Julius Thomsen and classical thermochemistry

The British Journal for the History of Science (Impact Factor: 0.4). 10/1984; 17(03):255 - 272. DOI: 10.1017/S0007087400021294

ABSTRACT Classical thermochemistry is inextricably bound up with the problem of chemical affinity. In 1851, when Julius Thomsen began his career in thermochemistry, the concept of chemical affinity had been in the centre of chemical enquiry for more than a century. In spite of many suggestions, preferably to explain affinity in terms of electrical or gravitational forces, almost nothing was known about the cause and nature of affinity. In this state of puzzling uncertainty some chemists felt it more advantageous to establish an adequate experimental measure of affinity, whatever its nature was. One way of providing affinity with a quantitative description was by means of the heats evolved in chemical processes.

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    Ninth International History Philosophy & Science Teaching Conference, Calgary. Canada; 06/2007
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    ABSTRACT: The first systematic studies on the velocity of chemical reactions (now called reaction rates) were published in the 1850s and 1860s. Inquiring about the course of chemical change, their authors established empirical equations on the basis of their measurement results. But these laws, which represented reaction velocities as proportional to the actual concentration of the reagents, could not be given a physical foundation. The chemists themselves regarded their propositions as mere ad hoc hypotheses. In 1867 Leopold Pfaundler formulated a qualitative theory of chemical processes based on Clausius's version of the kinetic gas theory (and more specifically on his theory of evaporation), and on Saint-Claire Deville's investigations of dissociation processes. Pfaundler's theory was based on farreaching analogies: between evaporation and dissociation; between the gaseous state and the activated state; and between evaporation- and chemical-equilibrium. Four points of Pfaundler's theory must be regarded as essential: (1) the reduction of chemical change to randomly occurring molecular collisions, only showing regularities in great numbers according to the laws of probability; (2) the idea that molecules are in different states of internal and external motion, which determines whether a collision results in a reaction; (3) the view of the reaction step as a transition from internal to external motion and vice versa; and (4) the introduction of a new molecular-kinetic definition of chemical affinity as the maximum of internal motion. With these assumptions, Pfaundler provided the empirical rate equations with a new statistical interpretation and a physical Justification.
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