Walther Nernst

Walther Nernst (born June 25, 1864, Briesen, Prussia [now Wąbrzeźno, Poland]—died November 18, 1941, Zibelle, Germany [now Niwica, Poland]) was a German scientist who was one of the founders of modern physical chemistry. His theoretical and experimental work in chemistry, including his formulation of the heat theorem, known as the third law of thermodynamics, gained him the 1920 Nobel Prize for Chemistry.

Education

Nernst was educated at the University of Zürich in Switzerland, the University of Graz in Austria, and then in Germany at the University of Berlin before earning his doctorate in 1887 from the University of Würzburg. After graduation, he became an assistant to Wilhelm Ostwald, who, with his colleagues at the University of Leipzig, Jacobus van’t Hoff and Svante Arrhenius, was establishing the foundations of a new theoretical and experimental field of inquiry within chemistry. Through their joint investigations of phenomena in solutions, in particular the transport of electricity and matter, these investigators, who became collectively known as the Ioner (Ionists), not only obtained important new insights into chemical reactions but also established the independence of what became known as modern physical chemistry.

Early research

In Leipzig, Nernst devoted himself to the calculation of the diffusion coefficient of electrolytes for infinitely dilute solutions and to the establishment of a relationship between ionic mobility, diffusion coefficients, and the electromotive force in concentration cells. He developed this work more fully in his habilitation (university teaching certificate) thesis of 1889, in which he established a fundamental connection between thermodynamics and electrochemical solution theory (the Nernst equation). As a result, he was appointed associate professor at the University of Göttingen in 1891. During his early years there, Nernst published an important textbook, Theoretische Chemie vom Standpunkte der Avogadroschen Regel und der Thermodynamik (1893; Experimental and Theoretical Applications of Thermodynamics to Chemistry), in which he stressed the central importance of Avogadro’s law, thermodynamics, and both physics and chemistry in the treatment of chemical processes.

In 1894 Nernst was offered academic positions in Munich and Giessen. Instead, he obtained a chair of physical chemistry at the newly created Institute for Physical Chemistry and Electrochemistry in Göttingen (the only such institute in Germany at the time), where he launched an ambitious research program into chemical equilibria, solution theory, osmotic pressure, and electrochemistry.

Significantly, the years in Göttingen were also devoted to the development of a novel electric lightbulb. Immersed in both chemistry and electrotechnology, Nernst spent a decade of intensive research into improving the incandescent lamp. He found that a mixture of zirconium oxide and yttrium oxide became an electric conductor at higher temperatures, emitting a brilliant white light when employed as a filament. In 1897 he began work on the electric lightbulb, for which he obtained numerous patents in Europe and the United States. The Nernst lamp was manufactured for several years by Allgemeine Elektrizitätsgesellschaft (AEG) in Berlin, and thousands of Nernst lamps decorated a specially constructed German pavilion at the 1900 Paris International Exhibition. Nernst’s work on a number of similar dielectric bulbs and his research on metal filaments greatly spurred the development of modern conventional lightbulbs. Although his own designs, which required a preheating mechanism, had only short-lived and limited success, his “Nernst glower,” or “Nernst globar,” has survived as an important instrument in time-resolved infrared spectrophotometry.

Third law of thermodynamics

In 1905 Nernst was appointed professor and director of the Second Chemical Institute at the University of Berlin and a permanent member of the Prussian Academy of Sciences. The next year he announced his heat theorem, or third law of thermodynamics. Simply stated, the law postulates that the entropy (energy unavailable to perform work and a measure of molecular disorder) of any closed system tends to zero as its temperature approaches absolute zero (−273.15 °C, or −459.67 °F). In practical terms, this theorem implies the impossibility of attaining absolute zero, since as a system approaches absolute zero, the further extraction of energy from that system becomes more and more difficult. Modern science has attained temperatures less than a billionth of a degree above absolute zero, but absolute zero itself can never be reached.

The calculation of chemical equilibria from thermal measurements (such as heats of reaction, specific heats, and their thermal coefficients) had been an elusive goal for many of Nernst’s predecessors. It had been hoped that the direction of a chemical reaction and the conditions under which equilibrium is attained could be calculated only on the basis of the first two laws of thermodynamics and thermal measurements. These calculations had been hampered, however, by the indeterminate integration constant J, which obtained when integrating the Gibbs-Helmholtz equation relating the free energy change ΔF to the heat content change ΔH and the entropy change ΔS, ΔF = ΔH − TΔS.

Nernst’s great achievement was to recognize the special behavior of ΔF and ΔH as functions of the change in temperature in the vicinity of absolute zero. From the empirical data, Nernst hypothesized that, as they approach absolute zero, the two curves F and H become asymptotically tangent to each other—that is to say, in the vicinity of absolute zero, ΔF − ΔH → 0 (the difference approaches zero). From this form of the Gibbs-Helmholtz equation, it was then possible to calculate the integration constant on the basis of calorimetric measurements carried out in the laboratory.

Originally, Nernst’s heat theorem strictly applied only to condensed phases, such as solids. However, Nernst proceeded to extrapolate the validity of his theorem to gaseous systems. For this purpose, he embarked on a series of difficult and time-consuming experiments at low temperatures, where gaseous substances could be considered to be in a condensed phase. Between 1905 and 1914, Nernst and his many students and collaborators in Berlin designed a number of ingenious instruments, such as a hydrogen liquefier, thermometers, and calorimeters. These were used for the determination of specific heats for a series of substances. In a paper published in 1907, Albert Einstein had shown that the new theory of quantum mechanics, developed initially by the German theoretical physicist Max Planck in 1900, predicts that, in the vicinity of absolute zero temperature, the specific heats of all solids tend toward absolute zero. Thus, Nernst’s heat theorem and his empirical results reinforced the revolutionary quantum theory; conversely, Nernst felt that Einstein’s and Planck’s work confirmed his Wärmetheorem and established it, conceivably, as a new, third law of thermodynamics, despite the fact that it could not be deduced from the other two laws. As a result, Nernst became one of the earliest wholehearted supporters of Einstein and quantum mechanics. In particular, Nernst was instrumental in organizing the First Solvay Congress in Physics, held in Brussels in November 1911, which was devoted to a thorough evaluation of the new quantum hypothesis by a group of leading European physicists.

Later years

Nernst was engaged in military and administrative efforts, including chemical warfare research, during World War I, in which his two sons were killed. Following the war, he returned to academic life and engaged in myriad pursuits, among them studying photosynthesis, astrophysics, and cosmology and constructing an electronic piano with loudspeaker amplification, called the Neo-Bechsteinflügel.

Nernst was the chair of the physical chemistry department at the University of Berlin from 1905, the school’s rector from 1921, and the director of the school’s Institute for Experimental Physics from its founding in 1924, until his retirement in 1933. Between 1922 and 1924, Nernst was president of the German national bureau of physical standards.