This article is an overview of some of the contemporary debates in philosophy of chemistry. We discuss the nature of chemical substances, the individuation of chemical kinds, the relationship between chemistry and physics, and the nature of the chemical bond.

Pluralist and eliminativist positions have proliferated within both science and philosophy of science in recent decades. This paper asks the question why this shift of thinking has occurred, and where it is leading us. We provide an explanation which, if correct, entails that we should expect pluralism and eliminativism to transform other debates currently unaffected, and for good reasons. We then consider the question under what circumstances eliminativism will be appropriate, arguing that it depends not only on the term in (...) question, but also on the context of discussion and details of the debate at hand. The resultant selective eliminativism is an appealing compromise for various ‘pluralists’ and ‘eliminativists’ who are currently locking horns. (shrink)

Eric Scerri is the world-leading expert on Periodic Table and was quite recently named the second-most influential academic in the field of chemistry over the last decade by Academic Influence. In this interview we discuss his main questions of interest in the philosophy of chemistry—the question of reduction of chemistry to physics and the dual sense of chemical element—in the context of his main study object, the periodic table of elements. Among other things, we touch upon the more specific issues (...) related to chemical classification, such as pair reversal, the placement and order of certain elements, the structure and shape of periodic table, etc. We also discuss the status of chemical kinds as a traditional epitome of ‘natural kinds’, the relevance of philosophy of chemistry for chemical science, the implications of ‘turn to practice’ for philosophy of chemistry, and many other issues. Finally, Eric Scerri also discusses his most recent book, ‘What is a Chemical Element?’, co-edited with Elena Ghibaudi and published by Oxford University Press in 2020. (shrink)

We argue for an account of chemical reactivities as chancy propensities, in accordance with the ‘complex nexus of chance’ defended by one of us in the past. Reactivities are typically quantified as proportions, and an expression such as “A + B → C” does not entail that under the right conditions some given amounts of A and B react to give the mass of C that theoretically corresponds to the stoichiometry of the reaction. Instead, what is produced is a fraction (...) α < 1 of this theoretical amount, and the corresponding percentage is usually known as the yield, which expresses the relative preponderance of its reaction. This is then routinely tested in a laboratory against the observed actual yields for the different reactions. Thus, on our account, reactivities ambiguously refer to three quantities at once. They first refer to the underlying propensities effectively acting in the reaction mechanisms, which in ‘chemical chemistry’ (Schummer in Hyle 4:129–162, 1998) are commonly represented by means of Lewis structures. Besides, reactivities represent the probabilities that these propensities give rise to, for any amount of the reactants to combine as prescribed. This last notion is hence best understood as a single case chance and corresponds to a theoretical stoichiometric yield. Finally, reactivities represent the actual yields observed in experimental runs, which account for and provide the requisite evidence for/against both the mechanisms and single case chances ascribed. (shrink)

There is a persisting debate about what chemical bonds are and whether they exist. I argue that chemical bonds are real patterns of interactions between subatomic particles. This proposal resolves the problems raised in the context of existing understandings of the chemical bond and provides a novel way to defend the reality of chemical bonds.

Harold Kincaid in Individualism and the Unity of Science postulates a model of unity-without-reduction in order to accurately describe the relation between individualism and macroeconomics. I present this model and apply it to the description of the relation between chemistry and quantum mechanics. I argue that, when it comes to the description of molecular structure, chemistry and quantum mechanics are unified in Kincaid’s sense. Specifically, the two disciplines contribute to the formation of a unified body of knowledge with respect to (...) molecular structure. (shrink)

Robin Hendry has presented an account of two equally valid ways of understanding the nature of chemical bonding, consisting of what the terms the structural and the energetic views respectively. In response, Weisberg has issued a “challenge to the structural view”, thus implying that the energetic view is the more correct of the two conceptions. In doing so Weisberg identifies the delocalization of electrons as the one robust feature that underlies the increasingly accurate quantum mechanical calculations starting with the Heitler-London (...) method and moving on to such approaches as the valence bond and molecular orbital theories of chemical bonding. The present article provides a critical evaluation of Weisberg’s article and concludes that he fails to characterize the nature of chemical bonding in several respects. I claim that Hendry’s structural and energetic views remain as equally viable ways of understanding chemical bonding. Whereas the structural view is more appropriate for chemists, the energetic view is preferable to physicists. Neither view is more correct unless one subscribes to the naively reductionist view of considering that the more physical energetic view is the more correct one. (shrink)

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. (shrink)

The history of the hydrogen bond provides a good example of the of an important chemical concept. It illustrates the interplay between empirical and theoretical approaches to the problem of delimiting what has proved to be quite an elusive notion, with chemists whittling away at the particular sorts of case with a view to obtaining a precise, unitary concept. Even though there is a return to a more theoretically inspired notion in more recent research, empirical characterisations remain a feature of (...) the report of a Task Group recently set up by the IUPAC to reconsider the definition of the hydrogen bond, and this situation—by no means unusual for chemical concepts and principles—is unlikely to change in the foreseeable future. These developments are reviewed in this paper, which includes an extended discussion of the enormous significance hydrogen bonding has for the philosopher’s standard example of a “natural kind”, water. There is little to suggest a reduction to what philosophers of physics are pleased to call fundamental principles, and the details raise further questions about what essentialists could possibly have in mind when talking about the microscopic essence of water. (shrink)

When young Kant meditated upon the distinction between his right and left hands, he could not foresee that the problem of incongruent counterparts would revive in the twentieth century under a new form. In the early days of quantum chemistry, Friedrich Hund developed the so-called Hund paradox that arises from the supposed inability of quantum mechanics to account for the difference between enantiomers. In this paper, the paradox is expressed as a case of quantum measurement, stressing that decoherence does not (...) offer a way out of the problem. The main purpose is to argue for the need to adopt a clear interpretation of quantum mechanics in order to solve the paradox. In particular, I claim that the Modal-Hamiltonian Interpretation, which conceives measurement as a breaking-symmetry process, supplies the tools required to explain the dextro-rotation or levo-rotation properties of optical isomers. (shrink)

In the present paper we address the problem of optical isomerism embodied in the socalled “Hund’s paradox”, which points to the difficulty to account for chirality by means of quantum mechanics. In particular, we explain the answer to the problem proposed by the theory of decoherence. The purpose of this article is to challenge this answer on the basis of a conceptual analysis of the phenomenon of decoherence, that reveals the limitations of the theory of decoherence to solve the difficulties (...) posed by optical isomerism and, in general, by quantum measurement. (shrink)

This paper aims to show that there is a lot of philosophy in the philosophy of chemistry—not only in the problems and questions specific to chemistry, which this science brings up in philosophical discussions, but also in the topics of wider interest like reductionism and emergence, for which chemistry proves to be an ideal case study. The fact that chemical entities and properties are amenable to a quantitative understanding, to measurement and experiment to a greater extent than those in psychology (...) or biology, makes chemistry an ideal case study for those interested in reductionism and emergence. (shrink)

The many-faced relationship between chemistry and physics is one of the most discussed topics in the philosophy of chemistry. In his recent book Reducing Chemistry to Physics. Limits, Models, Consequences, Hinne Hettema conceives this relationship as a reduction link, and devotes his work to defend this position on the basis of a “naturalized” concept of reduction. In the present paper I critically review three kinds of issues stemming from Hettema’s argumentation: philosophical, scientific and methodological.

El propósito del presente trabajo consiste en abordar la pregunta por la ontología de la química cuántica. Para ello nos concentraremos en el concepto de enlace químico desde la perspectiva de los dos enfoques a través de los cuales la ecuación de Schrödinger se aplica a los sistemas químicos moleculares: la teoría del enlace de valencia (EV) y la teoría del orbital molecular (OM). Sobre la base de la presentación de ambos enfoques y su comparación, señalaremos que, a pesar de (...) su denominación tradicional, no pueden considerarse estrictamente como teorías científicas, sino que se ajustan mejor a la noción de modelo; en particular, son modelos que incorporan conceptos y leyes tanto del ámbito de la mecánica cuántica como del de la química estructural. Estas consideraciones nos permitirán argumentar que la química cuántica no posee un referente ontológico autónomo, sino que se trata de un ámbito científico cuya vigencia descansa sobre su éxito práctico en el cálculo y la predicción. Finalmente, indicaremos de qué modo los enfoques EV y OM del enlace químico abren una nueva perspectiva respecto de la noción misma de modelo en ciencias empíricas. (shrink)

In this article I argue that structure in chemistry is a creature of abstraction: attending selectively to structural similarities, we neglect differences. There are different ways to abstract, so abstraction is interest dependent. So is structure. First, there are two different and mutually irreducible notions of structure in chemistry: bond structure and geometrical structure. Second, structure is relative to scale : the same substance has different structures at different scales, and relationships of structural sameness and difference vary across the scales. (...) However, these facts have no tendency to undermine structure’s claim to reality, or its metaphysical seriousness. (shrink)

Perhaps the hottest topic in the philosophy of chemistry is that of the relationship between chemistry and physics. The problem finds one of its main manifestations in the debate about the nature of molecular structure, given by the spatial arrangement of the nuclei in a molecule. The traditional strategy to address the problem is to consider chemical cases that challenge the definition of molecular structure in quantum–mechanical terms. Instead of taking that top-down strategy, in this paper we face the problem (...) of the reduction of molecular structure to quantum mechanics from a bottom-up perspective: our aim is to show how the theoretical peculiarities of quantum mechanics stand against the possibility of molecular structure, defined in terms of the spatial relations of the nuclei conceived as individual localized objects. We will argue that, according to the theory, quantum “particles” are not individuals that can be identified as different from others and that can be reidentified through time; therefore, they do not have the ontological stability necessary to maintain the relations that can lead to a spatially definite system with an identifiable shape. On the other hand, although quantum chemists use the resources supplied by quantum mechanics with successful results, this does no mean reduction: their “approximations” add certain assumptions that are not justified in the context of quantum mechanics or are even inconsistent with the very formal structure of the theory. (shrink)

Although during the last decades the philosophy of chemistry has greatly extended its thematic scope, the main difficulties appear in the attempt to link the chemical description of atoms and molecules and the description supplied by quantum mechanics. The aim of this paper is to analyze how the difficulties that threaten the continuous conceptual link between molecular chemistry and quantum mechanics can be overcome or, at least, moderated from the perspective of BM. With this purpose, in “The quantum-mechanical challenges” section (...) the foundational incompatibility between chemical and SQM descriptions will be briefly recalled. “Bohmian mechanics” section will be devoted to explain the main features of BM. In “Empirical equivalence and underdetermination” section, the consequences of the empirical equivalence between SQM and BM will be discussed. Finally, in the Conclusion, we will stress the scope of the obtained conclusions and the philosophical difficulties that still remain even after adopting BM for foundational purposes. (shrink)

According to classical molecular chemistry, molecules have a structure, that is, they are sets of atoms with a definite arrangements in space and held together by chemical bonds. The concept of molecular structure is central to modern chemical thought given its impressive predictive power. It is also a very useful concept in chemistry education, due to its role in the rationalization and visualization of microscopic phenomena. However, such a concept seems to find no place in the ontology described by quantum (...) mechanics, since it appeals to classical notions such as the position of the atomic nuclei or the individuality of electrons. Although this problem has attracted the attention of several authors, the discussion is far from settled. Some authors adopt an explicitly reductionist position and advocate to reconstruct the concept of molecular structure within the framework of the quantum theory. Others, although acknowledging the conceptual discontinuity between quantum mechanics and molecular chemistry, keep the hope of future reduction alive. From an explicitly non-reductionist position, on the contrary, others authors conceive molecular structure as an emergent phenomenon. The purpose of this article is to propose a different line of argumentation to address this problem. By contrast to reduction and emergence, the admission of a multiplicity of ontologies, not necessarily linked by hierarchical connections, cancels the need of finding a relation of dependence between the molecular level and the quantum level. This ontologically pluralist position can be applied to the issue of molecular structure, in order to argue that it is possible to admit the existence of structure in the ontology of molecular chemistry, in spite of the fact that it does not exist in the quantum world. (shrink)

In a recent article entitled “The problem of molecular structure just is the measurement problem”, Alexander Franklin and Vanessa Seifert argue that insofar as the quantum measurement problem is solved, the problems of molecular structure are resolved as well. The purpose of the present article is to show that such a claim is too optimistic. Although the solution of the quantum measurement problem is relevant to how the problem of molecular structure is faced, such a solution is not sufficient to (...) account for the structure of molecules as understood in the field of chemistry. (shrink)

In the present paper we address the problem of optical isomerism embodied in the socalled “Hund’s paradox”, which points to the difficulty to account for chirality by means of quantum mechanics. In particular, we explain the answer to the problem proposed by the theory of decoherence. The purpose of this article is to challenge this answer on the basis of a conceptual analysis of the phenomenon of decoherence, that reveals the limitations of the theory of decoherence to solve the difficulties (...) posed by optical isomerism and, in general, by quantum measurement. (shrink)

The modal-Hamiltonian interpretation belongs to the modal family of interpretations of quantum mechanics. By endowing the Hamiltonian with the role of selecting the subset of the definite-valued observables of the system, it accounts for ideal and non-ideal measurements, and also supplies a criterion to distinguish between reliable and non-reliable measurements in the non-ideal case. It can be reformulated in an explicitly invariant form, in terms of the Casimir operators of the Galilean group, and the compatibility of the MHI with the (...) theory of decoherence has been proved. Nevertheless, perhaps its main advantage in the eyes of a scientist is given by its several applications to well-known physical situations, leading to results compatible with experimental evidence. The purpose of this paper is to add a new application to the list: the case of optical isomerism, which is a central issue for the philosophy of physics and of chemistry since it points to the core of the problem of the relationship between physics and chemistry. Here it will be shown that the MHI supplies a direct and physically natural solution to the problem, a solution that does not require putting classical assumptions in “by hand.”. (shrink)

Quantum physics is the foundation for chemistry, but the concept of chemical bonding is not easily reconciled with quantum mechanical models of molecular systems. The quantum theory of atoms in molecules, developed by Richard F.W. Bader and colleagues, seeks to define bonding using a topological analysis of the electron density distribution. The “bond paths” identified by the analysis are posited as indicators of a special pairwise physical relationship between atoms. While elements of the theory remain subject to debate, I argue (...) that QTAIM embodies a distinctive interactive conception of bonding that is an attractive alternative to others previously discussed. (shrink)

Understanding natural phenomena is an important aim of science. Since the turn of the millennium the notion of scientific understanding has been a hot topic of debate in the philosophy of science. A bone of contention in this debate is the role of truth and representational accuracy in scientific understanding. So-called factivists and non-factivists disagree about the extent to which the theories and models that are used to achieve understanding must be true or accurate. In this paper we address this (...) issue by examining a case from the practice of synthetic chemistry. We investigate how understanding is obtained in this field by means of an in-depth analysis of the famous synthesis of periplanone B by W. Clark Still. It turns out that highly idealized models—that are representationally inaccurate and sometimes even inconsistent—and qualitative concepts are essential for understanding the synthetic pathway and accordingly for achieving the synthesis. We compare the results of our case study to various factivist and non-factivist accounts of how idealizations may contribute to scientific understanding and conclude that non-factivism offers a more plausible interpretation of the practice of synthetic chemistry. Moreover, our case study supports a central thesis of the non-factivist theory of scientific understanding developed by De Regt, namely that scientific understanding requires intelligibility rather than representational accuracy, and that idealization is one way to enhance intelligibility. (shrink)

Chemistry is the study of the structure and transformation of matter. When Aristotle founded the field in the 4th century BCE, his conceptual grasp of the nature of matter was tailored to accommodate a relatively simple range of observable phenomena. In the 21st century, chemistry has become the largest scientific discipline, producing over half a million publications a year ranging from direct empirical investigations to substantial theoretical work. However, the specialized interest in the conceptual issues arising in chemistry, hereafter Philosophy (...) of Chemistry, is a relatively recent addition to philosophy of science. Philosophy of chemistry has two major parts. In the first, conceptual issues arising within chemistry are carefully articulated and analyzed. Such questions which are internal to chemistry include the nature of substance, atomism, the chemical bond, and synthesis. In the second, traditional topics in philosophy of science such as realism, reduction, explanation, confirmation, and modeling are taken up within the context of chemistry. (shrink)

One of Julian Barbour’s main aims is to solve the problem of time that appears in quantum geometrodynamics (QG). QG involves the application of canonical quantization procedure to the Hamiltonian formulation of General Relativity. The problem of time arises because the quantization of the Hamiltonian constraint results in an equation that has no explicit time parameter. Thus, it appears that the resulting equation, as apparently timeless, cannot describe evolution of quantum states. Barbour attempts to resolve the problem by allegedly eliminating (...) time from his interpretation of QG. In order to evaluate the efficacy of his solution, it is necessary to ascertain in what sense time has been eliminated from his theory. I proceed to do so by developing a form of conceptual analysis that is applicable to the concept of time in physical theories and applying this analysis to Barbour’s account. (shrink)

According to conventional wisdom, local gauge symmetry is not a symmetry of nature, but an artifact of how our theories represent nature. But a study of the so-called theta-vacuum appears to refute this view. The ground state of a quantized non-Abelian Yang-Mills gauge theory is characterized by a real-valued, dimensionless parameter theta—a fundamental new constant of nature. The structure of this vacuum state is often said to arise from a degeneracy of the vacuum of the corresponding classical theory, which degeneracy (...) allegedly arises from the fact that “large” (but not “small”) local gauge transformations connect physically distinct states of zero field energy. If that is right, then some local gauge transformations do generate empirical symmetries. In defending conventional wisdom against this challenge I hope to clarify the meaning of empirical symmetry while deepening our understanding of gauge transformations. I distinguish empirical from theoretical symmetries. Using Galileo’s ship and Faraday’s cube as illustrations, I say when an empirical symmetry is implied by a theoretical symmetry. I explain how the theta-vacuum arises, and how “large” gauge transformations differ from “small” ones. I then present two analogies from elementary quantum mechanics. By applying my analysis of the relation between empirical and theoretical symmetries, I show which analogy faithfully portrays the character of the vacuum state of a classical non-Abelian Yang-Mills gauge theory. The upshot is that “large” as well as “small” gauge transformations are purely formal symmetries of non-Abelian Yang-Mills gauge theories, whether classical or quantized. It is still worth distinguishing between these kinds of symmetries. An analysis of gauge within the constrained-Hamiltonian formalism yields the result that “large” gauge transformations should not be classified as gauge transformations; indeed, nor should “global” gauge transformations. In a theory in which boundary conditions are modeled dynamically, “global” gauge transformations may be associated with physical symmetries, corresponding to translations of these extra dynamical variables. Such translations are symmetries if and only if charge is conserved. But it is hard to argue that these symmetries are empirical, and in any case they do not correspond to any constant phase change in a quantum state. (shrink)

Although during the last decades the philosophy of chemistry has greatly extended its thematic scope, the main difficulties appear in the attempt to link the chemical description of atoms and molecules and the description supplied by quantum mechanics. The aim of this paper is to analyze how the difficulties that threaten the continuous conceptual link between molecular chemistry and quantum mechanics can be overcome or, at least, moderated from the perspective of BM. With this purpose, in “The quantum-mechanical challenges” section (...) the foundational incompatibility between chemical and SQM descriptions will be briefly recalled. “Bohmian mechanics” section will be devoted to explain the main features of BM. In “Empirical equivalence and underdetermination” section, the consequences of the empirical equivalence between SQM and BM will be discussed. Finally, in the Conclusion, we will stress the scope of the obtained conclusions and the philosophical difficulties that still remain even after adopting BM for foundational purposes. (shrink)