THÔNG TIN TÀI LIỆU
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,
[...]... body of the chapter provides an overview of recent developments in our understanding of binary and ternary phase diagram construction based on modern theoretical 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... the method of visual observations is used for determination of phase equilibria at elevated temperatures and pressures, sometimes – for determination 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... 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 classification of phase diagrams and led to a period of intense experimental studies These pioneer publications at the end of the nineteenth and. .. other phase In our attempt to classify the available experimental methods for studying the hydrothermal equilibria there are five groups that differ in the technique of obtaining information on phase equilibria and on coexisting phase compositions 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. .. composition (static apparatus); Flw.Sampl – the method of flow-sampling is used for determination of solution composition (Flow-apparatus); Fl.inclus – the method of fluid 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... INTRODUCTION Defining the phase composition of the mixture at a certain pressure and temperature is the first step in any scientific 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... derivation 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 thermodynamic surfaces Modern knowledge of phase diagrams construction allows us to classify the main types of. .. technical problems and moderate accuracy of solubility measurements Only in the publication of Alekhin and Vakulenko (1987) there is a description of an apparatus for continuous determination of the hydrothermal fluid 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 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 Types of phase equilibria: Soly – solid solubility equilibria, heterogeneous equilibria with solid phase( s) LGE – in... solute in aqueous electrolyte and nonelectrolyte solutions under suband 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 thermodynamics of hydrothermal systems Chapter 3 (High Temperature Potentiometry, . M. (Vladimir Mikhailovich) Hydrothermal properties of materials : experimental data on aqueous phase equilibria and solution properties at elevated temperatures and pressures / Vladimir Valyashko. . 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. 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
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