Iodate-arsenous Acid Reaction Research Articles

Surface-Tension-Driven Dynamic Contact Line in Microgravity.

We study the effect of Marangoni flow on a dynamic contact line formed by a propagating reaction front and a liquid-air interface. The self-sustained iodate-arsenous acid reaction maintains the production of the weakly surface active iodine leading to an unbalanced surface force along the tip of the reaction front. The experiments, performed in microgravity to exclude the contribution of buoyancy, reveal that the fluid flow generated by the surface tension gradient is localized to the contact line. The penetration depth of the surface stress is measured as 1-2 mm; therefore, with greater fluid height the liquid advancement on the upper surface does not lead to enhanced mixing in the bulk. Because the propagation velocity of the reactive interface remains at that of reaction-diffusion, the leading edge consists of two straight lines; a tilted segment connects the contact line on the surface with the vertical segment on bottom. Modeling calculations of the reaction-diffusion-advection system in three dimensions reconstruct the experimental observations and along with the experiments validate a model based on geometric spreading. According to the calculated flow field, the direction of significant fluid flow follows the concentration gradients and hence coincides with the propagation of the reaction front, allowing only negligible transverse flow in the upper fluid layer.

Acceleration of chemical reaction fronts

Chemical fronts and waves travelling in reaction-diffusion systems frequently induce hydrodynamic flow. This adds an additional transport process to the mechanism of spatio-temporal structure formation and can lead to an acceleration of the chemical (reaction) front. We report on the acceleration of travelling chemical fronts elicited by convection, as caused by the Marangoni effect in the monostable iodate-arsenous acid reaction in a thin liquid film. At a stoichiometric excess of iodate over arsenous acid, the reaction produces a large amount of iodine, which is surface-active. At the reaction front, iodine is transferred from the bulk to the surface inducing spatio-temporal gradients of surface tension that lead to capillary flows. These flows, in turn, promote further iodine adsorption at the surface through hydrodynamic mixing effects. As a consequence, an acceleration of the chemical fronts is observed, even if the concentration difference across the front is constant. After the transient acceleration of the reaction front, it settles at a constant propagation velocity, which is assumed to be regulated by a balance in the mass transfer between the bulk and the surface.

Acceleration of chemical reaction fronts

The propagation of reaction-diffusion fronts in an open liquid solution layer is critically affected by mass transfer between the liquid solution and the adjacent gas phase. This is the case in the iodate–arsenous acid (IAA) reaction when run under stoichiometric excess of iodate. Here, iodine is the reaction product, which has a low solubility in the liquid phase, hence, excess iodine rapidly evaporates. In the gas phase, it diffuses and overtakes the reaction front propagating in the liquid medium because its diffusion coefficient in the gas phase is considerably larger than that in aqueous solution. Evaporated iodine is re-dissolved into the reaction medium ahead of the reaction front. Since iodine is the autocatalytic species of the IAA reaction, this additional gas-phase transport may lead to an acceleration of the propagating reaction front.

Effects of the Starch Indicator on the Buoyantly Unstable Iodate‐Arsenous Acid Reaction Front

AbstractBuoyantly unstable chemical fronts, which propagated in the iodate arsenous acid reaction system, were studied experimentally in 3D space and numerically in vertical 2D space. The fronts invaded the reaction solution from the left top corner in horizontal and vertical directions. Before the starch effects were examined condition under which friction did not influence the front propagation were found both experimentally and numerically. The critical solution depth and the critical distance between lateral walls, above which the front speed is not influenced by friction, were determined. Moreover, the results also show that the 2D simulations correspond to a vertically oriented plane placed the 3D experiments in 1/2 of the walls distance and along the x axis of the reactor. Importantly, those results also show that friction caused by the presence of solid side walls exclude pseudo 2D experiments to be compared with 2D simulations, when flow is involved. The effects of starch on the IAA fronts were studied experimentally at conditions, at which the friction did not influence the front propagation. Although the starch is used in very low concentrations as an iodine indicator, the experimental results show that starch presence strongly affects the dynamics of the liquid IAA reaction system. The presence of starch decreases the front velocity independently on the direction of the front propagation. Starch also affects the pattern formation. A possible mechanism is discussed.

Surface tension driven flow on a thin reaction front

Surface tension driven convection affects the propagation of chemical reaction fronts in liquids. The changes in surface tension across the front generate this type of convection. The resulting fluid motion increases the speed and changes the shape of fronts as observed in the iodate-arsenous acid reaction. We calculate these effects using a thin front approximation, where the reaction front is modeled by an abrupt discontinuity between reacted and unreacted substances. We analyze the propagation of reaction fronts of small curvature. In this case the front propagation equation becomes the deterministic Kardar-Parisi-Zhang (KPZ) equation with the addition of fluid flow. These results are compared to calculations based on a set of reaction-diffusion-convection equations.

A Simple Kinetic Model for Description of the Iodate–Arsenous Acid Reaction: Experimental Evidence of the Direct Reaction

The autocatalytic iodate-arsenous acid reaction was investigated by a stopped-flow instrument under strongly acidic medium (pH ≤ 1) by monitoring the absorbance-time profiles at 468 nm. The kinetic traces were found to exhibit a perfect sigmoidal shape in stoichiometric excess of iodate with a well-defined and reproducible induction period that depends on the initial concentration of the reactants as well as on the pH. All the experimental curves can be globally fitted by a simple kinetic model involving the direct reaction between the reactants to produce iodide ion, the Dushman and the Roebuck reactions, and two rapid equilibria. Our measurements along with simultaneous evaluation of the kinetic traces clearly support that indeed the initiation reaction exists at strongly acidic conditions and contributes to the overall kinetics. The measured traces cannot be described adequately by the iodide ion impurity-driven Dushman and Roebuck reactions with assuming no direct reaction at all.

Initial inhomogeneity-induced crazy-clock behavior in the iodate-arsenous acid reaction in a buffered medium under stirred batch conditions.

It is unambiguously demonstrated that in the case of an autocatalytic reaction, initial inhomogeneities induced by the imperfectly mixed part of the overall volume may result in a serious irreproducibility of the individual kinetic runs. A statistically meaningful number of repetitions, however, gives rise to a reproducible cumulative probability distribution curve often referred to as a support of the stochastic feature. The iodate-arsenous acid reaction being autocatalytic with respect to both iodide and hydrogen ions displays clock behavior. However, the time lag necessary for the appearance of iodine, even in buffered solution, varies in an apparently random manner. Careful analysis of the variation of the different parameters like stirring rate, overall volume, geometry of the reactor and the way of mixing the reactants led us to conclude that the fate of the individual samples is determined at the initial stage when the reacting system is per se inhomogeneous. The place, the size of the so-called ignition volume, where the reacting system is imperfectly stirred, as well as the residence time spent there by the imperfectly mixed reactants all seem to depend on external factors.

Marangoni instability in the iodate–arsenous acid reaction front

Horizontally propagating chemical fronts leading to the formation of a single stable convection roll are investigated in the iodate-arsenous acid reaction with arsenous acid stoichiometrically limiting, leaving the surface active iodine present in the product mixture. In sufficiently thin solution layers with open upper surface, the contribution of Marangoni instability is significantly enhanced. Acting in the same direction as buoyancy driven instability, it distorts the entire tilted reaction front that becomes 50% more elongated. The corresponding three-dimensional calculations based on the empirical rate-law of the reaction corroborate the experimental findings.

Hydrodynamic instability in the open system of the iodate–arsenous acid reaction

Hydrodynamic instability arising in horizontally propagating vertical chemical fronts leading to the formation of a single stable convection roll is investigated experimentally in the iodate-arsenous acid reaction for various stoichiometry. In the presence of a free surface, the tilted reaction front becomes more elongated due to the evaporation of the surface active iodine and the decrease in the surface tension during the reaction. The experimental conditions are then identified where Marangoni instability represents the driving force for the distortion of the reaction front at the surface.

Relation between shape of liquid-gas interface and evolution of buoyantly unstable three-dimensional chemical fronts

Buoyantly unstable 3D chemical fronts were seen traveling through an iodate-arsenous acid reaction solution. The experiments were performed in channel reactors with rectangular cross sections, where the top of the reaction solution was in contact with air. A concave or convex meniscus was pinned to reactor lateral walls. Influence of the meniscus shape on front development was investigated. For the concave meniscus, an asymptotic shape of fronts holding negative curvature was observed. On the other hand, fronts propagating in the solution with the convex meniscus kept only positive curvature. Those fronts were also a bit faster than fronts propagating in the solution with the concave meniscus. A relation between the meniscus shape, flow distribution, velocity, and shape is discussed.

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.

The dependence of scaling law on stoichiometry for horizontally propagating vertical chemical fronts

Horizontally propagating fronts in the iodate-arsenous acid reaction are investigated experimentally in a vertically oriented Hele-Shaw cell by varying the height of liquid layer for various stoichiometry. At the preset conditions, a stable pattern develops which can be characterized by its mixing length defined as the standard deviation of the front position in the direction of propagation. The mixing length scales with the height of the reaction vessel, and although the exponent significantly changes by varying the ratio of the reactants, it has a universal value when the reaction front is thin and simple convection arises.

Autocatalytic plume pinch-off

A localized source of buoyancy flux in a nonreactive fluid medium creates a plume. The flux can be provided by either heat, a compositional difference between the fluid comprising the plume and its surroundings, or a combination of both. For autocatalytic plumes produced by the iodate-arsenous acid reaction, however, buoyancy is produced along the entire reacting interface between the plume and its surroundings. Buoyancy production at the moving interface drives fluid motion, which in turn generates flow that advects the reaction front. As a consequence of this interplay between fluid flow and chemical reaction, autocatalytic plumes exhibit a rich dynamics during their ascent through the reactant medium. One of the more interesting dynamical features is the production of an accelerating vortical plume head that in certain cases pinches-off and detaches from the upwelling conduit. After pinch-off, a new plume head forms in the conduit below, and this can lead to multiple generations of plume heads for a single plume initiation. We investigated the pinch-off process using both experimentation and simulation. Experiments were performed using various concentrations of glycerol, in which it was found that repeated pinch-off occurs exclusively in a specific concentration range. Autocatalytic plume simulations revealed that pinch-off is triggered by the appearance of accelerating flow in the plume conduit.

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.

Conduits of steady-state autocatalytic plumes

Plumes are typically formed when a continuous source of buoyancy is supplied at a localized source. We studied laminar plumes where buoyancy is supplied by an autocatalytic chemical reaction: The iodate-arsenous acid (IAA) reaction. The nonlinear kinetics of the IAA reaction produces a sharp propagating front at which buoyancy is produced by exothermicity and compositional change. When the reaction is initiated in an unconfined volume of reactant, a starting plume with a mushroom shaped head connected to the initiation point by a long conduit is formed. After the initial transient during the ascent of the head, we observed the emergence of a steady state in the conduit morphology and flow. Autocatalytic plumes were compared to nonreacting, compositionally buoyant plumes using the Gradient Echo Rapid Velocity and Acceleration Imaging Sequence (GERVAIS), an MRI velocimetric technique. Autocatalytic conduits had axisymmetric bimodal velocity profiles and cone-shaped morphologies, in contrast to the Gaussian profiles and cylindrical shapes of nonreacting conduits. The bimodal distribution for autocatalytic plumes is a consequence of the unique effect of entrainment in this system. Rather than the usual effect of entrainment in nonreacting plumes, where less buoyant fluid is incorporated into the plumes, entrainment in autocatalytic plumes provides a buoyancy flux along the entire conduit by means of chemical reaction, thereby delocalizing the buoyancy source.

Flow-field development during finger splitting at an exothermic chemical reaction front

Fingertip splitting may be observed at chemical reaction fronts subject to buoyancy-induced Rayleigh-Taylor fingering, as investigated in ascending fronts of the iodate-arsenous acid reaction in vertical Hele-Shaw cells. We study the properties of the flow-field evolution during a tip-splitting event both experimentally and theoretically. Experimental particle-image velocimetry techniques show that the flow field associated to a finger displays a quadrupole of vortices. The evolution of the flow field and the reorganization of the vortices after a tip-splitting event are followed experimentally in detail. Numerical integration of a model reaction-diffusion-convection system for an exothermic reaction taking into account possible heat losses through the walls of the reactor shows that the nonlinear properties of the flow field are different whether the walls are insulating or conducting. In insulating systems, the flow field inside one finger features only one pair of vortices. A quadrupole of flow vortices arranged around a saddle-node structure similar to the one observed experimentally is obtained in the presence of heat losses suggesting that heat effects, even if of very small amplitude, are important in understanding the nonlinear properties of fingering of exothermic chemical fronts.

Spatio-temporal behaviors of a clock reaction in an open gel reactor

The concentration profiles along the feeding direction of a one side fed gel reactor are analyzed for the iodate-arsenous acid reaction. Multiplicity of inhomogeneous stationary solutions is derived. It is also shown that such profiles may undergo oscillatory bifurcations under long range activation conditions. The bifurcation diagram is analyzed using a Galerkin approximation, the asymptotic validity of which is discussed.

Electric field induced instabilities: Waves and stationary patterns

We examine a prototypical ionic reaction-diffusion system involving the well-known iodate-arsenous acid reaction in an electric field at a constant current density. By taking into consideration of the spatial inhomogeneities in electric field intensity and charge density due to ionic migration and diffusion using charge balance condition, we look for the different instability regions in the appropriate parameter space. We show that the model admits of both absolute and convective instability resulting in the development of propagating waves and also stationary spatial patterns at times.

Travelling waves in the iodate–arsenous acid system

The equations describing travelling waves in the iodate–arsenous acid reaction are discussed, with kinetics based on the Dushman–Roebuck scheme. These equations are used to show how the structure of the wave (its propagation speed and final reaction products) depends on the stoichiometry factor S0, the initial concentration of arsenous acid relative to iodate. Different forms are seen in the ranges 0 3. An asymptotic analysis, based on a large parameter arising in the system, is undertaken. This shows that wave structures and propagation speeds are different in these three ranges of S0.