to arrive at some temporary consensus model or models; and to present reliable physical data pertaining to water under a range of conditions, i.e., "Dorsey revisited," albeit on a less ambitious scale. I should like to acknowledge a debt of gratitude to several of my col leagues, to Prof. D. J. G. Ives and Prof. Robert L. Kay for valuable guidance and active encouragement, to the contributors to this volume for their willing cooperation, and to my wife and daughters for the understanding shown to a husband and father who hid in his study for many an evening. My very special thanks go to Mrs. Joyce Johnson, who did all the cor respondence and much of the arduous editorial work with her usual cheerful efficiency. F. FRANKS Biophysics Division Unilever Research Laboratory ColworthjWelwyn Colworth House, Sharnbrook, Bedford March 1972 Contents Chapter 1 Introduction-Water, the Unique Chemical F. Franks I. lntroduction ........................................ . 2. The Occurrence and Distribution of Water on the Earth 2 3. Water and Life ...................................... 4 4. The Scientific Study of Water-A Short History ........ 8 5. The Place of Water among Liquids . . . . . . . . . . . . . . . 13 . . . . . Chapter 2 The Water Moleeule C. W. Kern and M. Karplus 1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 . . . . . . . . . . 2. Principles of Structure and Spectra: The Born-Oppenheimer Separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 . . . . . . . . . . . . 3. The Electronic Motion ............................... 26 3.1. The Ground Electronic State of Water ............ 31 3.2. The Excited Electronic States of Water ........... 50 4. The Nuclear Motion ................................. 52 5. External-Field Effects ................................. 70 5.1. Perturbed Hartree-Fock Method . . . . . . . . . . . . . . . 74 . . .

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.

For many processes and applications in science and technology a basic knowledge of liquids and solutions is a must. Gaining a better understanding of the behavior and properties of pure liquids and solutions will help to improve many processes and to advance research in many different areas. This book provides a comprehensive, self-contained and integrated survey of this topic and is a must-have for many chemists, chemical engineers and material scientists, ranging from newcomers in the field to more experienced researchers. The author offers a clear, well-structured didactic approach and provides an overview of the most important types of liquids and solutions. Special topics include chemical reactions, surfaces and phase transitions. Suitable both for introductory as well as intermediate level as more advanced parts are clearly marked. Includes also problems and solutions.

Chemical Oceanography, Third Edition, is a survey of essential concepts that contains a wealth of new data and maps, resulting in a more in-depth examination of oceanic biogeochemical processes. The most up-to-date compilation of essential concepts and data available on the subject, this book responds to the need for a thorough, yet straightforward approach to the subject for students, researchers, and other professionals in marine science, geochemistry, and environmental chemistry. The third edition of Chemical Oceanography incorporates significant findings on the properties of oceans from recent, large-scale oceanographic programs and valuable new data derived from additional experiments. It also discusses the interactions of metals with inorganic and natural organic ligands and the effect of speciation of metals on bioavailability and toxicity. The section on carbonate systems now examines the input of fossil fuel CO2 into the ocean and its effect on the pH of the world oceans. Frank J. Millero, a world-renowned marine researcher and professor of undergraduate and graduate courses at the University of Miami for nearly 40 years, presents a time-tested and user-friendly resource specifically designed for both classroom use and self-study.

Over the past ten years, a number of new large-scale oceanographic programs have been initiated. These include the Climate Variability Program (CLIVAR) and the recent initiation of the Geochemical Trace Metal Program (GEOTRACES). These studies and future projects will produce a wealth of information on the biogeochemistry of the world's oceans. Aut

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.