Autocatalytic Reaction Fronts Research Articles

Interaction of Pure Marangoni Convection with a Propagating Reactive Interface under Microgravity.

A reactive interface in the form of an autocatalytic reaction front propagating in a bulk phase can generate a dynamic contact line upon reaching the free surface when a surface tension gradient builds up due to the change in chemical composition. Experiments in microgravity evidence the existence of a self-organized autonomous and localized coupling of a pure Marangoni flow along the surface with the reaction in the bulk. This dynamics results from the advancement of the contact line at the surface that acts as a moving source of the reaction, leading to the reorientation of the front propagation. Microgravity conditions allow one to isolate the transition regime during which the surface propagation is enhanced, whereas diffusion remains the main mode of transport in the bulk with negligible convective mixing, a regime typically concealed on Earth because of buoyancy-driven convection.

Frozen fronts selection in flow against self-sustained chemical waves

Autocatalytic reaction fronts between two reacting species in the absence of fluid flow propagate as solitary waves. The coupling between an autocatalytic reaction front and a forced hydrodynamic flow may lead to a stationary front whose velocity and shape depend on the underlying flow field. We focus on the chemohydrodynamic opposition between forced advection and self-sustained chemical waves, which can lead to static stationary fronts, i.e., frozen fronts (FFs). Toward that end, we perform experiments, analytical computations, and numerical simulations with the autocatalytic iodate-arsenious acid reaction (IAA) over a wide range of flow velocities around a solid disk. For the same set of control parameters, we observe two types of frozen fronts: an upstream FF, which avoids the solid disk, and a downstream FF with two symmetric branches emerging from the solid disk surface. We map the range over which we observe these frozen fronts. We also address the relevance of the so-called eikonal, thin front limit to describe the observed fronts and select the frozen front shapes.2 MoreReceived 29 September 2016DOI:https://doi.org/10.1103/PhysRevFluids.2.043302©2017 American Physical SocietyPhysics Subject Headings (PhySH)Research AreasPatterns in complex systemsReacting flowsTechniquesChemical wavesFluid Dynamics

Avalanches dynamics in reaction fronts in disordered flows.

We report on numerical studies of avalanches of an autocatalytic reaction front in a porous medium. The front propagation is controlled by an adverse flow resulting in upstream, static, or downstream regimes. In an earlier study focusing on front shape, we identified three different universality classes associated with this system by following the front dynamics experimentally and numerically. Here, using numerical simulations in the vicinity of the second-order transition, we identify an avalanche dynamics characterized by power-law distributions of avalanche sizes, durations, and lateral extensions. The related exponents agree well with the quenched-Kardar-Parisi-Zhang theory, which describes the front dynamics. However, the geometry of the propagating front differs slightly from that of the theoretical one. We show that this discrepancy can be understood in terms of the nonquasistatic correction induced by the finite front velocity.

Self-Assembly of Charged Nanoparticles by an Autocatalytic Reaction Front.

In this work we present that aggregation of charged and pH sensitive nanoparticles can be spatiotemporally controlled by an autonomous way using the chlorite-tetrathionate autocatalytic front, where the front regulates the electrostatic interaction between nanoparticles due to protonation of the capping (carboxylate-terminated) ligand. We found that the aggregation and sedimentation of nanoparticles in liquid phase with the effect of reversible binding of the autocatalyst (H(+)) play important roles in changing the front stability (mixing length) and the velocity of the front in both cases when the fronts propagate upward and downward. Calculation of interparticle interactions (electrostatic and van der Waals) with the measurement of front velocity revealed that the aggregation process occurs fast (within a few seconds) at the front position.

Three-dimensional convection-driven fronts of the exothermic chlorite-tetrathionate reaction.

Horizontally propagating autocatalytic reaction fronts in fluids are often accompanied by convective motion in the presence of gravity. We experimentally and numerically investigate the stable complex three-dimensional pattern arising in the exothermic chlorite-tetrathionate reaction as a result of the antagonistic thermal and solutal contribution to the density change. By particle image velocimetry measurements, we construct the flow field that stabilizes the front structure. The calculations applied for incompressible fluids using the empirical rate-law model reproduce the experimental observations with good agreement.

Autocatalytic reaction fronts inside a porous medium of glass spheres.

We analyze experimentally chemical wave propagation in the disordered flow field of a porous medium. The reaction fronts travel at a constant velocity that drastically depends on the mean flow direction and rate. The fronts may propagate either downstream and upstream but, surprisingly, they remain static over a range of flow rate values. Resulting from the competition between the chemical reaction and the disordered flow field, these frozen fronts display a particular sawtooth shape. The frozen regime is likely to be associated with front pinning in low velocity zones, the number of which varies with the ratio of the mean flow and the chemical front velocities.

Phase diagram of sustained wave fronts opposing the flow in disordered porous media

Using lattice Boltzmann simulations, we analyze the different regimes of propagation of an autocatalytic reaction front in heterogenous porous media. The heterogeneities of the porous medium are characterized by the standard deviation of its log-normal distribution of permeability and its correlation length. We focus on the situation where chemical reaction and flow field act in opposite directions. In agreement with previous experiments we observe upstream, downstream fronts as well as static, frozen ones over a range of flow velocity which depends drastically on the heterogeneities of the flow field. The transition between the static regime and the downstream one account for large enough low-velocity zones, whereas the transition from static to upstream regime is found to be given by a kind of percolation path.

Influence of a simple magnetic bar on buoyancy-driven fingering of traveling autocatalytic reaction fronts

Magnetic fields have been shown experimentally to modify convective dynamics developing around traveling chemical fronts in presence of unfavorable density gradients. To understand the conditions in which such magnetic fields affect autocatalytic fronts, we study theoretically the influence of a simple magnetic bar on buoyancy-driven density fingering of a chemical front by numerical simulations of a reaction-diffusion-convection system. The model couples Darcy's law for the flow velocity to an evolution equation for the concentration of the autocatalytic product, which affects both the density of the solution and the magnetic force. The solutions of both products and reactants are assumed to be diamagnetic (i.e., negative magnetic susceptibility) and the magnetization is oriented perpendicularly to the plane in which the front travels. We show that, when aligned along the direction of front propagation, the magnetic force is able to suppress or enhance the convective instability depending on the value of the magnetic Rayleigh number of the problem. If the magnetic force is oriented transversely to the front propagation direction, tilted drifting convective patterns are obtained.

The heads and tails of buoyant autocatalytic balls

Buoyancy produced by autocatalytic reaction fronts can produce fluid flows that advect the front position, giving rise to interesting feedback between chemical and hydrodynamic effects. In this paper, we numerically investigate the evolution of autocatalytic iodate-arsenous acid reaction fronts initialized in spherical configurations. Deformation of these “autocatalytic balls” is driven by buoyancy produced by the reaction. In our simulations, we have found that depending on the initial ball radius, the reaction front will develop in one of three different ways. In an intermediate range of ball size, the flow can evolve much like an autocatalytic plume: the ball develops a reacting head and tail that is akin to the head and conduit of an autocatalytic plume. In the limit of large autocatalytic balls, however, growth of a reacting tail is suppressed and the resemblance to plumes disappears. Conversely, very small balls of product solution fail to initiate sustained fronts and eventually disappear.

CHEMO-hydrodynamic coupling between forced advection in porous media and self-sustained chemical waves

Autocatalytic reaction fronts between two reacting species in the absence of fluid flow, propagate as solitary waves. The coupling between autocatalytic reaction front and forced simple hydrodynamic flows leads to stationary fronts whose velocity and shape depend on the underlying flow field. We address the issue of the chemico-hydrodynamic coupling between forced advection in porous media and self-sustained chemical waves. Towards that purpose, we perform experiments over a wide range of flow velocities with the well characterized iodate arsenious acid and chlorite-tetrathionate autocatalytic reactions in transparent packed beads porous media. The characteristics of these porous media such as their porosity, tortuosity, and hydrodynamics dispersion are determined. In a pack of beads, the characteristic pore size and the velocity field correlation length are of the order of the bead size. In order to address these two length scales separately, we perform lattice Boltzmann numerical simulations in a stochastic porous medium, which takes into account the log-normal permeability distribution and the spatial correlation of the permeability field. In both experiments and numerical simulations, we observe stationary fronts propagating at a constant velocity with an almost constant front width. Experiments without flow in packed bead porous media with different bead sizes show that the front propagation depends on the tortuous nature of diffusion in the pore space. We observe microscopic effects when the pores are of the size of the chemical front width. We address both supportive co-current and adverse flows with respect to the direction of propagation of the chemical reaction. For supportive flows, experiments and simulations allow observation of two flow regimes. For adverse flow, we observe upstream and downstream front motion as well as static front behaviors over a wide range of flow rates. In order to understand better these observed static state fronts, flow experiments around a single obstacle were used to delineate the range of steady state behavior. A model using the "eikonal thin front limit" explains the observed steady states.

Lock-exchange experiments with an autocatalytic reaction front

A viscous lock-exchange gravity current corresponds to the reciprocal exchange of two fluids of different densities in a horizontal channel. The resulting front between the two fluids spreads as the square root of time, with a diffusion coefficient reflecting the buoyancy, viscosity, and geometrical configuration of the current. On the other hand, an autocatalytic reaction front between a reactant and a product may propagate as a solitary wave, namely, at a constant velocity and with a stationary concentration profile, resulting from the balance between molecular diffusion and chemical reaction. In most systems, the fluid left behind the front has a different density leading to a lock-exchange configuration. We revisit, with a chemical reaction, the classical situation of lock-exchange. We present an experimental analysis of buoyancy effects on the shape and the velocity of the iodate arsenous acid autocatalytic reaction fronts, propagating in horizontal rectangular channels and for a wide range of aspect ratios (1/3 to 20) and cylindrical tubes. We do observe stationary-shaped fronts, spanning the height of the cell and propagating along the cell axis. Our data support the contention that the front velocity and its extension are linked to each other and that their variations scale with a single variable involving the diffusion coefficient of the lock-exchange in the absence of chemical reaction. This analysis is supported by results obtained with lattice Bathnagar-Gross-Krook (BGK) simulations Jarrige et al. [Phys. Rev. E 81, 06631 (2010)], in other geometries (like in 2D simulations by Rongy et al. [J. Chem. Phys. 127, 114710 (2007)] and experiments in cylindrical tubes by Pojman et al. [J. Phys. Chem. 95, 1299 (1991)]), and for another chemical reaction Schuszter et al. [Phys. Rev. E 79, 016216 (2009)].

Stability of convective patterns in reaction fronts: A comparison of three models

Autocatalytic reaction fronts generate density gradients that may lead to convection. Fronts propagating in vertical tubes can be flat, axisymmetric, or nonaxisymmetric, depending on the diameter of the tube. In this paper, we study the transitions to convection as well as the stability of different types of fronts. We analyze the stability of the convective reaction fronts using three different models for front propagation. We use a model based on a reaction-diffusion-advection equation coupled to the Navier-Stokes equations to account for fluid flow. A second model replaces the reaction-diffusion equation with a thin front approximation where the front speed depends on the front curvature. We also introduce a new low-dimensional model based on a finite mode truncation. This model allows a complete analysis of all stable and unstable fronts.

Numerical simulations of a buoyant autocatalytic reaction front in tilted Hele-Shaw cells

We present a numerical analysis of solutal buoyancy effects on the shape and the velocity of autocatalytic reaction fronts, propagating in thin tilted rectangular channels. We use two-dimensional (2D) lattice Bathnagar-Gross-Krook (BGK) numerical simulations of gap-averaged equations for the flow and the concentration, namely a Stokes-Darcy equation coupled with an advection-diffusion-reaction equation. We do observe stationary-shaped fronts, spanning the width of the cell and propagating along the cell axis. We show that the model accounts rather well for experiments we performed using an Iodate Arsenous Acid reaction propagating in tilted Hele-Shaw cells, hence validating our 2D modelization of a three-dimensional problem. This modelization is also able to account for results found for another chemical reaction (chlorite tetrathionate) in a horizontal cell. In particular, we show that the shape and the traveling velocity of such fronts are linked with an eikonal equation. Moreover, we show that the front velocity varies nonmonotonically with the tilt of the cell, and nonlinearly with the width of the cell.

Measurement of the temperature profile of an exothermic autocatalytic reaction front

Autocatalytic reactions may propagate as solitary waves, namely, at a constant front velocity and with a stationary concentration profile, resulting from a balance between molecular diffusion and chemical reaction. When the reaction is exothermic, a thermal wave is linked to the chemical front. As the thermal diffusivity is nearly two orders of magnitude larger than the molecular one, the temperature profile spreads over length scales (mm) two orders of magnitude larger than the concentration one. Using an infrared camera, we measure the temperature profiles for a chlorite-tetrathionate autocatalytic reaction. The profiles are compared quantitatively to lattice Bhatnagar-Gross-Krook (BGK) numerical simulations. Our analysis also accounts for the lack of observation of the thermal wave for the iodate arsenous acid reaction.

The effects of a complexing agent on the transverse stability of cubic autocatalytic reaction fronts

The effects of adding a complexing agent on the propagation and transverse stability of reaction fronts in a system based on cubic autocatalysis is considered. Adding the complexing agent is seen to reduce the propagation speed, alter the reaction dynamics and the concentration of the final reaction product of the propagating reaction fronts. A linear stability analysis (LSA) is considered to determine how the complexing agent affects the stability of planar reaction fronts through the numerical calculation of dispersion curves, plots of the growth rate sigma against wavenumber k. These dispersion curves show that adding the complexing agent can make the system unstable when it would otherwise be stable and, when the system is diffusionally unstable without the complexing agent, weaken this instability. An analysis valid for small values of k is undertaken, which confirms the results from the LSA and indicates how the critical value D(c) of the diffusion coefficient ratio D for the onset of an instability is changed by the addition of the complexing agent.

Interaction between buoyancy and diffusion-driven instabilities of propagating autocatalytic reaction fronts. II. Nonlinear simulations

The nonlinear dynamics resulting from the interplay between diffusive and buoyancy-driven Rayleigh-Taylor (RT) instabilities of autocatalytic traveling fronts are analyzed numerically for fronts ascending or descending in the gravity field and for various values of the relevant parameters, the Rayleigh numbers R(a) and R(b) of the reactant A and autocatalytic product B, respectively, and the ratio D=D(B)/D(A) of the diffusion coefficients of the two key chemical species. The interaction between the coarsening dynamics characteristic of the RT instability and the fixed short wavelength dynamics of the diffusive instability leads in some parameter regimes to complex dynamics dominated by the irregular succession of birth and death of fingers. Large single convective fingers with a tip deformed by the short wavelength diffusive instability are also observed. If D is sufficiently small and the RT instability is active, the concentration of the slower diffusing species B can be convected to values above its fully reacted concentration. Experimental conditions that would allow the observation of the dynamics predicted here are described.

Interaction between buoyancy and diffusion-driven instabilities of propagating autocatalytic reaction fronts. I. Linear stability analysis

The interaction between buoyancy-driven and diffusion-driven instabilities that can develop along a propagating reaction front is discussed for a system based on an autocatalytic reaction. Twelve different cases are possible depending on whether the front is ascending or descending in the gravity field, whether the reactant is heavier or lighter than the products, and whether the reactant diffuses faster, slower, or at the same rate as the product. A linear stability analysis (LSA) is undertaken, in which dispersion curves (plots of the growth rate sigma against wave number k) are derived for representative cases as well as an asymptotic analysis for small wave numbers. The results from the LSA indicate that, when the initial reactant is denser than the reaction products, upward propagating fronts remain unstable with the diffusion-driven instability enhancing this instability. Buoyantly stable downward propagating fronts become unstable when the system is also diffusionally unstable. When the initial reactant is lighter than the reaction products, any diffusionally unstable upward propagating front is stabilized by small buoyancy effects. A diffusional instability enhances the buoyant instability of a downward propagating front with there being a very strong interaction between these effects in this case.

Taylor’s regime of an autocatalytic reaction front in a pulsative periodic flow

Autocatalytic reaction fronts between reacted and unreacted species may propagate as solitary waves, that is, at a constant front velocity and with a stationary concentration profile, which result from a balance between molecular diffusion and chemical reaction. A velocity field in the supporting medium may affect the propagation of such fronts through different phenomena: advection, diffusion enhancement, front shape changes, etc. Here, we report on an experimental study and lattice Bhatnagar–Gross–Krook numerical simulations of the effect of an oscillating flow on the autocatalytic reaction between iodate and arsenous acid in a Hele–Shaw cell. In the low frequency range covered by the experiments, the front behavior is controlled by the flow across the gap and is reproduced with two-dimensional numerical simulations. It is shown that the front velocity oscillates at the frequency of the flow, whereas the front width oscillates at twice that frequency. Moreover, the Taylor regime in the presence of a Poiseuille flow is fully investigated: The description obtained in the case of a stationary flow provides an analytical prediction for the sinusoidal flow. The range of parameters, for which the prediction applies, is delineated and discussed.

Convective chemical fronts in a Poiseuille flow

Autocatalytic reaction fronts propagating in a Poiseuille flow present a change of speed and curvature depending on the strength of the flow and on the direction of front propagation. These chemical fronts separate reacted and unreacted fluids of different densities, consequently convection will always be present due to the horizontal density gradient of the curved front. In this paper, we find the change of speed caused by gravity for fronts propagating in vertical tubes under a Poiseuille flow. For small density differences, we find axisymmetric fronts. Our theory predicts a transition to nonaxisymmetric fronts as the distance between the walls is increased. The transition depends on the average speed of the Poiseuille flow.

Effects of a constant electric field on the diffusional instability of cubic autocatalytic reaction fronts

An electric field applied in the direction of propagation of a chemical reaction-diffusion front can affect the stability of this front with regard to diffusive instabilities. The influence of an applied constant electric field is investigated by a linear stability analysis and by nonlinear simulations of a simple chemical system based on the cubic autocatalytic reaction A-+2B--->3B-. The diffusional stability of the front is seen to depend on the intensity E and sign of the applied field, and D, the ratio diffusion coefficients of the reactant species. Depending on E, the front can become more or less diffusively unstable for a given value of D. Above a critical value of E, which depends on D, electrophoretic separation of the two fronts is observed.