Front motion in an A+B→CA+B\to C type reaction-diffusion process: Effects of an electric field

We study the effects of an external electric field on both the motion of the reaction zone and the spatial distribution of the reaction product, $C$, in an irreversible $A^- +B^+ \to C$ reaction-diffusion process. The electrolytes $A\equiv (A^+,A^-)$ and $B\equiv (B^+,B^-)$ are initially separated in space and the ion-dynamics is described by reaction-diffusion equations obeying local electroneutrality. Without an electric field, the reaction zone moves diffusively leaving behind a constant concentration of $C$-s. In the presence of an electric field which drives the reagents towards the reaction zone, we find that the reaction zone still moves diffusively but with a diffusion coefficient which slightly decreases with increasing field. The important electric field effect is that the concentration of $C$-s is no longer constant but increases linearly in the direction of the motion of the front. The case of an electric field of reversed polarity is also discussed and it is found that the motion of the front has a diffusive, as well as a drift component. The concentration of $C$-s decreases in the direction of the motion of the front, up to the complete extinction of the reaction. Possible applications of the above results to the understanding of the formation of Liesegang patterns in an electric field is briefly outlined.Comment: 13 pages, 13 figures, submitted to J. Chem. Phy

Drifting diffusion on a circle as continuous limit of a multiurn Ehrenfest model

We study the continuous limit of a multibox Erhenfest urn model proposed before by the authors. The evolution of the resulting continuous system is governed by a differential equation, which describes a diffusion process on a circle with a nonzero drifting velocity. The short time behavior of this diffusion process is obtained directly by solving the equation, while the long time behavior is derived using the Poisson summation formula. They reproduce the previous results in the large $M$ (number of boxes) limit. We also discuss the connection between this diffusion equation and the Schr$\ddot{\rm o}$dinger equation of some quantum mechanical problems.Comment: 4 pages prevtex4 file, 1 eps figur

Yang-Lee zeroes for an urn model for the separation of sand

We apply the Yang-Lee theory of phase transitions to an urn model of separation of sand. The effective partition function of this nonequilibrium system can be expressed as a polynomial of the size-dependent effective fugacity $z$. Numerical calculations show that in the thermodynamic limit, the zeros of the effective partition function are located on the unit circle in the complex $z$-plane. In the complex plane of the actual control parameter certain roots converge to the transition point of the model. Thus the Yang-Lee theory can be applied to a wider class of nonequilibrium systems than those considered previously.Comment: 4 pages, 3 eps figures include

Probabilistic ballistic annihilation with continuous velocity distributions

We investigate the problem of ballistically controlled reactions where particles either annihilate upon collision with probability $p$, or undergo an elastic shock with probability $1-p$. Restricting to homogeneous systems, we provide in the scaling regime that emerges in the long time limit, analytical expressions for the exponents describing the time decay of the density and the root-mean-square velocity, as continuous functions of the probability $p$ and of a parameter related to the dissipation of energy. We work at the level of molecular chaos (non-linear Boltzmann equation), and using a systematic Sonine polynomials expansion of the velocity distribution, we obtain in arbitrary dimension the first non-Gaussian correction and the corresponding expressions for the decay exponents. We implement Monte-Carlo simulations in two dimensions, that are in excellent agreement with our analytical predictions. For $p<1$, numerical simulations lead to conjecture that unlike for pure annihilation ($p=1$), the velocity distribution becomes universal, i.e. does not depend on the initial conditions.Comment: 10 pages, 9 eps figures include

Energy fluctuations in vibrated and driven granular gases

We investigate the behavior of energy fluctuations in several models of granular gases maintained in a non-equilibrium steady state. In the case of a gas heated from a boundary, the inhomogeneities of the system play a predominant role. Interpreting the total kinetic energy as a sum of independent but not identically distributed random variables, it is possible to compute the probability density function (pdf) of the total energy. Neglecting correlations and using the analytical expression for the inhomogeneous temperature profile obtained from the granular hydrodynamic equations, we recover results which have been previously observed numerically and which had been attributed to the presence of correlations. In order to separate the effects of spatial inhomogeneities from those ascribable to velocity correlations, we have also considered two models of homogeneously thermostated gases: in this framework it is possible to reveal the presence of non-trivial effects due to velocity correlations between particles. Such correlations stem from the inelasticity of collisions. Moreover, the observation that the pdf of the total energy tends to a Gaussian in the large system limit, suggests that they are also due to the finite size of the system.Comment: 13 pages, 10 figure

The second and third Sonine coefficients of a freely cooling granular gas revisited

In its simplest statistical-mechanical description, a granular fluid can be modeled as composed of smooth inelastic hard spheres (with a constant coefficient of normal restitution $\alpha$) whose velocity distribution function obeys the Enskog-Boltzmann equation. The basic state of a granular fluid is the homogeneous cooling state, characterized by a homogeneous, isotropic, and stationary distribution of scaled velocities, $F(\mathbf{c})$. The behavior of $F(\mathbf{c})$ in the domain of thermal velocities ($c\sim 1$) can be characterized by the two first non-trivial coefficients ($a_2$ and $a_3$) of an expansion in Sonine polynomials. The main goals of this paper are to review some of the previous efforts made to estimate (and measure in computer simulations) the $\alpha$-dependence of $a_2$ and $a_3$, to report new computer simulations results of $a_2$ and $a_3$ for two-dimensional systems, and to investigate the possibility of proposing theoretical estimates of $a_2$ and $a_3$ with an optimal compromise between simplicity and accuracy.Comment: 12 pages, 5 figures; v2: minor change

Lattice theory of trapping reactions with mobile species

We present a stochastic lattice theory describing the kinetic behavior of trapping reactions $A + B \to B$, in which both the $A$ and $B$ particles perform an independent stochastic motion on a regular hypercubic lattice. Upon an encounter of an $A$ particle with any of the $B$ particles, $A$ is annihilated with a finite probability; finite reaction rate is taken into account by introducing a set of two-state random variables - "gates", imposed on each $B$ particle, such that an open (closed) gate corresponds to a reactive (passive) state. We evaluate here a formal expression describing the time evolution of the $A$ particle survival probability, which generalizes our previous results. We prove that for quite a general class of random motion of the species involved in the reaction process, for infinite or finite number of traps, and for any time $t$, the $A$ particle survival probability is always larger in case when $A$ stays immobile, than in situations when it moves.Comment: 12 pages, appearing in PR

Fluctuations in granular gases

A driven granular material, e.g. a vibrated box full of sand, is a stationary system which may be very far from equilibrium. The standard equilibrium statistical mechanics is therefore inadequate to describe fluctuations in such a system. Here we present numerical and analytical results concerning energy and injected power fluctuations. In the first part we explain how the study of the probability density function (pdf) of the fluctuations of total energy is related to the characterization of velocity correlations. Two different regimes are addressed: the gas driven at the boundaries and the homogeneously driven gas. In a granular gas, due to non-Gaussianity of the velocity pdf or lack of homogeneity in hydrodynamics profiles, even in the absence of velocity correlations, the fluctuations of total energy are non-trivial and may lead to erroneous conclusions about the role of correlations. In the second part of the chapter we take into consideration the fluctuations of injected power in driven granular gas models. Recently, real and numerical experiments have been interpreted as evidence that the fluctuations of power injection seem to satisfy the Gallavotti-Cohen Fluctuation Relation. We will discuss an alternative interpretation of such results which invalidates the Gallavotti-Cohen symmetry. Moreover, starting from the Liouville equation and using techniques from large deviation theory, the general validity of a Fluctuation Relation for power injection in driven granular gases is questioned. Finally a functional is defined using the Lebowitz-Spohn approach for Markov processes applied to the linear inelastic Boltzmann equation relevant to describe the motion of a tracer particle. Such a functional results to be different from injected power and to satisfy a Fluctuation Relation.Comment: 40 pages, 18 figure

Nonequilibrium Statistical Mechanics of the Zero-Range Process and Related Models

We review recent progress on the zero-range process, a model of interacting particles which hop between the sites of a lattice with rates that depend on the occupancy of the departure site. We discuss several applications which have stimulated interest in the model such as shaken granular gases and network dynamics, also we discuss how the model may be used as a coarse-grained description of driven phase-separating systems. A useful property of the zero-range process is that the steady state has a factorised form. We show how this form enables one to analyse in detail condensation transitions, wherein a finite fraction of particles accumulate at a single site. We review condensation transitions in homogeneous and heterogeneous systems and also summarise recent progress in understanding the dynamics of condensation. We then turn to several generalisations which also, under certain specified conditions, share the property of a factorised steady state. These include several species of particles; hop rates which depend on both the departure and the destination sites; continuous masses; parallel discrete-time updating; non-conservation of particles and sites.Comment: 54 pages, 9 figures, review articl

Quantification of three macrolide antibiotics in pharmaceutical lots by HPLC: Development, validation and application to a simultaneous separation

A new validated high performance liquid chromatographic (HPLC) method with rapid analysis time and high efficiency, for the analysis of erythromycin, azithromycin and spiramycin, under isocratic conditions with ODB RP18 as a stationary phase is described. Using an eluent composed of acetonitrile –2-methyl-2-propanol –hydrogenphosphate buffer, pH 6.5, with 1.5% triethylamine (33:7: up to 100, v/v/v), delivered at a flow-rate of 1.0 mL min-1. Ultra Violet (UV) detection is performed at 210 nm. The selectivity is satisfactory enough and no problematic interfering peaks are observed. The procedure is quantitatively characterized and repeatability, linearity, detection and quantification limits are very satisfactory. The method is applied successfully for the assay of the studied drugs in pharmaceutical dosage forms as tablets and powder for oral suspension. Recovery experiments revealed recovery of 97.13–100.28%