Jacobus Henricus van ’t Hoff

Jacobus Henricus van ’t Hoff (born Aug. 30, 1852, Rotterdam, Neth.—died March 1, 1911, Berlin, Ger.) was a Dutch physical chemist and the first winner of the Nobel Prize for Chemistry (1901), for his work on rates of chemical reaction, chemical equilibrium, and osmotic pressure.

Education and early career

Van ’t Hoff was the son of a physician and among the first generation to benefit from the extensive Dutch education reforms of the 1860s. He attended the newly formed Hoogere Burgerschool (High School) in Rotterdam. These new schools emphasized the study of mathematics and science to prepare students for a career in the growing industrial economy of the Netherlands. Beginning in 1869, van ’t Hoff studied chemistry at the Technical University in Delft and mathematics and physics at the University of Leiden before traveling to Germany to study chemistry with August Kekule at the University of Bonn and then France to study chemistry with Charles-Adolphe Wurtz at the École de Medicine. He finally returned to the University of Utrecht to complete his doctoral dissertation in 1874.

Before he completed his dissertation, van ’t Hoff published an 11-page pamphlet in which he proposed that if the four bonds (or valence electrons) of the carbon atom pointed toward the corners of a tetrahedron, it would explain some puzzling cases of isomerism and also explain why solutions of certain chemical compounds would rotate a plane of polarized light. His theory is today one of the fundamental concepts in organic chemistry and the foundation of stereochemistry, or the study of the three-dimensional properties of molecules. This idea was also published independently, in a slightly different form, by the French chemist Joseph Achilles Le Bel, whom van ’t Hoff had met during his stay in Wurtz’s laboratory earlier in the year.

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Despite this innovative pamphlet, van ’t Hoff’s future in science was uncertain until he was appointed in 1876 to a new position lecturing chemistry and physics at the Imperial Veterinary College in Utrecht. In 1878 he was appointed professor of chemistry, mineralogy, and geology at the newly created University of Amsterdam.

Birth of physical chemistry

In the late 1870s, van ’t Hoff turned away from organic chemistry and became interested in explaining why various chemical reactions occur at widely different rates. In 1884 he published the innovative book Études de dynamique chimique (“Studies in Chemical Dynamics”), in which he used the principles of thermodynamics to provide a mathematical model for the rates of chemical reactions based on the changes in the concentration of reactants with time. In the Études, van ’t Hoff showed how the previously independently developed concepts of dynamic equilibrium (that chemical equilibrium results when the rates of forward and reverse reactions are equal), the law of mass action (that the concentration of substances affects the rate of reaction), and the equilibrium constant (the ratio of the concentrations of starting materials to products at equilibrium) together formed a coherent model for understanding the nature of chemical reactions. Finally, he showed mathematically how temperature, pressure, and mass affected the rate of chemical reactions and how the heat generated by a reaction could be calculated from the mathematical equation governing the final equilibrium state. This relationship between heats of reaction and equilibrium allowed van ’t Hoff to define chemical “affinity,” an old concept in the history of chemistry that had been difficult to define in terms of its effects, specifically the amount of work that a reversible chemical reaction could perform.

One of the central assumptions van ’t Hoff made in the Études was that the behaviours of gases and solutions were analogous, and in a series of papers published in 1886 and 1887 he set out to justify that assumption by modeling the behaviour of dilute solutions, using the principles of thermodynamics. He showed that osmotic pressure, the tendency of a pure solvent to cross a semipermeable membrane to dilute a solution on the opposite side, was directly proportional to the concentration of the solution and could be modeled by the same equation (the perfect gas law) that governed the behaviour of ideal gases.

In 1887 van ’t Hoff and the German chemist Wilhelm Ostwald founded the Zeitschrift für physikalische Chemie (“Journal of Physical Chemistry”) as a forum for the new physical chemistry based on thermodynamics that he, Ostwald, and the Swedish chemist Svante Arrhenius had created during the 1880s. On the basis of his innovative and successful treatment of chemical affinity, van ’t Hoff was awarded the first Nobel Prize for Chemistry in 1901.

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Van ’t Hoff accepted an appointment in 1896 to the Academy of Sciences in Berlin, where he turned to another problem in chemical equilibrium—the conditions under which salt deposits are formed in the ocean, specifically the salt deposits at Stassfurt, Ger. In order to understand the conditions behind the precipitation of salts, van ’t Hoff modeled the deposition process as an equilibrium between the solution and solid phases of the components in water at a constant temperature. This work was published in 1905 and 1909 as the two-volume Zur Bildung der ozeanischen Salzablagerungen (“On the Formation of Oceanic Salt Deposits”). Van ’t Hoff died in 1911 of pulmonary tuberculosis shortly after completing this work.