hydrothermal properties of materials experimental data on aqueous phase equilibria and solution properties at elevated temperatures and pressures

Hydrothermal Experimental Data
Hydrothermal Experimental Data Edited by V.M. Valyashko
© 2008 John Wiley & Sons, Ltd. ISBN: 978-0-470-09465-5
Hydrothermal Experimental Data
Edited by
Vladimir M. Valyashko
A John Wiley & Sons, Ltd., Publication
This edition fi rst published 2008
© 2008 John Wiley & Sons, Ltd
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Library of Congress Cataloging-in-Publication Data
Valyashko, V. M. (Vladimir Mikhailovich)
Hydrothermal properties of materials : experimental data on aqueous phase equilibria and solution properties at elevated
temperatures and pressures / Vladimir Valyashko.
p. cm.
Includes bibliographical references and index.
ISBN 978-0-470-09465-5 (cloth)
1. High temperature chemistry. 2. Solution (Chemistry) 3. Phase rule and equilibrium. 4. Materials–Thermal properties.
I. Title.
QD515.V35 2008
541′.34 – dc22
2008027453
British Library Cataloguing in Publication Data
A catalogue record for this book is available from the British Library
ISBN 978-0-470-09465-5
Typeset in 10/12 pt Times New Roman PS by SNP Best-set Typesetter Ltd., Hong Kong
Printed and bound in Singapore by Markono Print Media Pte Ltd, Singapore
Dedication
This book is dedicated to the memory of Professor Dr E. U. Franck (Ulrich Franck) (1920–2004) who made fundamental
contributions in the fi eld of solution chemistry and phase equilibria in aqueous systems at high temperatures and pressures,
and whose idea to create an ‘Atlas on Hydrothermal Chemistry’ was realised with the publication of Aqueous Systems at
Elevated Temperatures and Pressures in 2004 and this book.
Contents

CD Table of Contents ix
Foreword xi
Preface xiii
Acknowledgements xv
1 Phase Equilibria in Binary and Ternary Hydrothermal Systems 1
Vladimir M. Valyashko
1.1 Introduction 1
1.2 Experimental methods for studying hydrothermal phase equilibria 3
1.2.1 Methods of visual observation 73
1.2.2 Methods of sampling 74
1.2.3 Methods of quenching 80
1.2.4 Indirect methods 82
1.3 Phase equilibria in binary systems 86
1.3.1 Main types of fl uid phase behavior 86
1.3.2 Classifi cation of complete phase diagrams 87
1.3.3 Graphical representation and experimental examples of binary phase diagrams 91
1.4 Phase equilibria in ternary systems 103
1.4.1 Graphical representation of ternary phase diagrams 103
1.4.2 Derivation and classifi cation of ternary phase diagrams 105
References 119
2 pVTx Properties of Hydrothermal Systems 135
Horacio R. Corti and Ilmutdin M. Abdulagatov
2.1 Basic principles and defi nitions 135
2.2 Experimental methods 136
2.2.1 Constant volume piezometers (CVP) 136
2.2.2 Variable volume piezometers (VVP) 137
2.2.3 Hydrostatic weighing technique (HWT) 138
2.2.4 Vibrating tube densimeter (VTD) 139
2.2.5 Synthetic fl uid inclusion technique 140
2.3 Theoretical treatment of pVTx data 140

2.3.1 Excess volume 140
2.3.2 Models for the standard partial molar volume 153
2.4 pVTx data for hydrothermal systems 159
2.4.1 Laboratory activities 159
2.4.2 Summary table 185
References 186
3 High Temperature Potentiometry 195
Donald A. Palmer and Serguei N. Lvov
3.1 Introduction 195
3.1.1 Reference electrodes 198
3.1.2 Indicator electrodes 198
3.1.3 Diffusion, thermal diffusion, thermoelectric, and streaming potentials 199
3.1.4 Reference and buffer solutions 200
3.2 Experimental methods 200
3.2.1 Hydrogen-electrode concentration cell 200
3.2.2 Flow-through conventional potentiometric cells 202
3.3 Data treatment 203
References 205
4 Electrical Conductivity in Hydrothermal Binary and Ternary Systems 207
Horacio R. Corti
4.1 Introduction 207
4.2 Basic principles and defi nitions 207
4.3 Experimental methods 215
4.3.1 Static high temperature and pressure conductivity cells 215
4.3.2 Flow-through conductivity cell 217
4.3.3 Measurement procedure 218
4.4 Data treatment 219
4.4.1 Dissociated electrolytes 219
4.4.2 Associated electrolytes 219
4.4.3 Getting information from electrical conductivity data 221

4.5 General trends 221
4.5.1 Specifi c conductivity as a function of temperature, concentration and density 221
4.5.2 The limiting molar conductivity 222
4.5.3 Concentration dependence of the molar conductivity and association constants 223
4.5.4 Molar conductivity as a function of temperature and density 224
4.5.5 Conductivity in ternary systems 224
References 224
5 Thermal Conductivity 227
Ilmutdin M. Abdulagatov and Marc J. Assael
5.1 Introduction 227
5.2 Experimental techniques 228
5.2.1 Parallel-plate technique 228
5.2.2 Coaxial-cylinder technique 235
5.2.3 Transient hot-wire technique 239
5.2.4 Conclusion 241
5.3 Available experimental data 242
5.3.1 Temperature dependence 242
5.3.2 Pressure dependence 244
5.3.3 Concentration dependence 245
5.4 Discussion of experimental data 245
References 246
6 Viscosity 249
Ilmutdin M. Abdulagatov and Marc J. Assael
6.1 Introduction 249
6.2 Experimental techniques 252
6.2.1 Capillary-fl ow technique 253
6.2.2 Oscillating-disk technique 255
6.2.3 Falling-body viscometer 257
6.2.4 Conclusion 259
6.3 Available experimental data 260

6.3.1 Temperature dependence 261
6.3.2 Pressure dependence 261
6.3.3 Concentration dependence 264
6.4 Discussion of experimental viscosity data 265
References 267
7 Calorimetric Properties of Hydrothermal Solutions 271
Vladimir M. Valyashko and Miroslav S. Gruszkiewicz
7.1 Batch techniques 272
7.2 Flow techniques 272
7.3 Summary table 274
References 284
Index 289
viii Contents
CD Table of Contents
Appendix to Chapter 1 pTX
Appendix to Chapter 2 pVTX
Appendix to Chapter 3 Potentiometry
Appendix to Chapter 4 Electrical Conductivity
Appendix to Chapter 5 Thermal Conductivity
Appendix to Chapter 6 Viscosity
Appendix to Chapter 7 Calorimetric
Foreword
Dr. Vladimir Valyashko invited me to write the foreword
to this substantial book that contains all existing evaluated
experimental data on thermodynamic, electrochemical, and
transport properties of two- and three-component aqueous
systems in the hydrothermal region. This invitation is
unquestionably quite an honor. However, accepting it did
make me feel somewhat of an impostor. The person who
should have written this foreword is our revered predeces-

sor, colleague and friend Ulrich Franck, but unfortunately,
he did not live to see the completion of an endeavor that he
had most arduously advocated. It is therefore with trepida-
tion that I, who consider myself at best as one of his many
disciples, act here as his substitute.
An immense amount of experimental material on water/
steam and aqueous systems has been obtained during the
past century, and even before, in laboratories around the
world, much of it not readily accessible. Especially during
the cold-war years, the International Association for Proper-
ties of Water and Steam (IAPS, later IAPWS) was among
the few international organizations in which experts in the
former Soviet Union actively participated. Franck, impressed
by the access IAPWS had to experimental data obtained
worldwide, repeatedly urged the organization to collect and
evaluate these data, bundling them in what he used to call
an Atlas.
This book presents evaluated experimental data acquired,
as well as some of the theoretical models developed, for
two-and three-component hydrothermal systems. These are
aqueous solutions containing both molecular and/or electro-
lytic solutes at high temperature and pressure, approaching
and exceeding water’s critical temperature. Hydrothermal
systems are ubiquitous, in the deep ocean and in the earth’s
crust, and of major importance in geology, geochemistry,
mining, and in industrial practices such as metallurgy and
the synthesis and growth of crystals.
The theoretical understanding of the phase behavior of
fl uid mixtures was developed in the second half of the 19
th

century, starting with the work of Gibbs (1873–1878) and
culminating in Van der Waals’s theory of mixtures (1890),
which was a generalization of his 1873 equation of state.
The fi rst phase separation experiments by Kuenen (early
1890s) involved binary mixtures of simple organics both
below and above the critical point of the more volatile
component. Gradually, between the early 1890s and 1903,
the various types of binary fl uid phase separation became
known. Van Laar actually was able to derive them from a
version of Van der Waals’s mixture equation. Nature’s most
unusual fl uid: “associating” water, however, with its very
high critical point, and its high dielectric constant yielding
electrolytic properties in the liquid phase, was not expected
to behave as air constituents and organics.
The question of how the solvent water would behave
around and above its critical point was fi rst addressed by
the Dutch chemist Bakhuis Roozeboom and his school, who
were experts at measuring and classifying the phase separa-
tion of binary and ternary mixtures, including solid phases.
By 1904, Bakhuis Roozeboom had explored the case of the
liquid-vapor-solid curve intersecting the critical line of a
binary mixture in two critical endpoints and predicted that
this would also happen in aqueous solutions of poorly
soluble salts, as his successors indeed confi rmed in 1910.
His experiments and classifi cation scheme pertain to a mul-
titude of both non-aqueous and aqueous binary and ternary
systems.
Somewhat fortuitously, Göttingen became the nexus
from which “phase theory” would spread to Russia. The

Russian organic chemist Vittorf (1869–1929) met Bakhuis
Roozeboom in Göttingen in 1904. Vittorf then used Bakhuis
Roozeboom’s phase theory and classifi cation as the basis
for his own 1909 book “Theory of Alloys in Application to
Metallic Systems”. From the late 1930s through the 1980s,
physical chemist Krichevskii and his many collaborators,
thoroughly familiar with the work of the Dutch School,
studied fl uid phase behavior and critical phenomena experi-
mentally, and discovered several predicted effects, such as
tricriticality, as well as gas-gas phase separation in both
nonaqueous and aqueous mixtures. Starting just after WWII,
thermal physicist Stirikovich, physical chemists Mashovetz
and Ravich, and geochemist Khitarov, began to explore
phase behavior and solution properties of aqueous systems
up to high temperatures and pressures.
Göttingen professors Nernst, Tammann, and Eucken had
built a physical chemistry laboratory for electrochemistry,
as well as for high-pressure phase equilibria studies and
calorimetry. It was there that Franck, a pupil of Eucken,
began his life’s work on the experimental exploration of the
properties of high-temperature, high-pressure aqueous solu-
tions of air constituents, acids, bases, and salts, studying
phase behavior as well as dielectric and electrochemical
properties. He and his disciples explored this fi eld through-
out the second half of the 20
th
century.
In the USA, just after WWI, geochemist Morey began
the fi rst phase equilibria studies in hydrothermal systems.
By the middle of the 20

th
century, there was a fl ourishing
discipline in geochemistry in the USA, culminating the
work of Kennedy and collaborators on phase separation
in aqueous salt solutions at high pressures and tempera-
tures. Time and again, it was rediscovered that the phase
xii Foreword
separation characteristics of fl uid mixtures fi rst classifi ed by
Bakhuis Roozeboom do apply to aqueous systems as well.
Valyashko, the chief editor of the present book, has,
throughout the years, exhaustively classifi ed the experimen-
tal phase diagrams of binary and ternary aqueous solutions
including solid phases in the hydrothermal range. He fre-
quently consulted with Franck, and assembled the work in
collaboration with Lentz, from the Franck school. This
work forms a substantial part of the present book.
Independently, however, in the 20
th
century, physical
chemists studying aqueous electrolyte solutions set up a
framework of description unlike that used for fl uid mix-
tures. It is founded on increasingly more detailed and accu-
rate measurement and modeling of electrolyte solution
properties in the solvent water, usually below the boiling
temperature. Here the pure solvent at the same pressure and
temperature, and the infi nite-dilution properties of the
solute, serve as an asymmetric reference state. Kenneth
Pitzer was a pioneer in this fi eld, systematically pushing the
modeling of solution behavior to higher concentrations and
temperatures. Geochemist Helgeson and his school intro-

duced practical models for use in the fi eld.
On approaching the critical point, however, water’s
unusual dielectric and electrolytic properties diminish, its
compressibility increases hugely, and its behavior becomes
more like that of other, simpler near-critical fl uids. The
asymmetric solution model then becomes increasingly
strained. This message was brought home forcefully in the
early 1980s by the elegant experimental data of Wood and
coworkers on partial molar properties of the solute in dilute
electrolyte solutions near the water critical point. These
usually well-behaved properties exhibited divergences at
that critical point, while higher derivatives, such as the
partial molar heat capacity, displayed wild swings in water’s
critical region. When Wood et al. repeated the experiments
in the argon-water system, however, similar anomalies were
found, be it of the opposite sign and of smaller amplitude – a
sure sign that the effects they had seen were not electrolytic
in origin, but a general thermodynamic property of a dilute
near-critical mixture. In fact, in the early 1970s, Krichevskii
and coworkers had discovered the divergence of the
infi nite-dilution partial molar volume of the solute experi-
mentally, and explained it correctly.
Aqueous mixtures near and above the water critical point
can then be modeled by Van der Waals-like descriptions of
fl uid mixtures that treat the solvent and solutes equivalently
but ignore the charges. Franck and coworkers, for instance,
produced the phase separations observed in several binary
and ternary aqueous systems in the hydrothermal range
from simple Van-der-Waals type models.
A theory that combines in a unifi ed way the electrolytic

behavior with Van-der Waals-like classical critical behavior
(let alone the actual non-classical critical behavior known
to characterize water as well as all other fl uids) remains a
formidable challenge. Recent fundamental work by M.E.
Fisher and coworkers is making this increasingly clear.
The various chapters of the present book, instead, offer
a practical and useful overview of modeling approaches,
focused on the current needs, methods and understanding
of a wide range of hydrothermal systems. They show a
discipline still in development, one of the last enduring
challenges in the fi eld of thermodynamics and electrochem-
istry of solutions. The book may transcend Franck’s original
concept of an “Atlas,” but he certainly would have been
most pleased with the authors’ efforts of understanding and
representing data, an effort that he himself amply exempli-
fi ed in his scientifi c output of half a century. It is my hope
and expectation that the book will be received by a diverse
class of users as a highly useful compendium of knowledge
about hydrothermal systems, accumulated globally over
more than a century.
Johanna (Anneke) Levelt Sengers
Scientist Emeritus
National Institute of Standards and Technology
Gaithersburg, MD, USA
Preface
Knowledge of equilibria in aqueous systems as well as
understanding the processes occurring in hydrothermal
mixtures are based to a large extent on experimental data
on phase equilibria and solution properties for aqueous
systems at temperatures above 150–200 °C. These data have

been extensively applied in a variety of fi elds of science and
technology, ranging from development of the chemistry of
solutions and heterogeneous mixtures, thermophysics, crys-
tallography, geochemistry and oceanography to industrial
and environmental applications, such as electric power gen-
eration, hydrothermal technologies of crystal growth and
nanoparticle syntheses, hydrometallurgy and the treatment
of sewage and the destruction of hazardous waste.
The available experimental data for binary and ternary
systems can be used as primary reference data, or as the
initial values for further refi nement, in order to obtain rec-
ommended values, particularly, the internally consistent
values that are used for thermodynamic calculations and
modelling of multicomponent equilibria and reactions.
However, the recommended values are derivatives and
largely depend on the method of treatment based on more
or less rigorous and varying models. Thus, a collection of
experimental data not only incorporates original informa-
tion from widely scattered scientifi c publications, it is fun-
damental and provides the foundation for modern and future
databases, and recommended values.
The main goals of this book are to collect, collate and
compile the available original experimental data on phase
equilibria and solution properties for binary and ternary
hydrothermal systems, to review these data, and to consider
the employed experimental methods and the ways these data
were refi ned/processed and presented.
The work on collecting hydrothermal experimental data
was started in the mid-1990s by Dr V. M. Valyashko (Kur-
nakov Institute of General and Inorganic Chemistry, Russian

Academy of Sciences (KIGIC RAS), Moscow, Russia) and
Dr H. Lentz (University of Siegen, Germany) and was sup-
ported by the Russian Fund for Basic Research and the
Deutsche Forschungsgemeinschaft. After the retirement of
Dr Lentz in 1999, collection of data at temperatures above
200 °C was continued by Dr Valyashko and Mrs Ivanova
(KIGIC RAS).
The development of the project was supported by the
International Association for the Properties of Water and
Steam (IAPWS), the organization which is renowned for
setting international standards for properties of pure water
and high-temperature aqueous systems.
According to the IAPWS project accepted in 2004, this
book should have had seven chapters – Phase equilibria
data, pVTX data, Calorimetric data, Electrochemical data,
Electrical conductivity data, Thermal conductivity data and
Viscosity data. However, the planned chapter on calorimetry
was not forthcoming due to personal commitments of the
author. Only a summary table of calorimetric data with a
short introduction about the experimental methods used for
hydrothermal measurements are provided in Chapter 7 of
this book but a collection of the experimental calorimetric
data is available on the CD.
In the fi nal version of this book each chapter consists of
two parts: the descriptive text part that appears in the pages
of this book and the data part which appears as appendices
organized on the CD. The descriptive part contains the basic
principles and defi nitions, description of experimental
methods, discussion of available data and reviews of theo-
retical or empirical approaches used for treatment of the

original experimental values. The accompanying summary
tables, arranged in alphabetic order of the nonaqueous com-
ponents, list the temperatures, pressures and concentrations,
types of data and experimental methods employed in their
measurements, the uncertainty claimed by the authors as
well as the references (the fi rst author and the year of pub-
lication). The table code refers the reader to the original data
set in the appendices on the CD. The tables of experimental
data (with brief comments on each set of experimental
measurements) in the appendices are also arranged in alpha-
betic order of nonaqueous components. However, the order
of the systems in the appendices is usually not exactly the
same as in the summary tables. There are no subdivisions
in appendices, whereas in the summary tables the binary
and ternary systems are often placed in separate divisions
or subdivisions such as inorganic and organic compounds
or electrolytes, nonelectrolytes, acids, etc.
The text parts of the chapters, besides the general char-
acteristics of the available experimental data mentioned
above, usually contain several special topics and aspects of
material presentation.
Chapter 1 (Phase Equilibria in Binary and Ternary Hydro-
thermal Systems, V. M. Valyashko, Russia) contains a
description of the general trends of sub- and supercritical
phase behaviour in binary and ternary systems taking into
account both stable and metastable equilibria. A presenta-
tion of the various types of phase diagrams aims to show
the possible versions of phase transitions under hydrother-
mal conditions and to help the reader with the determination
of where the phase equilibrium occurs in p–T–X space, and

what happens to this equilibrium if the parameters of state
are changed. Special attention is paid to continuous phase
transformations taking place with variations of temperature,
pressure and composition of the mixtures, and to a system-
atic classifi cation and theoretical derivation of binary and
ternary phase diagrams.
Chapter 2 (pVTx Properties of Hydrothermal Systems,
H. R. Corti (Argentina) and I. M. Abdulagatov (Russia/
USA)) describes many theories and models developed to
accurately reproduce the excess volumetric properties and
to assess the standard partial molar volumes of the solute in
aqueous electrolyte and nonelectrolyte solutions under sub-
and supercritical conditions. Most of these models and
equations, particularly the equations of state, are used to
compute both the thermodynamic properties of solutions
and the phase equilibria. This chapter is concerned with
theoretical approaches in modern chemical thermodynam-
ics of hydrothermal systems.
Chapter 3 (High Temperature Potentiometry, D. A. Palmer
and S. N. Lvov (USA)) focuses on ionization equilibria that
are an important part of acid–base, metal–ion hydrolysis,
metal complexation and metal–oxide solubility studies
under hydrothermal conditions. Most of the hydrothermal
investigations used potentiometric measurements with
various types of electrochemical cells, mainly covering
ranges of temperature below 200 °C, the minimum limit
generally adhered to in this book. Therefore, the experimen-
tal data discussed in the text part, collected in the appendix
and in the summary tables include both high-temperature
(up to 400–450 °C) and low-temperature results available in

the literature.
xiv Preface
Special attention in Chapter 4 (Electrical Conductivity in
Hydrothermal Binary and Ternary Systems, H. R. Corti
(Argentina)) is paid to the procedures for obtaining infor-
mation on the thermodynamic properties of electrolytes
(including a determination of the limiting conductivity and
association constants) from the measured electrical conduc-
tivity of diluted solutions above 200 °C. However, the
behaviour of specifi c and molar conductivity in concen-
trated electrolyte solutions is also carefully discussed in the
chapter.
Chapters 5 and 6 (Thermal Conductivity and Viscosity,
I. M. Abdulagatov (Russia/USA) and M. J. Assael (Greece))
show not only the typical temperature, pressure and con-
centration dependencies of properties in hydrothermal
solutions, but also make a preliminary comparison of
various datasets for several systems to help the reader
choose which values to use. The empirical and semi-
empirical correlations which are necessary because of the
lack of theoretical background, employed in the reviewed
literature are also discussed.
Chapter 7 (Calorimetric Properties of Hydrothermal
Solutions, V. M. Valyashko (Russia) and M. S. Gruszkiewicz
(USA)), indicates the experimentally determined calorimet-
ric quantities of considerable current use, gives a brief
description of experimental methods for hydrothermal mea-
surements and contains a summary table with information
about the systems studied and the corresponding calorimet-
ric measurements.

Acknowledgements
Preparing this book required the talents and cooperation of
many individuals. It was a long and sometimes painful
process. However, it was very interesting and fulfi lling
project for me to accumulate and fi nally see the results.
I would like to thank my colleagues and co-authors Dr
Ilmutdin M. Abdulagatov, Dr Marc J. Assael, Dr Horacio R.
Corti, Dr Miroslav S. Gruszkiewicz, Mrs Nataliya N.
Ivanova, Dr Serguey N. Lvov and Dr Donald A. Palmer for
their tremendous work, initiative and their patience during
the long and diffi cult gestation of this book.
We are all grateful to Dr Johanna M. H. Levelt Sengers
(Anneke Sengers), who played a signifi cant role in the
development of this project within IAPWS and agreed to
write a Foreword for us, and to Dr Peter G. T. Fogg for his
assistance in searching for a publisher.
I would like to acknowledge our colleagues from differ-
ent countries for their help. Since we started this project
these people donated their time, assisted with references,
fi les, publications, useful information, recommendations
and comments. My sincere gratitude goes to R. J.
Fernandez-Prini (Argentina), T. A. Akhundov, N. D. Azizov,
N. V. Lobkova, D. T. Safarov (Azerbaijan), P. Tremaine
(Canada), I. Cibulka (Czech Republic), K. Ballerat-Busse-
rolles, R. Cohen-Adad, (France), J. Barthel, E. U. Franck,
H. Lentz, K. Todheide, G. M. Schneider, H. Voigt, W. Voigt,
G. Wiegand (Germany), Th. W. de Loos, C. J. Peters (Neth-
erlands), A. M. Aksyuk, A. A. Aleksandrov, I. L. Khodako-
vsky, S. V. Makaev, S. D. Malinin, O. I. Martinova, A. A.
Migdisov, A.Yu Namiot, T. I. Petrova, L. V. Puchkov, K.

I. Schmulovich, A. A. Slobodov, N. A. Smirnova, N. G.
Sretenskaya, M. A. Urusova, A. S. Viktorov, I. V. Zakirov,
V. I. Zarembo, A. V. Zotov (Russia), L. Z. Boshkov
(Ukraine), R. B. Dooley, A. H. Harvey, P. C. Ho, W. L.
Marshall, R. E. Mesmer, A. V. Plyasunov, J. M. Simonson,
R. H. Wood (USA).
Finally, I also would like to express my thanks to my wife
Luba and daughters Aliona and Katya for their constant
support and understanding.
Vladimir M.Valyashko
Moscow
1
Phase Equilibria in Binary and Ternary
Hydrothermal Systems
Vladimir M. Valyashko
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia
1.1 INTRODUCTION
Defi ning the phase composition of the mixture at a certain
pressure and temperature is the fi rst step in any scientifi c
investigation and obligatory information for any practical
application of that mixture.
If the physical state of aqueous or any other systems at
ambient conditions can easily be determined, the phase
composition of the systems at high temperatures and
pressures should be specially studied using fairly complex
equipment.
Systematic scientifi c studies of infl uence of temperature
and pressure on a phase state of individual compounds
and mixtures were begun in the eighteenth century (D.
Fahrenheit, R. Reaumur, A. Celsius, M.V. Lomonosov, A.

Lavoisier, D. Dalton, W. Henry). However, the variety and
complexity of phase behavior at superambient conditions in
early experiments, even in two-component systems, seemed,
at fi rst, chaotic. The discovery of the phase rule by Gibbs
in 1875 and the investigations of van der Waals and his
school on the equation of state and the thermodynamics of
mixture, lasting until about 1915, brought a measure of
order by providing a framework for the interpretation and
classifi cation of phase diagrams and led to a period of
intense experimental studies. These pioneer publications at
the end of the nineteenth and beginning of the twentieth
centuries laid a foundation for the modern theory of hetero-
geneous equilibria and phase diagrams. During the fi rst
half of the last century interest in high-temperature high-
pressure equilibria was quite limited and concentrated
mainly around certain aspects of power engineering and
geological problems. As a result progress was not compa-
rable with the previous fi fty years; moreover knowledge
accumulated earlier gradually disappeared from the litera-
ture of physics and chemistry.
The most famous discovery of that time was the experi-
mental observation of gas–gas equilibria by I.R. Krichevskii
in N
2
– NH
3
, CH
4
– NH
3

, He
2
– CO
2
, He
2
– NH
3
and in
Ar – NH
3
mixtures (Krichevskii and Bol’shakov, 1941;
Krichevskii, 1952; Tsiklis, 1969), that confi rmed theo -
retical prediction of Van der Waals (Van der Waals and
Kohnstamm, 1927). It was shown that a separation of super-
critical fl uids can exist in the temperature range above the
highest critical temperature of the less volatile component.
Another important result obtained in the last century was
also connected with the critical phenomena. In 1926
Kohnstamm (Kohnstamm, 1926) pointed out the theoretical
possibility of fi nding a critical point ‘of second order’ in a
ternary liquid mixture – a point at which three coexisting
fl uid phases simultaneously become identical. In 1962–70
this point was confi rmed experimentally in two Russian
aboratories (of Prof. I.R. Krichevskii and Prof. R.V.
Mertslin) (Radyshevskaya et al., 1962; Krichevskii et al.,
1963; Myasnikova et al., 1969; Efremova and Shvarts, 1966,
1969, 1972; Shvarts and Efremova, 1970; Nikurashina
et al., 1971). In the 1970s such a type of phase transition,
called ‘a tricritical point’, was theoretically interpreted

within a framework of ‘classical’ and ‘non-classical’ phe-
nomenological models (Griffi ths, 1970; Widom, 1973;
Griffi ths and Widom, 1973; Griffi ths, 1974; Kaufman and
Griffi ths, 1982; Anisimov, 1987/1991).
At the same time, it was thought that the sets of phase
equilibria in water-salt (electrolyte) systems were different
from those in water-organic, water-gas and organic systems
due to a special nature of ion-molecular interactions in
aqueous electrolyte solutions. In particular, the phase
diagram with the two critical endpoints in solid saturated
solutions was known for a long time only for systems with
the molecular species (without ions) such as ether (C
4
H
10
O)
– anthraquinone (C
14
H
8
O
2
), CO
2
– diphenylamine
((C
6
H
5
)

2
NH) and ethylene (C
2
H
4
)) – p-chloroaniline (o-
xylidin (C
8
H
11
N), o-nitrophenol (C
6
H
5
NO
3
), m-chloronitro-
benzene (C
6
H
4
ClNO
2
)) (Smits, 1905, 1911; Buechner, 1906,
1918; Scheffer and Smittenberg, 1933).
However, the fi rst experimental studies of H
2
O – SiO
2
,

H
2
O – Na
2
SO
4
, H
2
O – Li
2
SO
3
and H
2
O – Na
2
CO
3
systems
Hydrothermal Experimental Data Edited by V.M. Valyashko
© 2008 John Wiley & Sons, Ltd. ISBN: 978-0-470-09465-5
2 Hydrothermal Experimental Data
(Kennedy et al., 1961, 1962; Ravich and Borovaya,
1964a,b,c) proved that the same phase equilibria can be
observed also in water–electrolyte mixtures.
A revival of interest in hydrothermal phase behavior
occurred in the middle and second half of the last century,
sparked by the growth of chemical engineering technology
(hydrothermal crystal growth, hydrometallurgy, natural gas
and petroleum industry, supercritical fl uid extraction and

material synthesis, supercritical water oxidation for hazard-
ous waste destruction) and of fossil and nuclear power engi-
neering. The main volume of experimental data for aqueous
systems at high temperatures and pressures now available
was obtained during the past 50–60 years, whereas the most
precise measurements of hydrothermal solution properties
became possible only from the 1980s onwards (Wood,
1989).
Van der Waals and his school developed the ‘classical
approach’ to phase diagram derivation, in which phase
behavior of mixtures was established by investigation of the
behavior of thermodynamic functions (free energy) in p-V-
T-x space, calculated with the equation of state. Originally,
theoretical derivations of phase diagrams were done by a
topological method. After the main features of a geometry
of thermodynamic surfaces (p-V-T-x dependences of
Helmholtz or Gibbs free energy) were obtained from limited
calculations available at that time using the equation of
state. The following continuous transformations and combi-
nations of the geometrical features of the surfaces were
determined topologically as well as a derivation of topologi-
cal schemes of phase diagrams from the interplay of the
thermodynamic surfaces. As a result of such investigations
it was established that there is a limited number of various
types of fl uid phase diagram for binary systems. A topologi-
cal approach and knowledge of the regularities of phase
behavior and intersections of thermodynamic surfaces for
various phases (included the solid phase) permitted deriva-
tion of not only several types of fl uid phase diagrams but
also of the schemes of phase diagrams with solid phase

(Roozeboom, 1899, 1904; Tammann, 1924; Van der Waals
and Kohnstamm, 1927). In contrast to the term ‘fl uid phase
diagrams’, which means the phase diagrams, which describe
the phase behavior of mixture without solid phase, the term
‘complete phase diagrams’ is for the diagrams which display
any equilibria between liquid, gas and/or solid phases in a
wide range of temperature and pressure.
Since the fi rst publication of Scott and van Konynenburg
in 1970 on global phase behavior of binary fl uid mixtures
based on the Van der Waals equation of state, the classical
approach to the derivation of phase diagrams has changed
from topological method to analytical method. The analyti-
cal method of derivation for various liquid-gas equations
of state shows the same main types of fl uid phase behavior
for different kind of molecular interactions and the same
sequences of transformation of one type of binary phase
diagram into another due to continuous alteration of mo -
lecular parameters in the equations of state (Scott and van
Konynenburg, 1970; Boshkov, 1987; Deiters and Pegg 1989;
van Pelt et al., 1991; Harvey, 1991; Kraska and Deiters,
1992; Yelash and Kraska, 1998, 1999a,b; Thiery et al., 1998;
Yelash et al., 1999; Kolafa et al., 1999). Most of the types
of fl uid phase behavior described by Van der Waals and his
school as well as by recent experimentalists can be recog-
nized in analytically derived global phase diagrams. Those
diagrams describe (in the coordinates of molecular param-
eters of each model) the regions of different types of fl uid
phase diagrams generated from the equations of state.
Due to the absence of a general liquid-gas-solid equation
of state such analytical method would not work for deriva-

tion of phase equilibria with solid phases. To do so either
simultaneous investigation of two equations of state (for
liquid-gas and for solid phases) should be considered or the
usage of the topological method at the level of topological
schemes of phase diagram rather than at the level of thermo-
dynamic surfaces. Modern knowledge of phase diagrams
construction allows us to classify the main types of dia-
grams and to defi ne a few regularities of transformation of
one type of phase diagram into another.
This chapter reviews general characteristics of phase
behavior in sub- and supercritical binary and ternary aqueous
systems obtained in theoretical and experimental studies. It
starts with a brief presentation of the main experimental
methods employed to study the hydrothermal phase
equilibria.
The major body of the chapter provides an overview of
recent developments in our understanding of binary and
ternary phase diagram construction based on modern theo-
retical approaches to phase diagram derivation and on the
available experimental data. In case of binary system special
attention is drawn to the method of continuous topological
transformation of phase diagrams and to a demonstration of
systematic classifi cation of complete phase diagrams, which
describe all possible types of phase behavior in a wide range
of parameters. The main types of binary phase diagrams are
represented by topological schemes illustrated by experi-
mental results.
Methods of topological schemes for fl uid and complete
phase diagrams derivation and main features of phase
behavior at sub- and supercritical conditions for ternary

systems are discussed later in the chapter. The available
experimental data are used to demonstrate some regularity
of solid solubility, liquid immiscibility and critical behavior
in ternary mixtures.
The original experimental data on phase equilibria (solu-
bility of solid in fl uid phases, heterogeneous fl uids, liquid-
gas (vapor) equilibria, immiscibility of liquids and critical
phenomena) at elevated temperatures (mainly above 200 °C)
and pressures are presented in Appendix 1.1. The values
were extracted from the papers in national and international
journals, monographs and collected articles, as well as from
the deposited materials, reports and dissertations. For litera-
ture search, besides the Chemical Abstracts Data Base, the
database system ELDAR (Prof. J. Barthel, Institute for
Physical and Theoretical Chemistry, the Regensburg Uni-
versity, Germany) (Barthel and Popp, 1991) and the data-
bank for water-organic systems (Prof. N.I. Smirnova, Prof.
A.I. Viktorov, Department of Physical Chemistry, the St
Petersburg University, Russia), the following reference
books were used (Seidell, 1940, 1941; Seidell and Linke,
Phase Equilibria in Binary and Ternary Hydrothermal Systems 3
1952; Pel’sh et al., 1953–2004; Linke and Seidell, 1958;
Timmermans, 1960; Kogan et al., 1961–63, 1969, 1970;
Kirgintsev et al., 1972; Valyashko et al., 1984; Buksha and
Shestakov, 1997; Harvey and Bellows, 1997). However, the
main volume of bibliography were obtained from references
in ordinary papers and reviews.
This information, arranged in alphabetical order of non-
aqueous components is presented in the Summary table
(Table 1.1). Each line of the Summary table contains brief

information (types of studied phase equilibria, experimental
methods, ranges of studied temperature, pressure and com-
position) about the experimental data obtained for one
system or several relevant systems from the publication(s)
and collected in Appendix 1.1.
1.2 EXPERIMENTAL METHODS FOR STUDYING
HYDROTHERMAL PHASE EQUILIBRIA
Over the years different experimental techniques at high
parameters of state were implied to study phase behaviors
(Tsiklis, 1968, 1976; Laudise, 1970; Ulmer, 1971; Jones
and Staehle, 1976; Styrikovich and Reznikov, 1977; Isaacs,
1981; Garmenitskiy and Kotelnikov, 1984; Zharikov et al.,
1985; Sherman and Tadtmuller, 1987; Ulmer and Barnes,
1987; Byrappa and Yoshimura, 2001; Hefter and Tomkins,
2003). The purpose of this review is to summarize existing
experimental methods for studing phase equilibria in
aqueous systems over a wide range of p-T-x parameters, to
describe briefl y major features of experimental procedures,
and to provide examples of the method related apparatus
along with their advantages and limitations.
Experimental methods could be considered as either ‘syn-
thetic’ and ‘analytic’ or static and dynamic (fl ow) methods.
In the ‘synthetic’ methods the phase transitions are studied
and the p-T parameters of phase transformations are recorded,
whereas the compositions of the coexistent phases are deter-
mined from the composition of initial mixture charged into
the cell. The ‘analytic’ methods determine compositions of
equilibrium phases directly at given temperature and pres-
sure, ignoring the study of phase transitions. The dynamic
(fl ow) methods are distinguished from the static ones by the

fact that at least one of the phases in the system is subjected
to a fl ow with respect to the other phase.
In our attempt to classify the available experimental
methods for studying the hydrothermal equilibria there are
fi ve groups that differ in the technique of obtaining informa-
tion on phase equilibria and on coexisting phase composi-
tions at high temperatures and pressures. These groups
comprise:
1. methods of visual observation of phase equilibria (‘Vis.
obs.’ in Table 1.1);
2. methods of solution sampling under experimental condi-
tions (‘Sampl’, ‘Flw.Sampl’ and ‘Isopiest’ in Table 1.1);
3. methods of quenching of high temperature phase equi-
libria (‘Quench’ in Table 1.1) and of weight loss of
crystal (‘Wt-loss’ in Table 1.1);
4. method using potentiometric determination (‘Potentio’
in Table 1.1) for salt solubility measurements;
5. indirect methods – determination of discontinuities
(‘break points’) in the property-parameter curves;
description of the behavior of interdependent parameters
and/or properties of the system during the phase trans-
formation (methods of p-T, p-V, p-x, T-V, T-Cv, p-∆H
curves, ‘Therm.anal.’ and VTFD in Table 1.1).
The sixth group ‘Methods using radioactive tracers’ (‘Rad.
tr’ in Table 1.1) could be added to the list. However, those
methods are used rarely in hydrothermal investigations due
to the environmental risk, technical problems and moderate
accuracy of solubility measurements. Only in the publica-
tion of Alekhin and Vakulenko (1987) there is a description
of an apparatus for continuous determination of the hydro-

thermal fl uid composition and salt solubility in vapor by
measuring the intensity of radiation of aqueous solution
without sampling or quenching. There are several cases of
tentative experiments on solubility measurements of sul-
fi des (Ag
2
S, SnS and ZnS) at elevated temperatures (below
200 °C) (Olshanski et al., 1959; Nekrasov et al., 1982) and
in temperature gradient conditions (Relly, 1959). In some
cases the radioactive tracers are used only to determine the
concentration of samples obtained by the method of sam-
pling or quenching (Ampelogova et al., 1989). The experi-
mental studies of isotope partitioning in hydrothermal
systems (e.g. Shmulovich et al., 1999; Driesner and Seward,
2000; Chacko et al., 2001; Horita and Cole, 2004 etc.) are
relevant to isotope chemistry in aqueous reactions but do
not pursue the goal of phase equilibria determination and
will be not discussed in this chapter.
Certainly, this classifi cation is largely arbitrary and not
exhaustive because in reality experimental methods are
highly diversifi ed and often contain the combinations of
various techniques in one run. For instance, the measure-
ments using the visual cell with a movable piston (for chang-
ing the inner volume of the vessel and for separation of the
studied mixture from the pressure medium) (see Figure 1.1)
permit us to observe the phase transformation, to determine
the break points (corresponding to the phase transition) on
the pressure versus temperature isochore or on the pressure
versus volume isotherm for the known composition and to
sample the equilibrium phases at predetermined tempera-

tures and pressures (Lentz, 1969 etc.). The apparatus,
described by Khaibullin and Borisov (1965, 1966), permits
us to determine both the density and composition of coexist-
ing liquid and vapor solutions (at temperatures up to 450 °C
and pressures up to 40 MPa) by measuring intensity of the
g-ray beams (pass through the bomb on different levels from
the outside radioactive sources) (‘g-ray’ in Table 1.1) and by
sampling the equilibrium phases.
Besides methods which involve determination of phase
compositions of equilibrium associations, other approaches
to phase equilibria studies are possible. An example is the
special method for determining the vapor pressure of solu-
tions with a given composition (‘Vap.pr.’ and ‘Vap.pr.diff’
in Table 1.1). In such apparatus the composition is not
measured but taken from the initial charge, whereas the
vapor pressure is measured directly with a pressure gage
(Mashovets et al., 1973; Bhatnagar and Campbell, 1982;
4 Hydrothermal Experimental Data
Table 1.1 Summary of experimental data on phase equilibria in hydrothermal systems
COMMENTS: Each line contains a breaf information about the experimental data obtained for one system or several relevant system
s from the publication(s) and in the table(s) collected in
the Appendix. This information includes the name of aqueous system (only the
non-aqueous component(s) is(are) shown in the 1
st
column), the studied types of phase equilibria – Phase
equilibria (2
nd
column), the experimental methods employed for studies – Methods (3
rd
column), the ranges of studied temperature – Temperature (4

th
column), pressure – Pressure (5
th

column), and composition – Composition (6
th
column). The numbers of tables with hydrothermal experimental data, located in the Appendix (
Tables), and the literature sources of that data
(Reference) are indicated in the 7
th
and 8
th
columns, respectively.
Although the tables in the Appendix contain only high-temperature data (usually starting from 200
°C and above), an information about the low-temperature data available from the
publications is indicated in the Summary table. The oblique (/) indicates and separates the low-temperature and high-temperatur
e values of properties or parameters represented in Table 1.1.
Non-aqueous components Phase equilibria Methods Temperature
Pressure Composition Tables REFERENCE
CH
4
(Methane) H-Fl Sampl 298/473; 518 K 1.3/3.2; 6.5 MPa 2.1 * 10
−4
/4.1 * 10
−4
–0.49/0.998 (CH
4
) mol.fr. ptx-CH
4
-7.1 Crovetto et al., 1982

For example, the line means – the publication [Crovetto et al., 1982] contains the experimental data for H
2
O – CH
4
system on heterogeneous fl uids (H-Fl ) obtained by the method of fl uid
phase sampling (Sampl) at temperatures from 298 up to 518 K and pressures from 1.3 up to 6.5
MPa. However, the table ptx-CH
4
-7.1 (in the Appendix) contains only data at 473 and 518 K,
3.3 and 6.5 MPa. The composition of studied phases is varied from 0.00021 to 0.998
mol.fr. of CH
4
, whereas the variation of CH
4
concentration in high-temperature phases shown in the
Appendix’s table are 0.00041–0.49 mol.fr. Sometimes the box ‘Composition’ shows a composition of equilibrium phases (as in the example), in other cases it could be the chemical
compositions of initial mixtures used for phase equilibria studies or the phase composition of studied equilibria.
The contractions for types of phase equilibria and the experimental methods are shown below. SVP is a saturation vapor pressure
. ‘??’ indicates that the information is absent or the symbol
accompanied by ‘??’ is questionable.
Types of phase equilibria:
Soly – solid solubility equilibria, heterogeneous equilibria with solid phase(s).
LGE – in the most cases it is liquid-gas equilibrium, but could be another heterogeneous equilibria with gas phase, where the vapo
ur pressure is measured (for example, in the case of
equilibrium L-G-S) or used for measurements (such as in the isopiestic molality measurements (LGE; isop-m)).
H-Fl – indiscernible heterogeneous sub- and supercritical fl uid equilibria. In the most cases it is two-phase fl uid equilibria such as LGE, L
1
-L
2
and G

1
-G
2
, which continuously transform one
into another with a small variation of pTx- parameters. Sometimes it is the more complex fl
uid equilibria (especially, in ternary system).
Immisc – immiscibility equilibria such as L
1
-L
2
; L
1
-L
2
-G; L
1
-L
2
-S etc. Cr.ph-critical phenomena
Methods:
Sampl – the method of fl uid phase sampling is used for determination of solution composition (static apparatus);
Flw.Sampl – the method of fl ow-sampling is used for determination of
solution composition (Flow-apparatus); Fl.inclus – the method of fl uid inclusions is used for phase equilibria studies in hydrothermal conditions, sometimes for determination not only the
types of phase equilibria, but the composition of phases at high temperatures also;
Isopiest – the method of isopiestic measurements is used for determination of the isopiestic molality
(molality at a known activity of water in aqueous solutions); Quench – the method of quenching is used to fi x the high-temperature equilibria by a fast cooling and to determine both the
hydrothermal equilibria and the composition of high-temperature phases; Wt-loss – the method of weight-loss of crystalls is used for measurements of solid solubility;
Vis.obs. – the method
of visual observations is used for determination of phase equilibria at elevated temperatures and pressures, sometimes – for de
termination the composition of phases; p-T, p-V, p-x, T-V, T-Cv,

p-DH curves – the methods of p-V-T-x-Cv-∆H curves are used for determination the parameters of phase transformations in hydrothermal conditions;
Vap.pr. – the method of direct
measurements of equilibrium vapor pressure; Vap.pr.diff. – the measurements of vapor pressure difference between the vapor pressures of pure water and solutions;
Therm.anal. – the method
of high-pressure thermal analysis (Diff. thermal analysis); VTFD – the method for determination of hydrothermal phase transition (an appearance/disapprearance of liquid-gas equilibrium)
using the vibration tube fl ow densimeter masurments; Potentio – the potentiometric measurements for studies of solubility equilibria;
Calcul. – the methods of calculation/estimation; g-ray –
determination of concentration and density of hydrothermal solution by the method of
g-ray adsorption measurements; Rad.tr – method using radioactive tracers for phase equilibria studies.
Phase Equilibria in Binary and Ternary Hydrothermal Systems 5
Units:
Temperature: C – grad. Celsium (°C); K – Kelvin
Pressure: MPa – mega-pascales (10
6
* Pa); GPa – giga-pascales (10
9
* Pa); Kbar – kilo-bars (10
3
bar); bar; kg/cm
2
; atm; mm of Hg; 1 MPa = 10 bar = 10.197 kg/cm
2
= 9.87 atm =
7502.4 mm Hg
Concentration: Basic quantities used in defi nitions of concentration in aqueous solution are based on mass, chemical amount of substance and/or volume and are designed by
the traditional
symbols such as m - molality (moles of solute per kilogram of solvent (H
2
O); 1 m = 10
3

mm = 10
6
mm; (- log m) is a negative decimal logarithm of molality, mol/L - molarity (moles of
solute per a liter of solution usually at room temperature), mass.% or mol.% - mass or mole per cent, mol.fr., mass.fr. or vol.fr. - mole, mass or volume fraction, ppm or ppb - parts per
million or parts per billion, or by the complex symbols, such as g/100g H
2
O; mmol/kg; mg/mL; cm
3
/100cm
3
H
2
O etc, which are the proper fractions where the numerator indicates the number
of units of solute and the denominator shows the number of units (usually one unit) of solution (or of solvent, if it is indic
ated). A designation of the units - g (gram), mol (mole), L (liter),
cm (centimeter) and the decimal prefi x - m (micro, 10
−6
), m (milli, 10
−3
), c (centi, 10
−2
), k (kilo, 10
3
), M (mega, 10
6
), G (giga, 10
9
)
Non-aqueous
components Phase equil Methods Temperature Pressure Composition Table REFERENCE

123456
78
Ag + buff. Soly Quench 300; 450 C SVP; 500 atm (0.5–2) * 10
−6
(Ag) m;
Buff: Fe
2
O
3
/Fe
3
O
4
; Ni/NiO; Al.
ptx-Ag-1.1 Zotov et al., 1985a
Ag in CH
2
O
(formaldehyde)
Soly Quench 200 C SVP (2.7–4.1) * 10
−5
(Ag); 0.34–0.5 (CH
2
O) m ptx-Ag +
CH
2
O-1.1
Kozlov and
Khodakovskiy,
1983

Ag in (HCl + H
2
) Soly Quench 200; 280 C SVP
(1.2–52) * 10
−5
(Ag); 0.0001–0.1 (HCl) m ptx-Ag + HCl-1.1 Kozlov and
Khodakovskiy,
1983
Ag in (HCl + KCl + H
2
) Soly Wt-loss;
Quench
450 C 500; 1000 bar 0.004–0.019 (Ag); 0.1 (HCl); 0.2 (KCl) m
ptx-Ag + HCl +
KCl-1.1
Tagirov et al., 1997
Ag in (HCl + NaCl + H
2
) Soly Quench 200 C SVP (5.6–50) * 10
−5
(Ag) 0.016–0.056 (HCl);
0.064–0.09 (NaCl) m
ptx-Ag + HCl +
NaCl-1.1
Kozlov and
Khodakovskiy,
1983
Ag in (HCl + NaCl) Soly Wt-loss;
Quench
350–500 C 500–2500 bar 0.0013–0.0246 (Ag); 0.02–0.25 (HCl);

0.2–1 (NaCl) m
ptx-Ag + HCl +
NaCl-2.1
Tagirov et al., 1997
(Ag + AgCl) in (HCl +
buff)
Soly Quench 450–800 C 1; 2 kbar 0; 3 (HCl) mol/L; Buff: Fe
2
O
3
/Fe
3
O
4
; Ni/NiO ptx-Ag + AgCl +
HCl-1.1
Chou and Frantz,
1977
(Ag/Au + AgCl) in (HCl
+ NaCl)
Soly Wt-loss;
Sampl
300 C SVP 1.92–0.4 (Ag); 5.8–1.8 (Au) (−log m);
0.01–3 (HCl); 0–3 (NaCl) m
ptx-Ag/Au +
AgCl-1.1
Gammons and
Williams-Jones,
1995
Ag

x
Au
y
S
z
Soly Sampl 91/150; 250 C SVP (2–6)*10
−5
(Au); (2–6)*10
−7
(Ag); 0.5 (S); 0.002
(NaOH) m
ptx- Ag
x
Au
y
S
z
-1.1 Tagirov et al., 2006
(Ag + Cu) in HCl Soly Wt-loss;
Sampl
40/200–300 C SVP 5.8–3.54 (Ag); 2.8–0.72 (Cu) (−log m);
0.004–1.0 (HCl) m
ptx-Ag + Cu +
HCl-1.1
Xiao et al., 1998
(Ag + Cu) in (HCl +
NaCl)
Soly Wt-loss;
Sampl
40/200–300 C SVP 5.92–4.12 (Ag); 2.56–1.01 (Cu) (−log m)];

0.001–0.1 (HCl); 0.01–0.9 (NaCl) m
ptx-Ag + Cu +
HCl + NaCl-1.1
Xiao et al., 1998
(Ag/Pd + AgCl) in (HCl
+ NaCl)
Soly Wt-loss 300 C SVP 1.58–0.4 (Ag); 5.7–3.4 (Pd) (−log m);
0.1; 1 (HCl); 0.1–3 (NaCl) m
ptx-Ag/Pd +
AgCl-1.1
Gammons et al.,
1993
AgBr Soly Wt-loss 20/269–349 C SVP 44.7 * 10
−7
/0.007–0.013 (AgBr) m ptx-AgBr-1.1 Gavrish and
Galinker, 1955
AgBr; AgBr in NaBr Soly Wt-loss;
Sampl
200; 300 C SVP 3.9–1.5 (AgBr) (−log m); 0–1 m NaBr ptx-AgBr +
NaBr-1.1
Gammons and Yu,
1997
6 Hydrothermal Experimental Data
Table 1.1 Continued
Non-aqueous
components Phase equil Methods Temperature Pressure Composition Table REFERENCE
123456
78
AgCl Soly Wt-loss 20/220–359 C SVP 10.8 * 10
−5

/0.013–0.059 (AgCl) m ptx-AgCl-1.1 Gavrish and
Galinker, 1955
AgCl Soly Quench 250; 300 C SVP 0.0025–0.0029 (AgCl) m ptx-AgCl-2.1 Zotov et al., 1985c
AgCl Soly Wt-loss;
Quench
450 C 500–1500 bar 0.008–0.05 (Ag) m
ptx-AgCl-3.1 Levin, 1993
AgCl Soly Sampl 300–360 C 41–183 bar 9.82–7.9 (AgCl) (−log mol.fr.) ptx-AgCl-4.1; 4.2 Migdisov et al.,
1999
AgCl in HCl Soly Sampl 100/200–350 C SVP 0.03 * 10
−4
/0.0007–0.125 (AgCl);
6.4 * 10
−5
–3.5 (HCl) m
ptx-AgCl +
HCl-1.1
Ruaya and Seward,
1987
AgCl in (HCl + NaCl +
NdCl
3
)
Soly Sampl 200; 300 C SVP 2.69–0.86 (Ag) (−log m);
0.03–1 (HCl + NaCl); 0–0.24 (NdCl
3
) m
ptx-AgCl +
H,Na,Nd/Cl-1.1
Gammons et al.,

1995
AgCl in (HCl + Nd
2
O
3
) Soly Sampl 40/200–300 C SVP 4.63/3.68–1 (Ag) (−log m);
0.03–5 (HCl); 0–1.16 (NdO
1.5
) m
ptx-AgCl + HCl +
Nd
2
O
3
-1.1
Gammons et al.,
1995
AgCl in (HCl + ZnCl
2
) Soly Sampl 100/200–350 C SVP 2.4 * 10
−4
/0.00263–0.099 (AgCl);
0.29–3.54 (HCl); 0.1 (ZnCl
2
) m
ptx-AgCl + HCl +
ZnCl
2
-1.1
Ruaya and Seward,

1986
AgCl in KCl Soly Wt-loss;
Quench
300 C SVP 0.0051–1.35 (Ag); 0.025–6 (KCl) m ptx-AgCl +
KCl-1.1
Levin, 1991
AgCl in KCl Soly Wt-loss;
Quench
450 C 500; 1000 bar 0.041–0.22 (Ag); 0.46; 0.9 (KCl) m
ptx-AgCl +
KCl-2.1
Levin, 1993
AgCl in NaCl Soly Sampl 100/197–353 C SVP 2.2 * 10
−5
/5.3 * 10
−4
–0.256 (AgCl);
5 * 10
−5
–3 (NaCl) m
ptx-AgCl +
NaCl-1.1
Seward, 1976
AgCl in NaCl Soly Quench 300 C SVP 0.0021–0.334 (AgCl); 0.0001–3 (NaCl) m ptx-AgCl +
NaCl-2.1
Zotov et al., 1986
AgCl in NaCl Soly Wt-loss;
Quench
300 C SVP 0.005–0.86 (Ag); 0.025–7 (NaCl) m ptx-AgCl +
NaCl-3.1

Levin, 1991
AgCl in NaCl Soly Wt-loss;
Quench
450 C 500–1750 bar 0.04–1.05 (Ag); 0.09–2.56 (NaCl) m
ptx-AgCl +
NaCl-4.1
Levin, 1993
AgCl in NaCl Soly Wt-loss;
Quench
400; 425 C 500–1500 bar 0.08–0.17 (AgCl); 0.2; 0.5 (NaCl) m
ptx-AgCl +
NaCl-5.1
Tagirov 1997
AgCl in (NaCl +
NaClO
4
)
Soly Quench 200; 250 C SVP 0.0038–0.028 (AgCl); 0.2; 0.5 (NaCl);
0–1 (NaClO
4
) m
ptx-AgCl + NaCl
+ NaClO
4
-1.1
Zotov et al., 1986
AgCl in (NaCl +
NaClO
4
)

Soly Wt-loss;
Quench
250 C SVP 0.01–0.03 (Ag); 0.2; 0.5 (NaCl);
0–1 (NaClO
4
) m
ptx-AgCl + NaCl
+ NaClO
4
-2.1
Levin, 1991
AgCl in (NaCl + NaClO
4

+ NaOH)
Soly Quench 200–300 C SVP 0.0038–0.093 (AgCl); 0.2; 0.5 (NaCl);
0–0.3 (NaClO
4
); 0–0.3 (NaOH) m
ptx-AgCl +
Na/Cl,ClO
4
,OH-1.1
Zotov et al., 1982
AgCl in NaClO
4
Soly Quench 250; 300 C SVP 0.0026–0.0054 (AgCl); 0.01–1 (NaClO
4
) m ptx-AgCl +
NaClO

4
-1.1
Zotov et al., 1985
Ag
2
CrO
4
Soly Sampl 25/195–260 C SVP 0.0036/0.08–0.12 (Ag
2
CrO
4
) g/100 g H
2
O ptx-Ag
2
CrO
4
-1.1 Gavrish and
Galinker, 1970
AgF Soly Sampl 22/200;
250 C
SVP 176/143; 97.4 (AgF) g/100 g H
2
O ptx-AgF-1.1 Gavrish and
Galinker, 1970
Phase Equilibria in Binary and Ternary Hydrothermal Systems 7
Non-aqueous
components Phase equil Methods Temperature Pressure Composition Table REFERENCE
123456
78

AgI Soly Wt-loss 20/300–365 C SVP 1.4 * 10
−6
/0.0008–0.0029 (AgI) m ptx-AgI-1.1 Gavrish and
Galinker, 1955
AgI in NaI Soly Sampl;
Wt-loss
150/200;
250 C
SVP 5.6/4.2–1.2 (AgI) (−log m); 0.001–0.89 (NaI) m ptx-AgI + NaI-1.1 Gammons and Yu,
1997
AgNO
3
Soly Vis.obs. 112/173–198 C SVP 91.6/98–99.4 (AgNO
3
) mass.% ptx-AgNO
3
-1.1 Benrath et al., 1937
AgNO
3
LGE Vap.pr. 152/219 C SVP (2.53/3.3–21.2
bar)
8.4–89.6 (AgNO
3
) mol.% ptx-AgNO
3
-2.1 Geerlings and
Richter, 1997
Ag
2
O Soly Sampl 25/200–260 C SVP 0.0022/0.063–0.022 (Ag

2
O) g/100 g H
2
O ptx-Ag
2
O-1.1 Gavrish and
Galinker, 1970
Ag
2
S in (NaOH + H
2
S) Soly Sampl 25/200;
250 C
SVP 0.1/0.2–2140 (Ag) ppm; 0–4.1 (NaOH) m;
0.8–54.3 atm P
H2S
ptx-Ag
2
S + NaOH
+ H
2
S-1.1
Sugaki et al., 1987
Ag
2
S in (NaOH + H
2
S) Soly Sampl 18/199–302 C 1.3/18.7–121 bar 0.28/2.6–331.5 (Ag) ppm;
0.05–1.64 (NaOH); 0.46–5.39 (H
2

S) mol.%
ptx-Ag
2
S + NaOH
+ H
2
S-2.1
Gammons and
Barnes, 1989
Ag
2
S in (NaOH + S) Soly Flw.Sampl 25/200–400 C 1/40–500 bar (0.01/0.02–8.5) * 10
−5
(Ag); 0–0.4 (NaOH);
0.014–0.12/0.18 (S) m
ptx-Ag
2
S + NaOH
+ S-1.1
Stefansson and
Seward, 2003a
Ag
2
SO
4
in D
2
SO
4
Soly Vis.obs. 25/195–234 C SVP 0.02/0.029–0.67 (AgSO

4
); 0–1 D
2
SO
4
mol/kg
D
2
O
ptx-Ag
2
SO
4
+
D
2
SO
4
-1.1
Lietzke and
Stoughton, 1963
Ag
2
SO
4
in H
2
SO
4
Soly Vis.obs. 25/200;

250 C
SVP 0.02/0.12–0.68 (AgSO
4
); 0.1–1 H
2
SO
4
m ptx-Ag
2
SO
4
+
H
2
SO
4
-1.1
Lietzke and
Stoughton, 1956
Ag
2
SO
4
in UO
2
SO
4
Soly Vis.obs. 36/197–259 C SVP 1.04/12.8–17.3 (Ag
2
SO

4
) mass.%;
0.13/1.35 (UO
2
SO
4
) m
ptx-Ag
2
SO
4
+
UO
2
SO
4
-1.1
Jones et al., 1957
Ag
2
SO
4
in UO
2
SO
4
Soly Vis.obs. 25/175;
200 C
SVP 0.22–0.73 (Ag
2

SO
4
); 0.1/0.41–1.35 UO
2
SO
4
m ptx-Ag
2
SO
4
+
UO
2
SO
4
-2.1
Lietzke and
Stoughton, 1960
AlOOH (boehmite) +
Buff
Soly Sampl 150/200;
250 C
100 bar 0.018/0.023–470/933 (AlOOH) mg/kg;
Buffer soln. (pH
25
= 1.17–9.44)
ptx-AlOOH +
Buff-1.1; 1.2
Bourcier et al.,
1993

AlOOH (boehmite) in
(C
2
H
4
O
2
+ C
2
H
3
O
2
Na)
Soly Sampl 170; 200 C SVP 6.37–6.09 (AlOOH) (−log m);
0.01–0.02 (C
2
H
4
O
2
); 0.01 (C
2
H
3
O
2
Na) m
ptx-AlOOH +
C

2
H
4
O
2

+
C
2
H
3
O
2
Na-1.1
Castet et al., 1993
AlOOH (boehmite) in
(HCl + NaCl)
Soly Sampl 90/200–350 C SVP 6.8/6.54–4.96/3.56 (AlOOH) (−log m);
(1.05/1.35–105)
*
10
−
4
(HCl);
0–0.01/0.025 (NaCl) m
ptx-AlOOH +
HCl +
NaCl-1.1
Castetet al., 1993
AlOOH (boehmite) in

(HCl + SiO
2
)
Soly Sampl 300 C SVP (86 bar) 6.65–4.26 (Al); 3.19–2.33 (Si) (−log m);
0.00074–0.038 (HCl) m
ptx-AlOOH +
HCl + SiO
2
-1.1
Salvi et al., 1998
AlOOH (boehmite) in
HClO
4
Soly Quench 150/200;
250 C
SVP (0.01–6/183)
*
10
−
4
(AlOOH);
3.1 * 10
−
6
–0.1 (HClO
4
) m
ptx-AlOOH +
HClO
4

-1.1
Kuyunko et al.,
1983
AlOOH (boehmite) in
(NH
3
/NH
4
Cl + SiO
2
)
Soly Sampl 300 C SVP (86 bar) 5.9–4.26 (Al); 3.37–1.97 (Si) (−log m);
0.005–16.5 (NH
3
) m
ptx-AlOOH +
NH
3
/NH
4
Cl +
SiO
2
-1.1
Salvi et al., 1998
AlOOH (boehmite) in
(NH
4
OH + NH
4

Cl)
Soly Sampl 70/200 C SVP?? 5.25–4.60 (AlOOH) (−log m);
(pH
21
= 9.44–10.14)
ptx-AlOOH +
NH
4
OH +
NH
4
Cl-1.1
Verdes et al., 1992
AlOOH (boehmite) in
(NH
4
OH + NH
4
Cl)
Soly Sampl 150/200–350 C SVP 3.02/2.98–2.13 (AlOOH) (−log m);
0.0034–0.28 (NH
4
OH); 0.01 (NH
4
Cl) m
ptx-AlOOH +
NH
4
OH +
NH

4
Cl-2.1
Castet et al., 1993
8 Hydrothermal Experimental Data
Table 1.1 Continued
Non-aqueous
components Phase equil Methods Temperature Pressure Composition Table REFERENCE
123456
78
AlOOH (boehmite) in
(NaCl + HCl/NaOH)
Soly Potentio;
Sampl
100/203–290 C SVP-68 bar 7.3/6.5–2.0 (Al) (−log m);
pH = 1.7–8.5 (HCl/NaOH)
ptx-AlOOH-NaCl
+ HCl/NaOH-
1.1; 1.2; 1.3;
1.4
Palmer et al., 2001
AlOOH (boehmite) in
(NaCl + HCl/NaOH)
Soly Potentio;
Sampl
101.5/203–290 C SVP 7.2/6.9–2.4 (Al) (−log m);
pH = 2.2–8.3 (HCl/NaOH)
ptx-AlOOH-NaCl
+
HCl/NaOH-2.1
Benezeth et al.,

2001
AlOOH (boehmite) in
NaOH
Soly Sampl 250; 300 C SVP 6.8–37.6 (Al
2
O
3
); 5.9–24.3 (Na
2
O) mass.% ptx-AlOOH +
NaOH-1.1; 1.2
Bernshtein and
Matsenok, 1961
AlOOH (boehmite) in
NaOH
Soly Sampl 200; 250 C SVP 0.016–3.78 (AlOOH); 0.0088/2.04 (NaOH) m ptx-AlOOH +
NaOH-2.1
Kuyunko et al.,
1983
AlOOH (boehmite) in
(NaOH + NaCl)
Soly Sampl 135/200–300 C SVP?? 3.71/3.45–2.08 (AlOOH) (−log m);
0.001–0.01 (NaOH); 0.002–0.05 (NaCl) m
ptx-AlOOH +
NaOH +
NaCl-1.1
Verdes et al., 1992
AlOOH (boehmite) in
(NaOH + NaCl)
Soly Sampl 170/200–350 C SVP 3.02/2.98–2.13 (AlOOH) (−log m);

0.0025–0.009 (NaOH); 0.001–0.0075 (NaCl) m
ptx-AlOOH +
NaOH +
NaCl-2.1
Castet et al., 1993
AlOOH (boehmite) in
(NaOH + SiO
2
)
Soly Sampl 300 C SVP (86 bar) 2.44 (Al); 3.24 (Si) (
−log m); 0.004 (NaOH) m ptx-AlOOH +
NaOH +
SiO
2
-1.1
Salvi et al., 1998
AlO
2
H (diaspore) in
NaOH
Soly Sampl 250; 300 C SVP 8.3–33.7 (Al
2
O
3
); 6.4–22.9 (Na
2
O) mass.% ptx-AlO
2
H +
NaOH-1.1

Bernshtein and
Matsenok, 1965
AlO
2
H (diaspore) in
NaOH
Soly Wt-loss;
Quench
523–598 K SVP?? 0.08–4.34 (AlO
2
) equiv/L;
4.9–150.7 (Na
2
O) g/L
ptx-AlO
2
H +
NaOH-2.1
Chang et al., 1979
AlO
2
H (diaspore) in
(NaOH + NaCl)
Soly Sampl 135/200–300 C SVP?? 3.28/2.89–2.22 (AlO
2
H) (−log m);
0.005; 0.01 (NaOH); 0/0.01–0.02 (NaCl) m
ptx-AlOOH +
NaOH +
NaCl-1.1

Verdes et al., 1992
Al
2
O
3

(corundum) Soly Quench 380–420 C 25–49 MPa 0.00006–0.0009 (Al
2
O
3
) m ptx-Al
2
O
3
-1.1 Yalman et al., 1960
Al
2
O
3

(corundum) Soly Wt-loss 700–900 C 6–6.75 kbar 0.043–0.105 (Al
2
O
3
) mass.% ptx-Al
2
O
3
-2.1 Anderson and
Burnham, 1967

Al
2
O
3

(corundum) Soly Wt-loss 500–800 C 6 kbar 0.0008–0.0059 (Al
2
O
3
) mass.% ptx-Al
2
O
3
-3.1 Burnham et al.,
1973
Al
2
O
3

(corundum) Soly Wt-loss 350–500 C 200–2000 kg/cm
2
0.008–0.19 (Al
2
O
3
) g/L ptx-Al
2
O
3

-4.1 Ganeev and
Rumyancev, 1974
Al
2
O
3

(corundum) Soly Wt-loss 666–700 C 2.5–20 kbar 2.7–139.4 (Al
2
O
3
) ppm ptx-Al
2
O
3
-5.1 Becker et al., 1983
Al
2
O
3

(corundum) Soly Sampl 400–720 C 730–3120 kbar 1.0–4.2 (Al) ppm ptx-Al
2
O
3
-6.1 Ragnarsdottir and
Walther, 1985
Al
2
O

3
(corundum) Soly Wt-loss 700–1100

C 500–2000 MPa (−3.4)-(−1.56) (Al) (log m) ptx-Al
2
O
3
–8.1 Tropper and
Manning, 2007
Al
2
O
3

(corundum) Soly Sampl 272–600 C 500–2480 bar 3.005–4.994 (Al) (−log m) ptx-Al
2
O
3
-7.1 Walther, 1997
Al
2
O
3

(corundum) in
AlCl
3
Soly Quench 600 C 2 kbar 2.4 (Al
2
O

3
) (−log mol/L); 0.1;
1 (AlCl
3
) mol/L
ptx-Al
2
O
3
+
AlCl
3
-1.1
Korzhinskiy, 1987
Phase Equilibria in Binary and Ternary Hydrothermal Systems 9
Non-aqueous
components Phase equil Methods Temperature Pressure Composition Table REFERENCE
123456
78
Al
2
O
3

(corundum) in
Ba(OH)
2
Soly Wt-loss 430; 600 C 1450 bar 2 (Ba(OH)
2
) m; Solid ph not Al

2
O
3
ptx-Al
2
O
3

+
Ba(OH)
2
-1.1
Barns et al., 1963
Al
2
O
3

(corundum) in
CaCl
2
Soly Quench 600 C 2 kbar 2.23; 2.37 (Al
2
O
3
) (−log mol/L);
1 CaCl
2

mol/L

ptx-Al
2
O
3
+
CaCl
2
-1.1
Korzhinskiy, 1987
Al
2
O
3

(corundum) in
CaCl
2
Soly Sampl 198–600 C 625–2100 bar 2.83–3.99 (Al
2
O
3
) (−log m);
0.1 (CaCl
2
) m
ptx-Al
2
O
3
+

CaCl
2
-2.1
Walther, 2002
Al
2
O
3

(corundum) in
Cs
2
CO
3
Soly Wt-loss 430; 600 C 1450 bar 3.4; 4.8 (Al
2
O
3
) mass.%;
2 (Cs
2
CO
3
) m
ptx- Al
2
O
3
+
Cs

2
CO
3
-1.1
Barns et al., 1963
Al
2
O
3

(corundum) in
CsOH
Soly Wt-loss 430; 600 C 1450 bar 5.2; 5.7 (Al
2
O
3
) mass.%;
2 (CsOH) m
ptx-Al
2
O
3
+
CsOH-1.1
Barns et al., 1963
Al
2
O
3

(corundum) in
HCl
Soly Wt-loss 430 1450 bar <0.2 (Al
2
O
3
) mass.%;
3.3 (HCl) m
ptx-Al
2
O
3
+
HCl-1.1
Barns et al., 1963
Al
2
O
3

(corundum) in
HCl
Soly Quench 450–700 C 1; 2 kbar 4.42–1.72 (Al
2
O
3
) (−log mol/L);
0.07–1.9 HCl mol/L
ptx-Al
2

O
3
+
HCl-2.1
Korzhinskiy, 1987
Al
2
O
3

(corundum) in HF Soly Wt-loss 430 C 1450 bar 7.8 (HF) m;
Solid ph [Al(OHF)
3
]
ptx-Al
2
O
3
+
HF-1.1
Barns et al., 1963
Al
2
O
3

(corundum) in
K
2
CO

3
Soly Wt-loss 430; 600 C 1450 bar 4.3; 5.8 (Al
2
O
3
) mass.%; 2 (K
2
CO
3
) m ptx-Al
2
O
3
+
K
2
CO
3
-1.1
Barns et al., 1963
Al
2
O
3

(corundum) in
KCl
Soly Wt-loss 430 1450 bar <2 (Al
2
O

3
) mass.%; 2–20 (KCl) m ptx-Al
2
O
3
+
KCl-1.1
Barns et al., 1963
Al
2
O
3

(corundum) in
KCl
Soly Wt-loss 800 C 6; 6.17 kbar 0.13; 0.15 (Al
2
O
3
) mass.%; 4.6 (KCl) m ptx-Al
2
O
3
+
KCl-2.1
Anderson and
Burnham, 1967
Al
2
O

3

(corundum) in
KCl
Soly Quench 600 C 2 kbar 2.3 (Al
2
O
3
) (−log mol/L); 1 (KCl) mol/L ptx-Al
2
O
3
+
KCl-3.1
Korzhinskiy, 1987
Al
2
O
3

(corundum) in KF Soly Quench 400 C ??50 MPa 0.0032; 0.0066 (Al
2
O
3
) m;
0.01; 0.2 (KF) mol/L
ptx-Al
2
O
3

+
KF-1.1
Yalman et al., 1960
Al
2
O
3

(corundum) in KF Soly Wt-loss 430; 600 C 1380; 1450 bar 2; 10 (KF) m;
Solid ph [K
3
AlF
6
]
ptx-Al
2
O
3
+
KF-2.1
Barns et al., 1963
Al
2
O
3

(corundum) in
KOH
Soly Wt-loss 430; 600 C 1450 bar 6.6; 6.9 (Al
2

O
3
) mass.%; 2 (KOH) m ptx-Al
2
O
3
+
KOH-1.1
Barns et al., 1963
Al
2
O
3

(corundum) in
KOH
Soly Wt-loss 600–900 C 2–6 kbar 1.3–7.2 (Al
2
O
3
) mass.%; 0.35–1.5 (KOH) m ptx-Al
2
O
3
+
KOH-2.1
Anderson and
Burnham, 1967
Al
2

O
3

(corundum) in
KOH
Soly Wt-loss 500–700 C 1.86–2.65 kbar 0.09–0.89 (Al); 0.1–1.0 (KOH) m ptx-Al
2
O
3
+
KOH-3.1
Pascal and
Anderson, 1989
Al
2
O
3

(corundum) in
KOH
Soly Wt-loss 400 C 0.5–2 kbar (0.064–7.1)
*
10
−
2
(Al
2
O
3
); 0.001–0.1 (KOH) m ptx-Al

2
O
3
+
KOH-4.1
Azaroual et al.,
1996
Al
2
O
3

(corundum) in
LiOH
Soly Wt-loss 430 C 1450 bar 4 (LiOH) m;
Solid-[LiAlO
2
]
ptx-Al
2
O
3
+
LiOH-1.1
Barns et al., 1963
Al
2
O
3

(corundum) in
MgCl
2
Soly Quench 600 C 2 kbar 2.3 (Al
2
O
3
) (−log mol/L); 1 (MgCl
2
) mol/L ptx-Al
2
O
3
+
MgCl
2
-1.1
Korzhinskiy, 1987
Al
2
O
3

(corundum) in
NH
4
OH
Soly Wt-loss 430–600 C 1450–2760 bar <2 (Al
2
O

3
) mass.% ptx-Al
2
O
3
+
NH
4
OH-1.1
Barns et al., 1963
Al
2
O
3

(corundum) in
Na
2
CO
3
Soly Quench 450 C 1000 atm 1.12–3.46 (Al
2
O
3
); 14 (Na
2
CO
3
) mass.% ptx-Al
2

O
3
+
Na
2
CO
3
-1.1
Yamaguchi et al.,
1962
10 Hydrothermal Experimental Data
Table 1.1 Continued
Non-aqueous
components Phase equil Methods Temperature Pressure Composition Table REFERENCE
123456
78
Al
2
O
3

(corundum) in
Na
2
CO
3
Soly Wt-loss 430; 600 C 1450 bar 4.9; 7.0 (Al
2
O
3

) mass.%; 2 (Na
2
CO
3
) m ptx-Al
2
O
3
+
Na
2
CO
3
-2.1
Barns et al., 1963
Al
2
O
3

(corundum) in
NaCl
Soly Wt-loss 430 C 1450 bar <0.02 (Al
2
O
3
) mass.%; 20 (NaCl) m ptx-Al
2
O
3

+
NaCl-1.1
Barns et al., 1963
Al
2
O
3

(corundum) in
NaCl
Soly Wt-loss 800 C 6.0 kbar 0.092 (Al
2
O
3
) mass.%; 0.90 (NaCl) m ptx-Al
2
O
3
+
NaCl-2.1
Anderson and
Burnham, 1967
Al
2
O
3

(corundum) in
NaCl
Soly Quench 600 C 2 kbar 2.3 (Al

2
O
3
) (−log mol/L); 1 (NaCl) mol/L ptx-Al
2
O
3
+
NaCl+-3.1
Korzhinskiy, 1987
Al
2
O
3

(corundum) in
NaCl
Soly Sampl 400–600 C 491–2010 bar 1.44–3.37 (Al
2
O
3
) (−log m); 0.1; 0.5 (NaCl) m ptx-Al
2
O
3
+
NaCl-4.1
Walther, 2001
Al
2

O
3
(corundum) in
NaCl
Soly Wt-loss 800

C 10 kbar 0.001–0.02 (Al
2
O
3
) (m); 0–0.6 (NaCl) mol.fr. ptx-Al
2
O
3
+
NaCl-5.1
Newton and
Manning, 2006
Al
2
O
3

(corundum) in
NaOH
Soly Quench 380–420 C 25–49 MPa 0.00021–0.1975 (Al
2
O
3
); 0–0.5 (NaOH) m ptx-Al

2
O
3
+
NaOH-1.1; 1.2
Yalman et al., 1960
Al
2
O
3

(corundum) in
NaOH
Soly Quench 400; 450 C 100–1500 atm 2.74–26.5 (Al
2
O
3
) mass.%;
31.25–400 (NaOH) g/L
ptx-Al
2
O
3
+
NaOH-2.1
Yamaguchi et al.,
1962
Al
2
O

3

(corundum) in
NaOH
Soly Wt-loss 400–600 C 140–2760 bar 2–31.5 (Al
2
O
3
) mass.%; 0.5–10 (NaOH) m ptx-Al
2
O
3
+
NaOH-3.1
Barns et al., 1963
Al
2
O
3

(corundum) in
NaOH
Soly Wt-loss 800; 900 C 6–6.13 kbar 0.64; 0.65 (Al
2
O
3
) mass.%; 0.113 (NaOH) m ptx-Al
2
O
3

+
NaOH-4.1
Anderson and
Burnham, 1967
Al
2
O
3

(corundum) in
NaOH
Soly Wt-loss 500; 700 C 2–2.62 kbar 0.1–0.81 (Al); 0.11–0.94 (NaOH) m ptx-Al
2
O
3
+
NaOH-5.1
Pascal and
Anderson, 1989
Ar H-Fl; Cr.ph Sampl 350–400 C 221–4000 bar 0–87 (Ar) mol.% ptx-Ar-1.1; 1.2 Tsiklis and
Prokhorov, 1966
Ar Cr.ph; H-Fl Vis.obs.;
p-T curves
375–400 C 230–3100 bar 1–28 (Ar) mol.%
ptx-Ar-2.1 Lentz and Franck,
1969
Ar H-Fl p-x curves 298/496–561 K SVP 0.009–0.021/0.074 (Ar) mol.% ptx-Ar-3.1 Potter II and
Clynne, 1978
Ar H-Fl; Cr.ph Vis.obs.;
p-T curves

477–663 10.4–337.2 MPa 0.05–0.8 (Ar) mol.fr.
ptx-Ar-4.1; 4.2 Wu et al., 1990
Ar LGE Sampl 307/454;
568 K
1.67/2.2; 9.7 MPa 0.027–52.12 (Ar) mol.% ptx-Ar-5.1 Crovetto et al., 1982
Ar in D
2
O H-Fl Sampl 297/461–584 K 1.32/2.7–13.28 MPa 0.04–53.8 (Ar) mol.% ptx-Ar + D
2
O-1.1 Crovetto et al., 1982
As
2
O
3

(claudetite) Soly Wt-loss 22/150–250 C SVP 0.21–1.2 (As) (log m) ptx-As
2
O
3
-1.1 Pokrovski et al.,
1996
As
2
O
3
; As
2
O
3
+ NaCl, in

HCl, H
2
S As
2
O
5
LGE; Soly Sampl;
Quench;
Potentio
130/250–450 C SVP (0–356 bar) 0–9 (NaCl); 0–0.09 (HCl); 0–0.2 (H
2
S) m ptx-As
2
O
3
-2.1–
2.5;
ptx-As
2
O
5
-1.1
Pokrovski et al.,
2002
As
2
S
3
(orpiment) in
(As

2
O
3
+ HCl)
Soly Wt-loss;
Sampl
200–300 C SVP 2.33–0.49 (As) (−log m); 0–740 (As
2
O
3
) mg;
0; 0.01 (HCl) mol/L
ptx-As
2
S
3
+
HCl-1.1
Pokrovski et al.,
1996
Non-aqueous
components Phase equil Methods Temperature Pressure Composition Table REFERENCE
Phase Equilibria in Binary and Ternary Hydrothermal Systems 11
components Phase

equil Methods Temperature Pressure Composition Table REFERENCE
123456
78
As
2

S
3
(orpiment) in Na
2
S Soly Sampl 25/200;
253 C
100–1500 bar 0.01/1.8–12.1 (As
2
S
3
);
0/0.55–3.43 (Na
2
S) mass.%
ptx-As
2
S
3
+
Na
2
S-1.1
Weissberg et al.,
1966
Au + buff. Soly Quench 300–500 C 500–1500 atm 8.13–6.46 (Au) (−log m);
Buff. (Ni-NiO; Fe
2
O
4
-Fe

2
O
3
; Cu-Cu
2
O)
ptx-Au-1.1; 1.2 Zotov et al., 1985b
Au in Cl
2
Soly Wt-loss 125/200–500 C 1 atm 0.08–9.54 (Au) mass. % (Wt-loss);
(Cl
2

+ H
2
O − gaseous stream)
ptx-Au + Cl
2
-1.1 Ogryzlo, 1935
Au in H
2
Soly Flw.Sampl 300–600 C 500–1500 bar (0.17–17.9)
*
10
−
7
(Au); 4 * 10
−
5
(H

2
) m ptx-Au + H
2
-1.1 Stefansson and
Seward, 2003b
Au in HCl Soly Quench 200; 300 C SVP 92–1.396 (Au) ppm; 0.05–0.5 (HCl) mol/L ptx-Au + HCl-1.1 Ogryzlo, 1935
Au in HCl Soly Quench;
Sampl
100/200 C SVP 3.67/3.05–2.0/1.79 (Au) (−log m);
0.02–1 (HCl) m
ptx-Au + HCl-2.1 Gammons et al.,
1997
Au in (HCl + H
2
) Soly Flw.Sampl 300–600 C 500–1800 bar (0.01–3.26)
*
10
−
5
(Au); 0.47–1.72 (HCl);
(3.76–5.73) * 10
−
5
(H
2
) m
ptx-Au + HCl +
H
2
-1.1

Stefansson and
Seward, 2003c
Au in (HCl + NaCl +
H
2
)
Soly Flw.Sampl 300–500 C 500–1800 bar (0.049–6.65) 10
−
6
(Au); 0.104–0.975 (NaCl);
1 * 10
−
9
–0.586 (HCl); (0.04–7.9) * 10
−
4
(H
2
) m
ptx-Au + HCl +
NaCl + H
2
-1.1
Stefansson and
Seward, 2003c
Au in H
2
S Soly Sampl 143/197–352 C 18.4/31–214 atm 7.04–5.69 (Au) (−log m); 0.8–1.93 (H
2
S) m ptx-Au + H

2
S-1.1 Shenberger and
Barnes, 1989
Au in (H
2
S + H
2
) Soly Sampl 150/200–300 C 500 bar 0.029–1.21 (Au) ppm; 0.011–0.11 (S) m;
0.036 (H
2
) bar
ptx-Au + H
2
S-2.1 Benning and
Seward, 1996
Au in (H
2
S + H
3
PO
4
+
H
2
)
Soly Sampl 150/200–400 C 500–1500 bar 0.001–0.365 (Au) ppm; 0.007–0.095 (S);
0.0007–0.144 (H
3
PO
4

) m; 0.036 (H
2
) bar
ptx-Au + H
2
S +
H
3
PO
4
+ H
2
-1.1
Benning and
Seward, 1996
Au in (H
2
S + H
3
PO
4
+
KH
2
PO
4
)
Soly Sampl 150/199.4–300.8 C 27/38–132 atm 7.8/7.24–6.13 (Au) (−log m); 0.73; 1.56 (H
2
S);

0.044; 0.17 (H
3
PO
4
); 7.8/0.015; 0.033
(KH
2
PO
4
) m
ptx-Au + H
2
S +
H,K/PO
4
-1.1
Shenberger and
Barnes, 1989
Au in (H
2
S + NaOH) Soly Sampl 133/196–356 C 22/37–210.8 atm 4.53/4.08–2.36 (Au) (−log m);
1.24; 2.13 (H
2
S); 0.05; 1.67 (NaOH) m
ptx-Au + H
2
S +
NaOH-1.1
Shenberger and
Barnes, 1989

Au in (H
2
S + NaOH +
H
2
)
Soly Sampl 150/200–400 C 500–1500 bar 2.075–108.4 (Au) ppm; 0.0176–0.114 (S);
0.0023–0.037 (NaOH) m;
0.036–0.37 (H
2
) bar
ptx-Au + H
2
S +
NaOH + H
2
-1.1
Benning and
Seward, 1996
Au in (H
2
S + NaOH +
Na
2
SO
4
)
Soly Sampl 296.2–351 C 96.4–234 atm 1.9–1.44 (Au) (−log m); 0.9–1.5 (H
2
S);

0.16–0.98 (NaOH); 0.07–0.12 (Na
2
SO
4
) m
ptx-Au + H
2
S +
Na/OH,SO
4
-1.1
Shenberger and
Barnes, 1989
Au in (KCl + buffer) Soly Quench 293–556 C 1; 2 kbar 2.9–2987 (Au) ppm; 0.5–2 (KCl) mol/L + buff. ptx-Au + KCl-1.1 Henley, 1973
Au in (KCl + buffer) Soly Sampl 350–450 C 500 bar 6.64–5.45 (Au) (−log m); 0.5 (KCl) m + buff. ptx-Au + KCl-2.1 Gibert et al., 1998
Au in (KCl+ buffer) Soly Sampl 350–500

C 500–1000 bar 5.8–7.5 (Au) (−log m);
0.001–0.1 (KCl) m + buff.
ptx-Au+KCl-3.1 Tagirov et al,
2005
Au in MgS Soly Quench 117/200–399 C 0.14–0.17 GPa 0.1–29.4 (Au) g/kg; 66 (MgS) mass.% ptx-Au +
MgS-1.1
Fleet and Knipe,
2000
Au in NaHS Soly Quench 200; 300 C SVP 648–2113 (Au) ppm;
5–13 (Na
2
S); 10.0; 10.7 (NaOH) mass.%
ptx-Au +

NaHS-1.1
Ogryzlo, 1935
Au in NaCl + NaOH +
H
2
Soly Flw.Sampl 300–450 C 500 bar (2.8–55.6) * 10
−
8
(Au); 0.51; 0.52 (NaCl);
0.11; 0.3 (NaOH); (3.56–3.78) * 10
−
5
(H
2
) m
ptx-Au + Na/
Cl,OH + H
2
-1.1
Stefansson and
Seward, 2003c
Au in (NaOH + buffer) Soly Quench 25/250 C SVP 0.4 * 10
−
9
/(0.3–9.1) * 10
−
7
(Au) mol/L;
pH = 7.7/9.2–14 (NaOH); Buff. (Fe
2

O
3
/Fe
3
O
4
)
ptx-Au +
NaOH-1.1
Baranova et al.,
1977
Au in (NaOH + H
2
) Soly Flw.Sampl 300–600 C 500–1500 bar (0.012–2) * 10
−
6
(Au); 0.05–0.5 (NaOH);
(3.58–3.98) * 10
−
5
(H
2
) m
ptx-Au + NaOH +
H
2
-1.1
Stefansson and
Seward, 2003b
Au in Na

2
S Soly Quench 590 C 0.15 GPa 0.1 (Au) g/kg; (Na
2
S) ptx-Au +
Na
2
S-1.1
Fleet and Knipe,
2000
12 Hydrothermal Experimental Data
Non-aqueous
components Phase equil Methods Temperature Pressure Composition Table REFERENCE
123456
78
B(OH)
3
LGE Sampl 452–645 K SVP 0.0007–0.11 (B(OH)
3
) m ptx-B(OH)
3
-1.1 Kukuljan et al.,
1999
B
2
O
3
; HBO
2
Soly Vis.obs. −0.76/169–450 C SVP 0.33–100 (B
2

O
3
) mol.% ptx-B
2
O
3
-1.1 Kracek et al., 1938
B
2
O
3
+ NaCl H-Fl Sampl 400; 450 C SVP 173–410 (B) ppm; 0.1–26(NaCl) mass.% ptx-B
2
O
3
+NaCl-1.1 Liebscher et al.,
2005
BaBr
2
Soly Vis.obs. 25/195–342 C SVP 50/65–81.5 (BaBr
2
) mass.% ptx-BaBr
2
-1.1 Benrath and
Lechner, 1940
BaBr
2
Soly Vis.obs. 350–415 C SVP 83–85 (BaBr
2
) mass.% ptx-BaBr

2
-2.1 Benrath, 1941
BaCl
2
Soly Vis.obs. 25/200–370 C SVP 37/50–0 (BaCl
2
) mass.% ptx-BaCl
2
-1.1 Benrath and
Lechner, 1940
BaCl
2
Soly Quench 426 C 273 kg/cm
2
0.04 (BaCl
2
) mass.% ptx-BaCl
2
-2.1 Gillingham, 1948
BaCl
2
Soly Therm. anal 209; 272 C SVP BaCl
2
* H
2
O ⇒ BaCl
2
* 0.5H
2
O ⇒ BaCl

2
ptx-BaCl
2
-3.1 Kessis, 1967
BaCl
2
LGE;
Isop-m
Isopiestc. 383/473.6 SVP 0.49/0.64–3.62 (BaCl
2
) m ptx-BaCl
2
-4.1 Holmes and
Mesmer, 1981a
BaCl
2
Soly; H-Fl;
Immisc;
Cr.ph
Vis.obs.;
Sampl;
p-V; p-x;
p-T curves
175/190–637 6/9.5–1405 kg/cm
2
3–67 (BaCl
2
) mass.% ptx-BaCl
2
-5.1;

5.2; 5.3; 5.4
Valyashko et al.,
1983
BaCl
2
LGE Vap.pr. 412/452.5–630 K 0.3/0.9–17.5 MPa 0.25–1.55 (BaCl
2
) m ptx-BaCl
2
-6.1 Matuzenko et al.,
1984
BaCl
2
LGE Vap.pr. 150/200–350 C 4.45/24–165 bar 0.1–1.45 (BaCl
2
) m ptx-BaCl
2
-7.1 Azizov and
Akhundov, 1995
BaCl
2
LGE;
Isop-m
Isopiestc. 383/474–524 K SVP 0.42–4.1 (BaCl
2
) m ptx-BaCl
2
-8.1 Holmes and
Mesmer, 1996b
BaF

2
Soly Sampl 200–395 C SVP 0.03–0.002 (BaF
2
) g/100 g H
2
O ptx-BaF
2
-1.1 Booth and Bidwell,
1950
BaF
2
in KF Soly Sampl 350–500 C SVP 0.09–3.3 (BaF
2
); 40–69 (KF) mass.% ptx-BaF
2
+
KF-1.1
Urusova and
Ravich, 1969
Ba(NO
3
)
2
Soly Vis.obs. 112/209–417 C SVP 28.4/45.5–82.3 (Ba(NO
3
)
2
) mass.% ptx-Ba(NO
3
)

2
-1.1 Benrath et al., 1937
BaSO
4
Soly Flw.Sampl 500 C 1000 bar 0.004 (BaSO
4
) mass.% ptx-BaSO
4
-1.1 Morey and
Hesselgesser,
1951b
BaSO
4
Soly Sampl 250 C SVP 0.5 * 10
−
5
(BaSO
4
) m ptx-BaSO
4
-2.1 Jones et al., 1957
BaSO
4
Soly Wt-loss;
Quench
100/200–600 C 1/15–2100 bar 3.0–10 (BaSO
4
) mg/kg H
2
O ptx-BaSO

4
-3.1;
3.2
Strübel, 1967
BaSO
4
soly Sampl 100/200–359 C 1/16–169 atm 4.4/4.5–5 (BaSO
4
) ppm ptx-BaSO
4
-4.1 Gundlach, et al.,
1972
BaSO
4
soly Sampl 23/189–279 C 36/92–1010 bar 0.02/0.01–0.005 (BaSO
4
) mmol/kg H
2
O ptx-BaSO
4
-5.1 Blount, 1977
BaSO
4
in CaCl
2
soly Wt-loss;
quench
100/210–255 C SVP 0.002–0.5 (CaCl
2
);

(0.3–22) * 10
−
4
(BaSO
4
) mol/L
ptx-BaSO
4
+
CaCl
2
-1.1
Uchameishvili et
al., 1966
BaSO
4
in KCl soly Wt-loss;
quench
110/210–300 C SVP 0.025 (KCl); (0.34–0.8/1.1) * 10
−
4
(BaSO
4
)
mol/L
ptx-BaSO
4
+
KCl-1.1
Uchameishvili et

al., 1966
Table 1.1 Continued
Non aqueous
Phase Equilibria in Binary and Ternary Hydrothermal Systems 13
Non
-
aqueous

components Phase equil Methods Temperature Pressure Composition Table REFERENCE
123456
78
BaSO
4
in MgCl
2
soly Wt-loss;
Quench
110/200–310 C SVP 0.02–1.0 (MgCl
2
);
(0.8–18.6) * 10
−
4
(BaSO
4
) mol/L
ptx-BaSO
4
+
MgCl

2
-1.1
Uchameishvili et
al., 1966
BaSO
4
in NaCl soly Wt-loss;
quench
95/200–370 C SVP 0.25–2.0 (NaCl);
(0.2–8.4) * 10
−
4
(BaSO
4
) mol/L
ptx-BaSO
4
+
NaCl-1.1
Uchameishvili et
al., 1966
BaSO
4
in NaCl Soly Wt-loss;
Quench
20/200–600 C D =
0.3–0.9/1.0 (g/cm
3
)
0.1/2.0 (NaCl) m;

10/145–970 (BaSO
4
) mg/kg H
2
O
ptx-BaSO
4
+
NaCl-2.1
Strübel, 1967
BaSO
4
in NaCl soly Sampl 20/200–450 C 1/15–915 atm 23/77–426–142 (BaSO
4
) ppm;
1; 2 (NaCl) mol/L
ptx-BaSO
4
+
NaCl-3.1
Gundlach et al.,
1972
BaSO
4
in NaCl soly Sampl 94/200–253 C 5/103–507 bar 0.1/0.7–0.06 (BaSO
4
) mmol/kg;
0.2, 4 (NaCl) m
ptx-BaSO
4

+
NaCl-4.1
Blount, 1977
BaSO
4
+ UO
2
SO
4
soly Sampl 250 C SVP
0.13–1.3 (UO
2
SO
4
); (1.5–40) * 10
−
5
(BaSO
4
) m ptx-BaSO
4
+
UO
2
SO
4
-1.1
Jones et al., 1957
BaSrSO
4

soly Sampl 25/195–350 C 0.03/14–169 atm 1.7/1.2–3.4 (Ba); 3.4/5.0–0.5 (Sr) ppm ptx-BaSrSO
4
-1.1 Gundlach et al.,
1972
BaSrSO
4
in NaCl soly Sampl 24/200–350 C 1/15–915 atm 1.7/5–3 (Ba); 48//91–40 (Sr) ppm;
1 (NaCl) mol/L
ptx-BaSrSO
4
+
NaCl-1.1
Gundlach et al.,
1972
BeO in HClO
4
Soly Quench;
Wt-loss
300 C SVP 5.1 * 10
−
6
–5.5 * 10
−
3
(BeO);
0–0.026 (HClO
4
) mol/L
ptx-BeO +
HClO

4
-1.1
Koz’menko et al.,
1986
BeO in HF Soly Quench;
Wt-loss
300 C SVP (7 * 10
−
6
–2 * 10
−
3
) (BeO); 0.00027–0.013 (HF)
mol/L
ptx-BeO +
HF-1.1
Koz’menko et al.,
1985
Bi
2
O
3
Soly Quench;
Wt-loss
75/200;
300 C
SVP (0.03 1.96–23.6) * 10
−
4
(Bi) m ptx-Bi

2
O
3
-1.1 Kolonin and Laptev,
1982
Bi
2
O
3
in HClO
4
Soly Quench;
Wt-loss
75/200;
300 C
SVP (0.2/3.03–25.9/68.5) * 10
−
4
(Bi);
(0.32/0.79–34) * 10
−
4
(HClO
4
) m
ptx-Bi
2
O
3
+

HClO
4
-1.1
Kolonin and Laptev,
1982
Bi
2
O
3
in NaOH Soly Quench;
Wt-loss
300 C SVP (16–73) * 10
−
4
(Bi); 0.0001–5.1 (NaOH) m ptx-Bi
2
O
3
+
NaOH-1.1
Kolonin and Laptev,
1982
CF
4
H-Fl;
Immisc
Vis.obs. 587–669 K 26–200 MPa 1.2–5.8 (CF
4
) mol.% ptx-CF
4

-1.1 Smits et al., 1997b
CF
4
+ NaCl H-Fl;
Immisc
Vis.obs. 586–663 K 35–200 MPa 0.76–3.35 (CF
4
); 0.3–1 (NaCl) mol.% ptx-CF
4
+
NaCl-1.1
Smits et al., 1997c
CHF
3
H-Fl;
Immisc
Vis.obs. 471–606 K 33–200 MPa 3–14 (CHF
3
) mol.% ptx-CHF
3
-1.1 Smits et al., 1997a
CHF
3
+ NaCl H-Fl;
Immisc
Vis.obs. 492–625 K 32–200 MPa 3–11 (CHF
3
); 0.5; 1 (NaCl) mol.% ptx-CHF
3
+

NaCl-1.1
Smits et al., 1997a
CH
4

(methane) H-Fl Sampl 38/204.4;
237.8 C
1.4/2.76–69 MPa 0.04/19.2–94.6 (CH
4
) mol.% ptx-CH
4
-1.1 Olds et al., 1942
CH
4

(methane) H-Fl Sampl 150/200–360 C 50–1100 kg/cm
2
0.985/0.96–0.074 (CH
4
) mol.fr. ptx-CH
4
-2.1; 2.2 Sultanov et al.,
1971
CH
4

(methane) H-Fl Sampl 150/200–360 C 50–1100 kg/cm
2
1/1.24–193 (CH
4

) cm
3
/g H
2
O ptx-CH
4
-3.1 Sultanov et al.,
1972a
CH
4

(methane) H-Fl Sampl 154/221–354 C 3.5/4–197 MPa 0.07/0.12–10.9 (CH
4
) mol.% ptx-CH
4
-4.1 Price, 1979
CH
4

(methane) H-Fl Sampl 4.5/200–300 C 1.1/6.9–13.3 MPa 1.13–3.1/7 MPa (Henry’s const) ptx-CH
4
-5.1 Cramer, S.D., 1982
CH
4

(methane) H-Fl;
Immisc
Sampl 323/478–589 K 1.4/6–17 MPa 0.02/0.13–84/99.9 (CH
4
) mol.% ptx-CH

4
-6.1 Gillespie, P.C.;
Wilson, G.M.,
1982