Dissertation committee:
Theodore Arabatzis, Professor, University of Athens
Aristotle Tympas, Professor, University of Athens
Stathis Arapostathis, Assistant Professor, University of Athens
Andreas Koutselos, Professor, University of Athens
Efthymios P. Bokaris, Associate Professor, University of Ioannina Efthymios Nicolaidis, Research Director, National Hellenic Research Foundation
Kostas Tampakis, Associate Researcher, National Hellenic Research Foundation
Summary:
The first volume of the Zeitschrift für Physikalische Chemie appeared with important articles by van t 'Hoff, Ostwald and Svante Arrhenius. Their publications in the journal, founded in 1887 by Ostwald and van ‘t Hoff, formed the theoretical basis of the new science of chemical thermodynamics.. Their papers constituted the theoretical basis of the new science of chemical thermodynamics. They succeeded to introduce thermodynamics into chemistry and provide the new science with a comprehensive theory of solutions based on the osmotic pressure and the dissociation of the electrolytes in solutions. The latter theory was the cause for their sobriquet “the ionists”. As in every science, the formulation of chemical thermodynamics presupposes the development and integration of a specific scientific background of theories and experimentation that preceded and made available to the ionists. This dissertation deals with the development of chemistry and thermodynamics in earlier years before the advent of the ionists’ theories. Chemical thermodynamics has deeper roots that go back to the works of the natural philosophers of the eighteenth and early nineteenth centuries.
The first part of this dissertation deals with the history of chemical thermodynamics during the first half of the nineteenth century. This period, which could be characterized as the prehistory of chemical thermodynamics, or else, the period of classical chemical thermodynamics. This part contains the endeavors of the natural philosophers to understand the formation and decomposition of substances. The natures of forces that bind the particles together or make them fall apart. In short, they sought to find explanations for the chemical affinity. The discovery of the effect of concentration of substances on chemical affinity by Claude Berthollet in the early nineteenth century posed new questions for the philosophers. This time, about the equilibrium conditions in chemical reactions. The discovery of the electric battery by Volta in 1799 and the study of the phenomenon of electrolysis lead prominent natural philosophers, such as Davy, Grotthus, Faraday, Ohm, Becquerel, and others to search for the causes of the decomposition of substances (chemical affinity) and the mechanism of propagation of electricity in liquid conductors. During the period 1830-1850, twelve natural philosophers discovered simultaneously the first law of thermodynamics. In the decade 1850, three eminent physicists Rudolf Clausius, William Rankine, and William Thomson (Lord Kelvin) enunciated the second law of thermodynamics. Chemists understood only the first law and used it in their laboratory signaling the beginning of a new branch of chemistry, thermochemistry. The first part of the dissertation concludes with a brief description of the evolution of the law of conservation of energy in the context of chemistry and physiology.
The second part of this dissertation describes the evolution of chemical thermodynamics at a higher level of development. During this period, fragmentary and unconnected theories and experiments of the first half of the nineteenth century began to systematize and integrate complex systems, both in electrochemistry and thermodynamics. Chemical thermodynamics benefited greatly from several scientific developments. First, the experimental methods, the innovative instrumentation, and the plethora of experimental results by two great electrochemists, Wilhelm Hittorf and Friedrich Kohlrausch. Second, the discovery of the battery of constant current intensity by John Daniell and William Grove. This innovation improved significantly the accuracy of electrochemical measurements. Third, the theoretical elaboration of the phenomenon of electrolysis and polarization of the electrodes by Rudolf Clausius and Herman von Helmholtz, respectively. Fourth, the advanced approaches to the thermodynamic theory developed by Josiah Willard Gibbs, Pierre Duhem, and Helmholtz.
Hittorf measured the relative velocity of the ions (anion and cation) of the electrolyte and their transference numbers (percentage of charge that each ion transfers in solution), whereas Kohlrausch employed electrical conductivity to quantitate the ability of electrolytic solutions to conduct electricity. From the multitude of measurements of the electrical conductivity of solutions of acids, bases, and salts, he derived the two laws of the electrolyte solutions. Also, during the second half of the nineteenth century, Helmholtz proposed his electrical double-layer as an effective theoretical model that explained the origin of the electrode polarization.
Josiah Willard Gibbs and Pierre Duhem were two physicists, whose thermodynamics had a major impact on the development of chemical thermodynamics, especially after the nineteenth century. The two scientists followed a different path from the molecular mechanics of Maxwell and Boltzmann. They also showed differences in their theoretical approaches to thermodynamics. Gibbs examined the stability (or instability) of equilibrium states in homogeneous and heterogeneous multi-component systems, while Pierre Duhem aimed at integrating thermodynamics with the principles of rational mechanics. He attempted to give a dynamic character to thermodynamics using the analytical mechanics of Lagrange. He believed that Lagrasian mechanics was the proper means to introduce time into thermodynamics. It deserves to emphasize Duhem’s relentless attempts to unify physics with chemistry, two sciences, which developed in parallel for almost the entire 19th century. The second part of this thesis involves an extensive analysis of their work in thermodynamics and ends with a thorough examination of the impact of Gibbs and Duhem’s thermodynamic approaches on the development of chemical thermodynamics.
The third part of this dissertation begins with the consideration of the various internal and external factors that influenced the development of chemical thermodynamics in Europe during the 19th century. The analysis of these factors led to a parallel investigation of the conditions that paved the way for the emergence of a new technological branch of chemistry, chemical engineering. The penetration of thermodynamics into chemistry, which marks the birth of modern chemical thermodynamics, is the subject of the next three chapters of the third part. During the last two decades of the nineteenth century, the three ionists, Arrhenius, van 't Hoff, and Ostwald succeeded to integrate various uncorrelated studies and presented a compact theoretical and experimental whole, which constituted their theory of solutions. The thesis describes the programs chosen by each ionist, his methodological approaches and interpretations, the experimental methods he used, the influences from his immediate and international scientific environment, and the cultural and scientific traditions of his country. In the same chapter, a brief account was given of the contribution to ionists’ chemical thermodynamics by Ostwald's collaborator, Walther Nernst, as well as the theoretical elaboration of the theory of solutions by Max Planck. The thesis examines the way the ionists communicated their results to the scientific community and each other, and their struggle to defend their theory of solutions, and in particular the electrolytic dissociation theory of Arrhenius, against the strong opposition and sometimes hostile criticism, especially from the British organic chemists.
The last chapter of this dissertation examines some aspects of the transfer and the development of chemical thermodynamics in America during the first two to three decades of the twentieth century. It is known that this transfer was realized by the American chemists, who trained in Germany, and in particular in Ostwald’s laboratory at Leipzig. When the first generation of American chemists returned to America, strove to establish a new science. However, American chemists were not mere carriers of the ionists’ theories, but they appropriated this knowledge. Except Bancroft, who adopted a research program based exclusively on Gibbs’ phase rule, most American chemists set forth research programs to investigate the anomalies of the ionists’ theory, for example, the abnormal behavior of strong electrolytes. One of the most interesting figures of the first generation of American chemists was Gilbert Newton Lewis, whose personality and research program serve as a case study in this dissertation.
Keywords:
thermodynamics, chemistry, physics, electrochemistry, chemical kinetics, chemical engineering, chemical affinity, chemical equilibrium, first and the second law of thermodynamics, ionic mobility, transference number, electrical conductivity, electrode polarization, potentials, phase rule, rational thermodynamics, ionic theory of dissociations, osmotic pressure, strong electrolytes, fugacity, activity, activity coefficient, ionic strength, free energy
