Fundamental Laws Of Thermodynamics Research Articles

The Winding Road from Origin to Emergence (of Life).

Humanity's strive to understand why and how life appeared on planet Earth dates back to prehistoric times. At the beginning of the 19th century, empirical biology started to tackle this question yielding both Charles Darwin's Theory of Evolution and the paradigm that the crucial trigger putting life on its tracks was the appearance of organic molecules. In parallel to these developments in the biological sciences, physics and physical chemistry saw the fundamental laws of thermodynamics being unraveled. Towards the end of the 19th century and during the first half of the 20th century, the tensions between thermodynamics and the "organic-molecules-paradigm" became increasingly difficult to ignore, culminating in Erwin Schrödinger's 1944 formulation of a thermodynamics-compliant vision of life and, consequently, the prerequisites for its appearance. We will first review the major milestones over the last 200 years in the biological and the physical sciences, relevant to making sense of life and its origins and then discuss the more recent reappraisal of the relative importance of metal ions vs. organic molecules in performing the essential processes of a living cell. Based on this reassessment and the modern understanding of biological free energy conversion (aka bioenergetics), we consider that scenarios wherein life emerges from an abiotic chemiosmotic process are both thermodynamics-compliant and the most parsimonious proposed so far.

A Novel Designation of Solid Oxide Fuel Cell-Integrated System Using LPG as Fuel for Marine Vessels

A Novel Designation of Solid Oxide Fuel Cell-Integrated System Using LPG as Fuel for Marine Vessels

Physicochemical Perspective of Biological Heterogeneity.

The vast majority of chemical processes that govern our lives occur within living cells. At the core of every life process, such as gene expression or metabolism, are chemical reactions that follow the fundamental laws of chemical kinetics and thermodynamics. Understanding these reactions and the factors that govern them is particularly important for the life sciences. The physicochemical environment inside cells, which can vary between cells and organisms, significantly impacts various biochemical reactions and increases the extent of population heterogeneity. This paper discusses using physical chemistry approaches for biological studies, including methods for studying reactions inside cells and monitoring their conditions. The potential for development in this field and possible new research areas are highlighted. By applying physical chemistry methodology to biochemistry in vivo, we may gain new insights into biology, potentially leading to new ways of controlling biochemical reactions.

Procedure for calculation and analysis of transcritical cycle CO<sub>2</sub> with parallel compression and ejector

Attempts to reduce the negative impact on the environment have led, among other things, to the use of so-called natural refrigerants. One of which is SO2.
 At food processing enterprises, this refrigerant is used in two main cycles - cascade and transcritical.
 Along with the negative impact on the environment, it is also necessary to take into account the increase in the efficiency of refrigeration plants, which is especially important for transcritical cycles.
 The purpose of the study was to develop a method for calculating and analyzing the transcritical cycle of SO2 with parallel compression and an ejector.
 The calculation of the transcritical cycle is based on the fundamental laws of thermodynamics, the analysis method is based on the entropy-statistical method of thermodynamic analysis. Cycle calculation includes analysis of compression loss by system components.
 Description of operation of transcritical cycle of SO2 with parallel compression and ejector with two temperature levels is given, procedure of calculation and analysis of losses in elements of refrigerating unit operating according to transcritical cycle of SO2 with parallel compression and ejector is given.
 The use of this method allows you to identify the elements and processes with the greatest losses and take further measures to improve the efficiency of the refrigeration system.

Real-space observation of ergodicity transitions in artificial spin ice

Ever since its introduction by Ludwig Boltzmann, the ergodic hypothesis became a cornerstone analytical concept of equilibrium thermodynamics and complex dynamic processes. Examples of its relevance range from modeling decision-making processes in brain science to economic predictions. In condensed matter physics, ergodicity remains a concept largely investigated via theoretical and computational models. Here, we demonstrate the direct real-space observation of ergodicity transitions in a vertex-frustrated artificial spin ice. Using synchrotron-based photoemission electron microscopy we record thermally-driven moment fluctuations as a function of temperature, allowing us to directly observe transitions between ergodicity-breaking dynamics to system freezing, standing in contrast to simple trends observed for the temperature-dependent vertex populations, all while the entropy features arise as a function of temperature. These results highlight how a geometrically frustrated system, with thermodynamics strictly adhering to local ice-rule constraints, runs back-and-forth through periods of ergodicity-breaking dynamics. Ergodicity breaking and the emergence of memory is important for emergent computation, particularly in physical reservoir computing. Our work serves as further evidence of how fundamental laws of thermodynamics can be experimentally explored via real-space imaging.

COVID infection in 4 steps: Thermodynamic considerations reveal how viral mucosal diffusion, target receptor affinity and furin cleavage act in concert to drive the nature and degree of infection in human COVID-19 disease

We have developed a mechanistic model of SARS-CoV-2 and SARS-CoV infection, exploring the relationship between the viral diffusion in the mucosa and viral affinity for the angiotensin converting enzyme 2 (ACE2) target. Utilising the structural similarity of SARS-CoV and SARS-CoV-2 and a shared viral target receptor (ACE2), but a dramatic difference in upper or lower respiratory tract infectivity, we were able to generate insights into the linkage of mucosal diffusion and target receptor affinity in determining the pathophysiological pathways of these two viruses.Our analysis reveals that for SARS-CoV-2 the higher affinity of ACE2 binding, the faster and more complete the mucosal diffusion in its transport from the upper airway to the region of the ACE2 target on the epithelium. This diffusional process is essential for the presentation of this virus to the furin catalysed highly efficient entry and infection process in the upper respiratory tract epithelial cells. A failure of SARS-CoV to follow this path is associated with lower respiratory tract infection and decreased infectivity. Thus, our analysis supports the view that through tropism SARS-CoV-2 has evolved a highly efficient membrane entry process that can act in concert with a high binding affinity of this virus and its variants for its ACE2 which in turn promotes enhanced movement of the virus from airway to epithelium. In this way ongoing mutations yielding higher affinities of SARS-CoV-2 for the ACE2 target becomes the basis for higher upper respiratory tract infectivity and greater viral spread. It is concluded that SARS-CoV-2 is constrained in the extent of its activities by the fundamental laws of physics and thermodynamics. Laws that describe diffusion and molecular binding. Moreover it can be speculated that the very earliest contact of this virus with the human mucosa defines the pathogenesis of this infection.

A micromechanical constitutive model of high-temperature shape memory alloys

In this work, a new micromechanical constitutive model is constructed for high-temperature shape memory alloys. Different from the classical constitutive models, the microstructural patterns, heterogeneities of stress and strain fields at the microscopic scale are addressed. In the proposed model, three different inelastic deformation mechanisms, i.e., reversible martensitic transformation, irreversible transformation-induced plasticity, viscoplasticity, as well as their complex interactions, are considered. In addition to the well-known austenite and martensite phases, a new austenite-martensite interface phase is introduced to address the high local stress induced by the martensitic transformation. The modified Mori-Tanaka's homogenization scheme and Hill's interfacial operator are employed to determine the non-uniform stress fields of the three phases. To satisfy the thermodynamic compatibility of the proposed model, the driving forces and evolution equations of the three inelastic deformation mechanisms are derived based on the constructed Helmholtz free energy and the fundamental laws of irreversible thermodynamics. Inheritances of the plastic deformation induced by moving austenite-martensite (A-M) interface during repeated martensitic transformation and its reverse are incorporated. Temperature evolution caused by internal heat production and heat exchange with the ambient medium is also addressed. To validate the capability of the new constructed model, the predicted results of creep behavior and stress-assisted two-way shape memory effect of NiTiPd high-temperature shape memory alloys are compared with the experimental ones. The proposed model provides a theoretical tool for simultaneously analyzing the deformation behaviors at the macroscopic scale and underlying mechanisms at the microscopic scale.

A two-scale thermo-mechanically coupled constitutive model for grain size- and rate-dependent deformation of nano-crystalline NiTi shape memory alloy

In this paper, a two-scale thermo-mechanically coupled constitutive model is established to predict the grain size (GS)- and rate-dependent deformation of nano-crystalline super-elastic NiTi shape memory alloy (SMA). At the mesoscopic scale, the polycrystalline representative volume element (RVE) is considered as an aggregation of individual grains. Owing to the relatively large volume fraction (VF) of grain boundary in nano-crystalline NiTi SMA, an individual grain is further considered as a composite containing the grain interior (GI) and grain boundary (GB) phases. For the GI phase, a crystal plasticity-based model accounting for the internal heat generation is developed through the fundamental laws of irreversible thermodynamics. The constraint of GB phase on the martensite transformation in the GI phase is considered by introducing a scaling law between the transformation hardening modulus (THM) and GS. Owing to its un-transformable nature and relatively high yielding stress, the GB phase is assumed to behavior constitutively linear thermo-elasticity. To evaluate the thermo-mechanical interactions among the grains, GI phase and GB phase, and obtain the overall response of the polycrystalline RVE, a double inclusion self-consistent homogenization scheme involving the material nonlinearity and thermo-mechanical coupling effect is developed in an incremental form. At the macroscopic scale, the overall thermo-mechanical responses for the specimen of nano-crystalline NiTi SMA are obtained by solving the equations of force balance, deformation compatibility, and thermodynamic equilibrium through an approximation method. Finally, considering the specific texture measured in experiments, the proposed model is validated by predicting the GS- and rate-dependent deformation of nano-crystalline NiTi SMA sheet. Furthermore, the anisotropic thermo-mechanical responses of the sheet caused by the texture are predicted and discussed.

A Thermodynamically-based Modeling for the Creep and Plasticity of Al 5083 Alloy

To ensure a thermodynamic consistency for a constitutive model is a higher request for modeling the mechanical behaviors of materials. This paper conducts a thermodynamic analysis for a creep-plasticity model for Al 5083 alloy. The constitutive equations are derived from the fundamental thermodynamic laws, maintaining a rigorous physical basis of the proposed model. The monotonic tensile and creep tests are introduced for modeling, illustrating the rationality and accuracy of the proposed model.

Ults entropy in the structure of natural and technical systems “natural environment–object of activity–population”

The purpose of this article is to evaluate the categorical concept of entropy in the structure of natural and technical systems related to the use of water resources, the quantitative and qualitative indicators of which are formed within the spatial limits of river basin geosystems. Using fundamental basic concepts as a universal measure of the forms of motion of matter – energy, time, system, system approach and important concepts – irreversibility, ecological state, environmental safety, as well as fundamental laws of thermodynamics – conservation and changes in the zones of influence of the “Object of Activity” in the form of a complex of hydraulic structures and associated buildings as part of natural-technical system “Natural Environment–Object of Activity–Population” (NTS “NE-OA-P”) on the use of water resources in economic and other activities, to give a detailed understanding of Entropy.

Design and Practice of Physical Chemistry STS (Science, Technology, Society) Exercises to Cultivate Higher-Order Thinking Skills: “Fundamental Laws of Thermodynamics” as an Example

Design and Practice of Physical Chemistry STS (Science, Technology, Society) Exercises to Cultivate Higher-Order Thinking Skills: “Fundamental Laws of Thermodynamics” as an Example

Конструирование релятивистской гидродинамики многокомпонентной жидкости. 1. Метод релятивистской необратимой термодинамики

The paper develops relativistic mechanics and irreversible thermodynamics of a cosmological liquid mixture in which thermal conduction, diffusion, viscous flow and their crossing phenomena can occur. The main thermodynamic fields that occur in relativistic irreversible thermodynamics are defined as statistical expressions using relativistic kinetics. The effects of the Eckart approach on the choice of the hydrodynamic velocity are shown. The equations of relativistic multicomponent hydrodynamics for local densities of momentum, energy and number of particles of different sort, are also obtained from the fundamental conservation laws of relativistic thermodynamics.. The energy conservation law (the first beginning of relativistic thermodynamics) is formulated. Covariant Gibbs relation and local form of the second principle of thermodynamics in the presence of entropy source were derived in order to obtain determining relations linearly connecting fluxes with corresponding thermodynamic forces. Equivalent forms of relativistic entropy production in the form of a bilinear expression in terms of thermodynamic forces were obtained. A new cross-effect between diffusion and conduction arising from the relativistic term in the thermodynamic force coupled to the heat flux is discussed. The synopsis presented is of interest for relativistic mechanics, astrophysics, and cosmology.

Large Eddy Simulation and Thermodynamic Design of the Organic Rankine Cycle Based on Butane Working Fluid and the High-Boiling-Point Phenyl Naphthalene Liquid Heating System

Large Eddy Simulation (LES) and Thermodynamic study have been performed on Organic Rankine Cycle (ORC) components (boiler, evaporator, turbine, pump, and condenser). The petroleum Coke burner provided the heat flux needed for the butane evaporator. High boiling point fluid (called phenyl-naphthalene) has been applied in the ORC. The high boiling liquid is safer (steam explosion hazard may be prevented) for heating the butane stream. It has best exergy efficiency. It is non-corrosive, highly stable, and flammable. Fire Dynamics Simulator software (FDS) has been applied in order to simulate the pet-coke combustion and calculate the Heat Release Rate (HRR). The maximal temperature of the 2-Phenylnaphthalene flowing in the boiler is much less than its boiling temperature (600 K). Enthalpy, entropy and specific volume required for evaluating the heat rates and the power have been computed by employing the THERMOPTIM thermodynamic code. The proposed design ORC is safer. This is because the flammable butane is separated from the flame produced in the petroleum coke burner. The proposed ORC obeys the two fundamental laws of thermodynamics. The calculated net power is 3260 kW. It is in good agreement with net power is reported in the literature. The thermal efficiency of the ORC is 18.0%.

Thermoelectric Refrigeration System

A thermoelectric refrigerator, also known as a thermoelectric cooler module or Peltier cooler, is an electric component made of semi-conductors that acts as a tiny heat pump. When a thermoelectric cooler module is powered by a low voltage direct current power source, heat is transferred from one side to the other. As a result, one module face will be cooled while the opposite face is heated at the same time. The same fundamental laws of thermodynamics govern both thermoelectric and mechanical refrigerators, and both refrigeration systems, despite their vastly different appearances, operate on the same principles.

A dual-scale elasto-viscoplastic constitutive model of metallic materials to describe thermo-mechanically coupled monotonic and cyclic deformations

Thermo-mechanical coupling effect often occurs during the deformation of the metallic materials, especially when they are subjected to cyclic loadings at a high loading rate. On one hand, the internal heat generation and accumulation originated from the energy dissipation during plastic deformation lead to the change of temperature field in the material. On the other hand, the variation of temperature field further changes the dissipation property of the material, since the stress-strain response depends on the temperature. These two factors influence with each other and result in a complex thermo-mechanical coupling effect. In this work, a dual-scale thermo-mechanically coupled elasto-viscoplastic constitutive model is developed to predict the monotonic, cyclic deformation and temperature field evolution of metallic materials under monotonic and cyclic loadings. At the mesoscopic scale, the polycrystalline representative volume element (RVE) is considered as an aggregation of individual grains. For an individual grain, a crystal plasticity model accounting for the internal heat generation is developed based on the fundamental laws of irreversible thermodynamics. A nonlinear kinematic hardening rule extended from the Ohno-Abdel-Karim model is adopted to capture the evolution of resolved shear back stress for each slip system, and the classical Bassani-Wu latent hardening rule is utilized to describe the interaction of dislocation slipping. To calculate the thermo-mechanical interactions among the grains, and obtain the overall responses of the polycrystalline RVE, a self-consistent (SC) homogenization scheme accounting for material nonlinearity and thermo-mechanical coupling effect is developed. At the macroscopic scale, the thermo-mechanical responses for the specimen are obtained by solving the equations of force balance, deformation compatibility, thermodynamic equilibrium and constitutive relationship through an approximation method. Finally, the proposed model is validated by predicting the monotonic, cyclic stress-strain responses and temperature evolution of 316L stainless steel.

Cyclic degeneration of elastocaloric effect for NiTi shape memory alloy: Experimental observation and constitutive model

Based on the cyclic tension-unloading tests with various peak strains (4%-12%), the effect of loading level on the cyclic deformation and evolution of elastocaloric effect (eCE) for NiTi shape memory alloy (SMA) wires was investigated. Experimental results show that the transformation ratchetting and degeneration of eCE simultaneously occur during the cyclic deformation, and these two phenomena aggravate with the increase of loading level. Although the refrigeration capacity (maximum temperature drop in the reverse phase transformation process) exhibits a positive relativity with loading level in the 1st loading cycle, it changes non-monotonically with the variation of loading level in the steady-state cycle, which can be attributed to the interaction between the phase transformation and plasticity deformation. Moreover, it is found that the phase transformation between austenite (A) and martensite (M) phases occurs as a two-step process involving an intermediate phase, rhombohedral (R) phase. Then, a thermo-mechanically coupled cyclic constitutive model is constructed based on the fundamental laws of irreversible thermodynamics. Besides the thermo-elastic deformation, four different inelastic deformation mechanisms, i.e., R phase transformation (RT), martensite transformation (MT), plasticity in A and R phases (ARP), transformation-induced plasticity (TRIP) and their interactions are considered in the proposed model. The volume fractions of R phase, M phase, martensite affecting zone (MAZ) and the free zone (FZ) of mixed A + R phases are introduced. The thermodynamic driving forces for the four considered inelastic deformation mechanisms, i.e., RT, MT, ARP and TRIP are derived by the energy dissipation inequality and a new proposed Helmholtz free energy. Internal heat generation caused by the mechanical dissipation and the latent heat of phase transformation, and the heat balance equation are obtained by applying the conservation law of energy. The forward and reverse inheritances of dislocation (i.e., plastic deformation) caused by the moving martensite interfaces during MT are addressed. Adopting a first-order approximation of the constitutive equations and lumped analysis of heat transfer, the proposed constitutive model for a material point is extended to describe the overall responses of the whole wire. Finally, the predicted results for the cyclic deformation of NiTi SMA and correspondent evolution of eCE are compared against the experimental ones to validate the capability of the proposed model.

A two-scale thermo-mechanically coupled model for anomalous martensite transformation and elastocaloric switching effect of shape memory alloy

Conventional shape memory alloys (SMAs) exhibit an approximately linear relationship between the critical stresses of martensite transformation (MT) and ambient temperature (Clausius-Clapeyron relationship). Meanwhile, depending on the sign of entropy difference between the parent and martensite phases, these alloys behavior either a conventional or an inverse elastocaloric effect which originates from the latent heat release/absorption during stress-induced MT. Recently, MT with a non-monotonic Clausius-Clapeyron relationship (denotes as anomalous MT) and an elastocaloric switching effect (changes from the inverse elastocaloric effect at relatively low temperature to the conventional elastocaloric effect at relatively high temperature) were reported in CoCr-based Heusler-type SMAs. In this paper, to understand and quantitatively describe these new phenomena, a two-scale thermo-mechanically coupled constitutive model is constructed. In the mesoscopic scale, the fine twinned structure and the potential correspondent variant pairs of martensite phase are analyzed based on the crystallographic symmetry and the geometrically nonlinear theory of MT. The classical Debye's model is employed to describe the lattice and electronic heat capacities of the parent and martensite phases; while, a Monte Carlo simulation for the three-dimensional (3D) Ising's model is performed and a scaling law for the magnetic heat capacity of parent phase is proposed. Then, a new constitutive model is established based on the fundamental laws of irreversible thermodynamics to describe the non-isothermal stress-induced MT between parent and martensite phases. To consider the thermo-mechanical interactions between the parent phase and correspondent martensite variant pairs, each variant pair is regarded as an inhomogeneous inclusion with a mobile interface and embedded in the parent phase. With the help of interfacial operator, the thermodynamic driving force of MT is derived from the constructed Helmholtz free energy and dissipative inequality. Internal heat generation originated from the thermo-elasticity, inelastic deformation dissipation and latent heat is derived from the conservation law of energy. In the macroscopic scale, the thermo-mechanical response of SMA specimen is obtained by solving the equations of force balance, deformation compatibility, and thermodynamic equilibrium through the full-field calculation and mean-field approximation. Finally, the proposed model is verified by comparing the predictions with the experiments. It can be found that the anomalous MT and elastocaloric switching effect of CoCrAlSi SMA can be well captured by the proposed model.

Theoretical estimation of methane’s phase components volumes in coal seams

The aim of the work is to estimate the quantities of methane contained in a coal seam as a solid coal-methane solution and adsorbed inside cracks and pores. The work uses an analytical research method based on the fundamental laws of gas and thermodynamics, as well as physical chemistry. The binding energy in the calculations is taken as averaged over the polymolecular adsorption layer. The Langmuir model to describe the process is used. It was found that the maximum possible total content of methane main phase components does not exceed 70-80 m3/ton of coal. This is significantly less than the volumes of methane that is released in the mine during the gas-dynamic phenomenon. It is concluded that a more accurate idea of the gas-dynamic and other anomalous phenomena that take place in the “coal-methane” system can be obtained only by studying its structure at the atomic-molecular level. It is also necessary to take into account the accompanying physicochemical processes arising at the stage of metamorphism and technogenic interference in the coal seam. The work is aimed at improving the theory of gas-dynamic phenomena for the effective prevention of dynamic manifestations of rock pressure in mine workings.

Procedure for calculation and analysis of transcritical cycle CO2 with parallel compression

The use of CO2 as a refrigerant in transcritical cycles requires additional measures to increase the efficiency of the refrigeration system. Transcritical refrigeration systems are widely used at food processing facilities
 Different modifications of the base cycle are used to increase efficiency, but the methods for calculating and analyzing such cycles are not sufficiently presented in the literature.
 Along with the calculation of cycles and the determination of parameters at the base points, it is necessary to conduct an efficiency analysis in order to determine the optimal parameters.
 The purpose of the study was to develop a method for calculating and analyzing the transcritical cycle of parallel compression CO2.
 The calculation of the transcritical cycle is based on the fundamental laws of thermodynamics, the analysis method is based on the entropy-statistical method of thermodynamic analysis. Cycle calculation includes analysis of compression loss by system components.
 The operation of the transcritical cycle of the parallel compression CO2 with two temperature levels is described, the procedure for calculating and analyzing losses in the elements of the refrigerating unit operating according to the transcritical cycle of the parallel compression CO2 is given.
 The use of this method allows you to identify the elements and processes with the greatest losses and take further measures to improve the efficiency of the refrigeration system.

A new thermodynamically based model for creep and cyclic plasticity

Creep and cyclic plasticity are two common mechanical behaviors in engineering, and their interaction significantly affects the performance and degradation of corresponding components and structures, especially at high temperatures. How to build a physically based model for describing materials’ mechanical response under complex loading is still a challenge. This study proposes a thermodynamically based model for describing complex creep plasticity behaviors, such as cyclic plasticity and creep. Unlike existing models, the proposed model can describe time-dependent cyclic plasticity and clarify the contribution of various creep mechanisms. Starting from the fundamental thermodynamic laws, Helmholtz free energy and dissipation analysis considering different creep mechanisms are introduced. Then, constitutive equations are derived according to the physical hypothesis of normality of dissipation space. In the proposed model, plastic deformation is thought to depend on static plasticity and creep, which is further decomposed into three parts based on diffusion and dislocation activities, and the contribution of each creep mechanism is explicitly described. Finally, a series experimental data of Ti-6-4 is used to verify the utility of the proposed model. Satisfactory modeling results are obtained, including primary creep, steady creep, power-law breakdown, and creep cyclic plasticity interactions, confirming the validity of the proposed model.