Nonequilibrium and irreversible thermodynamics

We propose a microphysical theory of the triboelectric effect by which mechanical rubbing separates charges across the interface between two surfaces. Surface electrons are treated as an open system, weakly coupled to two baths, corresponding to the bulk materials. We show that work can be extracted from the motion-induced population inversion of fermions, thus extending and generalizing Zel'dovich's theory of bosonic superradiance. We argue that this is consistent with the basic phenomenology of triboelectrification and triboluminescence as off-equilibrium processes.

In this paper, using the combination of the first and second laws of thermodynamics, the work bounds in thermodynamic cycles are investigated generally and, to show the application, the results are extracted for some physical systems. Also, a new concept on the available work limits is extracted. To provide information on the maximum or minimum amount of work to be done during a thermodynamic cycle, energy balance, as well as irreversibility, should be considered. Entropy production during a thermodynamic cycle as a limiting criterion for work to be done is expressed as Clausius inequality. Therefore an inequality extracted from the first and second laws of thermodynamic to obtain lower and upper bounds of available work. The obtained upper bound of the work to be done is in agreement with Carnot's rule. The lower bound is obtained at the maximum possible irreversibility during the respective cycle.

In order to study the human cardiovascular system, we develop a Windkessel model of the heart and the blood vessels. This model can be used to study the time evolution of various thermodynamic parameters, in different regimes of the heart (high blood pressure, low blood pressure, normal blood pressure, high speed, low speed, normal speed etc.). We draw qualitative pressure-volume diagrams in order to apply the Finite Speed Thermodynamics (FST) to this model.

Daniel R. Brooks and E. O. Wiley have proposed a theory of evolution in which fitness is merely a rate determining factor. Evolution is driven by nonequilibrium processes which increase the entropy and information content of species together. Evolution can occur without environmental selection, since increased complexity and organization result from the likely "capture" at the species level of random variations produced at the chemical level. Speciation can occur as the result of variation within the species which decreases the probability of sharing genetic information. Critics of the Brooks-Wiley theory argue that they have abused terminology from information theory and thermodynamics. In this paper I review the essentials of the theory, and give an account of hierarchical physical information systems within which the theory can be interpreted. I then show how the major conceptual objections can be answered.

In depth discussion of thermodynamics of a familiar system made of a room, a heater and
a window reveals the rich complexity underlying the deceptively simple assumption of
local thermodynamic equilibrium. It displays also the failure of available approaches to
non-equilibrium thermodynamics.

This paper presents an exergy and environmental assessment of a 1000 metric t/day ammonia production plant based on the steam methane reforming (SMR) process, including the syngas production, purification (CO 2 capture) and compression units, as well as the ammonia synthesis and purge gas treatment. An integrated heat recovery system produces power and steam at three pressure levels, besides exporting hot water, CO 2 and fuel gas, with no additional heat or power consumption being required. Two configurations for ammonia refrigeration process (À20 C) are compared in terms of power consumption. Exergy cost data for upstream processing stages of natural gas is used to calculate the extended exergy cost of the products of the plant, namely ammonia, CO 2 and fuel gas. Moreover, an appropriated methodology is employed to properly allocate the renewable and non-renewable exergy costs, as well as the CO 2 emissions of the reforming, shift and furnace stack among the products of the plant. By considering that the cost reduction of the combustion gases is a linear function of the exergy flow rate reduction in each component of the heat recovery system, an improved allocation of the CO 2 emission cost along the convection train is performed. A breakdown of the total exergy destruction rate of the plant (136.5 MW) shows that about 59% corresponds to the reforming process followed far behind by the ammonia synthesis and condensation (18.3%) and the gas purification units (13.2%). The overall exergy efficiency of the ammonia plant is calculated as 66.36%, which is enhanced by recovering the hydrogen-rich and fuel gases in the purge gas treatment process. The total and non-renewable exergy costs and CO 2 emission cost of the ammonia produced are calculated as 1.7950 kJ/kJ and 0.0881 kg CO2 /MJ, respectively. In addition, a rational exergy cost of 1.6370 kJ/kJ and CO 2 emission cost of 0.0821 kg CO2 /MJ are allocated to the CO 2 gas, which can be supplied as feedstock to an associated chemical plant (urea, methanol, polymers, etc.).

We review the progress made in extended irreversible thermodynamics during the ten years that have elapsed since the publication of our first review on the same subject (Rep. Prog. Phys. 1988 51 1105–72). During this decade much effort has been devoted to achieving a better understanding of the fundamentals and a broadening of the domain of applications. The macroscopic formulation of extended irreversible thermodynamics is reviewed and compared with other non-equilibrium thermodynamic theories. The foundations of EIT are discussed on the bases of information theory, kinetic theory, stochastic phenomena and computer simulations. Several significant applications are presented, some of them of considerable practical interest (non-classical heat transport, polymer solutions, non-Fickian diffusion, microelectronic devices, dielectric relaxation), and some others of special theoretical appeal (superfluids, nuclear collisions, cosmology). We also outline some basic problems which are not yet completely solved, such as the definitions of entropy and temperature out of equilibrium, the selection of the relevant variables, and the status to be reserved to the H-theorem and its relation to the second law. In writing this review, we had four objectives in mind: to show (i) that extended irreversible thermodynamics stands at the frontiers of modern thermodynamics; (ii) that it opens the way to new and useful applications; (iii) that much progress has been achieved during the last decade, and (iv) that the subject is far from being exhausted.

The first hurdle to understanding organisms in terms of physics is that they are highly differentiated, heterogeneous systems that transform energy at the level of individual molecules, whereas conventional physical theories apply to large ensembles of identical molecules. Beginning with a reformulation of thermodynamics that can apply to single molecules, I show how the space-time differentiation of organisms is thermodynamically and kinetically optimised for energy storage and transformation. I present heuristic arguments and empirical evidence towards a theory of the organism as a quantum coherent domain with infinitely many modes of coupled coherent activities. This leads to a new understanding of organic space-time as opposed to Newtonian space and time.

Disordered matter still presents stringent conceptual difficulties. The often confused concepts of amorphous and glassy states (and corresponding material substances) were re-examined and previous attempts to trace a distinction are revised and thoroughly discussed. We examine several rheological and thermodynamical aspects of glasses in the glass transformation region as well as the dynamics of associated relaxation processes.

In exothermic, equilibrium-limited processes such as ammonia synthesis, higher per-pass conversions are often achieved by withdrawing the enthalpy of reaction before the conversion has been completed. However, although inter-bed cooling may help controlling the bed feed temperatures and generates high pressure steam, it also shifts the reacting mixture away from equilibrium (i.e. by increasing the reacting driving force,-DG), thus increasing the process irreversibilities. In order to offset the unfavorable effects of the bed intercooling in the decreasing-volume reactive system as well as to reduce the power consumption , a catalytic once-through conversion section is introduced in a 1000 metric t NH3 /day ammonia synthesis unit. Three unit configurations are analyzed: two are based on single pressure loops (SP150, SP200), whereas the other one (DP) operates at two incremental levels of pressure (83/200 bar). The dual pressure process aims to show the relevance of the Counteraction Principle for driving the system ir-reversibilities down. The plant-wide and main components' performance are also compared in terms of exergy efficiency, economic revenues and utilities consumption. As a result, the syngas compressor, ammonia converter, waste heat recovery and ammonia refrigeration systems are found to be responsible for about 80e86% of total irreversibilities in the ammonia loop, which varies from 23.8 MW for DP and 27.2 MW for SP150. A cryogenic purge gas treatment unit allows improving the loop performance in 9e13% if compared to non-hydrogen-recovery systems.

The motivation for the continuous dimensionality of spacetime near the Fermi scale stems from two premises, namely, 1) dimensional regularization of perturbative quantum field theory (QFT), 2) the existence of non-trivial fixed points of Renormalization Group equations. Here we discuss a third reason, rooted in the behavior of non-equilibrium phase-space flows.

Ten necessary criteria for stability of various dissipative fluids and plasmas are derived from the first and the second principle of thermodynamics applied to a generic small mass element of the system, under the assumption that local thermodynamic equilibrium holds everywhere at all times. We investigate the stability of steady states of a mixture of different chemical species at the same temperature against volume-preserving perturbations. We neglect both electric and magnetic polarization, and assume negligible net mass sources and particle diffusion. We assume that both conduction- and radiation-induced heat losses increase with increasing temperature. We invoke no Onsager symmetry, no detailed model of heat transport and production, no “Extended
Thermodynamics,” no “Maxent” method, and no “new” universal criterion of stability for steady states of systems with dissipation. Each criterion takes the form of—or is a consequence of—a variational principle. We
retrieve maximization of entropy for isolated systems at thermodynamic equilibrium, as expected. If the
boundary conditions keep the relaxed state far from thermodynamic equilibrium, the stability criterion we
retrieve depends also on the detailed balance of momentum of a small mass element. This balance may include
the grad-p-related force, the Lorenz force of electromagnetism and the forces which are gradients of potentials. In
order to be stable, the solution of the steady-state equations of motion for a given problem should satisfy the
relevant stability criterion. Retrieved criteria include among others Taylor’s minimization of magnetic energy
with the constraint of given magnetic helicity in relaxed, turbulent plasmas, Rayleigh’s criterion of stability in
thermoacoustics, Paltridge et al.’s maximum entropy production principle for Earth’s atmosphere, Chandrasekhar’
minimization of the adverse temperature gradient in Bénard’s convective cells, and Malkus’ maximization of viscous power with the constraint of given mean velocity for turbulent shear flow in channels. It turns out that characterization of systems far from equilibrium, e.g., by maximum entropy production is not a
general property but—just like minimum entropy production—is reserved to special systems. A taxonomy of stability criteria is derived, which clarifies what is to be minimized, what is to be maximized and with which constraint for each problem.

Self-oscillatory and self-rotatory process driven by non-conservative forces have usually been treated as applications of the concepts of Hopf bifurcation and limit cycle in the theory of differential equations, or as instability problems in feedback control. Here we explore a complimentary approach, based on physical considerations of work extraction and thermodynamic irreversibility. From this perspective, the fact that a system can be destabilized by dissipation does not appear as a mathematical paradox, but rather as a straightforward consequence of the dissipative medium's motion. We apply this analysis to various mechanical and hydrodynamical systems of interest and show how it clarifies questions on which the literature remains contentious, such as the conditions for the appearance of non-conservative positional forces, or the roles of viscosity and turbulence in the raising of ocean waves by the wind.

Spatially uniform excitations can induce Floquet topological bandstructures within insulators which have equal characteristics to those of topological insulators. Going beyond we demonstrate in this article the evolution of Floquet topological quantum states for electromagnetically driven semiconductor bulk matter. We show the direct physical impact of the mathematical precision of the Floquet-Keldysh theory when we solve the driven system of a generalized Hubbard model with our framework of dynamical mean field theory (DMFT) in the non-equilibrium. We explain the physical consequences of the topological non-equilibrium effects in our results for correlated sysems with impact on optoelectronic applications.

An overview of the fundamental topics of Schr¨odinger’s seminal work, What is life? Chapters 6 and 7, respectively, and an analysis of them from the thermodynamic formalism of irreversible processes and complex systems is presented. In this way, a series of epistemological considerations are established that demonstrate the importance and topicality of Schr¨odinger’s work, not only from the physical point of view but also of its philosophical significance.

In this study we have incorporated the local nonequilibrium term into the Gibbs equation to obtain the local nonequilibrium correction to
the driving force for solidification of binary alloys. The local nonequilibrium correction has been used to calculate the effective liquidus slope andthe
interface temperature for the model with and without solute drag effects. It has been demonstrated that both the local nonequilibrium correction and
the solute drag play the most important role in the intermediate rage of the interface velocityV. When Vincreases up to VD, where VDis the char-acteristic diffusive velocity, a sharp transition to completely diffusionless and partitionless solidification occurs, which implies that the localnonequi-librium correction and the solute drag effects can be ignored. The transition is accompanied by a sharp change in the effective liquidus slope and the
interface temperature as functions of interface velocity. The model was applied to describe initial transient and steady-state solidification of Si–As
alloy and a good agreement between the model predictions and the available experimental data was obtained

Engines are open systems that can generate work cyclically, at the expense of an external disequilibrium. They are ubiquitous in nature and technology, but the course of mathematical physics over the last 300 years has tended to make their dynamics in time a theoretical blind spot. This has hampered the usefulness of statistical mechanics applied to active systems, including living matter. We argue that recent advances in the theory of open quantum systems, coupled with renewed interest in understanding how active forces result from positive feedback between different macroscopic degrees of freedom in the presence of dissipation, point to a more realistic description of autonomous engines. We propose a general conceptualization of an engine that helps clarify the distinction between its heat and work outputs. Based on this, we show how the external loading force and the thermal noise may be incorporated into the relevant equations of motion. This modifies the usual Fokker-Planck and Langevin equations, offering a thermodynamically complete formulation of the irreversible dynamics of simple oscillating and rotating engines.

Sustainability is a property of the complex system of which our species is only a part. We have come to know a great deal about that system, but still understand little about it. All of these ranking systems come from our knowledge, but fail to represent the kind of understanding critical to guiding our actions in such a way as not to undermine the security and coherence of the system. The more we try to expand and rely on our knowledge, the farther from understanding we tend to go. Such is the fundamental context of our modern age where science rules the roost. John Ehrenfeld (2009)

There is an urgent need for policies that can address both the challenges and opportunities for sustainable development in urban settings.
Within the past two decades, the idea of cities as fractal structures resulting from social and economic processes led to a transition in thinking of cities as machines to cities as organisms. Independently, the concept of ‘sustainable cities’ had emerged earlier, with many successful implementations already underway.
I propose to define a sustainable city as one able to feed and power itself as much as possible using land and energy efficiently with the least environmental pollution and impact on climate change, minimizing wastes and recycling and reconverting wastes into resources.
Coherent fractal space-time structures are the key to a circular thermodynamics of organisms and sustainable systems that achieves the state of minimum entropy production and dissipation that Ilya Prigogine had proposed as a conjecture. In this article, I explain how the principles of circular thermodynamics can be applied to sustainable cities.

The relation between macroscopic irreversibility and microscopic reversibility is a present unsolved problem. Constructal law is introduced to develop analytically the Einstein's, Schrödinger's, and Gibbs' considerations on the interaction between particles and thermal radiation (photons). The result leads to consider the atoms and molecules as open systems in continuous interaction with flows of photons from their surroundings. The consequent result is that, in any atomic transition, the energy related to the microscopic irreversibility is negligible, while when a great number of atoms (of the order of Avogadro's number) is considered, this energy related to irreversibility becomes so large that its order of magnitude must be taken into account. Consequently, macroscopic irreversibility results related to microscopic irreversibility by flows of photons and amount of atoms involved in the processes. In 1872, Boltzmann summarized his statistical mechanical results in his famous H-theorem. He introduced the irreversible evolution of any system towards a state of mechanical and thermal equilibrium. Loschmidt objected that this result is inconsistent, because any irreversible process cannot be obtained by using a time-symmetric dynamics 1. This controversy is no more than the problem of the link between the microscopic reversibility and the mac-roscopic irreversibility, named Loschmidt paradox. Despite the enormous advances of statistical mechanics in the description of equilibrium properties and transport processes in condensed matter, the problem of the non-contradictory microscopic foundation of both thermodynamics and kinetics remains unsolved 1. The analytical study of macroscopic irreversibility comes since 1789, when Benjamin Thompson (Count Rumford) highlighted that heat could be generated by friction 2. In 1803, Lazare Carnot analyzed the conservation of mechanical energy for pulleys and inclined planes, pointing out that, in any movement, there always exists a loss of " moment of activity " 3. But, the thermodynamic interpretation of this irreversibility was introduced first in 1824 by his son Sadi Carnot, who introduced the concept of the ideal engine, which is an ideal system which operates on a cycle in a completely reversible way, without any dissipation: unfortunately, efficiency of this ideal systems has an upper limit and isn't unitary. Surprisingly, even in ideal condition without any dissipation, there is something that prevents the conversion of all the energy absorbed, from an ideal reservoir, into work 4. This result was improved, in 1852, by Lord Kelvin, who pointed out that 5,6 :

We review the basic ideas and main results of our analysis of
shear-induced effects in polymer solutions and blends. The
analysis combines thermodynamic and hydrodynamic descriptions.
The flow contribution to the free energy of the solution
is described in the framework of extended irreversible
thermodynamics, which relates the viscoelastic constitutive
equations to a non-equilibrium entropy that depends on the
viscous pressure tensor. This yields, by differentiation, the
corresponding non-equilibrium equation of state for the
chemical potential, which couples diffusion flux to viscous
pressure in the presence of a flow. In some conditions, the
one-phase system becomes unstable and splits into two
phases, leading to a shift in the spinodal line. The theoretical
analysis is based on the stability of the mass and momentum
balance equations, the constitutive equations for viscous
pressure tensor and diffusion flux, and the equation of state
for the chemical potential. The resulting predictions corroborate
qualitatively the known experimental observations. Results
for dilute and entangled polymer solutions and for polymerblends are given

An in-depth study of the thermodynamics of nonequilibrium radiation is presented. The characterization of its nonequilibrium macroscopic state is performed in the framework of Informational Statistical Thermodynamics. This is done in terms of a nonequilibrium Dirac–Landau–Wigner single particle density matrix, or, alternatively, in terms of the conjugated intensive nonequilib-rium thermodynamic variables. When a local description is not required, the global one can be done by giving the nonequilibrium populations in the diierent modes. Also, alternatively, we can introduce a nonequilibrium temperature (quasi-temperature) per mode. This is compared to a couple of contracted descriptions. The evolution of the resulting nonequilibrium thermodynamic state and the eventual experimental determination are given in the follow-up article. c

We propose a dynamical theory of how the chemical energy stored in a battery generates the electromotive force (emf). In this picture, the battery's half-cell acts as an engine, cyclically extracting work from its underlying chemical disequilibrium. We show that the double layer at the electrode-electrolyte interface can exhibit a rapid self-oscillation that pumps an electric current, thus accounting for the persistent conversion of chemical energy into electrical work equal to the emf times the separated charge. We suggest a connection between this mechanism and the slow self-oscillations observed in various electrochemical cells, including batteries, as well as the enhancement of the current observed when ultrasound is applied to the half-cell. Finally, we propose more direct experimental tests of the predictions of this dynamical theory.

A mapping of non-extensive statistical mechanics with non-additivity parameter q = 1 into Gibbs' statistical mechanics exists (E. Vives, A. Planes, PRL 88 2, 020601 (2002)) which allows generalization to q = 1 both of Einstein's formula for fluctuations and of the 'general evolution criterion' (P. Glansdorff, I. Prigogine, Physica 30 351 (1964)), an inequality involving the time derivatives of thermodynamical quantities. Unified thermodynamic description of relaxation to stable states with either Boltzmann (q = 1) or power-law (q = 1) distribution of probabilities of microstates follows. If a 1D (possibly nonlinear) Fokker-Planck equation describes relaxation, then generalized Einstein's formula predicts whether the relaxed state exhibits a Boltzmann or a power law distribution function. If this Fokker-Planck equation is associated to the stochastic differential equation obtained in the continuous limit from a 1D, autonomous, discrete, noise-affected map, then we may ascertain if a a relaxed state follows a power-law statistics—and with which exponent—by looking at both map dynamics and noise level, without assumptions concerning the (additive or multiplicative) nature of the noise and without numerical computation of the orbits. Results agree with the simulations (J. R. Sánchez, R. Lopez-Ruiz, EPJ 143.1 (2007): 241–243) of relaxation leading to a Pareto-like distribution function.

Daniel Dennett's book, "Darwin's Dangerous Idea", is presented as an historical account and explication of evolutionary theory, and a demonstration of how Darwin's "dangerous idea" provides an explanation of the psychological or epistemic dimension of the world (or "mind in nature").  Its real agenda is to present Dennett's own theory theory of of the origin of "mind" in nature, a kind of computer age, neo-Pythagoreanism that seeks to legitimize the claims of artificial intelligence by locating the source of all agency, meaning, or "mind" in an otherwise "dead" world of physics and algorithms.  This approach continues the dominant tradition in modern science of radically separating the psychological and physical into two incommensurable parts, and it is this, the paradigmatic dualism at its core, and the erroneous and outdated empirical assumptions on which it is based, that are the book's undoing.  By correcting these assumptions, a principled basis is provided for grounding a commensurable theory dissolves the anomalies inherent in such Cartesian accounts.

We investigate the thermodynamical properties of quantum fields in curved spacetime. Our approach is to consider quantum fields in curved spacetime as a quantum system undergoing an out-of-equilibrium transformation. The non-equilibrium features are studied by using a formalism which has been developed to derive fluctuation relations and emergent irreversible features beyond the linear response regime. We apply these ideas to an expanding universe scenario, therefore avoiding assumptions on the relation between entropy and quantum matter. We provide a fluctuation theorem which allows us to understand particle production due to the expansion of the universe as an entropic increase. Our results pave the way towards a different understanding of the thermodynamics of relativistic and quantum systems in our universe.

In a viscous fluid, the past motion of an accelerating particle is retained as an imprint on the vorticity field, which decays slowly as t −3/2. At low Reynolds number, the Basset-Boussinesq-Oseen (BBO) equation correctly describes nonuniform particle motion, capturing hydrodynamic memory effects associated with this slow algebraic decay. Using the BBO equation, we numerically simulate driven single-particle transport to show that memory effects persist indefinitely under rather general driving conditions. In particular, when driving forces do not vary smoothly, hydrodynamic memory substantially lowers the effective transport friction. Remarkably, this enables coasting over a spatially uneven potential that otherwise traps particles modeled with pure Stokes drag. Our results provide direct physical insight into the role of particle-fluid coupling in nonequilibrium microparticle transport. Introduction.

It is widely assumed that the predictions, equations, and descriptions of Newtonian and Einsteinian physics are symmetrical with respect to time, prompting the question of how it is that known real-world asymmetries can result from time-symmetrical equations. We identify a fundamental time-asymmetry in the Newtonian Doppler equations, and explore its consequences. The "arrow of time" problem now appears solved for Newtonian theory, but not for theories based on special relativity.