Summary In this paper we examine the reaction of the Leiden low-temperature laboratory of Heike Kamerlingh Onnes to new ideas in quantum theory. Especially the contributions of Albert Einstein (1906) and Peter Debye (1912) to the theory of specific heat, and the concept of zero-point energy formulated by Max Planck in 1911, gave a boost to solid state research to test these theories. In the case of specific heat measurements, Kamerlingh Onnes's laboratory faced stiff competition from Walter Nernst's Institute (...) of Physical Chemistry in Berlin. In fact, Berlin got the better of it because Leiden lacked focus. After the liquefaction of helium in 1908, Kamerlingh Onnes transformed his laboratory into an international facility for low temperature research, and for this reason it was impossible to make headway with the specific heat measurements. In the case of zero-point energy, Leiden developed a magnetic research programme to test the concept. Initially the balance of evidence seemed to be tipping in favour of zero-point energy. After 1914, however, Leiden would desert the theory in fovour, of a concept from calssical physics. A curious move that illustrates Kamerlingh Onnes's discomfort with the new quantum theory. (shrink)

During the second half of the nineteenth century, electronegativity has been one of the most relevant chemical concepts to explain the relationships between chemical substances and their possible reactions. Specifically, EN is a property of the substances that allows them to attract external electrons in bonding situations. The problem arises because EN cannot be measured directly. Indeed, the only way to measure it is through different properties that do can be directly measured, for instance enthalpy, ionization energies or electron affinities. (...) What is particularly troubling about this case in quantum chemistry is that the different models used to describe and quantify EN are incompatible but, in a certain sense, equivalent because the same EN scale results in all of them. By analyzing Linus Pauling’s and Robert Mulliken’s models of EN, it will be argued that, if we remain cling to a traditional representative conception of models, we cannot understand the meaning of the information provided by those models. Indeed, if we do not want to adopt an instrumentalist point of view concerning chemical knowledge, we should reconsider by virtue of what a model represents the system, or, in other words, which the factors that determine the representative power of a model are. I will propose a new perspective that incorporates the role of experimental techniques in the very notion of representation; this perspective allows us to understand how supposedly incompatible models of the same target system can be both simultaneously representative. (shrink)

This article describes a descriptive-qualitative method for analyzing and reviewing several textbooks for high school as samples commonly used by teachers and students in their teaching–learning to reveal possible misconceptions. This study focused on the subjects of quantum numbers and electronic configuration. From the advanced literature review to analyze the samples the occurrence of various misconceptions was noted. All textbooks described correctly the four symbols of quantum numbers, but none correlates correctly the magnetic-angular quantum number to the Cartesian labeled orbitals. (...) All textbooks consider mistakenly the meaning of aufbau as the building-up energy of orbitals by following (n + ℓ, n) rules on describing the electronic configuration for all atoms. Only one textbook states that the electronic configuration of transition metal atoms (3d series) can be described in the following order of shell (n), thus giving rise to two types of electronic configurations, [Ar] 3d 4s (Type I) beside [Ar] 4s 3d (Type II), leading further misconception. All textbooks described favorably an unpaired electron of ms = + ½ due to the specific agreement, which is a potential misconception in applying Hund’s rule. In drawing the diagram boxes of orbitals, they are arranged in increasing or decreasing the numeric mℓ, due to the specific agreement, and again leading to a potential misconception on describing the quantum number of electrons issued. Three textbooks introduced the terms of the last and the xth electron associated with the quantum numbers, leading to serious further misconceptions. No books stated that the ordering energy of the (n + ℓ, n) rule is true only for the first twenty atoms. (shrink)

Application of Einstein special theory of relativity in chemistry seems to be superfluous; energies are too low. The average velocity of electron in hydrogen atom is 1/135 c, making its actual mass only 26,6 ppm bigger than the rest mass. However, for heavier elements relativistic effects have to be taken into account and, more, many phenomena cannot be explained without ascribing new mass to electrons, in accordance with Einstein theory. In this paper such phenomena are described: color of metallic (...) gold and Bi and Pb compounds, contraction of Ln-X bond of lanthanide trihalides, voltage of lead-acid and Zn/HgO battery, and the shape of gold clusters. Besides, essentials of Einstein theory and quantum chemistry were problems concerning the validity of Lavoisier law. (shrink)

This work utilizes examples from chemical sciences to present fundamentals of dialectics and synergetics. The laws of dialectics remain appropriate at the level of atoms, at the level of molecules, at the level of the reactions, and at the level of ideas. The law of the unity and conflict of opposites is seen, for instance, in the relationships between the ionization energy and electron affinity of atoms, between the forward and back reactions, as well as in the differentiation and (...) integration between the various areas of chemistry. The law of the passage of quantitative changes into qualitative changes describes the transformation properties of the compounds when the number and arrangement of atoms in the molecule undergoes changes. According to this law, the development is accompanied by breaks and jumps. This paper suggests equations for the description of these relationships. The law of the negation of the negation is manifested in the Periodic Law, in the evolution of ideas about the mutual transformation of chemical elements, in the development the concept of triads of elements, etc. Small changes in the conventional Periodic Table on the basis of previously rejected versions allow reflecting secondary and additional periodicity. Synergetics, similarly to dialectics, is dedicated to the studies of general laws of evolution. Synergetics includes highly advanced and specified ideas of dialectics. The cornerstone of synergetics is the principles of self-organization and nonlinearity. Mathematical development of these concepts was substantially facilitated by considering oscillating chemical reactions as an example. These reactions are quite complex and therefore provide adequate models for self-organization. Oscillations may exist only upon execution of specific thermodynamic, mathematical, and chemical conditions. Mechanisms of several oscillatory reactions are briefly reviewed. The construction of novel biomimetic or smart materials based on oscillating reactions is described. (shrink)

Frederick Soddy , one of the foremost radiochemists of his day, was awarded the 1921 Nobel Prize in chemistry. Soddy was also among the first of the scientific leaders of his age, along with Blackett , Bernal , and others, to become interested in the social implications of their work. In 1950 his colleague Paneth wrote that currently ‘there is widespread discussion on the responsibility towards the community of men of science and particularly experts in radioactivity; but a perusal (...) of Prof. Soddy's non-chemical writings of no less than thirty years ago [viz., during and after the first world war] shows how strongly he felt the duty to fight for a better order of things'. Soddy was a complex iconoclast often derided for dealing with what seemed to be disparate interests. What, it could be asked, could monetary reform possibly have to do with radiochemistry? But to make sense of Soddy, the question must rather be formulated in the other direction: What fundamental concern did Soddy have that enabled him to embrace holistically a variety of seemingly diverse activities? The answer can be given in a word: energy. And the way in which Soddy dealt with this issue involved him directly with social economics as well as with the social responsibility of scientists. (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)

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)

The essential biological processes that sustain life are catalyzed by protein nano-engines, which maintain living systems in far-from-equilibrium ordered states. To investigate energetic processes in proteins, we have analyzed the system of generalized Davydov equations that govern the quantum dynamics of multiple amide I exciton quanta propagating along the hydrogen-bonded peptide groups in α-helices. Computational simulations have confirmed the generation of moving Davydov solitons by applied pulses of amide I energy for protein α-helices of varying length. The stability and (...) mobility of these solitons depended on the uniformity of dipole-dipole coupling between amide I oscillators, and the isotropy of the exciton-phonon interaction. Davydov solitons were also able to quantum tunnel through massive barriers, or to quantum interfere at collision sites. The results presented here support a nontrivial role of quantum effects in biological systems that lies beyond the mechanistic support of covalent bonds as binding agents of macromolecular structures. Quantum tunneling and interference of Davydov solitons provide catalytically active macromolecular protein complexes with a physical mechanism allowing highly efficient transport, delivery, and utilization of free energy, besides the evolutionary mandate of biological order that supports the existence of such genuine quantum phenomena, and may indeed demarcate the quantum boundaries of life. (shrink)

In this paper, we outline the foundations of the time invariant, non-unitary covering of quantum chemistry known as hadronic chemistry, we illustrate its validity by reviewing the exact representations of the binding energies of the Hydrogen and water molecules, and present new advances.

By setting out the grammar of event causality, as developed by Hume and Mackie, in contrast to the grammar of agent causality in the natural sciences, a kind of hybrid hierarchical format for chemical explanations is sketched. From this starting point the history of agentive concepts in chemistry is displayed as a progression from Newton’s ‘forces’, through the nineteenth century concepts of ‘affinity’ and ‘valency’ to recent theories of molecular binding in terms of the migration of electrons and protons (...) as powerful particulars. The final stage of this development is the rewriting of chemical theory in terms of energy. (shrink)

Organic chemists have been able to develop a robust, theoretical understanding of the phenomena they study; however, the primary theoretical devices employed in this field are not mathematical equations or laws, as is the case in most other physical sciences. Instead it is diagrams, and in particular structural formulas and potential energy diagrams, that carry the explanatory weight in the discipline. To understand how this is so, it is necessary to investigate both the nature of the diagrams employed in (...) organic chemistry and how these diagrams are used in the explanations of the discipline. I will begin this paper by characterizing some of the major ways that structural formulas used in organic chemistry. Next I will present a model of the explanations in organic chemistry and describe how both structural formulas and potential energy diagrams contribute to these explanations. This will be followed by several examples that support my abstract account of the role of diagrams in the explanations of organic chemistry. In particular, I will consider both the appeal to ‘hyperconjugation’ in the explanation of alkene stability and how the idea of ‘ring strain’ was developed to explain the relative stability of cyclic compounds. (shrink)

Misconceptions about energy conservation abound due to the gap between physics and secondary school chemistry. This paper surveys this difference and its relevance to the 1690s–2010s Leibnizian argument that mind-body interaction is impossible due to conservation laws. Justifications for energy conservation are partly empirical, such as Joule’s paddle wheel experiment, and partly theoretical, such as Lagrange’s statement in 1811 that energy is conserved if the potential energy does not depend on time. In 1918 Noether generalized (...) results like Lagrange’s and proved a converse: symmetries imply conservation laws and vice versa. Conservation holds if and only if nature is uniform. The rise of field physics during the 1860s–1920s implied that energy is located in particular places and conservation is primordially local: energy cannot disappear in Cambridge and reappear in Lincoln instantaneously or later; neither can it simply disappear in Cambridge or simply appear in Lincoln. A global conservation law can be inferred in some circumstances. Einstein’s General Relativity, which stimulated Noether’s work, is another source of difficulty for conservation laws. As is too rarely realized, the theory admits conserved quantities due to symmetries of the Lagrangian, like other theories. Indeed General Relativity has more symmetries and hence more conserved energies. An argument akin to Leibniz’s finally gets some force. While the mathematics is too advanced for secondary school, the ideas that conservation is tied to uniformities of nature and that energy is in particular places, are accessible. Improved science teaching would serve the truth and enhance the social credibility of science. (shrink)

In modern German ‘Anschauung’ is translated as intuition. But in Kant’s technical philosophical context, it means an intuition derived from previous visualizations of physical processes in the world of perceptions. The nineteenth century chemists’ predilection for Kantian Anschauung led them to develop an intuitive representation of what exists beyond the bounds of the senses. Molecular structure is one of the illuminating outcomes. (Ochiai 2021, pp. 1–51) This mental habit seems to be dominant among chemists even in the twentieth century, as (...) is illustrated by the electronic theory of organic chemistry and the frontier orbital theory as well. The former assumes that (1) bonds are paired electrons shared by bonded atoms—in fact, electrons in molecules are not localized in bonds; (2) the difference of electronegativities between bonded atoms causes electron drifts—expressed by the curly arrow—that result in bond formation or bond cleavage. The latter focuses on the orbitals that make the greatest contribution to the energy of a system undergoing electron delocalization, while the LCAO method says, as is suggested by the word Linear Combination of Atomic Orbitals, molecular orbitals should be constructed from all of the atomic orbitals that have the appropriate symmetry. In other words, every molecular orbital contributes to some extent to the electronic state of a molecule. The curly arrow in the electronic theory and the orbital lobe in the frontier orbital theory illustrate an intuitive character of these theories. Although both theories rely on such simple and qualitative models rather than mathematically rigid quantum mechanical calculations, they are successful in explaining, predicting, and designing chemical reactions. What makes these prima facie intuitive theories so successful? In this study we address this problem from a historical and philosophical as well as scientific point of view. The key to solve this problem is that they are concerned with only bond formation or bond cleavage, in which the localized-bond principle holds. (shrink)

In his classic work The Mind and its Place in Nature published in 1925 at the height of the development of quantum mechanics but several years after the chemists Lewis and Langmuir had already laid the foundations of the modern theory of valence with the introduction of the covalent bond, the analytic philosopher C. D. Broad argued for the emancipation of chemistry from the crass physicalism that led physicists then and later—with support from a rabblement of philosophers who knew (...) as much about chemistry as etymologists—to believe that chemistry reduced to physics. Here Broad’s thesis is recast in terms more familiar to chemists. In the hard sell of particle physics, several prominent figures in chemistry—Hoffmann, Primas, and Pauling—have had their views interpreted to imply that they were sympathetic to greedy reductionism when in fact they were not. Indeed, being chemists without physicists as alter egos, they could not but side with Broad’s contention that chemistry, as a science that deals primarily in emergent phenomena which are beyond the purview of physicalism, owes no acquiescence to particle physics and its ethereal wares. Historically, among the most widely used expediencies in chemistry and materials science are additivity or mixture rules and their cohort transferability, all of which are devised and used under the mantle of naive reductionism. Here it is argued that while the transfer of functional groups between molecules works empirically to an extent, it is strictly outlawed by the no-cloning theorem of quantum mechanics. Several illustrative examples related to chemistry’s irreducibility to physics are presented and discussed. The failure of naive reductionism exhibited by the deep-inelastic scattering of leptons by A > 2 nuclei is traced to the same flawed reasoning that was the original basis of Moffitt’s ‘atoms in molecules’ hypothesis, the neglect of context, nuclei in the case of high-energy physics and molecules in the case of chemistry. A non-exhaustive list of other contexts from physics, chemistry, and molecular biology evidencing similar departures from the ideal of additivity or reductionism is provided for the perusal of philosophers. Had the call by the mathematician J. T. Schwartz for developments in mathematical linguistics possessed of a less single, less literal, and less simple-minded nature been met, perhaps it might have persuaded scientists to abandon their regressive fixation with unphysical reductionism and to adapt to new methodologies that engender a more nuanced handling of ubiquitous emergent phenomena as they arise in Nature than is the case today. (shrink)

The title of this work may seem to beg an important question, since it rests on the assumption that Diderot has a 'concept of physical energy'. Indeed the aim of the study is, in part, to assemble evidence in support of the acte de foi implicit in its title. I am using 'physical energy' in a loose sense, as a convenient term to denote 'what matter can do' as distinct from 'what matter is made of'. Hence it may (...) be taken as broadly synonymous with 'power' or 'force', encompassing both active and potential forms, and thus corresponding to a combination of the fourth and fifth senses identified by the Oxford English Dictionary: 4. Power actively and efficiently displayed or exerted. 5. Power not necessarily manifested in action; ability or capacity to produce an effect. Modern subatomic physics, of course, recognises no such distinction between 'being' and 'doing'; at a fundamental level, matter-as-substance and matter-as-energy are interchangeable (and, as I shall argue towards the end of the study, Diderot himself comes close to a similar position). Nevertheless, the division is both justifiable and useful within the context of eighteenth-century philosophies of nature. For, as many scholars have pointed out, the trend towards nature as an integrated, active phenomenon, in place of the cartesian view of passive tendue only incidentally endowed with motion, was crucial to the development of scientific thought in the mid-eighteenth century. Debate and development on such issues as Newtonian attraction, inertia, electricity and magnetism, chemical reactions, not only contributed directly to the advancement of physics and chemistry, but also (like cartesian mechanism) impinged upon the perennial biological questions, themselves being investigated from a new and exciting angle. As a philosopher rather than a practising scientist, Diderot was ideally placed to draw freely and creatively on all these areas, and his speculations on what we might call 'the nature of nature' are highly characteristic of the new approach. He comes increasingly to discuss and define natural phenomena (organic and inorganic alike) from the point of view of nature's powers - in the spirit of Renaissance naturalism, but from the perspective of up-to-date scientific findings. It is in this sense that I refer to a 'concept of physical energy'. Given the organic quality of Diderot's thought, it is not surprising to find the idea of energy recurring in other areas of his works. If man is composed of matter - active matter - than all human activity, be it moral, political, aesthetic, becomes capable of interpretation in terms of energy. I share Chouillet's conviction that this is a crucial aspect of Diderot's overall philosophy, which deserves to be more widely recognised and more fully understood. (shrink)

The drive towards clean technology in the chemical industry with an increasing emphasis on the reduction of waste at source requires a level of innovation and new technology that the chemical industry is beginning to adopt. The green chemistry revolution provides an enormous number of opportunities to discover and apply new synthetic approaches using alternative feedstocks; ecofriendly reaction conditions, energy minimizations and the design of less toxic and inherently safer chemicals. In this review exciting opportunities and some successful (...) examples of green chemistry in practice are described. While developments in the 20th century have brought various social and economic benefits to the people but these changes have also caused a range of environmental problems at both local and global levels. Over recent years, sustainable development has been accepted by government, industry and the public as a necessary goal for achieving social, economic and environmental objectives. Within this, green chemistry plays a key role in maintaining and improving quality of our life and preserving natural environments. The term ‘ Green Chemistry’ was first coined by the US Environmental Protection Agency in the early 1990s and major interest in green chemistry in the US began in earnest with the passage of the ‘Pollution Prevention Act’ of 1990. Thus Green Chemistry becoming a formal focus of the EPA in 1991. (shrink)

Summary In this paper we examine the reaction of the Leiden low-temperature laboratory of Heike Kamerlingh Onnes to new ideas in quantum theory. Especially the contributions of Albert Einstein (1906) and Peter Debye (1912) to the theory of specific heat, and the concept of zero-point energy formulated by Max Planck in 1911, gave a boost to solid state research to test these theories. In the case of specific heat measurements, Kamerlingh Onnes's laboratory faced stiff competition from Walter Nernst's Institute (...) of Physical Chemistry in Berlin. In fact, Berlin got the better of it because Leiden lacked focus. After the liquefaction of helium in 1908, Kamerlingh Onnes transformed his laboratory into an international facility for low temperature research, and for this reason it was impossible to make headway with the specific heat measurements. In the case of zero-point energy, Leiden developed a magnetic research programme to test the concept. Initially the balance of evidence seemed to be tipping in favour of zero-point energy. After 1914, however, Leiden would desert the theory in fovour, of a concept from calssical physics. A curious move that illustrates Kamerlingh Onnes's discomfort with the new quantum theory. (shrink)

After the birth of thermodynamics’ second principle—outlined in Carnot's Réflexions sur la puissance motrice du feu —several studies provided new arguments in the field. Mainly, they concerned the thermodynamics’ first principle—including energy conceptualisation—, the analytical aspects of the heat propagation, the statistical aspects of the mechanical theory of heat. In other words, the second half of nineteenth century was marked by an intense interdisciplinary research activity between physics and chemistry: new disciplines applied to the heat developed in the (...) form of analytical, mechanical and statistical theories. Inside all these theories, entropy—the brand-new function that Clausius coined in his Mechanical theory of heat—started to play a central epistemic role. In the present paper, we analyse some steps of the historical process of conceptualisation of such function from 1850 to 1902. Particularly, we retrace the historical–foundational path that—starting from Clausius’ Second Law—lead Boltzmann and Gibbs to their distinguished formulations of statistical entropy. As usual, our research has been unrolled through the analyses of primary sources and by leaning on critical readings of the secondary literature. As for the methodological approach, text analysis of historical documents constituted our privileged modus operandi. This paper is the expression of a collaborative historical research program focused on the thermodynamic foundations of physics–chemistry relationship; early results have already been published by the same authors upon the concepts of reversibility––and––thermal equilibrium. (shrink)

This work describes the concept of bond order. It shows that covalent bond energy is correlated to bond order. Simple expressions which included bond order are introduced to calculate bond energies of homo-nuclear and hetero-nuclear bonds. Calculated values of bond energies are compared with literature values and show there is very good agreement between and calculated and experimental values in the vast majority of cases. Bond order reveals the strength of a bond and shows the number of bonds in (...) both homo-nuclear and hetero-nuclear covalent bonds. (shrink)

Varieties of chemical and phase equilibria are controlled by the minimum Gibbs energy principle, according to which the Gibbs energy for a system will have the minimum value at any given temperature and pressure. It is understood that the minimum is with respect to all nonequilibrium states at the same temperature and pressure. The abstract relation between Gibbs energy and the equilibrium constant is deduced from fundamental laws of thermodynamics. However, actual use of this relation calls for (...) the Gibbs energy as a function of concentrations of the chemicals. Since thermodynamics is formulated without any reference to materials, how does one get that relation? This article provides the answer, and in the process shows that application of theory to experiments requires several intermediate layers where theory and experiment commingle. (shrink)

It has been claimed that kinetic energy is an objective physical quantity whilst at the same time maintaining that potential energy is not. However, by making use of the method of ‘inference to the best explanation’, it may be readily concluded that potential energy is indeed an objective physical quantity. This is done for an example drawn from the foundations of modern chemistry. In order to do so, the criteria of what counts as ‘most probable’ and (...) ‘most reasonable’ are defined and then employed for choosing the best explanation. (shrink)

This chapter first evokes the objects of chemistry and the role played by experimentation in the constitution of its objects. It then studies how chemists set up experimental protocols to deal with the dependence of chemical bodies on the inert or living environments in which they are found. To this end, its pays particular attention to the preparation of reference matrices for measurement and for the validation of results. In so doing, it stresses the fact that chemists use a (...) dizzying pluralism of instruments, procedures, reasonings, and methods in order to characterize and quantify substances, which are never truly detachable, except in the case of approximations satisfying particular objectives, from the empirical complex {apparatus-methods-chemical substances-associated medium} in which they are scrutinized. (shrink)

Mechanisms are the how of chemical reactions. Substances are individuated by their structures at the molecular scale, so a chemical reaction is just the transformation of reagent structures into product structures. Explaining a chemical reaction must therefore involve different hypotheses about how this might happen: proposing, investigating and sometimes eliminating different possible pathways from reagents to products. One distinctive aspect of mechanisms in chemistry is that they are broken down into a few basic kinds of step involving the breaking (...) and making of bonds between atoms. This is necessary for chemical kinetics, the study of how fast reactions happen, and what affects it. It draws on G.N. Lewis’ identification of the chemical bond as involving shared electrons, which from the 1920s achieved the commensuration of chemistry and physics. The breaking or making of a bond just is the transfer of electrons, so a chemical bond on one side of an equation might be balanced on the other side by the appearance of a corresponding quantity of excess charge. A bond is understood to have been exchanged for a pair of electrons. Since reaction mechanisms rely on identities, doesn’t the establishment of a reaction mechanism explain away the chemical phenomena, showing that they are no more than the movement of charges and masses? In one sense yes: these mechanisms seem to involve a conserved-quantity conception of causation. But in another sense no: the ‘lower-level’ entities can do what they do only when embedded in higher-level organisation or structure. There need be no threat of reduction. (shrink)

This article is a reflection of the project ‘Welcome Aboard’, which I collaborated on in 2011, with two scientists Nicola Armaroli (Ist. ISOF/CNR, Bologna and Molecular Photoscience Group, Bologna) and Vincenzo Balzani (Department of Chemistry G. Ciamician, University of Bologna). The video establishes a dialogue based on Buckminster Fuller’s ‘World Game’ where they offer possible scenarios for our planet running under renewable energy sources. Ultimately, a democratic system of energy sharing, between consumers and suppliers, was proposed to (...) be put at the forefront. The article begins with David Bohm’s focus on how a collective thought process can have drastic affects on our society. He proposes that we recognize the ‘whole’ in which we live to avoid becoming a society of fragmented incoherency. Similarly, as an engineer Buckminster Fuller has devoted himself to finding an effective action to change the world through a global approach, which he calls a whole-system perspective. The technology of the Smart Grid, proposed in the dialogue between the two scientists of ‘Welcome Aboard’ in which every individual produces, shares and consumes energy (electricity), seems to be a new tool that could be combined with other technologies to provide a connectivity between human beings. (shrink)

This work explores the nature of chemistry as an autonomous science and philosophical consequences of generalizations of some chemical aspects. Chemistry is regarded in its distinction from physics, going back to the alchemical aim for the ultimate experiment rather than for all explaining theory. Topology, shape, valence etc. are identified as typically chemical concepts. The contribution of chemistry to the general theory of complexity is demonstrated by approach of diminishing interactions by which smaller and smaller energy (...) increments are needed to move from one level to another one of higher complexity. (shrink)

In 1915, Frederick Soddy, later a winner of the Nobel Prize in Chemistry, warned publicly of the future dangers of atomic war. Hisforesight depended not only upon scientific knowledge, but also upon emotion, creativity, and many sorts of nonscientific knowledge. The latter, which played a role even in the content of Soddy's scientific discoveries, included such diverse sources as contemporary politics, history, science fiction, religion, and ancient alchemy. Soddy's story may offer important, guiding msights for today's efforts in technology (...) assessment. (shrink)

The prediction of protein–protein interactions based on independently obtained structural information for each interacting partner remains an important challenge in computational chemistry. Procedures where hypothetical interaction models (or decoys) are generated, then ranked using a biochemically relevant scoring function have been garnering interest as an avenue for addressing such challenges. The program PatchDock has been shown to produce reasonable decoys for modeling the association between pig alpha-amylase and the VH-domains of camelide antibody raised against it. We designed a biochemically (...) relevant method by which PatchDock decoys could be ranked in order to separate near-native structures from false positives. Several thousand steps of energy minimization were used to simulate induced fit within the otherwise rigid decoys and to rank them. We applied a partial free energy function to rank each of the binding modes, improving discrimination between near-native structures and false positives. Sorting decoys according to strain energy increased the proportion of near-native decoys near the bottom of the ranked list. Additionally, we propose a novel method which utilizes regression analysis for the selection of minimization convergence criteria and provides approximation of the partial free energy function as the number of algorithmic steps approaches infinity. (shrink)

This is the third of a series of essays on the development and reception of Wilhelm Ostwald’s energetics. The first essay described the chemical origins of Ostwald’s interest in the energy concept and his motivations for seeking a comprehensive science of energy. The second essay and the present one discuss his various attempts, beginning in 1891 and extending over almost 3 years, to develop a consistent and coherent energetic theory. A final essay will consider reactions to this work (...) and Ostwald’s replies, and will also seek to evaluate his program of research. Ostwald’s project—to reconstruct physics and chemistry “as a pure energetics”—is worth attending to for several reasons: first, because Ostwald did ground-breaking work in chemistry (he was awarded a Nobel Prize in 1909 for his studies in catalysis and rates of reaction); second, because an important school of physical chemistry formed around him at Leipzig, a school that promoted his ideas; and, finally, because he was a prominent and vigorous participant in debates at the end of the nineteenth century concerning the proper course of physical theory. (shrink)

A Zenonian supertask involving an infinite number of colliding balls is considered, under the restriction that the total mass of all the balls is finite. Classical mechanics leads to the conclusion that momentum, but not necessarily energy, must be conserved. Relativistic mechanics, on the other hand, implies that energy and momentum conservation are always violated. Quantum mechanics, however, seems to rule out the Zeno configuration as an inconsistent system.

Chemical structures are among the trademarks of our profession, as surely chemical as flasks, beakers and distillation columns. When someone sees one of us busily scribbling formulas or structures, he or she has no trouble identifying a chemist. Yet these familiar objects, which accompany our work from start to end, from the initial doodlings (Fig. I) to the final polished artwork in a publication (Fig. II), are deceptively simple. They raise interesting and difficult questions about representation. It is the intent (...) of this article to reflect upon molecular graphics. (shrink)

In lieu of an abstract, here is a brief excerpt of the content:Extractivist OntologiesLithium Mining and Anthropocene Imaginaries in Chile's Atacama DesertMauricio F. Collao Quevedo (bio)The term energy transition generally refers to efforts to switch from one energy system to another. In light of the current climate crisis, energy transition projects have sought to move societies away from their reliance on fossil fuels and toward a renewables-based energy system. Yet such projects have not been easy to (...) undertake. As Marie Forget and Vincent Bos point out, an energy system based on renewables requires a transformation of energy "regulatory frameworks, technical and organizational structures, geographic forms and network practices" (1). More specifically, current energy transition models rely on the expansion of lithium production, accompanying systems of private property rights, and complex logistical and technical strategies. This article examines the interplay between lithium extraction, national development, and Anthropocene imaginaries in Chile's Atacama Desert, arguing that the green brand of extractivism that characterizes the industry relies on elaborate institutional arrangements aimed at expanding and protecting extractivist ontological and epistemological regimes in the politically contested region. As such, struggles over lithium in Chile's Atacama region demonstrate the extent to which efforts to decolonize the Anthropocene and make possible non-extractive futures of collective survival must unfold on ontological grounds, against the consolidation of the Age of Man.Mining, Water Rights, and Indigenous Communities in the Atacama DesertAmong today's most promising energy sources and materials are sodium, copper, sulfur, nickel, cobalt, rare earth metals, and lithium. These [End Page 78] have become central to energy transition strategies and states seeking to attract investors for development (Lunde Seefeldt). As a report by the World Bank points out, demand for transition minerals like lithium, cobalt, and graphite could increase by 500% by 2050 ("Climate-Smart Mining"), highlighting the extent to which global energy transition efforts are counting on greater extraction of transition minerals and the expansion of extractive frontiers to previously unexplored or unexploited regions (Moore, Capitalism; World Bank Group). Lithium is at the center of this economic and technological shift toward green economies.Global lithium demand is growing rapidly, with investment and production rates growing significantly in recent years (Narins) and catching the attention of states (e.g., China) and corporate tech giants (e.g., Tesla) that are already trying to secure greater shares of the global market. The light metal's popularity is largely due to its internal chemistry, which meets many of the technical and practical requirements associated with green energy transition. Lithium is light, conducive, and energy-dense, which in the context of batteries means faster recharge, lower costs, and charge-holding abilities that make lithium-ion batteries more efficient than a nickel-metal hybrid equivalent (Perotti and Coviello). Because of this, lithium is increasingly being considered as promising for human development and survival as its energy predecessors, inspiring labels such as "white gold," "white petroleum," "the new copper," "the 21st century's petroleum," or the "new gasoline" of sustainability (Acuña and Tironi; Lunde Seefeldt; Voskoboynik and Andreucci).But the industry is not without its downsides. The negative impacts of lithium extraction in Chile's Atacama Desert have been challenged by local communities for whom the metal does not exist as a discrete entity that can be easily extracted from its socioecological context. For many of these communities, lithium is more than a transition metal found in an appropriable and materially heterogenous underground brine: it is an ontologically contested, socioecological entity that sustains and participates in complex webs of life-supporting, place-based, and more-than-human relations. Such accounts of the brine are radically incompatible with "official" state accounts of it, which are maintained through an institutional architecture that allows the ontological basis of the brine to be manipulated for extractive purposes by both corporate and state actors.In the following pages, I examine the ways in which Chile's legal and institutional arrangements, informed by imaginaries of green modernization, [End Page 79] create conditions under which extralocal actors can manipulate along extractivist lines the ontological ambiguity and material heterogeneity of lithium-containing brines in the salt flats of the Atacama Desert. Through an analysis of the ways in which lithium industries in the... (shrink)

A Zenonian supertask involving an infinite number of colliding balls is considered, under the restriction that the total mass of all the balls is finite. Classical mechanics leads to the conclusion that momentum, but not necessarily energy, must be conserved. Relativistic mechanics, on the other hand, implies that energy and momentum conservation are always violated. Quantum mechanics, however, seems to rule out the Zeno configuration as an inconsistent system.

Identifies methodological problems in the philosophy of science and contemporary science, particularly chemistry. Shows that Lonergan's generalized empirical method can solve these problems.

The widespread adoption of radioisotopes as tools in biomedical research and therapy became one of the major consequences of the "physicists' war" for postwar life science. Scientists in the Manhattan Project, as part of their efforts to advocate for civilian uses of atomic energy after the war, proposed using infrastructure from the wartime bomb project to develop a government-run radioisotope distribution program. After the Atomic Energy Bill was passed and before the Atomic Energy Commission was formally established, (...) the Manhattan Project began shipping isotopes from Oak Ridge. Scientists and physicians put these reactor-produced isotopes to many of the same uses that had been pioneered with cyclotron-generated radioisotopes in the 1930s and early 1940s. The majority of early AEC shipments were radioiodine and radiophosphorus, employed to evaluate thyroid function, diagnose medical disorders, and irradiate tumors. Both researchers and politicians lauded radioisotopes publicly for their potential in curing diseases, particularly cancer. However, isotopes proved less successful than anticipated in treating cancer and more successful in medical diagnostics. On the research side, reactor-generated radioisotopes equipped biologists with new tools to trace molecular transformations from metabolic pathways to ecosystems. The U.S. government's production and promotion of isotopes stimulated their consumption by scientists and physicians, such that in the postwar period isotopes became routine elements of laboratory and clinical use. In the early postwar years, radioisotopes signified the government's commitment to harness the atom for peace, particularly through contributions to biology, medicine, and agriculture. (shrink)

The main aim of the paper is to reinforce the notion that emergence is a basic characteristic of the molecular sciences in general and chemistry in particular. Although this point is well accepted, even in the primary reference on emergence, the keyword emergence is rarely utilized by chemists and molecular biologists and chemistry textbooks for undergraduates. The possible reasons for this situation are discussed. The paper first re-introduces the concept of emergence based on very simple geometrical forms; and (...) considers some simple chemical examples among low and high molecular weight compounds. On the basis of these chemical examples, a few interesting philosophical issues inherent to the field of emergence are discussed – again making the point that such examples, given their clarity and simplicity, permit one to better understand the complex philosophical issues. Thus, the question of predictability is discussed, namely whether and to what extent can emergent properties be predicted on the basis of the component’s properties; or the question of the explicability (a top down process). The relation between reductionism and emergentism is also discussed as well as the notion of downward causality and double causality (macrodeterminism); namely the question whether and to what extent the emergent properties of the higher hierarchic level affect the properties of the lower level components. Finally, the question is analyzed, whether life can be considered as an emergent property. More generally, the final point is made, that the re-introduction of the notion of emergence in chemistry, and in particular in the teaching, may bring about a deeper understanding of the meaning of chemical complexity and may bring chemistry closer to the humanistic areas of philosophy and epistemology. (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)

Climatology is a paradigmatic complex systems science. Understanding the global climate involves tackling problems in physics, chemistry, economics, and many other disciplines. I argue that complex systems like the global climate are characterized by certain dynamical features that explain how those systems change over time. A complex system's dynamics are shaped by the interaction of many different components operating at many different temporal and spatial scales. Examining the multidisciplinary and holistic methods of climatology can help us better understand the (...) nature of complex systems in general. -/- Questions surrounding climate science can be divided into three rough categories: foundational, methodological, and evaluative questions. "How do we know that we can trust science?" is a paradigmatic foundational question (and a surprisingly difficult one to answer). Because the global climate is so complex, questions like "what makes a system complex?" also fall into this category. There are a number of existing definitions of `complexity,' and while all of them capture some aspects of what makes intuitively complex systems distinctive, none is entirely satisfactory. Most existing accounts of complexity have been developed to work with information-theoretic objects (signals, for instance) rather than the physical and social systems studied by scientists. -/- Dynamical complexity, a concept articulated in detail in the first third of the dissertation, is designed to bridge the gap between the mathematics of contemporary complexity theory (in particular the formalism of "effective complexity" developed by Gell-Mann and Lloyd [2003]) and a more general account of the structure of science generally. Dynamical complexity provides a physical interpretation of the formal tools of mathematical complexity theory, and thus can be used as a framework for thinking about general problems in the philosophy of science, including theories, explanation, and lawhood. -/- Methodological questions include questions about how climate science constructs its models, on what basis we trust those models, and how we might improve those models. In order to answer questions about climate modeling, it's important to understand what climate models look like and how they are constructed. Climate model families are significantly more diverse than are the model families of most other sciences (even sciences that study other complex systems). Existing climate models range from basic models that can be solved on paper to staggeringly complicated models that can only be analyzed using the most advanced supercomputers in the world. I introduce some of the central concepts in climatology by demonstrating how one of the most basic climate models might be constructed. I begin with the assumption that the Earth is a simple featureless blackbody which receives energy from the sun and releases it into space, and show how to model that assumption formally. I then gradually add other factors (e.g. albedo and the greenhouse effect) to the model, and show how each addition brings the model's prediction closer to agreement with observation. After constructing this basic model, I describe the so-called "complexity hierarchy" of the rest of climate models, and argue that the sense of "complexity" used in the climate modeling community is related to dynamical complexity. -/- With a clear understanding of the basics of climate modeling in hand, I then argue that foundational issues discussed early in the dissertation suggest that computation plays an irrevocably central role in climate modeling. "Science by simulation" is essential given the complexity of the global climate, but features of the climate system--the presence of non-linearities, feedback loops, and chaotic dynamics--put principled limits on the effectiveness of computational models. This tension is at the root of the staggering pluralism of the climate model hierarchy, and suggests that such pluralism is here to stay, rather than an artifact of our ignorance. Rather than attempting to converge on a single "best fit" climate model, we ought to embrace the diversity of climate models, and view each as a specialized tool designed to predict and explain a rather narrow range of phenomena. Understanding the climate system as a whole requires examining a number of different models, and correlating their outputs. This is the most significant methodological challenge of climatology. -/- Climatology's role contemporary political discourse raises an unusually high number of evaluative questions for a physical science. The two leading approaches to crafting policy surrounding climate change center on mitigation (i.e. stopping the changes from occurring) and adaptation (making post hoc changes to ameliorate the harm caused by those changes). Crafting an effective socio-political response to the threat of anthropogenic climate change, however, requires us to integrate multiple perspectives and values: the proper response will be just as diverse and pluralistic as the climate models themselves, and will incorporate aspects of both approaches. I conclude by offering some concrete recommendations about how to integrate this value pluralism into our socio-political decision making framework. (shrink)

The success of a few theories in statistical thermodynamics can be correlated with their selectivity to reality. These are the theories of Boltzmann, Gibbs, end Einstein. The starting point is Carnot’s theory, which defines implicitly the general selection of reality relevant to thermodynamics. The three other theories share this selection, but specify it further in detail. Each of them separates a few main aspects within the scope of the implicit thermodynamic reality. Their success grounds on that selection. Those aspects can (...) be represented by corresponding oppositions. These are: macroscopic – microscopic; elements – states; relational – non-relational; and observable – theoretical. They can be interpreted as axes of independent qualities constituting a common qualitative reference frame shared by those theories. Each of them can be situated in this reference frame occupying a different place. This reference frame can be interpreted as an additional selection of reality within Carnot’s initial selection describable as macroscopic and both observable and theoretical. The deduced reference frame refers implicitly to many scientific theories independent of their subject therefore defining a general and common space or subspace for scientific theories (not for all). The immediate conclusion is: The examples of a few statistical thermodynamic theories demonstrate that the concept of “reality” is changed or generalized, or even exemplified (i.e. “de-generalized”) from a theory to another. Still a few more general suggestions referring the scientific realism debate can be added: One can admit that reality in scientific theories is some partially shared common qualitative space or subspace describable by relevant oppositions and rather independent of their subject quite different in general. Many or maybe all theories can be situated in that space of reality, which should develop adding new dimensions in it for still newer and newer theories. Its division of independent subspaces can represent the many-realities conception. The subject of a theory determines some relevant subspace of reality. This represents a selection within reality, relevant to the theory in question. The success of that theory correlates essentially with the selection within reality, relevant to its subject. (shrink)

In 1891 Cambridge biologist William Bateson (1861–1926) announced his idea that the symmetrical segmentation in living organisms resulted from energy peaks of some vibratory force acting on tissues during morphogenesis. He also demonstrated topographically how folding a radially symmetric organism could produce another with bilateral symmetry. Bateson attended many lectures at the Cambridge Philosophical Society and viewed mechanical models prepared by eminent physicists that illustrated how vibrations affected materials. In his subsequent research, Bateson utilized analogies and metaphors based upon (...) his observations of nature to build a thought model on the effects of vibrations on living tissue, because he realized that the chemistry and biology of his day lacked technologies to perform actual experiments on the subject. He concluded the production of organic segmentation was both a chemical and mechanical phenomenon. By the time of his death Bateson had incorporated new ideas about embryonic organizer regions to suggest a center from which a rhythmic force emanated and then produced the observed repetitive segmentation as a common feature in living organisms. (shrink)

A new theory of particles proposed in an earlier paper is now applied to explain energy. Having earlier derived the Rydberg formula for atomic spectra without using the Pauli principle, the authors now derive the photoelectric effect, deflection of light by gravitation, and Planck's law for blackbody radiation without using Planck's assumption on energy quanta or Einstein's theory of general relativity.

The paper investigates the status of gravitational energy in Newtonian Gravity, developing upon recent work by Dewar and Weatherall. The latter suggest that gravitational energy is a gauge quantity. This is potentially misleading: its gauge status crucially depends on the spacetime setting one adopts. In line with Møller-Nielsen’s plea for a motivational approach to symmetries, we supplement Dewar and Weatherall’s work by discussing gravitational energy–stress in Newtonian spacetime, Galilean spacetime, Maxwell-Huygens spacetime, and Newton–Cartan Theory. Although we ultimately (...) concur with Dewar and Weatherall that the notion of gravitational energy is problematic in NCT, our analysis goes beyond their work. The absence of an explicit definition of gravitational energy–stress in NCT somewhat detracts from the force of Dewar and Weatherall’s argument. We fill this gap by examining the supposed gauge status of prima facie plausible candidates—NCT analogues of gravitational energy–stress pseudotensors, the Komar mass, and the Bel-Robinson tensor. Our paper further strengthens Dewar and Weatherall’s results. In addition, it sheds more light upon the subtle link between sufficiently rich inertial structure and the definability of gravitational energy in NG. (shrink)

Teaching chemistry remains a profoundly challenging activity. This paper arises from reflection on the challenges of creating meaningful assessments. Herein a simple framework to assist in making more visible the different kinds of knowledge required for mastery of chemistry is described. Building from a realist foundation the purpose of this paper is to lay the intellectual scaffolding for the framework. By situating the framework theoretically, it is intended to highlight the value of engaging with philosophy for the project (...) of knowledge building in chemistry. Use of this framework has laid bare some significant limitations to the ways in which organic chemistry has been assessed. Making the visible to students aids in their engagement with knowledge and for a small minority has developed their understanding of science more generally. The framework provides a simple, easily usable tool for the evaluation of chemistry assessments. (shrink)

The function of metaphor in science has been labeled as decorative, persuasive, heuristic, instrumental, facilitating or obstructing. It has sometimes been regarded as inspiring, provoking, perverting or destroying rational thought. Metaphor’s positive role has been noted by philosophers, historians of chemistry, and science education researchers. It has been hailed as a descriptive and explanatory device that stimulates and shapes concept development. I discuss how metaphor functions in science generally, then refine this idea through an examination metaphor’s role in chemical (...) thinking in three contexts: the history and philosophy of chemistry, laboratory research practice, and chemical education. I aim to show how metaphor is already operative in the chemist’s use of the concept of chemical element and that this understanding characterizes chemical thinking in general. The chapter concludes with a discussion of a specifically chemical understanding of metaphor. (shrink)