The aim of this article is to analyse the relation between the second law of thermodynamics and the so-called arrow of time. For this purpose, a number of different aspects in this arrow of time are distinguished, in particular those of time-reversal (non-)invariance and of (ir)reversibility. Next I review versions of the second law in the work of Carnot, Clausius, Kelvin, Planck, Gibbs, Caratheodory and Lieb and Yngvason, and investigate their connection with these aspects of the arrow of time. It (...) is shown that this connection varies a great deal along with these formulations of the second law. According to the famous formulation by Planck, the second law expresses the irreversibility of natural processes. But in many other formulations irreversibility or even time-reversal non-invariance plays no role. I therefore argue for the view that the second law has nothing to do with the arrow of time. (shrink)

In the history of science, the birth of classical chemistry and thermodynamics produced an anomaly within Newtonian mechanical paradigm: force and acceleration were no longer citizens of new cited sciences. Scholars tried to reintroduce them within mechanistic approaches, as the case of the kinetic gas theory. Nevertheless, Thermodynamics, in general, and its Second Law, in particular, gradually affirmed their role of dominant not-reducible cognitive paradigms for various scientific disciplines: more than twenty formulations of Second Law—a sort of indisputable intellectual wealth—are (...) conceived after 1824 Sadi Carnot’s original statement and a multitude of entropy functions are proposed after 1865 Clausius’ former definition. Furthermore, at the end of nineteenth century, thermodynamics extended its cognitive domain to chemistry. Mainly thanks to Gibbs, a brand new discipline—chemical thermodynamics or physical chemistry—gradually affirmed its role inside the scientific community. This paper reports the former results of collaborative research program in the History and Epistemology of Science as well as Nature of Science Teaching aimed at retracing the foundations of the physical chemistry. Specifically, the research is structured in three parts: historical-epistemic reflections on fundamental thermodynamic concepts and principles—such as reversible process, heat, temperature, thermal equilibrium and Clausius’ Second Law—that play a structural role inside modern physical chemistry; panoramic overview on the entropy, whose polysemy makes it one of the most demanding concepts for scholars, teachers and students while approaching thermodynamics; conceptualization of chemical equilibrium as complex entity according to the dual epistemological approach offered by Gibbs’ thermodynamic model and the kinetic standpoint by Guldberg and Waage. In particular, the present work details an original reading of thermodynamic principles with the aim of setting forth a rationalized multidisciplinary substrate whereon the foundational concepts of reversible process and thermal equilibrium can be set. (shrink)

In the history of science, the birth of classical chemistry and thermodynamics produced an anomaly within Newtonian mechanical paradigm: force and acceleration were no longer citizens of new cited sciences. Scholars tried to reintroduce them within mechanistic approaches, as the case of the kinetic gas theory. Nevertheless, Thermodynamics, in general, and its Second Law, in particular, gradually affirmed their role of dominant not-reducible cognitive paradigms for various scientific disciplines: more than twenty formulations of Second Law—a sort of indisputable intellectual wealth—are (...) conceived after 1824 Sadi Carnot’s original statement and a multitude of entropy functions are proposed after 1865 Clausius’ former definition. Furthermore, at the end of nineteenth century, thermodynamics extended its cognitive domain to chemistry. Mainly thanks to Gibbs, a brand new discipline—chemical thermodynamics or physical chemistry—gradually affirmed its role inside the scientific community. This paper reports the former results of collaborative research program in the History and Epistemology of Science as well as Nature of Science Teaching aimed at retracing the foundations of the physical chemistry. Specifically, the research is structured in three parts: historical-epistemic reflections on fundamental thermodynamic concepts and principles—such as reversible process, heat, temperature, thermal equilibrium and Clausius’ Second Law—that play a structural role inside modern physical chemistry; panoramic overview on the entropy, whose polysemy makes it one of the most demanding concepts for scholars, teachers and students while approaching thermodynamics; conceptualization of chemical equilibrium as complex entity according to the dual epistemological approach offered by Gibbs’ thermodynamic model and the kinetic standpoint by Guldberg and Waage. In particular, the present work details an original reading of thermodynamic principles with the aim of setting forth a rationalized multidisciplinary substrate whereon the foundational concepts of reversible process and thermal equilibrium can be set. (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)

Standard descriptions of thermodynamically reversible processes attribute contradictory properties to them: they are in equilibrium yet still change their state. Or they are comprised of non-equilibrium states that are so close to equilibrium that the difference does not matter. One cannot have states that both change and no not change at the same time. In place of this internally contradictory characterization, the term “thermodynamically reversible process” is here construed as a label for a set of real processes of change involving (...) only non-equilibrium states. The properties usually attributed to a thermodynamically reversible process are recovered as the limiting properties of this set. No single process, that is, no system undergoing change, equilibrium or otherwise, carries those limiting properties. The paper concludes with an historical survey of characterizations of thermodynamically reversible processes and a critical analysis of their shortcomings. (shrink)

Bodies as conceived in macroscopic theories are loosely spoken of as participating in processes. But are there any systematic reasons for regarding processes as part of the ontology of macroscopic theory? The present paper suggests that suitable motivation can be found within a project of describing a phenomenological, macroscopic ontology for equilibrium thermodynamics, and outlines some aspects of the interrelation between continuant bodies and processes.

It is well-known that the invocation of `equilibrium processes' in thermodynamics is oxymoronic. However, their prevalence and utility, particularly in elementary accounts, presents a problem. We consider a way in which their role can be played by sets of sequences of processes demarcated by curves carrying the property of accessibility. We also examine the vexed question of whether equilibrium processes are necessarily reversible and the revision of this property in relation to sets of sequences of such processes.

This paper presents an in-depth analysis of the anatomy of both thermodynamics and statistical mechanics, together with the relationships between their constituent parts. Based on this analysis, using the renormalization group and finite-size scaling, we give a definition of a large but finite system and argue that phase transitions are represented correctly, as incipient singularities in such systems. We describe the role of the thermodynamic limit. And we explore the implications of this picture of critical phenomena for the questions of (...) reduction and emergence. (shrink)

This project is about the asymmetry of time. The main source of discontent for physicists and philosophers alike is that even though in every physical theory we developed and/or discovered for explaining how the universe functions, the laws are time reversal invariant; there seems to be a very genuine asymmetry between the past and the future. The aim of this project is to examine several attempts to solve this friction between the laws of physics and the asymmetry and provide a (...) new proposal that makes use of modern cosmology. In the recent history of physics and in contemporary philosophy of science there have been several attempts to explain the asymmetry of time and reconcile this asymmetry with time reversal invariant physical laws. David Albert developed one of the most recent attempts at solving the problem in Time and Chance (2000). Albert claims that there is a conclusive solution to the problem of asymmetry of time: namely, combining the laws of mechanics with several novel concepts that he introduces, the most important of which is what he calls "the past hypothesis". Eric Winsberg developed another modern attempt to solve the problem of the asymmetry of time. Winsberg combines Hans Reichenbach's branch systems proposal with a "framework" view of laws to solve the problem. Although this version of the branch systems proposal overcomes several problems associated with Reichenbach's original construction of the proposal, certain aspects of it are still open to critique. Following a brief introduction, my chapters include 1) a history of the problem of the asymmetry of time, in which I provide a historical overview of the issues particularly discussed by Boltzmann and his interlocutors, 2) a detailed evaluation of David Albert's account of the asymmetry of time, where he argues that we can solve all the problems if we use a combination of laws of physics and the past hypothesis, 3) a detailed overview of Eric Winsberg's account that depends a specific way of looking at the laws of physics--the framework view, and 4) my account, which attempts to solve the problem of the asymmetry of time, making extensive use of the developments on modern cosmology, specifically regarding the inflationary mechanism. I claim that if we take into account recent developments in modern cosmology and proposals for laws for initial conditions, then we cannot maintain the metaphysical status of the past hypothesis in Albert's project. Specifically, I argue that in order for a theory to make use of initial conditions of the universe, it has to include a set of laws from modern cosmology pertaining to that initial condition. I defend the position that inflation can supply the source of asymmetry when supported by the aggregate view of laws, which I introduce in the last chapter. The explanation of the asymmetry of time requires the use of dynamical equations from modern cosmology that would produce the boundary conditions. The boundary condition produced in this way would fill in for the source of the asymmetry of time. Consequently, I argue that the explanation of the asymmetry of time is encoded in the laws of modern cosmology. (shrink)