The periodic table of the elements is one of the most powerful icons in science: a single document that captures the essence of chemistry in an elegant pattern. Indeed, nothing quite like it exists in biology or physics, or any other branch of science, for that matter. One sees periodic tables everywhere: in industrial labs, workshops, academic labs, and of course, lecture halls. It is sometimes said that chemistry has no deep ideas, unlike physics, which can boast quantum mechanics and (...) relativity, and biology, which has produced the theory of evolution. This view is mistaken, however, since there are in fact two big ideas in chemistry. They are chemical periodicity and chemical bonding, and they are deeply interconnected. The observation that certain elements prefer to combine with speciﬁc kinds of elements prompted early chemists to classify the elements in tables of chemical afﬁnity. Later these tables would lead, somewhat indirectly, to the discovery of the periodic system, perhaps the biggest idea in the whole of chemistry. Indeed, periodic tables arose partly through the attempts by Dimitri Mendeleev and numerous others to make sense of the way in which particular elements enter into chemical bonding. (shrink)
The debate about the relative epistemic weights carried in favour of a theory by predictions of new phenomena as opposed to accommodations of already known phenomena has a long history. We readdress the issue through a detailed re-examination of a particular historical case that has often been discussed in connection with it—that of Mendeleev and the prediction by his periodic law of the three ‘new’ elements, gallium, scandium and germanium. We find little support for the standard story that these predictive (...) successes were outstandingly important in the success of Mendeleev's scheme. Accommodations played an equal role—notably that of argon, the first of the ‘noble gases’ to be discovered; and the methodological situation in this chemical example turns out to be in interesting ways different from that in other cases—invariably from physics—that have been discussed in this connection. The historical episode when accurately analysed provides support for a different account of the relative weight of prediction and accommodation—one that is further articulated here. (shrink)
In his latest book, Eric Scerri presents a completely original account of the nature of scientific progress. It consists of a holistic and unified approach in which science is seen as a living and evolving single organism. Instead of scientific revolutions featuring exceptionally gifted individuals, Scerri argues that the "little people" contribute as much as the "heroes" of science. To do this he examines seven case studies of virtually unknown chemists and physicists in the early 20th century quest to discover (...) the structure of the atom. They include the amateur scientist Anton van den Broek who pioneered the notion of atomic number as well as Edmund Stoner a then physics graduate student who provided the seed for Pauli's Exclusion Principle. Another case is the physicist John Nicholson who is virtually unknown and yet was the first to propose the notion of quantization of angular momentum that was soon put to good use by Niels Bohr. Instead of focusing on the logic and rationality of science, Scerri elevates the role of trial and error and multiple discovery and moves beyond the notion of scientific developments being right or wrong. While criticizing Thomas Kuhn's notion of scientific revolutions he agrees with Kuhn that science is not drawn towards an external truth but is rather driven from within. The book will enliven the long-standing debate on the nature of science, which has increasingly shied away from the big question of "what is science?". (shrink)
The philosophy of chemistry has been sadly neglected by most contempory literature in the philosophy of science. This paper argues that this neglect has been unfortunate and that there is much to be learned from paying greater philosophical attention to the set of issues defined by the philosophy of chemistry. The potential contribution of this field to such current topics as reduction, laws, explanation, and supervenience is explored, as are possible applications of insights gained by such study to the philosophy (...) of mind and the philosophy of social science. (shrink)
There is now a considerable body of published work on the epistemology of modern chemistry, especially with regard to the nature of quantum chemistry. In addition, the question of the metaphysical underpinnings of chemistry has received a good deal of attention. The present article concentrates on metaphysical considerations including the question of whether elements and groups of elements are natural kinds. It is also argued that an appeal to the metaphysical nature of elements can help clarify the re-emerging controversies among (...) chemists regarding the placement of the elements hydrogen and helium in the periodic system and the question of whether there exists a best form of the periodic table. (shrink)
The historical development of the electronic configuration model is traced and the status of the model with respect to quantum mechanics is examined. The successes and problems raised by the model are explored, particularly in chemical ab initio calculations. The relevance of these issues to whether chemistry has been reduced to quantum mechanics is discussed, as are some general notions on reduction.
The article examines a recent interventionist account of causation by Ross, in which electronic configurations of atoms are considered to be the cause of chemical behavior. More specifically I respond to the claim that a change in electronic configuration of an atom, such as occurs in the artificial synthesis of elements, causes a change in the behavior of the atom in question. I argue that chemical behavior is governed as much by the nuclear charge of an atom as it is (...) by its electronic structure. It is suggested that an adequate analysis requires attention to the dynamical interactions between nuclear charges and those of electrons, as typically carried out through the application of the Schrödinger equation. It is concluded that electronic configurations can only be said be causal in a weak sense that is somewhat analogous to the causal arguments that are invoked in folk physics. (shrink)
I claim that the question of whether chemistry is reduced to quantum mechanics is more ambiguous and multi-faceted than generally supposed. For example, chemistry appears to be both reduced and not reduced at the same time depending on the perspective that one adopts. Similarly, I argue that some conceptual issues in quantum mechanics are ambiguous and can only be laid to rest by embracing paradox and ambiguity rather than regarding them as obstacles to be overcome. Recent work in the reduction (...) of chemistry is also reviewed, including discussions of the ontological reduction of chemistry and the question of the emergence of chemistry from physics. (shrink)
Differing views on reduction are briefly reviewed and a suggestion is made for a working definition of 'approximate reduction'. Ab initio studies in quantum chemistry are then considered, including the issues of convergence and error bounds. This includes an examination of the classic studies on CH2 and the recent work on the Si2C molecule. I conclude that chemistry has not even been approximately reduced.
This article considers two important traditions concerning the chemical elements. The first is the meaning of the term “element” including the distinctions between element as basic substance, as simple substance and as combined simple substance. In addition to briefly tracing the historical development of these distinctions, I make comments on the recent attempts to clarify the fundamental notion of element as basic substance for which I believe the term “element” is best reserved. This discussion has focused on the writings of (...) Fritz Paneth which are here analyzed from a new perspective. The other tradition concerns the reduction of chemistry to quantum mechanics and an understanding of chemical elements through their microscopic components such as protons, neutrons and electrons. I claim that the use of electronic configurations has still not yet settled the question of the placement of several elements and discuss an alternative criterion based on maximizing triads of elements. I also point out another possible limitation to the reductive approach, namely the failure, up to now, to obtain a derivation of the Madelung rule. Mention is made of some recent similarity studies which could be used to clarify the nature of ‘elements’. Although it has been suggested that the notion of element as basic substance should be considered in terms of fundamental particles like protons and electrons, I resist this move and conclude that the quantum mechanical tradition has not had much impact on the question of what is an element which remains an essentially philosophical issue. (shrink)
Although the periodic system of elements is central to the study of chemistry and has been influential in the development of quantum theory and quantum mechanics, its study has been largely neglected in philosophy of science. The present article is a detailed criticism of one notable exception, an attempt by Hettema and Kuipers to axiomatize the periodic table and to discuss the reduction of chemistry in this context.
The main thrust of the paper involves a theoretical and philosophical analysis of the claim made in September 1999 that atomic orbitals have been directly imaged for the first time. After a brief account of the recent claims the paper reviews the development of the orbit and later orbital concepts and analyzes the theoretical status of atomic orbitals. The conclusion is that contrary to these claims, atomic orbitals have not in fact been observed. The non-referring nature of modern atomic orbitals (...) is discussed in the context of Laudan's writings on realism, the success of theories, and whether or not scientific terms refer. I conclude that the failure to observe orbitals is a good prima facie case for divorcing the success of theories from the question of whether their central terms refer. The added relevance of this case is that it concerns a current and highly successful theory. Finally, the relevance of this 'floating model' to contemporary discussions on scientific models is briefly considered. (shrink)
The article concerns five traditionally difficult issues that chemical educators encounter and how they should be resolved. In some cases I propose the examination of necessary and sufficient conditions in order to cast light on the relationships under discussion. The five educational issues are, the notion that a pH value of seven implies a neutral solution of water and vice versa, the use of Le Châtelier’s Principle, the relative occupation and ionization of 4s and 3d orbitals, the explanation of anomalous (...) electronic configurations and the elements that make up group 3 of the periodic table. (shrink)
The chemical nature of element 72, subsequently named hafnium, is generally regarded as a prediction from Bohr's theory of the periodic system and hence as a prediction from quantum theory. It is argued that both of these views and in particular the latter are mistaken. The claim in favour of Bohr's theory is weakened by his accommodation of independent chemical arguments and the claim in favour of quantum theory is untenable since the prediction is not strictly deductive.
Some recent work in mathematical chemistry is discussed. It is claimed that quantum mechanics does not provide a conclusive means of classifying certain elements like hydrogen and helium into their appropriate groups. An alternative approach using atomic number triads is proposed and the validity of this approach is defended in the light of some predictions made via an information theoretic approach that suggests a connection between nuclear structure and electronic structure of atoms.
The main thrust of the paper involves a theoretical and philosophical analysis of the claim made in September 1999 that atomic orbitals have been directly imaged for the first time. After a brief account of the recent claims the paper reviews the development of the orbit and later orbital concepts and analyzes the theoretical status of atomic orbitals. The conclusion is that contrary to these claims, atomic orbitals have not in fact been observed. The non-referring nature of modern atomic orbitals (...) is discussed in the context of Laudan's writings on realism, the success of theories, and whether or not scientific terms refer. I conclude that the failure to observe orbitals is a good prima facie case for divorcing the success of theories from the question of whether their central terms refer. The added relevance of this case is that it concerns a current and highly successful theory. Finally, the relevance of this ‘floating model’ to contemporary discussions on scientific models is briefly considered. (shrink)
Robin Hendry has recently argued that although the term ‘element’ has traditionally been used in two different senses, there has nonetheless been a continuity of reference. The present article examines this author’s historical and philosophical claims and suggests that he has misdiagnosed the situation in several respects. In particular it is claimed that Hendry’s arguments for the nature of one particular element, oxygen, do not generalize to all elements as he implies. The second main objection is to Hendry’s view that (...) the qua problem can be illuminated by appeal to the intention of scientists.Keywords: Element; Simple substance; Basic substance; Antoine Lavoisier; Dmitri Mendeleev; Reference; Qua problem. (shrink)
This article carefully analyzes a recent paper by Weisberg in which it is claimed that when Mendeleev discovered the periodic table he was not working as a modeler but instead as a theorist. I argue that Weisberg is mistaken in several respects and that the periodic table should be regarded as a classification, not as a theory. In the second part of the article an attempt is made to elevate the status of classifications by suggesting that they provide a form (...) of ‘side-ways explanation’. (shrink)
Two articles on the reduction of chemistry are examined. The first, by McLaughlin (1992), claims that chemistry is reduced to physics and that there is no evidence for emergence or for downward causation between the chemical and the physical level. In a more recent article, Le Poidevin (2005) maintains that his combinatorial approach provides grounding for the ontological reduction of chemistry, which also circumvents some limitations in the physicalist program. †To contact the author, please write to: Department of Chemistry and (...) Biochemistry, UCLA, 607 Charles E. Young Drive East, Box 951569, Los Angeles, CA 90095-1569; e-mail: [email protected] (shrink)
A critique of LaPorte's views on chemical kinds, like jade and ruby, is presented. More positively, a new slant is provided on the question of whether elements are natural kinds. This is carried out by appeal to the dual nature of elements, a topic that has been debated in the philosophy of chemistry but not in the natural kinds literature. It is claimed that the abstract notion of elements, as opposed to their being simple substances, is relevant to the Kripke–Putnam (...) approach to natural kinds and to some criticisms that have been raised against it, although I do not support the K–P account. The proposed view avoids the traditional microstructuralist approach to natural kinds. The article also addresses the question of whether natural kinds concern metaphysical or epistemological considerations. Recent attempts by chemists to modify the periodic table are brought to bear on the question of classification and consequently on whether the identification of elements is interest dependent. (shrink)
Sir Karl Popper is one of the few authors to have discussed the reduction of chemistry. His approach consists of what I term naturalistic reduction, which I suggest bears close similarities to the way in which scientists regard reduction. The present article aims to build on Popper's insights into the nature of reduction in science and more specifically to suggest an approach to characterizing a specific sense of the notion of approximate reduction in the context of chemistry. In the course (...) of the discussion, one of Popper's better known passages on the reduction of chemistry is analysed in some detail. (shrink)
The article disputes the recent claim featured in "Nature" magazine and many other science magazines to the effect that atomic orbitals have been observed for the first time. The claim is incorrect in view of the unconvincing nature of the evidence adduced and since atomic orbitals are deemed unobservable in principle by quantum mechanics. In addition, the possible educational drawbacks of this incorrect claim are discussed.
Philosophy of Chemistry—A New Interdisciplinary Field? What could possibly be the connection between chemistry and philosophy, apart from the obvious superficial one of their both representing quests for knowledge? How do contemporary chemists and philosophers generally view one another? These are some of the questions I will try to put before going on to describe the connections that have recently been forged between these two seemingly very diverse fields of academic study.
The philosopher of chemistry Andrea Woody has recently published a wide-ranging article concerning the turn to practice in the philosophy of science. Her primary example consists of the use of diﬀerent forms of representations by Lothar Meyer and Mendeleev when they presented their views on chemical periodicity. Woody believes that this distinction can cast light on various issues including why Mendeleev was able to make predictions while Meyer was not. Secondly, she claims that it can clarify the much-debated question concerning (...) the relative values of prediction and accommodation of data in the way that the periodic system was accepted. Thirdly, Woody believes that such diﬀerences in the representation of periodicity can be used to argue for the explanatory nature of the periodic table in contrast with the more traditional view that the periodic table is not explanatory. (shrink)
Since 1969, the international chemistry community has only held conferences on the topic of the Periodic Table three times, and the 2012 conference in Cusco, Peru was the first in almost a decade. The conference was highly interdisciplinary, featuring papers on geology, physics, mathematical and theoretical chemistry, the history and philosophy of chemistry, and chemical education, from the most reputable Periodic Table scholars across the world. Eric Scerri and Guillermo Restrepo have collected fifteen of the strongest papers presented at this (...) conference, from the most notable Periodic Table scholars. The collected volume will contain pieces on chemistry, philosophy of science, applied mathematics, and science education. (shrink)
The Pauli Exclusion Principle and the reduction of chemistry have been the subject of considerable philosophical debate, The present article considers the view that the lack of derivability of the Exclusion Principle represents a problem for physics and denies the reduction of chemistry to quantum mechanics. The possible connections between the Exclusion Principle and the hidden variable debate are also briefly criticised.
I present a response to Vollmer's review of the book Of Minds and Molecules, and especially her comments on my own article therein. This provides an opportunity to discuss two central ideas in the philosophy of chemistry. These are the distinction between elements as simple substances (element-1) and elements as basic substances (element-2) and Paneth's proposed intermediate position for philosophy of chemistry. The response also discusses the question of isotopes in relationship to the nature of the elements and their classification (...) as well as the philosophical status of atomic orbitals. (shrink)
This comprehensive volume marks a new standard in scholarship in the still emerging field of the philosophy of chemistry. With selections drawn from a wide range of scholarly disciplines, philosophers, chemists, and historians of science here converge to ask some of the most fundamental questions about the relationship between philosophy and chemistry. What can chemistry teach us about longstanding disputes in the philosophy of science over such issues as reductionism, autonomy, and supervenience? And what new issues may chemistry bring to (...) the forefront now that it has joined physics and biology as a serious topic for philosophical reflection? This newest addition to the prestigious Boston Studies in the Philosophy of Science series marks the true arrival of philosophy of chemistry within the corpus of the philosophy of science. (shrink)
For a period of several years the philosopher of science Hasok Chang has promoted various inter-related views including pluralism, pragmatism, and an associated view of natural kinds. He has also argued for what he calls the persistence of everyday terms in the scientific view. Chang claims that terms like phlogiston were never truly abandoned but became transformed into different concepts that remain useful. On the other hand, Chang argues that some scientific terms such as acidity have suffered a form of (...) “rupture”, especially in the case of the modern Lewis definition of acids. Chang also complains that the degree of acidity of a Lewis acid cannot be measured using a pH meter and seems to regard this as a serious problem. The present paper examines some of these views, especially what Chang claims to be a rupture in the definition of acidity. It is suggested that there has been no such rupture but a genuine generalization, on moving from the Brønsted-Lowry theory to the Lewis theory of acidity. It will be shown how the quantification and measurement of Lewis acidity can easily be realized through the use of equilibrium theory and the use of stability constants. (shrink)
Most contemporary chemists consider quantum mechanics to be the foundational theory of their discipline, although few of the calculations that a strict reduction would seem to require have ever been produced. In this essay I discuss contemporary algebraic and diagrammatic representations of molecular systems derived from quantum mechanical models, specifically configuration interaction wavefunctions for ab initio calculations and molecular orbital energy diagrams. My aim is to suggest that recent dissatisfaction with reductive accounts of chemical theory may stem from both the (...) inability of standard accounts of reduction to incorporate the diverse forms of representation found in chemical practice and our philosophical predilection to analyze all connections between theories in terms of logical reduction. (shrink)
This article consists of a critique of the writings of Peter Atkins. The topics discussed include the quantum mechanical explanation of the periodic system, the aufbau principle and the order of occupation of orbitals by electrons. It is also argued that Atkins fails to appreciate the philosophical significance of the more general version of the Pauli Exclusion Principle and that this omission has ramifications in the popular presentation of chemistry as well as chemical education and philosophy of chemistry in general.
The paper examines critically some recently published views by Ramsey on the contrast between ab initio and parametrized theories. I argue that, all things being equal, ab initio calculations are indeed regarded more highly in the physics and chemistry communities. A case study on density functional approaches in theoretical chemistry is presented in order to re‐examine the question of ab initio and parametrized approaches in a contemporary context.
The article begins with a response to a recent contribution by Jensen, in which he has criticized several aspects of the use of triads of elements, including Döbereiner’s original introduction of the concept and the modern use of atomic number triads by some authors including myself. Such triads are groups of three elements, one of which has approximately the average atomic weight of the other two elements, as well as having intermediate chemical reactivity. I also examine Jensen’s attempted reconstruction Mendeleev’s (...) use of triads in predicting the atomic weights of three hitherto unknown elements, that were subsequently named gallium, germanium and scandium. The present article then considers the use of atomic number triads, in conjunction with the phenomenon of first member anomaly, in order to offer support for Janet’s left-step periodic table, in which helium is relocated into group 2 of the table. Such a table features triads in which the 2nd and third elements of each group, without fail, fall into periods of equal length, a feature that is absent in the conventional 18-column or the conventional 32-column table. The dual sense of the term element, which is the source of much discussion in the philosophy of chemistry, is alluded to in further support of such a relocation of helium that may at first appear to contradict chemical intuition. (shrink)
A critique is given of the attempt by Hettema and Kuipers to formalize the periodic table. In particular I dispute their notions of identifying a naïve periodic table with tables having a constant periodicity of eight elements and their views on the different conceptions of the atom by chemists and physicists. The views of Hettema and Kuipers on the reduction of the periodic system to atomic physics are also considered critically.
This commentary provides a critical examination of a recent article by Allen and Knight in which the authors claim to provide the long-sought explanation for the Madelung, or n + ℓ, n rule for the order of orbital filling in many-electron atoms. It is concluded that the explanation is inadequate for several reasons.