/GAN] garnet+orthopyroxene ~
s·
::::z
0.0977 0.4589 0.0876 1252 2.0 0.289 0.127 0.030 0.44 0.25 0.040 0
....,
1479 2.6 0.281 0.136 0.031 0.22 0.13 0.040 "0
::::z-
0.1319 0.4657 0.0687 1252 2.0 0.387 0.209 0.026 0.49 0.30 0.031 I"
(1)
"'
1330 2.6 0.385 0.208 0.019 0.42 0.26 0.026 tl
1479 2.6 0.373 0.218 0.029 0.44 0.29 O.o31 p;·
(JQ
0.40 0.24 0.034 .....
1479 2.55 0.372 0.219 0.030 0.64 0.47 0.029 3
0.1333 0.4662 0.0676 1330 2.6 0.390 0.212 0.019 0.36 0.26 0.026
"'
1479 2.6 0.378 0.223 0.029 0.34 0.22 0.038
0.24 0.15 0.044
0.1592 0.4581 0.0838 1252 2.0 0.432 0.250 0.025 0.58 0.38 0.024
0.1907 0.4670 0.0659 1252 2.0 0.517 0.332 0.024 0.56 0.37 0.028
1330 2.6 0.514 0.333 0.018 0.53 0.34 0.025
1578 3.75 0.502 0.340 0.017 0.46 0.31 0.034
1680 4.55 0.503 0.338 0.013 0.55 0.42 0.027
0.2535 0.4695 0.0698 1680 4.35 0.771 0.618 0.019 0.61 0.47 0.026
0.3170 0.4683 0.0721 1680 4.33 0.634 0.480 O.o17 0.63 0.50 0.026
0.3801 0.4658 0.0683 1252 2.0 0.900 0.742 0.019 0.91 0.83 0.018
1330 2.6 0.897 0.744 0.018 0.85 0.72 0.009
1578 3.95 0.888 0.750 0.019 0.81 0.69 0.021
Harley [84HAR] orthopyroxene+garnet+quartz

0.1471 0.5678 0.0648 1173 1.0 0.503 0.371 0.047 0.545 0.349 0.050
1323 1.5 0.489 0.328 0.045 0.536 0.443 0.048
(continued)
Bulk composition T,K P,GPa Calculation Experiment

XfeO XSi0 2 XAI203 X Aim XFs XOCor X Aim XFs XOCor
1423 2.0 0.484 0.332 0.039 0.374 0.257 0.060

0.2406 0.5801 0.0672 1173 1.0 0.770 0.567 0.035 0.750 0.566 0.033
1323 1.5 0.755 0.582 0.038 0.730 0.624 0.030
1423 1.5 0.747 0.588 0.051 0.716 0.602 0.057
1423 2.0 0.749 0.590 0.037 0.610 0.454 0.048
Eckert and Bohlen [92ECK/BOH] orthopyroxene+garnet

0.2987 0.4308 0.1385 1273 2.2 0.700 0.511 0.020 0.705 0.507 0.013 ...,
:::;"
(1)
0.4093 0.4308 0.1385 1173 2.2 0.954 0.836 0.011 0.950 0.877 0.013 'Tl
1273 2.2 0.954 0.848 0.017 0.950 0.901 0.011 ~
1373 2.2 0.953 0.855 0.024 0.950 0.895 0.031
>
[./)
[./)
'-<
~
(1)
s
~
'"1::1
.....
(1)
'J>
'J>
~
(1)
'J>
.§
0
'"1::1
p:>
0'<
1.0 0.012
T=1373 K, P=-5 GPa T:1373 K, ?=5 GPa
C)83KAWIM-'T
0.9 e]~JKAW!MIIT (!)
0.010 (!)
0.8 (!)
a;
(')
('J
0.7 0.008 (!)
~
('J
C!J Cl'l (')
.s 0.6
I:J (!) ('JCJ('J
C!l (')
C!l
Oi X 0.006 CJ
~ 0.5 a.
+
,
Q)
0
u.. 0.4 CJ
o:
.!: 0.004
~ 0.3
CJ
u.. CJ
<(
0.2 0.002
0.1 i!jjJ
0
0 0 0.2 0.4 0.6 0.8 '
1.0
0 0.2 0.4 0.6 0.8 1.0
Fe(Fe+Mg) in Opx
Fe/(Fe+Mg) in Opx
Fig. 5.9d,e. Phase diagrams of the Fe0-Mg0-Ah03-Si0 2 system at 1373 K and pres-
sure of 5 GPa. Equilibrium pyroxene + garnet in the FMAS system at 5 GPa along with
experimental data of Kawasaki and Matsui [83KAW/MAT]. The Fe/(Fe+Mg) ratio in gar-
net and mole fraction of A[z0 3 in orthopyroxene vs. Fe/(Fe+Mg) ratio in orthopyroxene,
respectively.
1.0 0.025
T:1573 K, P=5 GPa
0.9
<!) 83KAW/MAT
0.8
a; 0.020
C!J 0.7 ¢
.s 0.6 <t><t>¢~ $
0.015
Oi X ¢
~ 0.5 0. $
0
+
Q)
u.. 0.4 " 0.010 $ ¢
(i)
u.. 0.3 ¢
¢¢
~
0.2
¢
l 0.005
0.1
s
0 0
0 0.2 0.4 0.6 0.8 1.0 0 0.2 0.4 0.6 0.8 1.0
Fe/{Fe+Mg) in Opx
Fe(Fe+Mg) in Opx
Fig. 5.9f,g. Phase diagrams of the FeO-MgO-Al20rSi0 2 system at 1573 K and pres-
sure of 5 GPa. Equilibrium pyroxene + garnet in the FMAS system at 5 GPa along with
experimental data of Kawasaki and Matsui [83KA W/MAT]. The Fe/(Fe+Mg) ratio in gar-
net and mole fraction of Al2 0 3 in orthopyroxene vs. Fe/(Fe+Mg) ratio in orthopyroxene,
respectively.
Table 5.3. Comparison of calculated and experimental data of Gasparik [87GAS] for the
equilibrium othopyroxene + spinel + olivine.
Bulk composition
XFeO Xsio2 XA!203 Xfa XHer Xfs xocor
P=l.l GPa, T=1613 K

0.0 0.3645 0.1402 0.000 0.000 0.000 0.090 1
0.000 0.000 0.000 0.090 2
0.0571 0.3524 0.1429 0.092 0.171 0.089 0.091 1
0.092 0.132 0.075 0.094 2
0.1143 0.3524 0.1429 0.207 0.298 0.186 0.096 1
0.232 0.295 0.186 0.094 2
0.1748 0.3398 0.1456 0.333 0.411 0.281 0.103 1
0.299 0.364 0.231 0.099 2
P=l.8 GPa, T=1613 K

0.0 0.360 0.120 0.000 0.000 0.000 0.092 1
0.000 0.000 0.000 0.092 2
0.048 0.36 0.12 0.070 0.176 0.070 0.090 1
0.070 0.114 0.057 0.094 2
0.1143 0.3524 0.1429 0.195 0.334 0.178 0.094 1
0.189 0.276 0.171 0.095 2
0.1714 0.3524 0.1429 0.323 0.443 0.277 0.102 1
0.279 0.343 0.221 0.102 2
0.2330 0.3204 0.1650 0.450 0.534 0.367 0.112 1
0.447 0.546 0.338 0.101 2
0.2970 0.2871 0.1881 0.575 0.619 0.454 0.124 1
0.472 0.570 0.366 0.104 2
0.3030 0.2727 0.1919 0.569 0.616 0.451 0.124 1
0.527 0.634 0.406 0.104 2
equilibrium olivine + spinel + garnet Xfa XIIer XAlm

0.541 0.611 0.564 1
0.527 0.614 0.509 2
1 - calculation, 2 - experimental data
5.9
The FMAS System at Pressures up to 30 GPa
The calculated Fe/(Fe+Mg) ratio in perovskite (Pv) at fixed A}z0 3 content in

perovskite in equilibrium with magnesiowustite (Mw) and experimental data of
Wood and Rubie [96WOO/RUB] are presented in Table 5.4. It is possible to re-
Table 5.4. Fe-Mg partition between perovskite and magnesiowustite at T=l873 K and ex-
perimental data of Wood and Rubie [96WOO/RUB] and Irifune [941Rl].
P, wt%Al203 Fe/(Fe+Mg) Fe/(Fe+Mg) in Pv

GPa inPv inMw calc. exper.
25 6.8 0.125 0.042 0.155

25 8.9 0.168 0.056 0.168
25 4.3 0.185 0.044 0.185
25 4.0 0.154 0.039 0.180
25 4.1 0.094 0.029 0.096
25 4.5 0.121 0.041 0.169
28 5.0 0.151 0.033 0.188*
*-data from Irifune [941RI];, the other data are from Wood and Rubie
[96WOO/RUB]
produce the experimental trends in the Fe/Mg partitioning between perovskite and
magnesiowustite, if the Fe-Al mixing parameter in perovskite has a highly nega-
tive value. However, there will be disagreement with other data. The sequence of
phase transformations will be inconsistent with experimental data of Irifune
[94IRI] at 24-28 GPa. Perovskite will be stable for almandine composition at pres-
sures ~30 GPa, in contradiction with experiments of Kesson et al. [95KES/FIT].
In this study, interaction between Fe and A1 is assessed to get agreement with data
of lrifune [941RI] and Kesson et al. [95KES/FIT]. Wood and Rubie [96WOO/
RUB] assumed that Fe-enrichment in perovskite is caused by coupling between
Fe+J and Al+3, forming a hypothetical FeA103 compound. To describe the effect of
Fe-enrichment in perovskite, probably it is necessary to take into account the pres-
ence ofFe+3 ions in perovskite.
Calculated phase compositions for stable assemblages in the FMAS system at
10-28 GPa together with experimental data are presented in Table 5.5. The bulk
compositions are recalculated for the FMAS system to obtain the same
Fe/(Fe+Mg) ratio, Si02 and Ah0 3 contents as in the experiments. Occasionally the
calculated and experimental phase equilibria data are presented at different pres-
sure (within uncertainty limits) as having the same phase assemblage. Taking into
account high uncertainties of experimental data and calculations we may conclude
that they agree within uncertainty limits. Some inconsistencies between experi-
ments and calculations could be attributed to errors in pressure and temperature
measurements. Another reason could be the difference in calculated and experi-
mental compositions. High CaO content in experimentally studied mixtures influ-
ences phase relations (see [87ITO/TAK]). According to experimental data, Ca-
containing perovskite was formed as a separate phase and garnet contained re-
markable amount of Ca (for example, [87biRIIRIN], [87TAKIITO], [94IRI]).
There are other sources of experimental uncertainty, such as difficulties to achieve
Table 5.5. Phase equilibria in the Fe0-Mg0-Ab03-Si0 2 system.
Calculated phase composition Experimental data
1. Akaogi and Akimoto [79AKNAKI]

Bulk composition: Xsio2 = 0.3892, XAt203 = 0.0225, XFeo = 0.0688
P = 14.6 GPa, T=1473 K

Y(Gar,Al) = 0.4441 0.671
Y(Gar,Fe#1) = 0.2095 Fe/(Fe+Mg) in Gar
0.1879 0.1776
Y(Gar,Fe#2) = 0.0386
Y(Hpcpx,Fe) = 0.0202 0.0643
Y(~,Fe) = 0.0873 0.1266
2. lrifune et al. [86IRI/SEK]

Bulk composition: Xsio 2 = 0.4799, XAt2o3 = 0.0868, XFeo= 0.1533
P= 9.6 GPa, T= 1473 K

Y(Gar,Al) = 0.7478 0.9198
0.3851 0.382
Y(Gar,Fe#2) = 0.0496
Y(Hpcpx,Fe) = 0.1422 0.272
Stishovite
3. Irifune [871RI]
Bulk composition: Xsio 2 = 0.485, XAt203 = 0.0684, XFeo = 0.035
P = 10 GPa, T= 1473 K
Y(Gar,Al) = 0.860 0.855
0.1324 0.06635
Y(Gar,Fe#2) = 0.002
Y(Hpcpx,Fe) = 0.01 0.0586
Stishovite
P = 12 GPa, T = 1473 K
Y(Gar,Al) = 0.763 0.791
0.117 0.0908
Y(Gar,Fe#2) = 0.0025
Y(Hpcpx,Fe) = 0.0068 0.048
Stishovite
(continued)
Table 5.5. (continued)
P = 13.7 GPa, T= 1473 K

Y(Gar,Al) = 0.642 0.7435
0.097 0.0823
Y(Gar,Fe#2) = 0.003
Y(Hpcpx,Fe) = 0.0039 0.0336
Stishovite
P = 16.5 GPa, T= 1473 K

Y(Gar,Al) = 0.5313 0.524
0.0784 0.0747
Y(Gar,Fe#2) = 0.0044
Stishovite
4. Irifune and Ringwood [87a1RIIRIN]

Bulk composition : Xsio2 = 0.485, XAJ2o 3 = 0.0299, XFeo = 0.045
P= 12 GPa, T= 1573 K
Y(Gar,Al) = 0.679 0.750
0.226 0.158
Y(Gar,Fe#2) = 0.022
Y(Hpcpx,Fe) = 0.035 0.060
P = 20.5 GPa, T= 1573 K P=21 GPa, T=1573 K

Y(Gar,Al) = 0.621 0.564
0.1562 0.08306
Y(Gar,Fe#2) = 0.0053
Y(y,Fe) = 0.0630 0.08989
Stishovite
P = 23.3 GPa, T= 1573 K

Y(Gar,Al) = 0.765 0.516
0.2476 0.088
Y(Gar,Fe#2) = 0.0048
Y(Ilm,A1) = 0.006 0.034
Y(Ilm,Fe#1) = 0.0434 Fe/(Fe+Mg) in Ilm
0.0437 0.036
Stishovite
(continued)
P = 24.4 GPa, T= 1573 K

Y(Gar,Al) = 0.8361 0.434
0.2811 0.084
Y(Gar,Fe#2) = 0.0032
Y(Pv,Al) = 0.0067 0.024
Y(Pv,Fe#1) = 0.0415 Fe/(Fe+Mg) in Pv
0.0418 0.061
Stishovite
5. Irifune and Ringwood [87biRIIRIN]

Bulk composition: Xs;02 = 0.485, xA1p 3 = 0.0661, XFeo= 0.0315
P = 24.5 GPa, T= 1573 K

Y(Gar,Al) = 0.8771 0.835
0.1342 0.063
Y(Gar,Fe#2) = 0.00014
Y(Pv,Al) = 0.01580 0.0579
0.00284 0.0568
Stishovite
6. Irifune [94IRI]
Bulk composition: Xs; 02 = 0.4013, XAt2o 3 = 0.0216, XFeo = 0.0624
P = 24.665 GPa, T = 1773 K P = 24 GPa, T = 1773

Y(Gar,Al) = 0.8188 0.5655
0.2393 0.0921
Y(Gar,Fe#2) = 0.003
Y(Pv,Al) = 0.013 0.0401
0.03556 0.09403
Y(y,Fe) = 0.1095 0.09875
Y(Mw,Fe) = 0.1810 0.1446
P = 25 GPa, T = 1773 K
Y(Gar,Al) = 0.840 0.7441
0.2469 0.0941
Y(Gar,Fe#2) = 0.00256
Y(Pv,Al) = 0.0143 0.0411

Y(Pv,Fe#l) = 0.03605 Fe/(Fe+Mg) in Pv
0.03657 0.0983
Y(Mw,Fe) = 0.1906 0.1391
P= 28.5 GPa, T= 1873 K P =28 GPa, T= 1873 K

Y(Pv,Al) = 0.0510 0.0526
0.04404 0.10608
Y(Mw,Fe) = 0.2485 0.1362
7. Bertka and Fei [97BERIFEI]

Bulk composition: x 8;02 = 0.3938458, xA~zo 3 = O.ol 7603, XFea= 0.14709
P = 11.3 GPa, T= 1973 K P =13 GPa, T=1973 K

Y(Gar,Al) = 0.5549 0.7894
0.36309 0.28585
Y(Gar,Fe#2) = 0.11845
Y(Ol,Fe) = 0.109 0.21594
Y(Hpcpx,Fe) = 0.16738 0.17362
P= 12.3 GPa, T= 1983 K P=13.5 GPa, T=1983 K

Y(Gar,A1) = 0.49013 0.7760
0.30562 0.2863
Y(Gar,Fe#2) = 0.10786
Y(Ol,Fe) = 0.1634 0.21369
Y(y,Fe) = 0.4021 0.33598
Y(Hpcpx,Fe) = 0.11521 0.18355
P= 13 GPa, T= 1998 K P=14 GPa, T=1998 K

Y(Gar,Al) = 0.42815 0.6162
0.27423 0.2214
Y(Gar,Fe#2) = 0.10817
Y(~,Fe) = 0.25726 0.24484
Y(Hpcpx,Fe) = 0.16738 0.16611
(continued)
P = 13.7 GPa, T= 2023 K P= 15 GPa, T=2023 K

Y(Gar,Al) = 0.33327 0.7479
0.25506 0.23073
Y(Gar,Fe#2) = 0.12536
Y(~,Fe) = 0.24344 0.25032
Y(y,Fe) = 0.34639 0.33272
Y(Hpcpx,Fe) = 0.0858 0.16077
P = 17 GPa, T = 2023 K
Y(Gar,Al) = 0.32942 0.31164
0.20838 0.18434
Y(Gar,Fe#2) = 0.08723
Y(y,Fe) = 0.26746 0.270684
P = 23.8 GPa, T = 2038 K P=23.5 GPa, T=2038 K

Y(Gar,Al) = 0.62249 0.33914
0.2276 0.20065
Y(Gar,Fe#2) = 0.0193
Y(Pv,Al) = O.ol 196 0.02986
0.079513 0.16465
Y(Mw,Fe) = 0.53231 0.49523
. . (F e+2M
N otes on garnet compositiOn , g+2)3#I(]F +2M +2 Al+3)#2(Al+3 ,s·+4)#3s·
130 12 ; compositiOn
. . IS
.
8 e , g , 1
presented by Y(Gar,Al), mole fraction of At (equal in site 2 and 3}, Y(Gar,Fe#l), mole fraction
ofFe+2 in site 1 and Y(Gar,Fe#2), mole fraction ofFe+2 in site 2. The ratio ofFe/(Fe+Mg) calcu-
lated from data on Y(Gar,Fe#l) and Y(Gar,Fe#2) can be compared with experimental value given
beside.
A similar notation is accepted for perovskite (Fe,Mg,All\Al,Si/203:
Y(Pv,Fe#1) is the mole fraction ofFe+2 in site I, Y(Pv,Al) is mole fraction of Al+ 3, equal in site 1
and2.
equilibrium and Fe loss due to reduction [87TAKJITO]. The uncertainties of cal-

culated phase relations in the FMAS system contains the uncertainties of experi-
ments in the end-member systems, in equation of state parameters and in interac-
tion parameters of solid solutions.
For some bulk composition, such as "pyrolite minus olivine" [871RI] and oli-
vine tholeiite ([87biRIIRIN], [861RI/SEC]), stishovite should be stable at high
pressure, because the studied mixtures contained an excess of Si02 • The reason
why Si02 was not found in experiments is not clear. The calculated sequence of
phase transitions is the same as obtained in experiments of Irifune [871RI] as well

as those oflrifune and Ringwood [87biRIIRIN].
For "harzbugite minus olivine" composition experimentally studied at 1573 K,
Irifune and Ringwood [87aiRIIRIN] found that Gar+Hpcpx assemblage was stable
at 12-16.5 GPa, Gar+y at 21 GPa, Gar+Ilm at 23.3 GPa, and Gar+Pv at 24.4 GPa.
In our calculations at a similar composition and 1573 K, there are some differ-
ences in the sequence of phase transformations: Gar+Hpcpx assemblage is found
to be stable at 12-15.7 GPa, Gar+~+ Stat 16.5 GPa, Gar+ y+ Stat 20.5 GPa
and Gar+ lim+ y+ Stat 21 GPa. At pressures of23.3 and 24.4 GPa, both calcula-
tions and experiments indicate the same phase assemblages.
For the pyrolite composition X(Si02) = 0.4014, X(Ah03) = 0.0216, X(FeO) =
0.0624, X(MgO) = 0.5146 (see [94IRI]) the sequence of calculated phase transi-
tions is presented in Table 5.5. According to calculations, stishovite is found to
coexist withy-spinel and garnet at 19-20.5 GPa, in contradiction to experimental
data at 21 GPa (see [94IRI]). The pressure region of 21-23 GPa was not studied
experimentally. According to our calculations,an assemblage of 11m+ y +Gar+ St
32
30
28
26 Pv+Gar+Mw
co 24 Y+Pv+Gar
a.
(!)
..._ 22
Q.
20
18
13-+<lar
6
14
OI+Gar+Hpcpx
12
1500 1800 2100 2400
T/K
Fig. 5.10. P-T phase diagram of the Fe0-Mg0-AI20 3-Si02 system for pyrolite compo-
sition at pressures up to 30 GPa. The following phase assemblages are indicated by num-
bers: 1 - 01 + ~ + Gar+ Hpcpx, 2 - ~ + y + Gar, 3 - ~ + St + Gar, 4 - ~ + y + St + Gar, 5 -
y + St + 11m + Gar, 6- 01 + ~ + Gar.
is stable from 20.6 to 20.9 GPa, Ilm + y + Gar from 21 to 23 GPa and Pv + y +Gar
from 23 to 24.66 GPa. The calculated sequence of phase assemblages is the same
as in experiments at 24 to 28 GPa. Calculations at 1773 K indicate that Gar + Pv +
y + Mw is stable at 24.66 GPa; in experiments, this assemblage was stable at
24 GPa. Irifune [87IRI] found that Gar + Pv + Mw assemblage was stable at
25 GPa; calculations show the stability range for this assemblage to be 24.66-
28.97 GPa. At the temperature of 1873 K, the assemblage Pv + Mw is stable at
28.45 GPa in calculations and at 28 GPa in experiments.
Comparison of our calculations with experiments of Bertka and Fei [97BER/
FEI] shows the same sequence of phase transformations (Table 5.5). Some incon-
sistencies in pressure and phase composition are within experimental uncertainty
limits. According to calculations, y+Gar+St assemblage is stable at 20-23 GPa. In
some experimental determinations, stishovite was found, in some it was not found
under the same conditions. Ilmenite is found neither in calculations nor in experi-
ments.
Mantle mineralogical composition based on phase relations in the FMS system
was considered by Fabrichnaya [95FAB] and Saxena [96SAX]. Comparison of the
P-T phase diagram for the FMAS system, calculated in this study (Fig. 5.10), with
a similar diagram for the FMS system (see [95FAB]) shows the influence of the
Ah0 3 . The main peculiarities, such as transformations of olivine to ~- andy-spinel
and decomposition of y-spinel to mixture of perovskite and magnesiowustite are
also present in the phase diagram of the FMAS system. The negative dP/dT slopes
of the Ilm = Pv transition and y-spinel decomposition also remains. Comparison of
the phase diagrams for the FMS and FMAS systems shows that in the FMAS sys-
tem stishovite-bearing phase assemblages are stable in a more limited P-T range
and garnet is stable over a wider P-T range than in the FMS system.
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Subject and Substance Index
f following a page number indicates a figure

t following a page number indicates a table
bold font indicates a database entry.
italic font indicates solid solution data
Ah03-Si02 system phase relations 15 for equation of state data 59t, 113
Almandine (Fe3AbSi30t2) [in garnet s.s.] for thermodynamic and thermochemical
for equation of state data 95t, 117 data 601, 123
for thermodynamic and thermochemical Clinoferrosilite phase relations 10
data 94t, 12 7 Clinopyroxene (Hpcpx) s.s. 132
a-quartz (Si02) Coesite (Si02)
for equation of state data 27t, 110 for equation of state data 35t, 110
for thermodynamic and thermochemical for thermodynamic and thermochemical
data 26t, 119 data 34t, 120
Andalusite (AhSiOs Coesite = stishovite: dPidT and discrepan-
for equation of state data 43t, Ill cies 7
for thermodynamic and thermochemical Coesite = stishovite transformation 7
data 42t, 121 Coesite transforms to stishovite at 9-10 GPa 7
Assessment programs and principles 4 Corundum (AhOJ) [in ilmenite s.s.]
for equation of state data 991, 118
for thermodynamic and thermochemical
~-quartz (Si02) data 981, 12 7
for equation of state data 29t, II 0 Cristobalite (Si02)
for thermodynamic and thermochemical for equation of state data 33t, 110
data 28t, 119 for thermodynamic and thermochemical
~-quartz and coesite melting curve from 3 to 7
data 32t, 119
GPa8
13-quartz, high-tridymite, and 13-cristobalite
Equations of state 2
transitions 7 Equation of state data for end-members of
~-quartz transformation 7 solid solutions (odd numbers) 5lt-109t
~-spinel (Fe2Si04) [in ~-spinel s.s.] [~-spinel, s.s.] (odd numbers) 69t-73t,
for equation of state data 69t, 114 114
for thermodynamic and thermochemical ~-spinel (Fe2Si04) 69t, 114
data 68t, 124
~-spinel (wadsleite) (M~Si04) 711,
13-spinel, s.s. 129t 114
for equation of state data (odd numbers)
[y -spinel, s.s.] 751, 115
691-731, 114
y-spinel (Fe2Si04) 731, 115
data (even numbers) 68t-72t, 124 y-spinel (ringwoodite)
(Mg2Si04) 751, 115
~-spinel (wadsleite) (M~Si04) [in ~-spinel
[garnet s.s.], (odd numbers) 911-971, 116
s.s.]
almandine (FeJAhSiJOt2) 951, 117
for equation of state data 711, 114
garnet (FeSi03) 911, 116
garnet (majorite) (MgSi0 3) 931, 117
data 701, 124
pyrope (Mg 3AbSh012) 971, 117
Birch-Murnaghan equation of state 2
[hpclinopyroxene s.s.] (odd numbers)
771-791, 115
hpclinoenstatite (MgSi0 3) 791, 115
Charged wustite (FeO+) [in magnesiowustite
s.s.] hpclinoferrosilite (FeSiOJ) 771, 115
192 Subject and Substance Index
[ilmenite s.s.] (odd numbers) 99t-103t, Fe-Mg partition between perovskite and mag-
118 nesiowustite 164t
corundum (AlzOJ) 99t, 118 Fe-Mg-Si-0 system phase relations 12
ilmenite (FeSi03) JOlt, 118 Fe-0 system 138-140
ilmenite (MgSiOJ) 103t, 118 phase diagrams 138f, 139f, 140f
[magnesioferrite s.s.] (odd numbers) 51t- phase relations 8, 9
53t, 112 Fe-0 systems experimental phase diagram 8
magnetite (FeF1:204) Slt, 112 Fe0-Alz03-Si0z phase diagrams 153f, 154f
magnesioferrite (MgFe204) 531, 112 Fe0-Mg0-Ah03-Si0zphase diagrams 159f,
[magnesiowustite s.s.] (odd numbers) 162f
59t-63t, 113 For pyrolite composition 170f
charged wustite (Feo•) 61t, 113 Fe0-Mg0-Ah03-Si0z system, calc./exptl.
periclase (MgO) 631, 113 comparisons 165t
wustite (FeO) 59t 113 FeO-Mg0-02 phase diagrams 144£, 145f,
[olivine s.s.] (odd numbers) 65t-67t, 113 146f
fayalite (FezSi04) 651, 113 Fe0-Mg0-Si02 system 143-152
forsterite (M~Si04) 671, 114 phase diagrams 146f, 148f, 149f
[orthopyroxene s.s.] (odd numbers) 85t- 150£, 151f, 152(
89t, 116 Fe0-Si02-02 system 140-142
orthocorundum (AlzOJ) 85t, 116 phase diagrams 141f
orthoenstatite (MgSiOJ) 89t, 116 Fe-Si-0 system 10
orthoferrosilite (FeSi03) 87t, 116 Fe2Si04 system 10
[perovskite s.s.] (odd numbers) 105t- Fe4Si40iz-Fe3AhSb012 (Fs-Alm) system 16
109t, 118 FeSi03-MgSi03 phase relations 13, 14
perovskite (AlzOJ) lOSt, 118 FMAS (FeO-MgO-AhOJ-SiOz) system 19-21,
perovskite (FeSiOJ) 1071, 118 21t
perovskite (MgSiOJ) 1091, 119 at pressures up to 5 GPa 158-163
[protopyroxene s.s.] (odd numbers) 81t- at pressures up to 30 GPa 163-171
83t, 116 Forsterite (M~Si04)
protoenstatite (MgSiOJ) 83t, 115 for equation of state data 6 7t, 114
protoferrosilite (FeSi03) 811, 115 for thermodynamic and thermochemical
[spinel s.s.], (odd numbers 55t-57t, 112 data 661, 123
hercynite (FeA120 4) 551. 112
spinel (Mg Ah04) 571, 112
Equation of state data for substances (odd y-spinel (FezSi04) [in y-spinel s.s.]
numbers) 27t- 49t, for equation of state data 731, 115
a-quartz (Si02) 27t, II 0 for thermodynamic and thermochemical
andalusite (AhSiOs) 43t, 111 data 721, 124
!3-quartz (Si02) 29t, 110 y -spinel, s.s. 130t
coesite (Si02) 35t, 110 for equation of state data 751, 115
cristobalite (Si02) 33t, II 0 for thermodynamic and thermochemical
hematite Fe20 3) 49t, 112 data, 741, 124
iron-bee (Fe) 39t, Ill y-spinel (ringwoodite) (M~Si04 ) [in y-spinel
iron-fcc (Fe) 41t, Ill s.s.]
kyanite, (AlzSiOs) 47t, 112 for equation of state data 751, 115
sillimanite (AhSi05) 45t, 111 for thermodynamic and thermochemical
stishovite (Si02) 37t, 111 data 741, 124
tridyrnite (Si02) 31t, 110 Garnet s.s.
Experimental data for modeling 3 for equation of state data (odd numbers)
91t-97t, 116
FAS system 15,153-155 data (even numbers) 90t-96t, 126
FAS (Fe0-Ah03-Si0z) system 15 Garnet (FeSi03) [in garnet s.s.]
Fayalite (F1:2Si04) [in olivine s.s.] for equation of state data 9lt, 116
for equation of state data 65t, 113 for thermodynamic and thermochemical
for thermodynamic and thermochemical data 901, 126
data 641, 123 Garnet (majorite)(MgSiOJ) [in garnet s.s.]
for equation of state data 93t, 117
Subject and Substance Index 193
for thermodynamic and thermochemical for equation of state data (odd numbers)
data 921, 126 51t-53t, 112
Gamet end members 132, 133t for thermodynamic and thermochemical
Gamet mixing parameters 134t data (even numbers) 50t-52t, 122
Magnesiowustite s.s. 131t
Hematite high pressure phases 9 59t-63t, 113
Hercynite (FeAh04) [in spinel s.s.] for thermodynamic and thermochemical
for equation of state data 551, 112 data (even numbers) 581-621, 122
for thermodynamic and thermochemical Magnetite high-pressure phases 9
data 541, 12 2 MAS system 16-18, 155-158
Hpclinoenstatite (MgSi0 3 ) [in hpclinopyrox- Mg0-A]z0 3-Si02 system 16-18
ene s.s.] phase diagrams 155f, 156f, 157f
for equation of state data 79t, 115 Mg0-Si0 2 system 142
for thermodynamic and thermochemical phase diagrams 142£, 143f
data 781, 125 phase relations 11-12
Hpclinoferrosilite (FeSi0 3) [in hpclinopyro- Modeling thermodynamic functions 1
xene s.s.] Murnaghan and Birch-Murnaghan equations
for equation of state data 771, 115 of state 2
for thermodynamic and thermochemical Murnaghan equation of state 2
data 761, 125
Hpclinopyroxene s.s. 130
Hpclinopyroxene Olivine (Mg,Fe) 2Si04 129
for equation of state data (odd numbers) Olivine+magnesiowustite, K 0 F'(Ol/Mw),
77t-79t, ll5 calc./exptl. comparison 147t
for thermodynamic and thermochemical Olivine s.s. 1291
data (even numbers) 76t-78t, 125 for equation of state data (odd numbers)
65t-6 71, Jl3
Ilmenite (FeSi03 ) [in ilmenite s.s.] data (even numbers) 64t-66t, 123
for equation of state data 101 t, 118 Optimization program 4
for thermodynamic and thermochemical Orthocorundum (Ah03 ) [in orthopyroxene
data lOOt, 127 s.s.]
Ilmenite (MgSi0 3) [in ilmenite s.s.] for equation of state data 851, 116
for equation of state data 1031, 118 for thermodynamic and thermochemical
for thermodynamic and thermochemical data 841, 125
data 1021, 128 Orthoenstatite (MgSi0 3 ) [in orthopyroxene
Ilmenite s.s. s.s.]
for equation of state data (odd numbers) for equation of state data 891, 116
991-1031, 118 for thermodynamic and thermochemical
for thermodynamic and thermochemical data 88t, 125
data (even numbers) 98t-102t, 127 Orthoferrosilite (FeSi0 3) [in orthopyroxene
Ilmenite and perovskite, end members 135, s.s.]
134t for equation of state data 8 71, 116
Ilmenite and perovskite mixing parame- for thermodynamic and thermochemical
ters 135t data 86t, 125
Orthopyroxene s.s.
Magnetitie (FeFe 20 4) [in magnesioferrite s.s.] 85t-89t, 116
for equation of state data 51t, ll2 for thermodynamic and thermochemical
for thermodynamic and thermochemical data (even numbers) 84t-88t, 125
data 50t, 12 2 Orthopyroxene-garnet phase equilibrium 19
Magnesioferrite (MgFe 20.) [in magnesioferri- Orthopyroxene+gamet equilibria, calc./exptl.
te s.s.] comparison 160t
for equation of state data 53t, 112 Orthopyroxene+gamet+quartz equilibria 160t
for thermodynamic and thermochemical Orthopyroxene+spinel+olivine equilibria 163t
data 521, 122
Magnesioferrite s.s. 132t Periclase (MgO) [in magnesiowustite s.s.]
194 Subject and Substance Index
for equation of state data 631, 113 for equation of state data (odd numbers)
for thermodynamic and thermochemical 55t-57t, 112
data 621, 123 for thermodynamic and thermochemical
Perovskite (AhOJ) [in perovskite s.s.] data (even numbers) 54t-561, 122
for equation of state data 1051, 118 Stishovite (Si02)
for thermodynamic and thermochemical for equation of state data 37t, 111
data1041, 128 for thermodynamic and thermochemical
Perovskite (FeSi03) [in perovskite s.s.] data 36t, 120
for equation of state data 1071, 118 Sublattice model concept 3
for thermodynamic and thermochemical Thermodynamic modeling 1
data 1061, 128 Thermophysical and thermochemical data for
Perovskite (MgSi03) [in perovskite s.s.] end-members of solid solutions
for equation of state data 1091, 119 (even numbers) 501-1081
for thermodynamic and thermochemical [~-spinel, s.s.] (even numbers) 68t-72t,
data1081, 128 125
Perovskite s.s. ~-spinel (FezSi04) 681, 124
for equation of state data (odd numbers) ~-spinel (wadsleite) (Mg2Si04) 701,
1051-109t, 118 124
for thermodynamic and thermochemical [y-spinel, s.s.] 741, 124
data (even numbers) 1041-1081, 128
y-spinel (Fe2Si04) 72t, 124
Program for optimization 4
y -spinel (ringwoodite)
Protoenstatite (MgSi03) [in protopyroxene
s.s.] (MgzSi04) 741, 124
for equation of state data 831, 115 [garnet s.s.] (even numbers) 90t-961, 126
for thermodynamic and thermochemical almandine (FeJAbShOiz) 941, 127
data 821, 125 garnet (FeSi03) 90t, 126
Protoferrosilite (FeSi03) [in protopyroxene garnet (majorite) (MgSi03) 921, 126
s.s.] pyrope (Mg JAbShOiz) 961, 127
for equation of state data 811, 115 [hpclinopyroxene s.s.] (even numbers)
for thermodynamic and thermochemical 76t-78t, 125
data801, 125 hpclinoenstatite (MgSi03) 781, 125
Protopyroxene s.s. hpclinoferrosilite (FeSi03) 761, 125
for equation of state data (odd numbers) [ilmenite s.s.] (even numbers) 98t-102t,
811-831, 115 127
for thermodynamic and thermochemical corundum (AbOJ) 981, 127
data (even numbers) 801-821, 125 ilmenite (FeSi03) lOOt, 127
Pyrope (M~AhSh012) [in garnet s.s.] ilmenite (MgSi03) JOlt, 128
for equation of state data 971, 117 [rnagnesioferrite s.s.] (even numbers) 501-
for thermodynamic and thermochemical 521, 122
data 961, 127 magnetite (FeFe20 4) 501, 122
Pyroxene s.s. 1301 magnesioferrite (MgFe20 4) 52t, 122
[magnesiowustite s.s.] (even numbers)
58t-62t, 122
Quartz, tridymite, and cristobalite 7 charged wustite (FeO+) 60t, 123
periclase (MgO) 62t, 123
wustite (FeO) 58t, 122
Sillimanite (AhSi05) [olivine s.s.] (even numbers) 64t-661, 123
for equation of state data 45t, 111 fayalite (Fe2Si04) 641, 123
for thermodynamic and thermochemical forsterite (MgzSi04) 661, 123
data 44t, 121 [orthopyroxene s.s.] (even numbers) 841-
SiOz anhydrous melting 8 881, 125
SiOz system 7, 137 orthocorundum (A)z03) 841, 125
phase diagram 137f orthoenstatite (MgSi03) 881, 125
Spinel (MgA)z04) [in spinel s.s.] orthoferrosilite (FeSi03 ) 86t, 125
for equation of state data 57t, 112 [perovskite s.s.] (even numbers) 1041-
for thermodynamic and thermochemical 1081, 128
data 561, 122 perovskite (AhOJ) 104t, 128
Spinel s.s. 132, 1321 perovskite (FeSi03) 1061, 128
perovskite (MgSi03) lOSt, 128
Subject and Substance Index 195
[protopyroxene s.s.] (even numbers) 80t- iron-bee (Fe) 38t, 121

82t, 125 coesite (Si0 2) 34t, 120
protoenstatite (MgSi0 3 ) 82t, 125 ~-quartz (Si02) 28t, 119
protoferrosilite (FeSi03 ) SOt, 125 cristobalite (Si02) 32t, 119
[spinel s.s.] (even numbers) 54t-56t, 122 sillimanite (AlzSi0 5) 44t, 121
hercynite (FeAb0 4) 54t, 122 stishovite (Si0 2) 36t, 120
spinel (Mg Ab0 4) 56t, 122 tridymite (Si0 2) 30t, 119
Tridymite (Si0 2)
for equation of state data 31 t, 11 0
Ihermophysical and thermochemical data for for thermodynamic and thermochemical
substances (even numbers), 26t- 48t, data 30t, 119
!lOt Wustite (FeO) [in magnesiowustite s.s.]
a-quartz (Si0 2) 26t, 119 for equation of state data 59t, 113
andalusite (AlzSi0 5) 42t, 121 for thermodynamic and thermochemical
iron-fcc (Fe) 40t, 121 data 58t, 122
kyanite, (AizSi0 5) 46t, 121 Wustite high T and high P phases 9
hematite Fe 20 3) 48t, 121 Wustite's physical properties 8,9
Glossary
Si0 2 Al2Si0s Fe203

a-, ~-Quartz a-Q, ~-Q Andalusite And Hematite Hem
Tridymite Tr Sillimanite Sil
Cristobalite Cr Kyanite Ky
Coesite Coe
Stishovite St
Solid Solutions
Magnesioferrite (Fe +2, Mg +2)(Fe +3) 20 4 Mf

FeFe 20 4 Magnetite Magn
MgFe204 Mf
Spinel (Fe+2,Mg+3)Aiz04 Sp
FeAiz04 Hercynite Her
MgAiz04 Spinel Sp
Magnesiowustite (Fe+2,Fe +3 , Va)0 Mw

FeO Wustite Wu
MgO Periclase Per
Feo+ Wu+
Va Vacancy
Olivine (Fe+ 2,Mg+2 )zSi04 01

Fe 2Si0 4 Fayalite Fa
Mg2Si0 4 Forsterite Fo
~-Spinel (Fe+ 2 ,Mg+2 )zSi0 4

Fe 2Si04 ~-Spinel ~
Mg2Si04 ~-Spinel ~
y-Spinel (Fe+2 ,Mg+2 ) 2Si04 'Y

Fe 2 Si04 y-Spinel 'Y
Mg2Si04 y-Spinel 'Y
Pyroxenes Px
Orthopyroxene Al 20rFeSiOrM gSi0 3 Opx
Alz0 3 Orthocorund Ocor
MgSi0 3 Orthoenstati te En
FeSi0 3 Orthoferrosilite Fs
Protopyroxene (Mg+2,Fe +2)Si0 3 Prpx

MgSi0 3 Protoenstatite PrEn
FeSi0 3 Protoferrosilite PrFs
198 Glossary
Hpclinopyroxene (Mg+2,Fe+2)Si0 3 Hpcpx

MgSi0 3 Hpclinoenstatite HpcEn
FeSi03 Hpclinooferrosilite HpcFs
Gamet (Fe+2,Mg+2)J(Al+3,Fe+2,Mg+2)(A1+3,Si+4)Sh0 12 Gar

Mg3Al3Si30 12 Pyrope Py
Fe3AhSi30 12 Almandine Aim
M~Si 4 0 12 Garnet (Majorite) Gar
Fe4Si40 12 Garnet Gar
Mg3A!Si30\ 2 Garnet Gar
Fe3AlSi40+12 Garnet Gar
M~1Sh0- 12 Garnet Gar
Fe~1Sh0 12 Garnet Gar
Mg3FeSi40 12 Garnet Gar
Fe3MgSi40 12 Garnet Gar
Mg3FeAISh0-12 Garnet Gar
Fe3MgAISi30-12 Garnet Gar
Ilmenite (Al+3,Fe +2,Mg+2)(Al+3,Si+4)0 3 lim

Al20 3 Corundum Cor
MgSi0 3 Ilmenite Ilm
FeSi0 3 Ilmenite 11m
FeAl0-3 Ilmenite Ilm
MgAI0-3 Ilmenite Ilm
AlSiO+3 Ilmenite 11m
Al20 3-MgSi03 Al20 3-rich Ilmenite Ill
Perovskite (At+3,Fe+2,Mg+2)(Al+3,Si+4)03 Per

Ah03 Perovskite Per
FeSi03 Perovskite Per
MgSi0 3 Perovskite Per
FeAl0-3 Perovskite Per
MgAl0-3 Perovskite Per
A!Si0+3 Perovskite Per
Cordierite Mg2Al4Si50 18-Fe2Al4Si 50 18 Cord

Mg2Al4Si50 18 Cordierite Cord
Fe2Al4Si50 18 Fe-Cordierire Fcor

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Data and Knowledge in A Changing World: Scientific Publication Committee

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Data and Knowledge in a Changing World

Scientific Publication Committee

Chairman: H. Behrens (Germany)

Thermodynamic Data, Models,

An Assessment for Materials and Planetary Scientists Based on

ISBN 978-3-642-05730-4 ISBN 978-J-662-10504-7 (eBook)

Cataloging-in-Publication Data applied for

CODATA is an interdisciplinary Scientific Committee of the International Council

Fostering the improvement of the accessibility and quality of quantitative and

Promoting international cooperation in communication and data sharing. This

Introduction to the Series ....................................................................................... V

Acknowledgments ................................................................................................ VII

Table of Contents .................................................................................................. XI

Co-Authors ......................................................................................................... XIII

Vitae of Co-Authors ............................................................................................. XV

CODATA Task Group on Geothermodynamic Data ....................................... XXIII

Chapter 1. Thermodynamics and Modeling .......................................................... 1

Chapter 2. Experimental Phase Equilibrium Data ................................................. 7

Chapter 3. Thermodynamic Data for Stoichiometric Phases

Fe20 3 Tables .................................................................................... 48

Chapter 4. Solid Solution Models and Data ....................................................... 129

Chapter 5. Calculation of Phase Diagrams ......................................................... 137

References ........................................................................................................... 173

Subject and Substance Index ............................................................................... 191

Glossary ............................................................................................................... 197

Fabrichnaya, Olga, Ph.D.

Richet, Pascal, Ph.D.

Saxena, Surendra K., Ph.D.

Westrum, Edgar F. Jr., Ph.D.

Publications (26 total)

23. 0. Fabrichnaya and I. Nerad, "CaO·Si02 - CaO·Alz03·2Si02 - 2Ca0 Alz0 3

Education and Employment

4. Thermodynamic Data on Oxides and Silicates, S.K. Saxena, N. Chatterjee,

Selected Journal Publications

Selected Popularizations (15 total)

Selected Research Publications (120 Total)

Chapters in Books (6 total)

Edgar F. Westrum, Jr.

Education and Employment

1966-1992 Member, Executive Board of the (War Memorial) Phoenix

National Scientific Activities

International Scientific Involvement

1982- ICSU/CODATA Task Group for Chemical Thermodynamic

Professional and Other Society Memberships and Offices

which it had grown to its present page count and 12 issues

Chairman Corresponding Members

Members Executive Committee Liaison

where so298 is the entropy, .1.,H298

and Cp is the heat capacity given by

Cp =a+ bT + cT-2 + dT 2 + eT-3 + p-0.5 + gT-1

The molar volume as a function of pressure and temperature is calculated using

where K Tis isothermal bulk modulus expressed as

K~ = K~rr + K~r (T - Tr) ln(TjTr)

where v.o I,Tr

Fabrichnaya [95FAB] showed that the Murnaghan and Birch-Murnaghan equa-

.1-Gmix = 'LX1G1 + RT'LX1 In X 1 + .1-Gex

~Gex = LX;XiL(X; -Xi)"L7,j

~Gmix = L L LY/Yj1YkuGijk + RTL U 5 LY/ In Y;" + ~Gex

where Yi s is the mole fraction of constituent i on sub lattice s, us is the number of

~Gex = L L (LY/ Jq~

where e . are binary interaction parameters. Higher-order interaction parameters

Diverse kind of experimental information is used to derive internally consistent

l. Phases with well determined calorimetric data, e.g. MgO.