The Physical Chemistry of Electrolytic Solutions [antikvár]

Preface The science of solutions is very complex. It has evolved its own numerous experimental methods, and has required for its clarification many branches of mathematical physics, such as thermodynamics, statistical mechanics, electrostatics, and hydrodynamics. A great deal has been achieved by theory, but this achievement has been by no means enough to warrant the neglect of further experimental investigation. In writing this treatise on electrolytic solutions, we have tried to stress the importance of theory without neglecting that part of the subject which is empirical. At the same time, we have not hesitated to state the limitations of theory, or to criticize the accuracy of experimental data. We trust that the result approaches a well-balanced treatment, and hope that many of our readers will become aware of the many parts of the subject which are obscure, and which require further constructive effort. If we succeed in suggesting new and profitable fields of study to them, we shall be greatly repaid for our labor. Although many of the important fundamental principles of electrochemistry had been discovered in the last decades of the eighteenth century and the first eighty years of the nineteenth century, it was not until 1887 that an organized theoretical and experimental investigation of conducting solutions was begun. This was brought about by the monumental discovery of van't Hoff^ that solutions which readily conduct electric current possess freezing points, boiling points, osmotic pressures, and vapor pressures characteristic of a special class of systems, and the simultaneous and even more important discovery of Arrhenius^ that such systems contain electrically charged particles, or ions. It was van't Hoff who first applied the powerful methods of thermodynamics to solutions in a systematic manner. His treatment, however, lacked the generality which might have been achieved at that time if the system of thermodynamics developed by Gibbs' ten years earlier had been employed. Gibbs' great treatise provides all the essential basic principles required for the thermodynamics of solutions. The most important contribution of thermodynamics has been to reduce all measurements of systems in equilibrium to the determination of a single thermodynamic function. > J. H. van't Hoff, Z. physik. Chem., 1. 481 (1887). « S. Arrhenius, Z. physik. Chem., 1, 631 (1887). ' J. W. Gibbs, Transactions of Connecticut Academy of Sciences, 2, 309, 382 (1873) ; 3, 108, 343 (1875-1878). "Scientific Papers of J. Willard Gibbs," Vol. I, New York, Longmans, Green and Co., 1906. "The Collected Work of J. Willard Gibbs," Vol. I, New York, Longmans, Green and Co., 1928. ' II