Calorimetry is the art of measuring the heat effects involved in chemical, physical or biological processes. The devices used for the quantitative determination of the heat effects are the so-called calorimeters. The origins of Calorimetry date back to the eighteenth century, almost 200 years later than the modern principles of thermometry were established by Galileu Galilei (1564–1642). After the work and attempts of different scientists to define and establish a heat unit, it was the Swedish researcher M. Wilke who attempted to establish the measurement methods and to determine a heat unit in 1772. Soon after, in 13th June 1780, in a meeting at the French Academy, A. L. Lavoisier and P. S. Laplace, on their lecture Memoire sur la chaleur, presented the first ice calorimeter. They were the first scientists to call the device for measuring heat a calorimeter. These scientists used the original calorimeter and modified versions of it, to measure heats of combustion, heats of respiration, and specific heats. These are the first reported works on the energy changes of chemical reactions and so the period of 1780–1840, in which Lavoisier, Laplace, and Hess made the first measurements of heats of reaction, is considered the beginning of Thermochemistry, being calorimetry the oldest experimental technique for investigating the thermodynamics of chemical reactions. By 1840, Hess has established his Law, that the heat exchanged (evolved or absorbed) depends only of the initial and final states of the reaction being independent of the number of intermediate steps, which could either be postulated or observed. This Law is the basis of Thermochemistry and is in accord with the First Law of Thermodynamics, which was first formulated by Helmholtz only in 1847. In the later half of the nineteenth century, extensive studies on thermochemistry were made by Thomsen (1851– 1885) in Copenhagen and by Berthelot (1881–1905), at the College de France, in Paris, who were motivated by the mistaken idea that the driving force of a chemical reaction lay in the heat of reaction. With the realization, near the turn of the nineteenth century, that entropy changes must also to be considered as a component of the driving force of reaction, the impetus of this work declined and the classical period of thermochemistry ended. Notwithstanding the great improvement verified in the period of 1900–1930 on the design and development of combustion bombs with the prominent work of some distinguished scientists like Dickinson who published his classic paper on the procedures, apparatus, and calculations in combustion calorimetry, and the work of T. W. Richards and collaborators for the significant development and M. A. V. Ribeiro da Silva (&) Centro de Investigacao em Quimica, Faculty of Science, University of Porto, Porto, Portugal e-mail: risilva@fc.up.pt Guest Editor
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Dec 28, 2010
Michael Pepper 
Open Access
