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 Registered offi ce John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom For details of our global editorial offi ces, for customer services and for information about how to apply for permission to reuse the copyright material in this book please see our website at www.wiley.com. The right of the author to be identifi ed as the author of this work has been asserted in accordance with the Copyright, Designs and Patents Act 1988. All rights reserved. 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The fact that an organization or Website is referred to in this work as a citation and/or a potential source of further information does not mean that the Author or the Publisher endorses the information the organization or Website may provide or recommendations it may make. Further, readers should be aware that Internet Websites listed in this work may have changed or disappeared between when this work was written and when it is read. No warranty may be created or extended by any promotional statements for this work. Neither the Publisher nor the Author shall be liable for any damages arising herefrom. 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