The autonomy of chemistry: old and new problems

The autonomy of chemistry and the legitimacy of the philosophy of chemistry are usually discussed in the context of the issue of reduction of chemistry to physics, and defended making use of the failure of reductionistic claims. Until quite recent times a rather widespread viewpoint was, however, that the failure of reductionistic claims concerns actually epistemological aspect of reduction only, but the ontological reduction of chemistry to physics cannot be denied. The new problems of the autonomy of chemistry in the context of reductionism seem to be ontological and metaphysical. In the present paper it is argued that there is no need for some kind of metaphysical-ontological underpinning for rejection of the secondary positions of chemistry and philosophy of chemistry with respect to physics and philosophy of physics. The issue can be elucidated in terms of the philosophy of science accepting practical realism (also known by other names).     

How to handle nanomaterials? The re-entry of individuals into the philosophy of chemistry

In this paper we will argue that the categories of physical individuals and chemical stuff are not sufficient to face the chemical ontology if nanomaterials are taken into account. From a perspective that considers ontological questions and wonders which the items involved in science are, we will argue that the domain of nanoscience must be considered as populated by entities that are neither individuals, as those of physics, nor stuff, as those items of macro-chemistry. This discussion, in virtue of the analysis of the nature of nanomaterials, leads to propose a proper ontological category for nanoparticles: nanoindividuals. Nanomaterials are sorts of individuals, but they are different from physical individuals and from chemical stuff. We will also claim to contribute to the growing field of the philosophy of chemistry, especially regarding discussions that manifest not only epistemological but also ontological issues. In this scenario, the field on nanoscience is particularly challenging.     

Stuff versus individuals

The general question to be considered in this paper points to the nature of the world described by chemistry: what is macro-chemical ontology like? In particular, we want to identify the ontological categories that underlie chemical discourse and chemical practice. This is not an easy task, because modern Western metaphysics was strongly modeled by theoretical physics. For this reason, we attempt to answer our question by contrasting macro-chemical ontology with the mainstream ontology of physics and of traditional metaphysics. In particular, we introduce the distinction between stuff-ontology, proper of chemistry, and individual-ontology, proper of physics. These two ontologies differ from each other in the basic categories of their own structures. On this basis, we characterize individual-ontology in such a way that the features of stuff-ontology will arise by contrast with it.     

Matters are not so clear on the physical side

According to ontological reductionism, molecular chemistry refers, at last, to the quantum ontology; therefore, the ontological commitments of chemistry turn out to be finally grounded on quantum mechanics. The main problem of this position is that nobody really knows what quantum ontology is. The purpose of this work is to argue that the confidence in the existence of the physical entities described by quantum mechanics does not take into account the interpretative problems of the theory: in the discussions about the relationship between chemistry and physics, difficulties are seen only on the side of chemistry, whereas matters highly controversial on the side of physics are taken for granted. For instance, it is usually supposed that the infinite mass limit in the Born-Oppenheimer approximation leads by itself to the concept of molecular framework used in molecular chemistry. We will argue that this assumption is implicitly based on an interpretative postulate for quantum mechanics, which, in turn, runs into difficulties when applied to the explanation of the simplest model of the hydrogen atom.     

ONTOLOGICAL REDUCTION: A COMMENT ON LOMBARDI AND LABARCA

In a recent article in this journal (Foundations of Chemistry, 7 (2005), 125–148) Lombardi and Labarca call into question a thesis of ontological reduction to which several writers on reduction subscribe despite rejecting a thesis of epistemological reduction. Lombardi and Labarca advocate instead a pluralistic ontology inspired by Putnam’s internal realism. I suggest that it is not necessary to go so far, and that a more critical view of the ontological reduction espoused by the authors they criticise circumvents the need to resort to their radical alternative.     

Is there a quantum definition of a molecule?

The paper surveys how chemistry has developed over the past two centuries starting from Lavoisier’s classification of the chemical elements at the end of the eighteenth century; the subsequent development of the atomic–molecular model of matter preoccupied chemists throughout the nineteenth century, while the results of the application of quantum theory to the molecular model has been the story of this century. Whereas physical chemistry originated in the nineteenth century with the measurement of the physical properties of groups of chemical compounds that chemists identified as families, the goal of chemical physics is the explanation of the facts of chemistry in terms of the principles and theories of physics. Chemical physics as such was only possible after the discovery of the quantum theory in the 1920’s. By then the first of the sub‐atomic particles had been discovered and seemingly it is no longer possible to discuss chemical facts purely in terms of atoms and molecules – one has to recognize the electron and the nucleus, the parts of atoms. The combination of classical molecular structure with the quantum properties of the electron has given us a tremendously successful account of chemistry called ‘quantum chemistry’. Yet from the perspective of the quantum theory the deepest part of chemistry, the existence of chemical isomers and the very idea of molecular structure that rationalizes it, remains a central problem for chemical physics. This revised version was published online in July 2006 with corrections to the Cover Date.     

Linking chemistry with physics: arguments and counterarguments

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 (Reducing chemistry to physics. Limits, models, consequences, Rijksuniversiteit Groningen, Groningen, 2012) 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.     

In between worlds: G.N. Lewis, the shared pair bond and its multifarious contexts

In this paper, I will look at the rather convoluted discovery process which gave birth to the concept of the shared electron pair bond as developed by G.N. Lewis, to be subsequently appropriated by the American founders of quantum chemistry, and highlight the complex relations between conceptual development and the different contexts in which ideas are created and presented. I will show how the successive installments of Lewis's model of the chemical bond were supported by and gained credence from an epistemological background in which Lewis explored the relations of chemistry to physics. Furthermore, they were shaped by the changing public contexts in which the successive metamorphoses of the ideas took place and their epistemological background was outlined and explored. The complexities which are always associated with a discovery process can therefore be illuminated if one pays attention to different interactive realms-the conceptual, epistemological, and the presentational one.     

Another scientific practice separating chemistry from physics: thought experiments

Thought experiments in the history of science display a striking asymmetry between chemistry and physics, namely that chemistry seems to lack well-known examples, whereas physics presents many famous examples. This asymmetry, I argue, is not independent data concerning the chemistry/physics distinction. The laws of chemistry such as the periodic table are incurably special, in that they make testable predictions only for a very restricted range of physical conditions in the universe which are necessarily conditioned by the contingences of chemical investigation. The argument depends on how ‚thought experiment’ is construed. Here, several recent accounts of thought experiments are surveyed to help formulate what I call ‚crucial’ thought experiments. These have a historical role in helping to judge between hypotheses in physics, but are not helpful in chemistry past or present.     

Internal realism and the problem of ontological autonomy: a critical note on Lombardi and Labarca

This paper discusses the proposal made by Lombardi and Labarca (Found Chem 7:125–148, 2005) that internal realism can secure the ontological autonomy of chemistry. I argue that internal realism is not, by itself, sufficient to accomplish this task. The fact that conceptual schemes may differ with respect to their theoretical virtues, and the possibility that the relations between them may be reductive undermine the premise that each conceptual scheme has an equal right to define its own ontology, which is a key premise in Lombardi and Labarca’s proposal.     

What did “theory” mean to nineteenth-century chemists?

Some recent philosophers of science have argued that chemistry in the nineteenth century “largely lacked theoretical foundations, and showed little progress in supplying such foundations” until around 1900, or even later. In particular, nineteenth-century atomic theory, it is said, “played no useful part” in the crowning achievement of nineteenth-century chemistry, the powerful subdiscipline of organic chemistry. This paper offers a contrary view. The idea that chemistry only gained useful theoretical foundations when it began to merge with physics, it will be argued, is based on an implicit conception of scientific theory that is too narrow, and too exclusively oriented to the science of physics. A broader understanding of scientific theory, and one that is more appropriate to the science of chemistry, reveals the essential part that theory played in the development of chemistry in the nineteenth century. It also offers implications for our understanding of the nature of chemical theory today.     

The semantics of chemical education: constructivism, externalism and the language of chemistry

In this paper we present a semantic analysis of the application of didactic constructivism to chemical education. We show that the psychological basis of constructivism yield, when applied to chemistry, an internalist semantics for the chemical names. Since these names have been presented as typical examples of an externalism for kind terms, a fundamental incompatibility ensues. We study this situation, to conclude that it affects chemical education at every level. Finally, we present a preliminary analysis of this problem from the point of view of physics.     

Breaking the law: promoting domain-specificity in chemical education in the context of arguing about the periodic law

In this paper, domain-specificity is presented as an understudied problem in chemical education. This argument is unpacked by drawing from two bodies of literature: learning of science and epistemology of science, both themes that have cognitive as well as philosophical undertones. The wider context is students’ engagement in scientific inquiry, an important goal for science education and one that has not been well executed in everyday classrooms. The focus on science learning illustrates the role of domain specificity in scientific reasoning. The discussion on epistemology of science presents ideas from the emerging field of philosophy of chemistry to highlight the much neglected area of epistemology in chemical education. Domain-specificity is exemplified in the context of chemical laws, in particular the Periodic Law. The applications of the discussion for chemical education are explored in relation to argumentation, itself an epistemologically grounded discourse pattern in science. The overall implications include the need for reconceptualization of the nature of teaching and learning in chemistry to include more particular epistemological aspects of chemistry.     

Explanation and theory formation in quantum chemistry

In this paper I expand Eric Scerri’s notion of Popper’s naturalised approach to reduction in chemistry and investigate what its consequences might be. I will argue that Popper’s naturalised approach to reduction has a number of interesting consequences when applied to the reduction of chemistry to physics. One of them is that it prompts us to look at a ‘bootstrap’ approach to quantum chemistry, which is based on specific quantum theoretical theorems and practical considerations that turn quantum ‘theory’ into quantum ‘chemistry’ proper. This approach allows us to investigate some of the principles that drive theory formation in quantum chemistry. These ‘enabling theorems’ place certain limits on the explanatory latitude enjoyed by quantum chemists, and form a first step into establishing the relationship between chemistry and physics in more detail.     

Chemistry and dynamics in the thought of G.W. Leibniz I

Chemistry and dynamics are closely related in G.W. Leibniz's thinking, from the corpuscularism of his youth to the theory of conspiracy movements that he proposes in his later years. Despite the importance of chemistry and chemical thought in Leibniz's philosophy, interpreters have not paid enough attention to this subject, especially in the recent decades. This work aims to contribute to filling this gap in Leibnizian studies. In this first part of the work I will expose the theory of matter that the young Leibniz conceives under the influence of chemical corpuscularism. Leibniz uses R. Boyle's interpretation of the Aristotelian idea of form in order to give an explanation of the unity and cohesion of bodies. As opposed to the Cartesians, Leibniz puts forth the idea of a dependence between the variables of extension, movement and figure, without losing analytical clarity and with the aim of extending the explanatory power of physics to natural phenomena difficult to approach by Cartesian mechanics.

     

The emancipation of chemistry

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.     

Computing minimal entropy production trajectories: an approach to model reduction in chemical kinetics

Advanced experimental techniques in chemistry and physics provide increasing access to detailed deterministic mass action models for chemical reaction kinetics. Especially in complex technical or biochemical systems the huge amount of species and reaction pathways involved in a detailed modeling approach call for efficient methods of model reduction. These should be automatic and based on a firm mathematical analysis of the ordinary differential equations underlying the chemical kinetics in deterministic models. A main purpose of model reduction is to enable accurate numerical simulations of even high dimensional and spatially extended reaction systems. The latter include physical transport mechanisms and are modeled by partial differential equations. Their numerical solution for hundreds or thousands of species within a reasonable time will exceed computer capacities available now and in a foreseeable future. The central idea of model reduction is to replace the high dimensional dynamics by a low dimensional approximation with an appropriate degree of accuracy. Here I present a global approach to model reduction based on the concept of minimal entropy production and its numerical implementation. For given values of a single species concentration in a chemical system all other species concentrations are computed under the assumption that the system is as close as possible to its attractor, the thermodynamic equilibrium, in the sense that all modes of thermodynamic forces are maximally relaxed except the one, which drives the remaining system dynamics. This relaxation is expressed in terms of minimal entropy production for single reaction steps along phase space trajectories.     

高分子科学基础实验的互串互动教学初探

提出将高分子化学实验、高分子物理实验以及加工测试有机地串联起来,成为一门环环相扣、便于互动教学的高分子科学基础实验课的初步设想。     

Methods and Applications of Quantum Chemistry. Part I: Physical and Mathematical Basis

After an introduction to the fundamental concepts of quantum mechanics it is shown how to describe a chemical system in the language of theoretical physics. The equations which one obtains can not, in general, be solved in closed form. Approximate numerical methods that furnish sufficiently accurate solutions for many problems of interest are, however, available. The most important of these are presented briefly, and are given physically visualizable interpretations as far as this is possible. Special attention is devoted to more modern methods of quantum chemistry, to the basis assumptions underlying them, their scope, and their limitations. Treatment of the theory of the chemical bond is reserved for Part II.