A numerical model is built, simulating the principles of kinetic gas theory, to predict pressures of molecules in a spherical pressure vessel; the model tracks a single particle and multiplies the force on the spherical walls by a mole of molecules to predict the net pressure. An intermolecular attractive force is added for high-density simulations, to replicate a real fluid; the force is chosen to ensure the fluid matches the Peng-Robinson equation of state as it is compressed to a near supercritical density. The standard deviations of the molecule velocity with respect to temperature and density is studied to define the entropy. A parametric study of a Stirling cycle heat engine utilizing near-supercritical densities is modeled, to study how the temperature dependence of the attractive intermolecular Van der Waal forces can affect the net total entropy change to the surrounding environment. A practical, macroscopic-scale piston-cylinder engine was then built and demonstrated, utilizing a novel thermodynamic cycle that closely resembles the Carnot heat engine cycle, utilizing an arrangement of valves and pneumatic air to replicate the isothermal and isentropic compression and expansion of the working fluid. This heat engine cycle could be built without requiring advanced manufacturing, and utilized non-ideal carbon dioxide as the working fluid, to take advantage of the entropy effects of the Van der Waals forces demonstrated in the Argon simulations to boost the thermodynamic efficiency. This engine demonstrated this capability in a practical, macroscopic heat engine, and offers great opportunities to practical energy generation.
In the paper the behavior of density (or specific volume), the heat of evaporation and entropy per molecule for normal and heavy water on their coexistence curves is discussed. The special attention is paid on the physical nature of the similarity in the behavior of density and the heat of evaporation for water and argon as well as the nearest water homolog $H_{2} S$. It is shown that the appearance of this similarity is a consequence of the rotational motion of water molecules, which averages the inter-particle potential in water and leads it to the argon-like form. To describe the fine disti…
The probability distribution of the entropy production for the effusion of a relativistic ideal gas is calculated explicitly. This result is then extended to include particle and anti-particle pair production and annihilation. In both cases, the fluctuation theorem is verified.
Making statistical predictions requires tackling two problems: one must assign appropriate probability distributions and then one must calculate a variety of expected values. The method of maximum entropy is commonly used to address the first problem. Here we explore its use to tackle the second problem. We show how this use of maximum entropy leads to the Bogoliuvob variational principle which we generalize, apply to density functional theory, and use it to develop a mean field theory for classical fluids. Numerical calculations for Argon gas are compared with experimental data.
The approach of an ideal gas to equilibrium is simulated through a generalization of the Ehrenfest ball-and-box model. In the present model, the interior of each box is discretized, {\it i.e.}, balls/particles live in cells whose occupation can be either multiple or single. Moreover, particles occasionally undergo random, but elastic, collisions between each other and against the container walls. I show, both analitically and numerically, that the number and energy of particles in a given box eventually evolve to an equilibrium distribution $W$ which, depending on cell occupations, is binomial…
In this work we study the evolution of Boltzmann's entropy in the context of free expansion of a one dimensional interacting gas inside a box. Boltzmann's entropy is defined for single microstates and is given by the phase-space volume occupied by microstates with the same value of macrovariables which are coarse-grained physical observables. We demonstrate the idea of typicality in the growth of the Boltzmann's entropy for two choices of macro-variables -- the single particle phase space distribution and the hydrodynamic fields. Due to the presence of interaction, the growth curves for both t…
Ozawa et. al [1] presented numerical results for the configurational entropy density, $s_c$, of a model glass-forming liquid in the presence of random pinning. The location of a "phase boundary" in the pin density ($c$) - temperature ($T$) plane, that separates an "ideal glass" phase from the supercooled liquid phase, is obtained by finding the points at which $s_c(T,c) \to 0$. According to the theoretical arguments by Cammarota et. al. [2], an ideal glass transition at which the $α$-relaxation time $τ_α$ diverges takes place when $s_c$ goes to zero. We have studied the dynamics of the same sy…
A generalized entropy arising in the context of superstatistics is obtained for an ideal gas. The curvature scalar associated to the thermodynamic space generated by this modified entropy is calculated using two formalisms of the geometric approach to thermodynamics. Using the curvature/interaction hypothesis of the geometric approach to thermodynamic geometry it is found that as a consequence of considering a generalized statistics, an effective interaction arises but the interaction is not enough to give a phase transition. This generalized entropy seems to be relevant in confinement or in s…
We discuss the need for discretization to evaluate the configurational entropy in a general model. We also discuss the prescription using restricted partition function formalism to study the stationary limit of metastable states. We introduce a lattice model of dimers as a paradigm of molecular fluid and study metastability in it to investigate the root cause of glassy behavior. We demonstrate the existence of the entropy crisis in metastable states, from which it follows that the entropy crisis is the root cause underlying the ideal glass transition in systems with particles of all sizes. The…
We develop the method of Maximum Entropy (ME) as a technique to generate approximations to probability distributions. The central results consist in (a) justifying the use of relative entropy as the uniquely natural criterion to select a "best" approximation from within a family of trial distributions, and (b) to quantify the extent to which non-optimal trial distributions are ruled out. The Bogoliuvob variational method is shown to be included as a special case. As an illustration we apply our method to simple fluids. In a first use of the ME method the "exact" canonical distribution is appro…
We explore the use of the method of Maximum Entropy (ME) as a technique to generate approximations. In a first use of the ME method the "exact" canonical probability distribution of a fluid is approximated by that of a fluid of hard spheres; ME is used to select an optimal value of the hard-sphere diameter. These results coincide with the results obtained using the Bogoliuvob variational method. A second more complete use of the ME method leads to a better descritption of the soft-core nature of the interatomic potential in terms of a statistical mixture of distributions corresponding to hard …
The property that power means are monotonically increasing functions of their order is shown to be the basis of the second laws not only for processes involving heat conduction but also for processes involving deformations. In an $L$-potentail equilibration the final state will be one of maximum entropy, while in an entropy equilibrium the final state will be one of minimum $L$. A metric space is connected with the power means, and the distance between means of different order is related to the Carnot efficiency. In the ideal classical gas limit, the average change in the entropy is shown to b…
I present a generalization of the Ehrenfest urn model that is aimed at simulating the approach to equilibrium in a dilute gas. The present model differs from the original one in two respects: 1) the two boxes have different volumes and are divided into identical cells with either multiple or single occupancy; 2) particles, which carry also a velocity vector, are subjected to random, but elastic, collisions, both mutual and against the container walls. I show, both analytically and numerically, that the number and energy of particles in a given urn evolve eventually to an equilibrium probabilit…
A mathematical procedure is suggested to obtain deformed entropy formulas of type K(S_K) = sum_i P_i K(-ln P_i), by requiring zero mutual K(S_K)-information between a finite subsystem and a finite reservoir. The use of this method is first demonstrated on the ideal gas equation of state with finite constant heat capacity, C, where it delivers the Renyi and Tsallis formulas. A novel interpretation of the qstar = 2-q duality arises from the comparison of canonical subsystem and total microcanonical partition approaches. Finally a new, generalized deformed entropy formula is constructed for the l…
Collections of self-propelled particles that move persistently by continuously consuming free energy are a paradigmatic example of active matter. In these systems, unlike Brownian "hot colloids", the breakdown of detailed balance yields a continuous production of entropy at steady state, even for an ideal active gas. We quantify the irreversibility for a non-interacting active particle in two dimensions by treating both conjugated and time-reversed dynamics. By starting with underdamped dynamics, we identify a hidden rate of entropy production required to maintain persistence and prevent the r…
An experimental effort was conducted to measure the change in internal energy of non-ideal carbon dioxide as its volume rapidly expanded with the sudden opening of a valve from one to two compressed gas cylinders. This was achieved by measuring the mass heat capacity of the gas cylinders and the manifold-valve, and measuring the change in temperature from the sudden doubling of volume of the non-ideal carbon dioxide. It was determined that an empirical equation for the change in internal energy of a non-ideal fluid was more accurate than previous methods used for estimating the change in inter…
The probability distribution of the entropy production for the effusion of an ideal gas between two compartments is calculated explicitly. The fluctuation theorem is verified. The analytic results are in good agreement with numerical data from hard disk molecular dynamics simulations.
To illustrate Boltzmann's construction of an entropy function that is defined for a microstate of a macroscopic system, we present here the simple example of the free expansion of a one dimensional gas of non-interacting point particles. The construction requires one to define macrostates, corresponding to macroscopic variables. We define a macrostate $M$ by specifying the fraction of particles in rectangular boxes $Δx Δv$ of the single particle position-velocity space $\{x,v\}$. We verify that when the number of particles is large the Boltzmann entropy, $S_B(t)$, of a typical microstate of a …
This paper introduces the basic concepts of information theory. Based on these concepts, we regard the states in the state space and the types of ideal gases as the symbols in a symbol set to calculate the mixing entropy of ideal gas involved in Gibbs Paradox. The discussion above reveals that the non-need for distinguishing can resolve the contradiction of Gibbs Paradox, implying the introduction of indistinguishability is not necessary. Further analysis shows that the information entropy of gas molecular types does not directly correlate to the energy of a gas system, so it should not be use…
These comments are a response to the discussion presented in the above paper concerning the New comment on Gibbs Density Surface of Fluid Argon, Revised Critical Parameters by Umirzakov. Here we show that Woodcocks results obtained for the dependencies for the isochoric heat capacity, excess Gibbs energy and coexisting difference functional of argon, and coexisting densities of liquid and vapor of the van der Waals fluid and presented in all Figures are incorrect, his Table includes incorrect values of coexisting difference functional, his paper includes many incorrect equations, mathematical …
We have studied finite $N$-body $D$-dimensional nonextensive ideal gases and harmonic oscillators, by using the maximum-entropy methods with the $q$- and normal averages ($q$: the entropic index). The validity range, specific heat and Tsallis entropy obtained by the two average methods are compared. Validity ranges of the $q$- and normal averages are $0 < q < q_U$ and $q > q_L$, respectively, where $q_U=1+(ηDN)^{-1}$, $q_L=1-(ηDN+1)^{-1}$ and $η=1/2$ ($η=1$) for ideal gases (harmonic oscillators). The energy and specific heat in the $q$- and normal averages coincide with those in the Boltzmann…
A unified framework to describe the adiabatic class of ensembles in the generalized statistical mechanics based on Schwammle-Tsallis two parameter (q, q') entropy is proposed. The generalized form of the equipartition theorem, virial theorem and the adiabatic theorem are derived. Each member of the class of ensembles is illustrated using the classical nonrelativistic ideal gas and we observe that the heat functions could be written in terms of the Lambert's W-function in the large N limit. In the microcanonical ensemble we study the effect of gravitational field on classical nonrelativistic id…
Correlations reduce the configurational entropies of liquids below their ideal gas limits. By means of first principles molecular dynamics simulations, we obtain accurate pair correlation functions of liquid metals, then subtract the mutual information content of these correlations from the ideal gas entropies to predict the absolute entropies over a broad range of temperatures. We apply this method to liquid aluminum and copper and demonstrate good agreement with experimental measurements, then we apply it to predict the entropy of a liquid aluminum-copper alloy. Corrections due to electronic…
Landauer principle states that erasure of $N$ bit information requires an entropic cost of $Nk_B \ln 2$. This fact can easily be demonstrated by relaxation of an ideal gas consisting of $N$ particles inside a fixed volume. In this paper we discuss the modification of Landauer bound when we use non-ideal gas with inter-particle interactions for erasure procedure. We have found that the bound on the entropy production can be lowered when the interaction between particles is square-well potential.
The applicability of the Principle of Corresponding States (PCS) for the noble fluids is discussed. We give the thermodynamic evidences for the dimerization of the liquid phase in heavy noble gases like argon, krypton etc. which manifest itself in deviation from the PCS. The behavior of the rectilinear diameter of the entropy and the density is analyzed. It is shown that these characteristics are very sensitive to the dimerization process which takes place in the liquid phase of heavy noble gases.
Diffusivity, a measure for how rapidly a fluid self-mixes, shows an intimate, but seemingly fragmented, connection to thermodynamics. On one hand, the "configurational" contribution to entropy (related to the number of mechanically-stable configurations that fluid molecules can adopt) has long been considered key for predicting supercooled liquid dynamics near the glass transition. On the other hand, the excess entropy (relative to ideal gas) provides a robust scaling for the diffusivity of fluids above the freezing point. Here we provide, to our knowledge, the first evidence that excess entro…
The ideal gas laws are derived from the democritian concept of corpuscles moving in vacuum plus a principle of simplicity, namely that these laws are independent of the laws of motion aside from the law of energy conservation. A single corpuscle in contact with a heat bath and submitted to a $z$ and $t$-invariant force $-w$ is considered, in which case corpuscle distinguishability is irrelevant. The non-relativistic approximation is made only in examples. Some of the end results are known but the method appears to be novel. The mathematics being elementary the present paper should facilitate t…
We present a stability analysis of the classical ideal gas in a new theory of nonextensive statistics and use the theory to understand the phenomena of negative specific heat in some self-gravitating systems. The stability analysis is made on the basis of the second variation of Tsallis entropy. It is shown that the system is thermodynamically unstable if the nonextensive parameter is q>5/3, which is exactly equivalent to the condition of appearance of the negative specific heat.
Entropy has become increasingly central to characterize, understand and even guide assembly, self-organization and phase transition processes. In this work, we build on the analogous role of partition functions (or free energies) in isothermal ensembles and that of entropy in adiabatic ensembles. In particular, we show that the grand-isobaric adiabatic $(μ,P,R)$ ensemble, or Ray ensemble, provides a direct route to determine the entropy. This allows us to follow the variations of entropy with the thermodynamic conditions and thus to explore phase transitions. We test this approach by carrying …
We develop a maximum relative entropy formalism to generate optimal approximations to probability distributions. The central results consist in (a) justifying the use of relative entropy as the uniquely natural criterion to select a preferred approximation from within a family of trial parameterized distributions, and (b) to obtain the optimal approximation by marginalizing over parameters using the method of maximum entropy and information geometry. As an illustration we apply our method to simple fluids. The "exact" canonical distribution is approximated by that of a fluid of hard spheres. T…
We consider the ideal Fermi gas of indistinguishable particles without spin but with electric charge, confined to a Euclidean plane $\mathbb R^2$ perpendicular to an external constant magnetic field of strength $B>0$. We assume this (infinite) quantum gas to be in thermal equilibrium at zero temperature, that is, in its ground state with chemical potential $μ\ge B$ (in suitable physical units). For this (pure) state we define its local entropy $S(Λ)$ associated with a bounded (sub)region $Λ\subset \mathbb R^2$ as the von Neumann entropy of the (mixed) local substate obtained by reducing the in…
Carnot's four-part ideal-gas cycle includes both isothermal and adiabatic expansions and compressions. Analyzing this cycle provides the fundamental basis for statistical thermodynamics. We explore the cycle here from a pedagogical view in order to promote understanding of the macroscopic thermodynamic entropy, the state function associated with thermal energy changes. From the alternative microscopic viewpoint the Hamiltonian ${\cal H}(q,p)$ is the energy and entropy is the (logarithm of the) phase-space volume $Ω$ associated with a macroscopic state. We apply two novel forms of Hamiltonian m…
This article presents the results of research into the causes of the Gibbs paradox in the formulation discussed by J. W. Gibbs himself. In this formulation, we are talking about an inexplicable (paradoxical) jump in the entropy of mixing of two ideal gases during the transition from mixing different to mixing identical gases. It is shown that the entropy of mixing of different ideal gases and the entropy of mixing of identical ideal gases are different (non-identical) functions of the same gas parameters. That, called a paradoxical jump in the entropy of mixing, is not a jump in the value of s…
We consider a boson gas on the stretched horizon of the Schwartzschild and Kerr black holes. It is shown that the gas is in a Bose-Einstein condensed state with the Hawking temperature $T_c=T_H$ if the particle number of the system be equal to the number of quantum bits of space-time $ N \simeq {A}/{ł_{p}^{2}}$. Entropy of the gas is proportional to the area of the horizon $(A)$ by construction. For a more realistic model of quantum degrees of freedom on the horizon, we should presumably consider interacting bosons (gravitons). An ideal gas with intermediate statistics could be considered as a…
