On inhibiting runaway in catalytic reactors

We consider the problem of heat and mass transfer in porous catalyst pellets. Both the steady and time dependent operating characteristics are studied. Accurate approximate equations are derived from the basic governing equations of motion. A nonlinear stability analysis is employed to account for the observation that under certain conditions reactions on catalyst pellets can pass transiently stably into a region which would correspond to instability in the steady state. One consequence of our analysis is a possible control mechanism which inhibits temperature runaway by extending the stable operating characteristics desirable in modern reactors

Structure And Dynamics Of Modulated Traveling Waves In Cellular Flames

We describe spatial and temporal patterns in cylindrical premixed flames in the cellular regime, $Le < 1$, where the Lewis number $Le$ is the ratio of thermal to mass diffusivity of a deficient component of the combustible mixture. A transition from stationary, axisymmetric flames to stationary cellular flames is predicted analytically if $Le$ is decreased below a critical value. We present the results of numerical computations to show that as $Le$ is further decreased traveling waves (TWs) along the flame front arise via an infinite-period bifurcation which breaks the reflection symmetry of the cellular array. Upon further decreasing $Le$ different kinds of periodically modulated traveling waves (MTWs) as well as a branch of quasiperiodically modulated traveling waves (QPMTWs) arise. These transitions are accompanied by the development of different spatial and temporal symmetries including period doublings and period halvings. We also observe the apparently chaotic temporal behavior of a disordered cellular pattern involving creation and annihilation of cells. We analytically describe the stability of the TW solution near its onset+ using suitable phase-amplitude equations. Within this framework one of the MTW's can be identified as a localized wave traveling through an underlying stationary, spatially periodic structure. We study the Eckhaus instability of the TW and find that in general they are unstable at onset in infinite systems. They can, however, become stable for larger amplitudes.Comment: to appear in Physica D 28 pages (LaTeX), 11 figures (2MB postscript file

An adaptive pseudo-spectral method for reaction diffusion problems

The spectral interpolation error was considered for both the Chebyshev pseudo-spectral and Galerkin approximations. A family of functionals I sub r (u), with the property that the maximum norm of the error is bounded by I sub r (u)/J sub r, where r is an integer and J is the degree of the polynomial approximation, was developed. These functionals are used in the adaptive procedure whereby the problem is dynamically transformed to minimize I sub r (u). The number of collocation points is then chosen to maintain a prescribed error bound. The method is illustrated by various examples from combustion problems in one and two dimensions

On the Birth of Isolas

Isolas are isolated, closed curves of solution branches of nonlinear problems. They have been observed to occur in the buckling of elastic shells, the equilibrium states of chemical reactors and other problems. In this paper we present a theory to describe analytically the structure of a class of isolas. Specifically, we consider isolas that shrink to a point as a parameter τ of the problem, approaches a critical value τ_0. The point is referred to as an isola center. Equations that characterize the isola centers are given. Then solutions are constructed in a neighborhood of the isola centers by perturbation expansions in a small parameter ε that is proportional to (τ-τo), with a appropriately determined. The theory is applied to a chemical reactor problem

Stochastic Chemical Reactions in Micro-domains

Traditional chemical kinetics may be inappropriate to describe chemical reactions in micro-domains involving only a small number of substrate and reactant molecules. Starting with the stochastic dynamics of the molecules, we derive a master-diffusion equation for the joint probability density of a mobile reactant and the number of bound substrate in a confined domain. We use the equation to calculate the fluctuations in the number of bound substrate molecules as a function of initial reactant distribution. A second model is presented based on a Markov description of the binding and unbinding and on the mean first passage time of a molecule to a small portion of the boundary. These models can be used for the description of noise due to gating of ionic channels by random binding and unbinding of ligands in biological sensor cells, such as olfactory cilia, photo-receptors, hair cells in the cochlea.Comment: 33 pages, Journal Chemical Physic

Mean Field Effects for Counterpropagating Traveling Wave Solutions of Reaction-Diffusion Systems

In many problems, e.g., in combustion or solidification, one observes traveling waves that propagate with constant velocity and shape in the x direction, say, are independent of y and z and describe transitions between two equilibrium states, e.g., the burned and the unburned reactants. As parameters of the system are varied, these traveling waves can become unstable and give rise to waves having additional structure, such as traveling waves in the y and z directions, which can themselves be subject to instabilities as parameters are further varied. To investigate this scenario we consider a system of reaction-diffusion equations with a traveling wave solution as a basic state. We determine solutions bifurcating from the basic state that describe counterpropagating traveling waves in directions orthogonal to the direction of propagation of the basic state and determine their stability. Specifically, we derive long wave modulation equations for the amplitudes of the counterpropagating traveling waves that are coupled to an equation for a mean field, generated by the translation of the basic state in the direction of its propagation. The modulation equations are then employed to determine stability boundaries to long wave perturbations for both unidirectional and counterpropagating traveling waves. The stability analysis is delicate because the results depend on the order in which transverse and longitudinal perturbation wavenumbers are taken to zero. For the unidirectional wave we demonstrate that it is sufficient to consider the cases of (i) purely transverse perturbations, (ii) purely longitudinal perturbations, and (iii) longitudinal perturbations with a small transverse component. These yield Eckhaus type, zigzag type, and skew type instabilities, respectively. The latter arise as a specific result of interaction with the mean field. We also consider the degenerate case of very small group velocity, as well as other degenerate cases, which yield several additional instability boundaries. The stability analysis is then extended to the case of counterpropagating traveling waves

Reactive-diffuse System with Arrhenius Kinetics: Peculiarities of the Spherical Goemetry

The steady reactive-diffusive problem for a non isothermal permeable pellet with first-order Arrhenius kinetics is studied. In the large activation-energy limit, asymptotic solutions are derived for the spherical geometry. The solutions exhibit multiplicity and it is shown that a suitable choice of parameters can lead to an arbitrarily large number of solutions, thereby confirming a conjecture based upon past computational experiments. Explicit analytical expressions are given for the multiplicity bounds (ignition and extinction limits). The asymptotic results compare very well with those obtained numerically, even for moderate values of the activation energy

Simple Model of Propagating Flame Pulsations

A simple model which exhibits dynamical flame properties in 1D is presented. It is investigated analytically and numerically. The results are applicable to problems of flame propagation in supernovae Ia.Comment: 10 pages, 8 figures, revised version accepted by MNRA

Observable and hidden singular features of large fluctuations in nonequilibrium systems

We study local features, and provide a topological insight into the global structure of the probability density distribution and of the pattern of the optimal paths for large rare fluctuations away from a stable state. In contrast to extremal paths in quantum mechanics, the optimal paths do {\it not} encounter caustics. We show how this occurs, and what, instead of caustics, are the experimentally observable singularities of the pattern. We reveal the possibility for a caustic and a switching line to start at a saddle point, and discuss the consequences.Comment: 10 pages, 3 ps figures by request, LaTeX Article Format (In press, Phys. Lett. A

Asymptotics of Reaction-Diffusion Fronts with One Static and One Diffusing Reactant

The long-time behavior of a reaction-diffusion front between one static (e.g. porous solid) reactant A and one initially separated diffusing reactant B is analyzed for the mean-field reaction-rate density R(\rho_A,\rho_B) = k\rho_A^m\rho_B^n. A uniformly valid asymptotic approximation is constructed from matched self-similar solutions in a reaction front (of width w \sim t^\alpha where R \sim t^\beta enters the dominant balance) and a diffusion layer (of width W \sim t^{1/2} where R is negligible). The limiting solution exists if and only if m, n \geq 1, in which case the scaling exponents are uniquely given by \alpha = (m-1)/2(m+1) and \beta = m/(m+1). In the diffusion layer, the common ad hoc approximation of neglecting reactions is given mathematical justification, and the exact transient decay of the reaction rate is derived. The physical effects of higher-order kinetics (m, n > 1), such as the broadening of the reaction front and the slowing of transients, are also discussed.Comment: final version, new title & combustion reference