Why was M. S. Tswett’s chromatographic adsorption analysis rejected?

The present paper claims that M. S. Tswett’s chromatographic adsorption analysis, which today is a ubiquitous and instrumentally sophisticated chemical technique, was either ignored or outright rejected by chemists and botanists in the first three decades of the twentieth century because it did not make sense in terms of accepted chemical theory or practice. Evidence for this claim is culled from consideration of the botanical and chemical context of Tswett’s technique as well as an analysis of the protracted debate over Tswett’s chromatographic analysis of chlorophyll between him and Leon Marchlewski, a noted chlorophyll chemist of the period. In this way, the paper expands and amends what it calls the ‘textbook story’ of the early history of chromatography, examples of which may be found in historical notes in many textbooks of chemical instrumental analysis and numerous short articles in chemistry journals. The paper also provides an accessible introduction to the early history of chromatography for historians of science likely to know little or nothing about it.     

Understanding science through its history: a response to Newman

The paper is a response to William Newman’s rebuttal of a critique of his account of the origins of modern chemistry by Alan Chalmers. A way in which the nature of science can be illuminated by history of science is identified and an account of how this can be achieved in the context of a study of the work of Boyle defended in the face of Newman’s criticism. Texts from the writings of Boyle that are cited by Newman as posing problems for Chalmers’ thesis are interpreted as in fact supporting it.     

Chemistry in the French tradition of philosophy of science: Duhem, Meyerson, Metzger and Bachelard

At first glance twentieth-century philosophy of science seems virtually to ignore chemistry. However this paper argues that a focus on chemistry helped shape the French philosophical reflections about the aims and foundations of scientific methods. Despite patent philosophical disagreements between Duhem, Meyerson, Metzger and Bachelard it is possible to identify the continuity of a tradition that is rooted in their common interest for chemistry. Two distinctive features of the French tradition originated in the attention to what was going on in chemistry.French philosophers of science, in stark contrast with analytic philosophers, considered history of science as the necessary basis for understanding how the human intellect or the scientific spirit tries to grasp the world. This constant reference to historical data was prompted by a fierce controversy about the chemical revolution, which brought the issue of the nature of scientific changes centre stage.A second striking—albeit largely unnoticed—feature of the French tradition is that matter theories are a favourite subject with which to characterize the ways of science. Duhem, Meyerson, Metzger and Bachelard developed most of their views about the methods and aims of science through a discussion of matter theories. Just as the concern with history was prompted by a controversy between chemists, the focus on matter was triggered by a scientific controversy about atomism in the late nineteenth-century.     

The Prussian Mining Official Alexander von Humboldt

From summer 1792 until spring 1797, Alexander von Humboldt was a mining official in the Franconian parts of Prussia. He visited mines, inspected smelting works, calculated budgets, wrote official reports, founded a mining school, performed technological experiments, and invented a miners’ lamp and respirator. At the same time he also participated in the Republic of Letters, corresponded with savants in all Europe, and was a member of the Leopoldine Carolinian Academy and the Berlin Gesellschaft Naturforschender Freunde. He collected minerals, made geognostic observations, performed chemical and physiological experiments, read the newest scientific journals, and prepared and published texts on mineralogy, geognosy, chemistry, botany and physiology. Humboldt did his scientific investigations alongside his administrative and technical work. This raises the question of whether there were fruitful interactions between Humboldt's technical-administrative work and (parts of) his natural inquiry. I argue that the mining official Humboldt was a late eighteenth-century figure of hybrid savant-technician. Mines and smelting works provided numerous opportunities for studies of nature. Humboldt systematically used inspection tours for mineralogical and geognostic observations. He transformed mines into chemical laboratories, and he transferred knowledge and material items from his natural inquiries in mines to academic institutions. The main objective of this paper is to illuminate the persona of savant-technician (or scientific-technological expert) along with Humboldt's mixed technological and scientific work during his term as mining official.     

The notion of nature in chemistry

If nature is by definition the object of the natural sciences, then the dichotomy ‘natural’ versus ‘chemical’, held by both chemists and nonchemists, suggests an idiosyncrasy of chemistry. The first part of the paper presents a selective historical analysis of the main notions of nature in chemistry, as developed in early Christian views of chemical crafts, alchemy, iatrochemistry, mechanical philosophy, organic chemistry, and contemporary drug research. I argue that the dichotomy as well as quasi-moral judgments of chemistry have been based on static and teleological notions of nature throughout history and that chemists, unlike physicists, have neglected the dynamic notion of nature. The second part provides a philosophical criticism of the former notions and argues for the latter as well as for an explicit discourse about values in chemistry.     

Aristotelian chemistry: A prelude to duhemian metaphysics

In 1904 Joachim published an influential paper dealing with ‘Aristotle's Conception of Chemical Combination’¹ which has provided the basis of much more recent studies.² About the same time, Duhem³ developed what he regarded as an essentially Aristotelian view of chemistry, based on his understanding of phenomenological thermodynamics. He does not present a detailed textual analysis, but rather emphasises certain general ideas. Joachim's classic paper contains obscurities which I have been unable to fathom and theses which do not seem to be fully explained, or which at least seem difficult for the modern reader to understand. An attempt is made here to provide a systematic account of the Aristotelian theory of the generation of substances by the mixing of elements by reconsidering Joachim's treatment in the light of the sort of points which most interested Duhem.The work described in this paper was undertaken with a view to providing a basis for presenting, evaluating and criticising Duhem's understanding of what was for him modern (i.e. 19th-century) chemistry. This latter project will be taken up on another occasion. I hope the present paper will be of some value to a broader philosophical readership in so far as it provides a fairly clear conception of matter which might be called Aristotelian, even if it is not precisely Aristotle's, and raises certain clear problems of interpretation. It may also be of interest to historians of chemistry in suggesting an analysis of the old chemical notion of a mixt independent of atomic theories.     

L'Analyse chimique des végétaux: Le cas du quinquina

In 1820, J. Pelletier and J.-B. Caventou, two French pharmacist-chemists working at the Ecole de Pharmacie of Paris, extracted quinine, a new substance, from cinchona bark. We use this example to illustrate the processes which lead from a crude natural product through the isolation of an active principle to the production of a pure manufactured drug. This allows us to discuss the development of chemical analysis in relation to pharmacy, natural history, medicine and the early pharmaceutical industry. The dynamics of the disciplines involved here show how organic chemistry, which was developing rapidly during these crucial years, expanded and became autonomous. Theoretical aspects (and in particular atomic theory) and practical innovations are relevant to the scientific methods developed by the first generation of those who integrated the new chemistry into their daily work. Beyond these historical issues, this paper aims to show how a holistic approach can contribute to the debate on discovery and invention in a science that is often considered empirical.     

The double transfer of thermodynamics: From physics to chemistry and from Europe to America

The aim of this study is twofold: to explore, first, the influence of the intellectual and social conditions on the transfer of thermodynamics to chemistry and thereby the making of chemical thermodynamics, and second, the way that this knowledge was transferred from Europe to America. Consequently, it is of interest to examine the methodological approaches used by physicists and chemists to transfer thermodynamics to chemistry, to evaluate the potential of this science to offer solutions to existing chemical problems, and to discuss the attitude of the scientific community towards these new ideas. The development of chemical thermodynamics in America followed a different route compared to the European experience. Although it was transferred from Europe, it had distinctive characteristics imposed by a different traditional, intellectual and social milieu. This study focuses on the content of the transferred knowledge to America and the direction that this knowledge assumed by the American scientists. As a paradigm, the chemical thermodynamics of Gilbert Newton Lewis will be considered.     

Boyle and the origins of modern chemistry: Newman tried in the fire

William Newman construes the Scientific Revolution as a change in matter theory, from a hylomorphic, Aristotelian to a corpuscular, mechanical one. He sees Robert Boyle as making a major contribution to that change by way of his corpuscular chemistry. In this article it is argued that it is seriously misleading to identify what was scientific about the Scientific Revolution in terms of a change in theories of the ultimate structure of matter. Boyle showed, especially in his pneumatics, how empirically accessible, intermediate causes, as opposed to ultimate, mechanical ones can be explored and identified by experiment. Newman is right to observe that Boyle constantly sought intimate links between chemistry and the mechanical philosophy. However, by doing so he did not thereby significantly aid the cause of attaining experimental knowledge of chemical phenomena and the support that Boyle’s chemistry provided for the mechanical philosophy was weaker than both Boyle and Newman imply. Boyle was intent on articulating and defending a strict, mechanical account of the ultimate structure of matter to be sure, but his contributions to the new experimental science in general, and chemistry in particular, are best seen as distinct from that endeavour.     

Is water a mixure? Bridging the distinction between physical and chemical properties

Two inter-linked theses are defended in this paper. One is the Duhemian theme that a rigid distinction between physical and chemical properties cannot be upheld. Duhem maintained this view not because the latter are reducible to the former, but because if physics is to remain consistent with chemistry it must prove possible to expand it to accommodate new features, and a rigid distinction would be a barrier to this process. The second theme is that naturally occurring isotopic variants of water are in fact distinct substances, and naturally occurring samples of water are mixtures of these substances. For most practical purposes it is convenient to treat protium oxide, deuterium oxide, and so on, as the same chemical substance, but to insist on this as a matter of principle would stand in conflict with the first thesis.     

Primordial chemistry and enzyme evolution in a hot environment

Ever since the publication of Darwin’s Origin of Species, questions have been raised about whether enough time has elapsed for living organisms to have reached their present level of complexity by mutation and natural selection. More recently, it has become apparent that life originated very early in Earth’s history, and there has been controversy as to whether life originated in a hot or cold environment. This review describes evidence that rising temperature accelerates slow reactions disproportionately, and to a much greater extent than has been generally recognized. Thus, the time that would have been required for primordial chemistry to become established would have been abbreviated profoundly at high temperatures. Moreover, if the catalytic effect of a primitive enzyme (like that of modern enzymes) were to reduce a reaction’s heat of activation, then the rate enhancement that it produced would have increased as the surroundings cooled, quite aside from changes arising from mutation (which is itself highly sensitive to temperature). Some nonenzymatic catalysts of slow reactions, including PLP as a catalyst of amino acid decarboxylation, and the Ce^IV ion as a catalyst of phosphate ester hydrolysis, have been shown to meet that criterion. The work reviewed here suggests that elevated temperatures collapsed the time required for early evolution on Earth, furnishing an appropriate setting for exploring the vast range of chemical possibilities and for the rapid evolution of enzymes from primitive catalysts.     

Berthelot's anti-atomism: A ‘matter of taste’?

The influential French chemist Marcelin Berthelot spoke against the use of Dalton's atomic theory and Avogadro's hypothesis in the second half of the nineteenth century. This paper argues that Berthelot conceded that atomism might be acceptable as a system of conventions, but he feared the power of such conventions in constructing a realistic picture of atoms which was not warranted empirically. Equally, Berthelot's anti-atomism was a last-ditch effort to assert the place of chemistry within the tradition of natural history and to deny the possible reduction of chemical science to the laws of nineteenth-century physics.     

The anatomical and physiological bibliography of George E. Day (1815–1872)

The history of the Greenlandic mineral cryolite is outlined from its discovery in late-eighteenth century to the mid-nineteenth century, when its potential for industrial use was first recognized by the Danish chemist Julius Thomsen. During the 1850s, several attempts were made to exploit cryolite for the production of soda and/or aluminium, of which only the soda process became implemented on an industrial scale. The main part of the paper examines the early cryolite soda manufacture, its chemical basis as well as its industrial significance. The focus is thus the intersection of chemical science and technology. It is argued that Thomsen's process depended intimately on current chemical knowledge, and that, with regard to the science-technology relationship, the cryolite soda manufacture signified a new kind of industrial chemistry.     

The introduction of the differential notation to Great Britain

In the history of chemistry, the Danish chemist Julius Thomsen (1826–1909) is best known for his contributions to thermochemistry. Throughout his life, he was a pronounced atomist and a tireless advocate of neo-Proutian views as to the constitution of matter. On many occasions, especially in his later years, he engaged in speculations concerning the unity of matter and the complexity of atoms. In this engagement, Thomsen was alone in Danish chemistry, but his works were representative of a large number of 19th-century chemists, particularly in England and Germany. Thomsen's ideas as to the constitution of matter, the periodic system and the noble gases, may be seen as typical of this vigorous trend in fin de siècle chemistry.     

Marcelin Berthelot's first publication in 1850, on the subjection of liquids to tension

The famous French chemist, Marcelin Berthelot, published his first scientific paper in 1850. However, reference to this paper has been largely ignored in the various accounts of his lasting contributions to chemistry. The probable reason for this is that this paper is concerned with a method of subjecting a liquid to tension, and it is more appropriate to regard it as a paper on physics rather than on chemistry. In the work described in this largely-forgotten paper, written whilst he was still a young research student, Berthelot showed that liquids contained in his ‘Berthelot tube’ could withstand a considerable tension; and he is the first person to have observed cavitation, a phenomenon which has been studied so widely this century. The next mention in the literature of the Berthelot tube method is at the turn of the present century, after which it again seems to have been forgotten until the 1940s; since then there has been considerable progress using the Berthelot tube technique. In this paper the work described in Berthelot's original paper is discussed in some detail, and the subsequent fruitful development of the method is also traced and assessed.     

John Dalton’s puzzles: from meteorology to chemistry

Historical research on John Dalton has been dominated by an attempt to reconstruct the origins of his so-called “chemical atomic theory”. I show that Dalton’s theory is difficult to define in any concise manner, and that there has been no consensus as to its unique content among his contemporaries, later chemists, and modern historians. I propose an approach which, instead of attempting to work backward from Dalton’s theory, works forward, by identifying the research questions that Dalton posed to himself and attempting to understand how his hypotheses served as answers to these questions. I describe Dalton’s scientific work as an evolving set of puzzles about natural phenomena. I show how an early interest in meteorology led Dalton to see the constitution of the atmosphere as a puzzle. In working on this great puzzle, he gradually turned his interest to specifically chemical questions. In the end, the web of puzzles that he worked on required him to create his own novel philosophy of chemistry for which he is known today.     

The promotion of mining and the advancement of science: the chemical revolution of mineralogy

This paper explores the origins of the analytical definition of simple substance, a concept whose central importance in the new chemistry of Lavoisier and his colleagues is now widely recognized. I argue that this notion derived from the practical activities of metallurgists and mineral assayers, and that the theoretical elaboration necessary for the analytical concept to be understood as relevant to chemistry was inspired by the efforts of enlightened rulers in Sweden and Germany to turn chemical science to the benefit of mining—and thus of the various state treasuries. The involvement of chemically-literate mineralogists in the mining industry led them to adopt the principle that analytically-determined composition was a far more essential aspect of minerals than any mere congeries of properties. The same men who pioneered the analytical notion of simple substance also inaugurated the attempt to define a nomenclature for chemistry based exclusively on composition, as determined in the laboratory.