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Foundations and Ubiquity of Classical Thermodynamics

A topical collection in Entropy (ISSN 1099-4300). This collection belongs to the section "Thermodynamics".

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Editor

Department of Mechanical Engineering, Northern Illinois University, DeKalb, IL 60115, USA
Interests: fundamental laws of nature; thermodynamics and heat transfer fundamentals; the second law of thermodynamics and entropy; energy efficiency; conservation and sustainability; fluids-thermal-energy components and systems; nanotechnology and nanofluids
Special Issues, Collections and Topics in MDPI journals

Topical Collection Information

Dear Colleagues,

Thermodynamics is a science of Energy and Entropy, and therefore, the very foundation of all other sciences and of all creative applications.

Classical thermodynamics crystallizes a diverse and complex reality to a fundamental cause-and-effect ubiquitous simplicity by its fundamental principles. That is why it is hard to understand thermodynamics “the first time or the second time through”.

The phenomenological Laws of Thermodynamics have much wider, including philosophical, significance and implications than their simple expressions based on experimental observations—they are The Fundamental Laws of Nature: The Zeroth (equilibrium existentialism), the First (conservational transformationalism), the Second (forced, irreversible–directional transformationalism), and the Third (unattainability of ‘emptiness’). These Laws define and unify our comprehension of all existence and transformations in the universe.

Classical thermodynamics, formalized in the nineteenth century by Sadi Carnot, Clausius, Joule, Helmholtz, Kelvin, Gibbs, and others, established the fundamental laws by corelating the energy of thermomechanical processes and macroproperties irrespective of the microstructure of material systems. The fundamental laws and macroscopic constitutive correlations have been deduced from reversible process-equivalency, from one to another equilibrium state, but are nevertheless conceptually universal and valid for all diverse irreversible processes at all space and time scales.

Phenomenological, classical thermodynamics, with its fundamental principles, paved the way for the development of modern thermodynamics in the twentieth century by Lars Onsager, Ilya Prigogine, and others, with branches in many areas of theoretical and practical sciences, by expanding classical, fundamental laws to the underlying microstructure of all existence and diverse processes in nature, the latter driven by free energy’s irreversible forcing and displacement of mass-energy towards mutual equilibrium uniformity, while dissipating nonequilibrium free energy to thermal heat and thus expanding the thermal displacement space, quantified by the entropy production and entropy property.

From classical to chemical to biological thermodynamics, from heat engines to so-called self-evolving dissipative structures and life processes, there are many challenges and opportunities to be comprehended and further developed. Human comprehension is always subjective, and more objective progress requires that all possible alternatives be recognized and considered to advance our knowledge. The causes and effects are entwined and often hard to differentiate. The irreversible processes are destroyers but also creators of order. Are creation of order and life processes within “dissipative structures” driven by dissipative processes or are the latter mere consequences of irreversible processes driven by nonequilibrium free energy? These are but some of the many challenges and opportunities to be comprehended and creatively exploited for the betterment of the society and sustainability of nature we live in.

Classical, phenomenological thermodynamics today has unjustifiably a dubious status. Some modern physicists regard classical thermodynamics as an obsolete relic. Often, mostly due to lack of comprehension, thermodynamics is considered as an engineering subject and thus not as the most fundamental science of energy and nature. Apart from the view that thermodynamics is obsolete, there is a widespread belief among scientists in thermodynamics’ absolute authority.

This Topical Collection focuses on original reasoning and new research results in fundamentals and applications in thermodynamics. Original manuscripts with a focus on phenomenological fundamentals and applications, including critical up-to-date reviews, are solicited. We welcome submissions addressing novel issues, as well as those on more specific topics. It is hoped that this collection will inspire and motivate scientists and practitioners to revisit important and critical issues related to the Laws of Thermodynamics as the most fundamental laws of nature.

Prof. Dr. Milivoje M. Kostic
Collection Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the collection website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Entropy is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Published Papers (5 papers)

2021

Jump to: 2020

15 pages, 994 KiB  
Article
First-Order Phase Transformation at Constant Volume: A Continuous Transition?
by Víctor F. Correa and Facundo J. Castro
Entropy 2022, 24(1), 31; https://0-doi-org.brum.beds.ac.uk/10.3390/e24010031 - 24 Dec 2021
Viewed by 5322
Abstract
We describe a first-order phase transition of a simple system in a process where the volume is kept constant. We show that, unlike what happens when the pressure is constant, (i) the transformation extends over a finite temperature (and pressure) range, (ii) each [...] Read more.
We describe a first-order phase transition of a simple system in a process where the volume is kept constant. We show that, unlike what happens when the pressure is constant, (i) the transformation extends over a finite temperature (and pressure) range, (ii) each and every extensive potential (internal energy U, enthalpy H, Helmholtz energy F, and Gibbs energy G), and the entropy S is continuous across the transition, and (iii) the constant-volume heat capacity does not diverge during the transition and only exhibits discrete jumps. These non-intuitive results highlight the importance of controlling the correct variables in order to distinguish between continuous and discontinuous transitions. We apply our results to describe the transition between ice VI and liquid water using thermodynamic information available in the literature and also to show that a first-order phase transition driven in isochoric condition can be used as the operating principle of a mechanical actuator. Full article
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21 pages, 592 KiB  
Article
Thermodynamic Derivation of Scaling at the Liquid–Vapor Critical Point
by Juan Carlos Obeso-Jureidini, Daniela Olascoaga and Victor Romero-Rochín
Entropy 2021, 23(6), 720; https://0-doi-org.brum.beds.ac.uk/10.3390/e23060720 - 05 Jun 2021
Viewed by 1809
Abstract
With the use of thermodynamics and general equilibrium conditions only, we study the entropy of a fluid in the vicinity of the critical point of the liquid–vapor phase transition. By assuming a general form for the coexistence curve in the vicinity of the [...] Read more.
With the use of thermodynamics and general equilibrium conditions only, we study the entropy of a fluid in the vicinity of the critical point of the liquid–vapor phase transition. By assuming a general form for the coexistence curve in the vicinity of the critical point, we show that the functional dependence of the entropy as a function of energy and particle densities necessarily obeys the scaling form hypothesized by Widom. Our analysis allows for a discussion of the properties of the corresponding scaling function, with the interesting prediction that the critical isotherm has the same functional dependence, between the energy and the number of particles densities, as the coexistence curve. In addition to the derivation of the expected equalities of the critical exponents, the conditions that lead to scaling also imply that, while the specific heat at constant volume can diverge at the critical point, the isothermal compressibility must do so. Full article
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2020

Jump to: 2021

11 pages, 233 KiB  
Editorial
The Second Law and Entropy Misconceptions Demystified
by Milivoje M. Kostic
Entropy 2020, 22(6), 648; https://0-doi-org.brum.beds.ac.uk/10.3390/e22060648 - 11 Jun 2020
Cited by 6 | Viewed by 9462
Abstract
The challenges and claims of hypothetical violations of the Second Law of thermodynamics have been a topic of many scientific, philosophical and social publications, even in the most prestigious scientific journals. Fascination with challenging the Second Law has further accelerated throughout the development [...] Read more.
The challenges and claims of hypothetical violations of the Second Law of thermodynamics have been a topic of many scientific, philosophical and social publications, even in the most prestigious scientific journals. Fascination with challenging the Second Law has further accelerated throughout the development of statistical and quantum physics, and information theory. It is phenomenologically reasoned here that non-equilibrium, useful work-energy potential is always dissipated to heat, and thus thermodynamic entropy (a measure of thermal disorder, not any other disorder) is generated always and everywhere, at any scale without exception, including life processes, open systems, micro-fluctuations, gravity or entanglement. Furthermore, entropy cannot be destroyed by any means at any scale (entropy is conserved in ideal, reversible processes and irreversibly generated in real processes), and thus, entropy cannot overall decrease, but only overall increase. Creation of ordered structures or live species always dissipate useful energy and generate entropy, without exception, and thus without Second Law violation. Entropy destruction would imply spontaneous increase in non-equilibrium, with mass-energy flux displacement against cause-and-effect, natural forces, as well as negate the reversible existence of the very equilibrium. In fact, all resolved challengers’ paradoxes and misleading violations of the Second Law to date have been resolved in favor of the Second Law and never against. We are still to witness a single, still open Second Law violation, to be confirmed. Full article
9 pages, 290 KiB  
Article
Derivation of the Critical Point Scaling Hypothesis Using Thermodynamics Only
by Víctor Romero-Rochín
Entropy 2020, 22(5), 502; https://0-doi-org.brum.beds.ac.uk/10.3390/e22050502 - 27 Apr 2020
Cited by 1 | Viewed by 2365
Abstract
Based on the foundations of thermodynamics and the equilibrium conditions for the coexistence of two phases in a magnetic Ising-like system, we show, first, that there is a critical point where the isothermal susceptibility diverges and the specific heat may remain finite, and [...] Read more.
Based on the foundations of thermodynamics and the equilibrium conditions for the coexistence of two phases in a magnetic Ising-like system, we show, first, that there is a critical point where the isothermal susceptibility diverges and the specific heat may remain finite, and second, that near the critical point the entropy of the system, and therefore all free energies, do obey scaling. Although we limit ourselves to such a system, we elaborate about the possibilities of finding universality, as well as the precise values of the critical exponents using thermodynamics only. Full article
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48 pages, 497 KiB  
Article
A History of Thermodynamics: The Missing Manual
by Wayne M. Saslow
Entropy 2020, 22(1), 77; https://0-doi-org.brum.beds.ac.uk/10.3390/e22010077 - 07 Jan 2020
Cited by 15 | Viewed by 11509
Abstract
We present a history of thermodynamics. Part 1 discusses definitions, a pre-history of heat and temperature, and steam engine efficiency, which motivated thermodynamics. Part 2 considers in detail three heat conservation-based foundational papers by Carnot, Clapeyron, and Thomson. For a reversible Carnot cycle [...] Read more.
We present a history of thermodynamics. Part 1 discusses definitions, a pre-history of heat and temperature, and steam engine efficiency, which motivated thermodynamics. Part 2 considers in detail three heat conservation-based foundational papers by Carnot, Clapeyron, and Thomson. For a reversible Carnot cycle operating between thermal reservoirs with Celsius temperatures t and t + d t , heat Q from the hot reservoir, and net work W, Clapeyron derived W / Q = d t / C ( t ) , with C ( t ) material-independent. Thomson used μ = 1 / C ( t ) to define an absolute temperature but, unaware that an additional criterion was needed, he first proposed a logarithmic function of the ideal gas temperature T g . Part 3, following a discussion of conservation of energy, considers in detail a number of energy conservation-based papers by Clausius and Thomson. As noted by Gibbs, in 1850, Clausius established the first modern form of thermodynamics, followed by Thomson’s 1851 rephrasing of what he called the Second Law. In 1854, Clausius theoretically established for a simple Carnot cycle the condition Q 1 / T 1 + Q 2 / T 2 = 0 . He generalized it to i Q i / T g , i = 0 , and then d Q / T g = 0 . This both implied a new thermodynamic state function and, with appropriate integration factor 1 / T , the thermodynamic temperature. In 1865, Clausius named this new state function the entropy S. Full article
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