Validity of path thermodynamics in reactive systems

Path thermodynamic formulation of nonequilibrium reactive systems is considered. It is shown through simple practical examples that this approach can lead to results that contradict well established thermodynamic properties of such systems. Rigorous mathematical analysis confirming this fact is presented

Reply to "Comment on `Validity of path thermodynamic description of reactive systems: Microscopic simulations'

The Comment's author argues that a correct description of reactive systems should incorporate the explicit interaction with reservoirs, leading to a unified system-reservoirs entity. However, this proposition has two major flaws. Firstly, as we will emphasize, this entity inherently follows a thermodynamic equilibrium distribution. In the Comment, no indication is provided on how to maintain such a system-reservoirs entity in a non-equilibrium state. Secondly, contrary to the author's claim, the inclusion of system-reservoir interaction in traditional stochastic modeling of reactive systems does not automatically alter the limited applicability of path thermodynamics to problematic reactive systems. We will provide a simple demonstration to illustrate that certain elementary reactions may not involve any changes in reservoir components, which seems to have been overlooked by the author.Comment: To appear in Physical Review

Hydrodynamic fluctuations in the Kolmogorov flow: Linear regime

The Landau-Lifshitz fluctuating hydrodynamics is used to study the statistical properties of the linearized Kolmogorov flow. The relative simplicity of this flow allows a detailed analysis of the fluctuation spectrum from near equilibrium regime up to the vicinity of the first convective instability threshold. It is shown that in the long time limit the flow behaves as an incompressible fluid, regardless of the value of the Reynolds number. This is not the case for the short time behavior where the incompressibility assumption leads in general to a wrong form of the static correlation functions, except near the instability threshold. The theoretical predictions are confirmed by numerical simulations of the full nonlinear fluctuating hydrodynamic equations.Comment: 20 pages, 4 figure

Spurious diffusion in particle simulations of the Kolmogorov flow

Particle simulations of the Kolmogorov flow are analyzed by the Landau-Lifshitz fluctuating hydrodynamics. It is shown that a spurious diffusion of the center of mass corrupts the statistical properties of the flow. The analytical expression for the corresponding diffusion coefficient is derived.Comment: 10 pages, no figure

Fluctuations in fluids in thermal nonequilibrium states below the convective Rayleigh-Benard instability

Starting from the linearized fluctuating Boussinesq equations we derive an expression for the structure factor of fluids in stationary convection-free thermal nonequilibrium states, taking into account both gravity and finite-size effects. It is demonstrated how the combined effects of gravity and finite size causes the structure factor to go through a maximum value as a function of the wave number $q$. The appearance of this maximum is associated with a crossover from a $q^{-4}$ dependence for larger $q$ to a $q^2$ dependence for very small $q$. The relevance of this theoretical result for the interpretation of light scattering and shadowgraph experiments is elucidated. The relationship with studies on various aspects of the problem by other investigators is discussed. The paper thus provides a unified treatment for dealing with fluctuations in fluid layers subjected to a stationary temperature gradient regardless of the sign of the Rayleigh number $R$, provided that $R$ is smaller than the critical value $R_\mathrm{c}$ associated with the appearance of Rayleigh-B\'{e}nard convection.Comment: 33 pages, 6 figures, accepted for publication: Physica

A discretized integral hydrodynamics

Using an interpolant form for the gradient of a function of position, we write an integral version of the conservation equations for a fluid. In the appropriate limit, these become the usual conservation laws of mass, momentum and energy. We also discuss the special cases of the Navier-Stokes equations for viscous flow and the Fourier law for thermal conduction in the presence of hydrodynamic fluctuations. By means of a discretization procedure, we show how these equations can give rise to the so-called "particle dynamics" of Smoothed Particle Hydrodynamics and Dissipative Particle Dynamics.Comment: 10 pages, RevTex, submitted to Phys. Rev.

Non-Newtonian Couette-Poiseuille flow of a dilute gas

The steady state of a dilute gas enclosed between two infinite parallel plates in relative motion and under the action of a uniform body force parallel to the plates is considered. The Bhatnagar-Gross-Krook model kinetic equation is analytically solved for this Couette-Poiseuille flow to first order in the force and for arbitrary values of the Knudsen number associated with the shear rate. This allows us to investigate the influence of the external force on the non-Newtonian properties of the Couette flow. Moreover, the Couette-Poiseuille flow is analyzed when the shear-rate Knudsen number and the scaled force are of the same order and terms up to second order are retained. In this way, the transition from the bimodal temperature profile characteristic of the pure force-driven Poiseuille flow to the parabolic profile characteristic of the pure Couette flow through several intermediate stages in the Couette-Poiseuille flow are described. A critical comparison with the Navier-Stokes solution of the problem is carried out.Comment: 24 pages, 5 figures; v2: discussion on boundary conditions added; 10 additional references. Published in a special issue of the journal "Kinetic and Related Models" dedicated to the memory of Carlo Cercignan