Conformation and Hydration of Sugars and Related Compounds in Dilute Aqueous Solution.- Studies of Hydrophobic Bonding in Aqueous Alcohols: Enthalpy Measurements and Model Calculations.- Structure in Aqueous Solutions of Nonpolar Solutes from the Standpoint of Scaled-Particle Theory.- Raman Spectra from Partially Deuterated Water and Ice VI to 10.1 kbar at 28°C.- Solvation Equilibria in Very Concentrated Electrolyte Solutions.- Ionic Association in Hydrogen-Bonding Solvents.- The Role of Solvent Structure in Ligand Substitution and Solvent Exchange at Some Divalent Transition-Metal Cations.- N.

The International Association for the Properties of Water and Steam (IAPWS) has produced this book in order to provide an accessible, up-to-date overview of important aspects of the physical chemistry of aqueous systems at high temperatures and pressures. These systems are central to many areas of scientific study and industrial application, including electric power generation, industrial steam systems, hydrothermal processing of materials, geochemistry, and environmental applications. The authors' goal is to present the material at a level that serves both the graduate student seeking to learn the state of the art, and also the industrial engineer or chemist seeking to develop additional expertise or to find the data needed to solve a specific problem. The wide range of people for whom this topic is important provides a challenge. Advanced work in this area is distributed among physical chemists, chemical engineers, geochemists, and other specialists, who may not be aware of parallel work by those outside their own specialty. The particular aspects of high-temperature aqueous physical chemistry of interest to one industry may be irrelevant to another; yet another industry might need the same basic information but in a very different form. To serve all these constituencies, the book includes several chapters that cover the foundational thermophysical properties (such as gas solubility, phase behavior, thermodynamic properties of solutes, and transport properties) that are of interest across numerous applications. The presentation of these topics is intended to be accessible to readers from a variety of backgrounds. Other chapters address fundamental areas of more specialized interest, such as critical phenomena and molecular-level solution structure. Several chapters are more application-oriented, addressing areas such as power-cycle chemistry and hydrothermal synthesis. As befits the variety of interests addressed, some chapters provide more theoretical guidance while others, such as those on acid/base equilibria and the solubilities of metal oxides and hydroxides, emphasize experimental techniques and data analysis.- Covers both the theory and applications of all Hydrothermal solutions - Provides an accessible, up-to-date overview of important aspects of the physical chemistry of aqueous systems at high temperatures and pressures- The presentation of the book is understandable to readers from a variety of backgrounds

This Volume, the last of the series, is devoted to water in its metastable forms, especially at sub-zero temperatures. The past few years have wit nessed an increasing interest in supercooled water and amorphous ice. If the properties of liquid water in the normal temperature range are already eccentric, then they become exceedingly so below the normal freezing point, in the metastable temperature range. Water can be supercooled to -39°C without too much effort, and most of its physical properties show a re markable temperature dependence under these conditions. Although ade quate explanations are still lacking, the time has come to review available knowledge. The study of amorphous ice, that is, the solid formed when water vapor is condensed on a very cold surface, is of longer standing. It has achieved renewed interest because it may serve as a model for the liquid state. There is currently a debate whether or not a close structural relation ship exists between amorphous ice and supercooled water. The nucleation and growth of ice in supercooled water and aqueous solutions is also still one of those grey areas of research, although these topics have received considerable attention from chemists and physicists over the past two decades. Even now, the relationships between degree of supercooling, nucleation kinetics, crystal growth kinetics, cooling rate and solute concentration are somewhat obscure. Nevertheless, at the empirical level much progress has been made, because these topics are of considerable importance to biologists, technologists, atmospheric physicists and gla ciologists.

Covers the fundamental principles of solute partitioning in aqueous two-phase systems, explains their important practical features, and furnishes methods of characterization. The information provided by the partition behaviour of a solute in an aqueous two-phase system is examined.

Sediments in aqueous systems are of increasing interest to academics, researchers, practitioners and stakeholders around the world. This book not only covers the characteristics of the sediments themselves, but also their physico-chemical impact on aquatic habitats and subsequent management implications. There is a strong focus on methods and instrumentation for collecting data and monitoring of environmental sediment quality and as a result, a wide range of environments are considered - from urban areas to freshwater estuaries and marine ecosystems. The chapters have been written by international specialists in the field, ensuring a good breadth of examples, experiences and case studies throughout. This book will appeal to a broad spectrum of interests from geographers, to engineers and environmental scientists, and at undergraduate to post graduate and academic researcher levels.

J.E. Enderby At the last NATO-ASI on liquids held in Corsica, (August 1977),Professor de Gennes, in his summary of that meeting, suggested that the next ASI should concentrate on some specific aspect of the subject and mentioned explicitly ionic solutions as one possibility. The challenge was taken up by Marie-Claire Bellissent-Funel and George Neilson; I am sure that all the participants would wish to congratulate our two colleagues for putting together an outstanding programme of lectures, round tables and poster session. The theory which underlies the subject was covered by four leading authorities: J.-P. Hansen (Paris) set out the general framework in terms of the statistical mechanics of bulk and surface properties; H.L. Friedman (Stony Brook) focused attention on ionic liquids at equilibrium, and J.B. Hubbard considered non-equilibrium properties such as the electrical conductivity and ionic friction coefficients. Finally, the basic theory of polyelectrolytes treated as charged linear polymers in aqueous solution was presented by J.M. Victor (Paris).

Understanding in detail the ion partitioning in mineralwater interactions is of fundamental importance to geochemical studies and ultimately to society. The solid-solution properties of minerals are a significant part of the complexity, and also the importance, of these ion-partitioning reactions.

This book provides a thorough discussion of the thermodynamics of aqueous solutions and presents tools for analyzing and solving scientific and practical problems arising in this area. It also presents methods that can be used to deal with ionic and nonionic aqueous solutions under sub- or supercritical conditions. Illustrations and tables give examples of procedures employed to predict thermodynamic quantities of the solutions, and an appendix summarizing statistical mechanical equations used to describe the systems is also provided. High-Temperature Aqueous Solutions: Thermodynamic Properties contains essential information for physical chemists, geochemists, geophysicists, chemical technicians, and scientists involved in electric power generation.

The chapters making up this volume had originally been planned to form part of a single volume covering solid hydrates and aqueous solutions of simple molecules and ions. However, during the preparation of the manu scripts it became apparent that such a volume would turn out to be very unwieldy and I reluctantly decided to recommend the publication of sepa rate volumes. The most sensible way of dividing the subject matter seemed to lie in the separation of simple ionic solutions. The emphasis in the present volume is placed on ion-solvent effects, since a number of excellent texts cover the more general aspects of electrolyte solutions, based on the classical theories of Debye, Huckel, On sager, and Fuoss. It is interesting to speculate as to when a theory becomes "classical." Perhaps this occurs when it has become well known, well liked, and much adapted. The above-mentioned theories of ionic equilibria and transport certainly fulfill these criteria. There comes a time when the refinements and modifications can no longer be related to physical significance and can no longer hide the fact that certain fundamental assumptions made in the development of the theory are untenable, especially in the light of information obtained from the application of sophisticated molecular and thermodynamic techniques.

vi the information collected and discussed in this volume may help toward the achievement of such an objective. I should like to express my debt of gratitude to the authors who have contributed to this volume. Editing a work of this nature can strain long established personal relationships and I thank my various colleagues for bearing with me and responding (sooner or later) to one or several letters or telephone calls. My special thanks once again go to Mrs. Joyce Johnson, who bore the main brunt of this seemingly endless correspondence and without whose help the editorial and referencing work would have taken several years. F. FRANKS Biophysics Division Unilever Research Laboratory Colworth/ Welwyn Colworth House, Sharnbrook, Bedford January, 1973 Contents Contents of Volume 1 ............................. . . . . . .. . . .. xv Contents of Volume 3 ........................ '. . . . . . . . . . . . xvi . . . . Contents of Volume 4 . . . . . . . . . . . . . . . . . . . . . . . . .. . . . xvii . . . . . . . . . . . Chapter 1 The Solvent Properties of Water F. Franks 1. Water, the Universal Solvent-the Study of Aqueous Solutions 2. Aqueous Solutions of Nonelectrolytes ................. . 5 2.1. Apolar Solutes ................................. . 6 2.2. Polar Solutes .................................. . 19 2.3. Ionic Solutes Containing Alkyl Residues-"Apolar Electrolytes" ................................... . 38 3. Aqueous Solutions of Electrolytes .................... . 42 3.1. Single Ion Properties ............................ . 42 3.2. Ion-Water Interactions ......................... . 43 3.3. Interionic Effects ............................... . 47 4. Complex Aqueous Mixtures 48 Chapter 2 Water in Stoichiometric Hydrates M. Falk and O. Knop 1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55 . . . . . . . . . . . . . 2. Symmetry and Types of Environment of the H0 Molecule 2 in Crystals .......................................... 57 vii Contents viii 2.1. Site Symmetry. . . . . . . . . . . . . . . . . . . . . . . . . 57 . . . . . . . . . .