The source of chemical bonding

Developments in the application of quantum mechanics to the understanding of the chemical bond are traced with a view to examining the evolving conception of the covalent bond. Beginning with the first quantum mechanical resolution of the apparent paradox in Lewis’s conception of a shared electron pair bond by Heitler and London, the ensuing account takes up the challenge molecular orbital theory seemed to pose to the classical conception of the bond. We will see that the threat of delocalisation can be overstated, although it is questionable whether this should be seen as reinstating the issue of the existence of the chemical bond. More salient are some recent developments in a longstanding discussion of how to understand the causal aspects of the bonding interaction—the nature of the force involved in the covalent link—which are taken up in the latter part of the paper.     

A Revolution that never happened

If we define scientific revolutions as changes of scientists' ontologies, types of causal explanation, and paradigmatic types of methods and instruments, Antoine-Laurent Lavoisier's contribution to chemistry did not amount to a scientific revolution. Contrary to the received view that Lavoisier initiated a “chemical revolution,” which is accepted by Chang and Kusch, I argue that Lavoisier shared with the phlogistonists their “flat ontology” of chemical substance, established decades before the 1770s, their types of explaining chemical transformation, and their quantitative methods. Based on my historical reconstruction, I criticize Chang's argument that the late eighteenth-century phlogistic systems and Lavoisier's system belonged to two different theoretical traditions. As a consequence, I also question Chang's argument that the acceptance of Lavoisier's system can be explained in terms of dominance of “compositionism” over “principlism.”     

From aether impulse to QED: Sommerfeld and the Bremsstrahlen theory

The radiation that is due to the braking of charged particles has been in the focus of theoretical physics since the discovery of X-rays by the end of the 19th century. The impact of cathode rays in the anti-cathode of an X-ray tube that resulted in the production of X-rays led to the view that X-rays are aether impulses spreading from the site of the impact. In 1909, Arnold Sommerfeld calculated from Maxwell׳s equations the angular distribution of electromagnetic radiation due to the braking of electrons. He thereby coined the notion of “Bremsstrahlen.” In 1923, Hendrik A. Kramers provided a quantum theoretical explanation of this process by means of Bohr׳s correspondence principle. With the advent of quantum mechanics the theory of bremsstrahlung became a target of opportunity for theorists like Yoshikatsu Sugiura, Robert Oppenheimer, and–again–Sommerfeld, who presented in 1931 a comprehensive treatise on this subject. Throughout the 1930s, Sommerfeld׳s disciples in Munich and elsewhere extended and improved the bremsstrahlen theory. Hans Bethe and Walter Heitler, in particular, in 1934 presented a theory that was later regarded as “the most important achievement of QED in the 1930s” (Freeman Dyson). From a historical perspective the bremsstrahlen problem may be regarded as a probe for the evolution of theories in response to revolutionary changes in the underlying principles.     

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.     

Chemistry and Chemists at the London Institution 1807-1912

The London Institution, established in the City of London in 1807, was devoted, as its full title proclaimed, to the 'advancement of Literature and the Diffusion of Useful Knowledge'. With its extensive lecture programme, splendid reference library, reading rooms, laboratory and other amenities, it provided for its members a scientific and cultural centre, modelled on the highly successful and fashionable Royal Institution in London's West End. Among its scientific activities, chemistry long maintained a leading role, in terms of both the sheer volume and variety of its presentations, and the high standing of its lecturers; they included Faraday, Playfair, Hofmann, Roscoe, Odling, Norman Lockyer, Meldola, and Sir William Ramsay, as well as other visiting lecturers, specially selected for their ability to present their subject in an interesting and attractive fashion to a wider lay public. The laboratory of the Institution, although limited in size and facilities, was the scene of instruction in practical chemistry, and between 1863 and 1884 attained the reputation of a significant centre of chemical research during the successive tenure of the professorship in chemistry by J. A. Wanklyn and H. E. Armstrong. Their publications, appearing under the device 'From the Laboratory of the London Institution', were a frequent feature of the leading chemical periodicals. Thus, within its many-sided activities, the Institution promoted significantly the public appreciation of the function of chemistry, as a contributor both to pure knowledge, and to technical and economic progress. It achieved this in an environment of influential City merchants, manufacturers and financiers and doubtless led to beneficient, if unrecorded, consequences. It was only towards the close of the nineteenth century, when the universities had become increasingly concerned with the systematic study of the discipline, that chemistry lost its direct impact in the London Institution, but continued to maintain a presence within its cultural framework.     

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.     

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.     

Whence chemistry?

Along with exploring some of the necessary conditions for the chemistry of our world given what we know about quantum mechanics, I will also discuss a different reductionist challenge than is usually considered in debates on the relationship of chemistry to physics. Contrary to popular belief, classical physics does not have a reductive relationship to quantum mechanics and some of the reasons why reduction fails between classical and quantum physics are the same as for why reduction fails between chemistry and quantum physics. However, a neoreductionist can accept that classical physics has some amount of autonomy from quantum mechanics, but still try to maintain that classical+quantum physics taken as a whole reduces chemistry to physics. I will explore some of the obstacles lying in the neoreductionist's path with respect to quantum chemistry and thereby hope to shed more light on the conditions necessary for the chemistry of our world.     

Paper tools in experimental cultures

The paper studies various functions of Berzelian formulas in European organic chemistry prior to the mid-nineteenth century from a semiotic, historical and epistemological perspective. I argue that chemists applied Berzelian formulas as productive ‘paper tools’ for creating a chemical order in the ‘jungle’ of organic chemistry. Beginning in the late 1820s, chemists applied chemical formulas to build models of the binary constitution of organic compounds in analogy to inorganic compounds. Based on these formula models, they constructed new classifications of organic substances. They further applied Berzelian formulas in a twofold way to experimentally investigate organic chemical reactions: as tools which supplemented laboratory tools and as tools for constructing interpretive models of organic reactions. The scrutiny of chemists' performances with chemical formulas on paper also reveals a dialectic which contributed considerably to the formation of the new experimental culture of synthetic carbon chemistry that emerged between the late 1820s and the early 1840s. In an unintended and unforeseen way, the tools reacted back on the goals of their users and contributed to conceptual development and a shift of scientific objects and practices (‘substitution’) which transcended the originally intended chemical order.     

The 'Hyperbola of Quantum Chemistry': the Changing Practice and Identity of a Scientific Discipline in the Early Years of Electronic Digital Computers, 1945-65

In 1965, John A. Pope presented a paper entitled 'Two-Dimensional Chart of Quantum Chemistry' to illustrate the inverse relationship between the sophistication of computational methods and the size of molecules under study. This chart, later called the 'hyperbola of quantum chemistry', succinctly summarized the growing tension between the proponents of two different approaches to computation–the ab initio method and semiempirical method–in the early years of electronic digital computers. Examining the development of quantum chemistry after World War II, I focus on the role of computers in shaping disciplinary identity. The availability of high-speed computers in the early 1950s attracted much attention from quantum chemists, and their community took shape through a series of conferences and personal networking. However, this emerging community soon encountered the problem of communication between groups that differed in the degree of reliance they placed on computers. I show the complexity of interactions between computing technology and a scientific discipline, in terms of both forming and splitting the community of quantum chemistry.     

A note on the prehistory of indistinguishable particles

In modern terms, quantum statistics differs from classical statistics for the indistinguishability of its elementary entities. An historical investigation of the emergence of Bose–Einstein statistics, however, shows that quantum statistics was initially interpreted as a statistics of non-independence, for it extended to gas particles the statistical correlation that was a long-recognized characteristic of light quanta. At the same time, the development of a quantum–statistical theory of the ideal gas was riddled with the question of the statistical significance of the exchange symmetry of a system of equal particles. Indistinguishability combines exchange symmetry and statistical correlation, and relates them to the loss of identity of particles in quantum mechanics. It is instructive, however, not to conflate these properties when analysing the historical emergence of quantum statistics. The statistical correlation of light quanta and the exchange symmetry of gas molecules remained two separate problems even though quantum gas theory and Bose–Einstein statistics were born from gas-radiation analogies in statistical theory.     

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.     

The Remarkable Fecundity of Leibniz's Work on Infinite Series

The publication in 1906 of Alexander Smith's Introduction to general inorganic chemistry inaugurated a decisive change in chemical pedagogy in the US, the effects of which are still evident. The nature and extent of Smith's innovations are described through a comparison of his text to its source material and contemporaries. His authoritative command of and whole-hearted commitment to the intellectual framework of Ionist physical chemistry set his text apart from its American competitors, while his efforts to make the tools of physical chemistry immediately useful to his readers distinguished it from its most immediate source material, Wilhelm Ostwald's Grundlinien der anorganischen Chemie. Smith's curricular innovations in chemistry were a practical expression of his radically restrictive view of the social role of collegiate education, which he conceived as solely of use for its ability to prepare students for professional life. During the fifteen years prior to the publication of his groundbreaking textbook, Smith underwent two critical, formative experiences. First, he retreated intellectually from the structural organic chemistry in which he was trained, ultimately adopting a professional identity as a physical inorganic chemist. His involvement in the controversy regarding the structure of 1,3-diketones reveals much about his reasons for eventually abandoning organic chemistry. Second, he served the National Education Association as chairman of the Sub-committee on College Entrance Requirements in Chemistry, in the process making a close study of the ends and methods of secondary and collegiate education. These experiences made him unique among proponents of physical chemistry in the US, and help account for the unique nature of his contributions to the development of the chemical professions.     

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.     

Pauling's Defence of Bent-Equivalent Bonds: A View of Evolving Explanatory Demands in Modern Chemistry

Linus Pauling played a key role in creating valence-bond theory, one of two competing theories of the chemical bond that appeared in the first half of the 20th century. While the chemical community preferred his theory over molecular-orbital theory for a number of years, valence-bond theory began to fall into disuse during the 1950s. This shift in the chemical community's perception of Pauling's theory motivated Pauling to defend the theory, and he did so in a peculiar way. Rather than publishing a defence of the full theory in leading journals of the day, Pauling published a defence of a particular model of the double bond predicted by the theory in a revised edition of his famous textbook, The Nature of the Chemical Bond. This paper explores that peculiar choice by considering both the circumstances that brought about the defence and the mathematical apparatus Pauling employed, using new discoveries from the Ava Helen and Linus Pauling Papers archive.     

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.