Long after its alleged demise, phlogiston was still presented, discussed and defended by leading chemists. Even some of the leading proponents of the new chemistry admitted its ‘absolute existence’. We demonstrate that what was defended under the title ‘phlogiston’ was no longer a particular hypothesis about combustion and respiration. Rather, it was a set of ontological and epistemological assumptions and the empirical practices associated with them. Lavoisier's gravimetric reduction, in the eyes of the phlogistians, annihilated the autonomy of chemistry together (...) with its peculiar concepts of chemical substance and quality, chemical process and chemical affinity. The defence of phlogiston was the defence of a distinctly chemical conception of matter and its appearances, a conception which reflected the chemist's acquaintance with details and particularities of substances, properties and processes and his skills of adducing causal relations from the interplay between their complexity and uniformity. (shrink)

In this paper it is performed a historical account of the theoretical roots that grounded the following four key basic ideas of chemical equilibrium: ‘incomplete reaction’, ‘reversibility’, ‘equilibrium constant’ and ‘molecular dynamics’. These notions developed in nineteenth-century as a consequence of the evolution of the concept of chemical affinity. The discussion begins with the presentation of the earliest affinity table [‘Table des rapports’] published in 1718 by Geoffroy. Afterwards, it is examined Bergman’s compilation. The theory supporting this arrangement assumed that (...) chemical displacement reactions were complete and could not be reversed. It is analysed how Berthollet’s model showed the inadequacy of this view. His new conceptual considerations established that the amount of the substances involved in a reaction was an essential factor determining its direction, which accounted for the early concepts of incomplete reaction and reversibility. Guldberg and Waage specified the role of mass in chemical equilibrium reactions as they considered the concentrations of the chemicals involved, formulating the first chemical equilibrium mathematical equation that approximates what is called nowadays chemical equilibrium constant. Finally, it is presented how Pfaundler was the first to consider the kinetic theory in the interpretation of the macroscopic properties of equilibrium reactions. (shrink)

Chemists do not aim at testing preconceptions or theoretical hypotheses only; they first and foremost produce and determine the object of chemical investigation: they learn through making. They never cease to create and stabilize heterogeneous devices, methods, models, and theories in order to act upon the world. Chemical bodies cannot be studied in isolation; their properties constitutively depend on what surrounds and acts upon them. Starting from the specificity of chemical practices, this paper investigates the meaning of consistency, inconsistency, and (...) that of the ceteris paribus clause, in this domain of science. In so doing, it defends the idea that studying what we call ‘a lack of consistency’ should always include the scrutiny of: the way a particular scientific practice is stabilized, and the ontological or pragmatic assumptions about the entities and processes upon which this practice revolves. (shrink)