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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.
An Introduction to Aqueous Electrolyte Solutions is a comprehensive coverage of the subject including the development of key concepts and theory that focus on the physical rather than the mathematical aspects. Important links are made between the study of electrolyte solutions and other branches of chemistry, biology, and biochemistry, making it a useful cross-reference tool for students studying this important area of electrochemistry. Carefully developed throughout, each chapter includes intended learning outcomes and worked problems and examples to encourage student understanding of this multidisciplinary subject. * a comprehensive introduction to aqueous electrolyte solutions including the development of key concepts and theories * emphasises the connection between observable macroscopic experimental properties and interpretations made at the molecular level * key developments in concepts and theory explained in a descriptive manner to encourage student understanding * includes worked problems and examples throughout An invaluable text for students taking courses in chemistry and chemical engineering, this book will also be useful for biology, biochemistry and biophysics students required to study electrochemistry.
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 . . . . . . . . . .
Surface tension provides a thermodynamic avenue for analyzing systems in equilibrium and formulating phenomenological explanations for the behavior of constituent molecules in the surface region. While there are extensive experimental observations and established ideas regarding desorption of ions from the surfaces of aqueous salt solutions, a more successful discussion of the theory has recently emerged, which allows the quantitative calculation of the distribution of ions in the surface region. Surface Tension and Related Thermodynamic Quantities of Aqueous Electrolyte Solutions provides a detailed and systematic analysis of the properties of ions at the air/water interface. Unifying older and newer theories and measurements, this book emphasizes the contributions of simple ions to surface tension behavior, and the practical consequences. It begins with a general discussion on Gibbs surface thermodynamics, offering a guide to his theoretical insight and formulation of the boundary between fluids. The text then discusses the thermodynamic formulae that are useful for practical experimental work in the analysis of fluid/fluid interfaces. Chapters cover surface tension of pure water at air/water and air/oil interfaces, surface tension of solutions and the thermodynamic quantities associated with the adsorption and desorption of solutes, and surface tension of simple salt solutions. They also address adsorption of ions at the air/water interface, surface tension of solutions and the effect of temperature, adsorption from mixed electrolyte solutions, and thermodynamic properties of zwitterionic amino acids in the surface region. Focusing on the thermodynamic properties of ions at air/fluid interfaces, this book gives scientists a quantitative, rigorous, and objectively experimental methodology they can employ in their research.
Inorganic Chemistry in Aqueous Solution reviews the chemistry of the elements in all their oxidation states in an aqueous environment. The nature of ions in solution is described in some detail and enthalpies and entropies of hydration of many ions are defined and recalculated from the best data available. These values are used to provide an understanding of the periodicities of standard reduction potentials. Standard reduction potential data for all of the elements, group-by-group, covering the s and p, d and f blocks of the Periodic Table is also included. Major sections are devoted to the acid/base behaviour and the solubilities of inorganic compounds in water. Inorganic Chemistry in Aqueous Solution is aimed at undergraduate chemistry students but will also be welcomed by geologists interested in this field. Ideal for the needs of undergraduate chemistry students, Tutorial Chemistry Texts is a major series consisting of short, single topic or modular texts concentrating on the fundamental areas of chemistry taught in undergraduate science courses. Each book provides a concise account of the basic principles underlying a given subject, embodying an independent-learning philosophy and including worked examples.
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.
Ionic Surfactants and Aqueous Solutions: Biomolecules, Metals and Nanoparticles covers a wide range of subjects related to aqueous systems, from reverse micelles as ion exchangers to the study of micellar phase transfer catalysis for nucleophilic substitution reactions. The diverse background, expertise and professional interests of the contributors to this book give to it a unique richness of approach in topics of relevance for biotechnology and environmental studies. Over sixty publications presenting research results are combined and expanded in this book by some of the original researchers. At a mature age, and at the summit of successful professional careers, they have taken a second look to the state of the art in the fields that they had pioneered. Eva Rodil and Ana Soto, who had their research formation in the group of Professor Alberto Arce at Universidade de Santiago de Compostela, Spain, are presently professors at that university, Maen Husein is a professor at University of Calgary, Canada. Remy Dumortier, Mohammad Khoshkbarchi, Hamid Rabie and Younok Dumortier Shin, are presently active leaders in the industrial world in Canada and the USA. The editors are retired academics from McGill University, Montreal, Canada, and coauthors of the book Classical Thermodynamics of Fluid Systems.
Expertise in electrolyte systems has become increasingly important in traditional CPI operations, as well as in oil/gas exploration and production. This book is the source for predicting electrolyte systems behavior, an indispensable "do-it-yourself" guide, with a blueprint for formulating predictive mathematical electrolyte models, recommended tabular values to use in these models, and annotated bibliographies. The final chapter is a general recipe for formulating complete predictive models for electrolytes, along with a series of worked illustrative examples. It can serve as a useful research and application tool for the practicing process engineer, and as a textbook for the chemical engineering student.
Although several monographs and reviews have appeared on individual polymers of this type, and their applications and other technical aspects have also been discussed, this is apparently the first book to deal with the physical chemistry of water-soluble synthetic polymers as a group. This collective survey enables their properties and behaviour to be compared, and to be correlated with their molecular structures for predictive purposes. However, this has made it necessary to critically re-appraise much of the earlier fundamental work, so that current discussion of more recent work can be put on ta proper basis. Thus, of the 1800 or so references cited, the middle two-thirds related to the twenty-year period centred on about 1968. Nevertheless, sufficient key recent references have also been included so that the existing ‘state of the art is delineated.