Thermal effects on chemically induced Marangoni convection around A + B → C reaction fronts.

Chemical reactions can induce Marangoni flows by changing the surface tension of a solution open to the air, either by changing the composition and/or by modifying the temperature. We consider the case of a simple A + B → C reaction front propagating in a thin horizontal system open to air. The effect of the three chemical species on the surface tension of the aqueous solution is quantified by three solutal Marangoni numbers, while the effect of temperature changes is determined by the thermal Marangoni number. By integrating numerically the incompressible Navier-Stokes equations coupled to reaction-diffusion-convection equations for the chemical concentrations and temperature taking into account the Lewis number (ratio between heat and mass diffusivities), we emphasize the importance of thermal changes occurring due to the heat of reaction on the dynamics of chemically induced Marangoni convection. Based on the reaction-diffusion profiles of concentrations and temperature, asymptotic analytical solutions for the surface tension profiles are obtained and classified as a function of the Marangoni numbers and the Lewis number. This new classification allows for the prediction of the convective patterns in thermo-solutal Marangoni flows. The analytical predictions are further confirmed by numerical results and additional extrema in surface tension profiles induced by the thermal effects are found to affect the nonlinear dynamics.

Effect of variable solubility on reactive dissolution in partially miscible systems.

When two partially miscible systems are put in contact, one phase, A, can dissolve into the other one with a given solubility. Chemical reactions in the host phase can impact this dissolution by consuming A and by generating products that impact the solubility of A. Here, we study theoretically the optimal conditions for transfer of a reactant A in a host phase containing a species B when a bimolecular A + B → C reaction generates a product C that linearly decreases the solubility of A. We have quantified numerically the influence of this variable solubility on the reaction-diffusion (RD) concentration profiles of all species in the host phase, on the temporal evolution of the position of the reaction front, and on the flux of A through the interface. We have also computed the analytical asymptotic concentration profiles, solutions at long times of the RD governing equations. For a fixed negative effect of C on the solubility of A, an increase in the initial concentration of reactant B or an increase in the diffusion rate of species B and C results in a larger flux of A and hence a larger amount of A dissolved in the host solution at a given time. However, when the influence of C on the solubility increases, the mass transfer decreases. Our results help understand to what extent a chemical reaction can optimize the reactive transfer of a solute to a host phase with application to, among other things, the geological sequestration of carbon dioxide in an aquifer.

Marangoni-driven nonlinear dynamics of bimolecular frontal systems: a general classification for equal diffusion coefficients.

When bimolecular fronts form in solutions, their dynamics is likely to be affected by chemically driven convection such as buoyancy- and Marangoni-driven flows. It is known that front dynamics in the presence of buoyancy-driven convection can be predicted solely on the basis of the one-dimensional reaction-diffusion concentration profiles but that those predictions fail for Marangoni-driven convection. With a two-dimensional reaction-diffusion-Marangoni convection model, we analyze here convective effects on the time scalings of the front properties, together with the influence of reaction reversibility and of the ratio of initial reactants' concentrations on the front dynamics. The effect of buoyancy forces is here neglected by assuming the reactive system to be in zero-gravity condition and/or the solution density to be spatially homogenous. This article is part of the theme issue 'New trends in pattern formation and nonlinear dynamics of extended systems'.

Complex dynamics of interacting fronts in a simple A+B→C reaction-diffusion system.

Pattern interaction has so far been restricted to systems with relatively complex reaction schemes, such as activator-inhibitor systems, that lead to rich spatio-temporal dynamics. Surprisingly, a simple second-order chemical reaction is capable of generating similar complex phenomena, such as attractive or repulsive interaction modes between the localized reaction zones (or fronts). We illustrate the latter statement both analytically and numerically with two initially separated A+B→C reaction-diffusion fronts when the solution of B is initially confined between two solutions of A. The nature of the front-front interaction changes from an attractive type to a repulsive one above a critical distance separating the two fronts initially. The complexity of the pattern dynamics emerges here due to finite-size effects. A scaling law relating the critical distance d_{c} above which the repulsion occurs and kinetic parameters gives insights into (i) extracting those parameters from experiments for bimolecular reactions and (ii) the control strategy of periodic patterns.

Chemically-driven convective dissolution.

When a solute A dissolves in a host phase with a given solubility, the resulting density stratification is stable towards convection if the density profile increases monotonically along the gravity field. We theoretically and numerically study the convective destabilization by reaction of this dissolution when A reacts with a solute B present in the host phase to produce C via an A + B→C type of reaction. In this reactive case, composition changes can give rise to non-monotonic density profiles with a local maximum. A convective instability can then be triggered locally in the zone where the denser product overlies the less dense bulk solution. First, we perform a linear stability analysis to identify the critical conditions for this reaction-driven convective instability. Second, we perform nonlinear simulations and compare the critical values of the control parameters for the onset of convection in these simulations with those predicted by linear stability analysis. We further show that the asymptotic dissolution flux of A can be increased in the convective regime by increasing the difference ΔRCB = RC-RB between the Rayleigh numbers of the product C and reactant B above a critical value and by increasing the ratio ß = B0/A0 between the initial concentration B0 of reactant B and the solubility A0 of A. Our results indicate that chemical reactions can not only initiate convective mixing but can also give rise to large dissolution fluxes, which is advantageous for various geological applications.

Making a Simple A+B→C Reaction Oscillate by Coupling to Hydrodynamic Effect.

We present a new mechanism through which chemical oscillations and waves can be induced in batch conditions with a simple A+B→C reaction in the absence of any nonlinear chemical feedback or external trigger. Two reactants A and B, initially separated in space, react upon diffusive contact and the product actively fuels in situ convective Marangoni flows by locally increasing the surface tension at the mixing interface. These flows combine in turn with the reaction-diffusion dynamics, inducing damped spatiotemporal oscillations of the chemical concentrations and the velocity field. By means of numerical simulations, we single out the detailed mechanism and minimal conditions for the onset of this periodic behavior. We show how the antagonistic coupling with buoyancy convection, due to concurrent chemically induced density changes, can control the oscillation properties, sustaining or suppressing this phenomenon depending on the relative strength of buoyancy- and surface-tension-driven forces. The oscillatory instability is characterized in the relevant parametric space spanned by the reactor height, the Marangoni (Ma_{i}) and the Rayleigh (Ra_{i}) numbers of the ith chemical species, the latter ruling the surface tension and buoyancy contributions to convection, respectively.

Enhanced convective dissolution due to an A + B → C reaction: control of the non-linear dynamics via solutal density contributions.

Chemical reactions can have a significant impact on convective dissolution in partially miscible stratifications in porous media and are able to enhance the asymptotic flux with respect to the non-reactive case. We numerically study such reactive convective dissolution when the dissolving species A increases the density of the host phase upon dissolution and reacts with a reactant B present in the host phase to produce C by an A + B → C reaction. Upon varying the difference ΔRCB = RC-RB between the Rayleigh numbers of the product C and the reactant B, we identify four regimes with distinct dynamics when the diffusion coefficients are the same. When ΔRCB < 0, the density profiles are non-monotonic and the non-linear dynamics are seen to depend on the relative values of the density at the interface and the initial density of the host phase. For ΔRCB > 0, the monotonic density profiles are destabilizing with respect to the non-reactive case above a certain critical value ΔRcr. We analyze quantitatively the influence of varying ΔRCB and the ratio ß = B0/A0 of the initial concentration of B and the solubility of A on the asymptotic steady flux, the wavelength of the fingers and the position of the reaction front. In the context of CO2 geological sequestration, understanding how such reactions can enhance the dissolution flux is crucial for improving the efficiency and safety of the process.

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.

Surface tension- and buoyancy-driven flows across horizontally propagating chemical fronts.

Chemical reactions can interplay with hydrodynamic flows to generate various complex phenomena. Because of their relevance in many research areas, chemically-induced hydrodynamic flows have attracted increasing attention in the last decades. In this context, we propose to give a review of the past and recent theoretical and experimental works which have considered the interaction of such flows with chemical fronts, i.e. reactive interfaces, formed between miscible solutions. We focus in particular on the influence of surface tension- (Marangoni) and buoyancy-driven flows on the dynamics of chemical fronts propagating horizontally in the gravity field.

Enhanced steady-state dissolution flux in reactive convective dissolution.

Chemical reactions can accelerate, slow down or even be at the very origin of the development of dissolution-driven convection in partially miscible stratifications when they impact the density profile in the host fluid phase. We numerically analyze the dynamics of this reactive convective dissolution in the fully developed non-linear regime for a phase A dissolving into a host layer containing a dissolved reactant B. We show for a general A + B → C reaction in solution, that the dynamics vary with the Rayleigh numbers of the chemical species, i.e. with the nature of the chemicals in the host phase. Depending on whether the reaction slows down, accelerates or is at the origin of the development of convection, the spatial distributions of species A, B or C, the dissolution flux and the reaction rate are different. We show that chemical reactions can enhance the steady-state flux as they consume A and can induce more intense convection than in the non-reactive case. This result is important in the context of CO2 geological sequestration where quantifying the storage rate of CO2 dissolving into the host oil or aqueous phase is crucial to assess the efficiency and the safety of the project.

Density profiles around A+B→C reaction-diffusion fronts in partially miscible systems: A general classification.

Various spatial density profiles can develop in partially miscible stratifications when a phase A dissolves with a finite solubility into a host phase containing a dissolved reactant B. We investigate theoretically the impact of an A+B→C reaction on such density profiles in the host phase and classify them in a parameter space spanned by the ratios of relative contributions to density and diffusion coefficients of the chemical species. While the density profile is either monotonically increasing or decreasing in the nonreactive case, reactions combined with differential diffusivity can create eight different types of density profiles featuring up to two extrema in density, at the reaction front or below it. We use this framework to predict various possible hydrodynamic instability scenarios inducing buoyancy-driven convection around such reaction fronts when they propagate parallel to the gravity field.

Influence of Marangoni flows on the dynamics of isothermal A + B → C reaction fronts.

The nonlinear dynamics of A + B → C fronts is analyzed both numerically and theoretically in the presence of Marangoni flows, i.e., convective motions driven by surface tension gradients. We consider horizontal aqueous solutions where the three species A, B, and C can affect the surface tension of the solution, thereby driving Marangoni flows. The resulting dynamics is studied by numerically integrating the incompressible Navier-Stokes equations coupled to reaction-diffusion-convection (RDC) equations for the three chemical species. We show that the dynamics of the front cannot be predicted solely on the basis of the one-dimensional reaction-diffusion profiles as is the case for buoyancy-driven convection around such fronts. We relate this observation to the structure of Marangoni flows which lead to more complex and exotic dynamics. We find in particular the surprising possibility of a reversal of the front propagation direction in time for some sets of Marangoni numbers, quantifying the influence of each chemical species concentration on the solution surface tension. We explain this reversal analytically and propose a new classification of the convective effects on A + B → C reaction fronts as a function of the Marangoni numbers. The influence of the layer thickness on the RDC dynamics is also presented. Those results emphasize the importance of flow symmetry properties when studying convective front dynamics in a given geometry.

Chemical control of dissolution-driven convection in partially miscible systems: theoretical classification.

Dissolution-driven convection occurs in the host phase of a partially miscible system when a buoyantly unstable density stratification develops upon dissolution. Reactions can impact such convection by changing the composition and thus the density of the host phase. Here we study the influence of A + B → C reactions on such convective dissolution when A is the dissolving species and B a reactant initially in solution in the host phase. We perform a linear stability analysis of related reaction-diffusion density profiles to compare the growth rate of the instability in the reactive case to its non reactive counterpart when all species diffuse at the same rate. We classify the stabilizing or destabilizing influence of reactions on the buoyancy-driven convection in a parameter space spanned by the solutal Rayleigh numbers RA,B,C of chemical species A, B, C and by the ratio ß of initial concentrations of the reactants. For RA > 0, the non reactive dissolution of A in the host phase is buoyantly unstable. In that case, we show that the reaction is enhancing convection provided C is sufficiently denser than B. Increasing the ratio ß of initial reactant concentrations increases the effect of chemistry but does not significantly impact the stabilizing/destabilizing classification. When the non reactive case is buoyantly stable (RA≤ 0), reactions can create in time an unstable density stratification and trigger convection if RC > RB. Our theoretical approach allows classifying previous results in a unifying picture and developing strategies for the chemical control of convective dissolution.

Control of convective dissolution by chemical reactions: general classification and application to CO(2) dissolution in reactive aqueous solutions.

In partially miscible two-layer systems within a gravity field, buoyancy-driven convective motions can appear when one phase dissolves with a finite solubility into the other one. We investigate the influence of chemical reactions on such convective dissolution by a linear stability analysis of a reaction-diffusion-convection model. We show theoretically that a chemical reaction can either enhance or decrease the onset time of the convection, depending on the type of density profile building up in time in the reactive solution. We classify the stabilizing and destabilizing scenarios in a parameter space spanned by the solutal Rayleigh numbers. As an example, we experimentally demonstrate the possibility to enhance the convective dissolution of gaseous CO_{2} in aqueous solutions by a classical acid-base reaction.

Impact of pressure, salt concentration, and temperature on the convective dissolution of carbon dioxide in aqueous solutions.

The convective dissolution of carbon dioxide (CO2) in salted water is theoretically studied to determine how parameters such as CO2 pressure, salt concentration, and temperature impact the short-time characteristics of the buoyancy-driven instability. On the basis of a parameter-free dimensionless model, we perform a linear stability analysis of the time-dependent concentration profiles of CO2 diffusing into the aqueous solution. We explicit the procedure to transform the predicted dimensionless growth rate and wavelength of the convective pattern into dimensional ones for typical laboratory-scale experiments in conditions close to room temperature and atmospheric pressure. This allows to investigate the implicit influence of the experimental parameters on the characteristic length and time scales of the instability. We predict that increasing CO2 pressure, or decreasing salt concentration or temperature destabilizes the system with regard to convection, leading to a faster dissolution of CO2 into salted water.

Marangoni-driven convection around exothermic autocatalytic chemical fronts in free-surface solution layers.

Gradients of concentration and temperature across exothermic chemical fronts propagating in free-surface solution layers can initiate Marangoni-driven convection. We investigate here the dynamics arising from such a coupling between exothermic autocatalytic reactions, diffusion, and Marangoni-driven flows. To this end, we numerically integrate the incompressible Navier-Stokes equations coupled through the tangential stress balance to evolution equations for the concentration of the autocatalytic product and for the temperature. A solutal and a thermal Marangoni numbers measure the coupling between reaction-diffusion processes and surface-driven convection. In the case of an isothermal system, the asymptotic dynamics is characterized by a steady fluid vortex traveling at a constant speed with the front, deforming and accelerating it [L. Rongy and A. De Wit, J. Chem. Phys. 124, 164705 (2006)]. We analyze here the influence of the reaction exothermicity on the dynamics of the system in both cases of cooperative and competitive solutal and thermal effects. We show that exothermic fronts can exhibit new unsteady spatio-temporal dynamics when the solutal and thermal effects are antagonistic. The influence of the solutal and thermal Marangoni numbers, of the Lewis number (ratio of thermal diffusivity over molecular diffusivity), and of the height of the liquid layer on the spatio-temporal front evolution are investigated.

Dynamics due to combined buoyancy- and Marangoni-driven convective flows around autocatalytic fronts.

A reaction-diffusion-convection (RDC) model is introduced to analyze convective dynamics around horizontally traveling fronts due to combined buoyancy- and surface tension-driven flows in vertical solution layers open to the air. This isothermal model provides a means for a comparative study of the two effects via tuning two key parameters: the solutal Rayleigh number Ra, which rules the buoyancy influence, and the solutal Marangoni number Ma governing the intensity of surface effects at the interface between the reacting solution and air. The autocatalytic front dynamics is probed by varying the relative importance of Ra and Ma and the resulting RDC patterns are quantitatively characterized through the analysis of the front mixing length and the topology of the velocity field. Steady asymptotic regimes are found when the bulk and the surface contributions to fluid motions act cooperatively i.e. when Ra and Ma have the same sign. Complex dynamics may arise when these numbers are of opposite signs and the two effects thus compete in an antagonistic configuration. Typically, spatiotemporal oscillations are observed as the control parameters are set in the region (Ra < 0, Ma > 0). Periodic behaviour develops here even in the absence of any double-diffusive interplay, which in previous literature was identified as a possible source of complexity.

Buoyancy-driven convection around exothermic autocatalytic chemical fronts traveling horizontally in covered thin solution layers.

Spatial variations of concentrations and temperature across exothermic chemical fronts can initiate buoyancy-driven convection. We investigate here theoretically the spatiotemporal dynamics arising from such a coupling between exothermic autocatalytic reactions, diffusion, and buoyancy-driven flows when an exothermic autocatalytic front travels perpendicularly to the gravity field in a thin solution layer. To do so, we numerically integrate the incompressible Stokes equations coupled to evolution equations for the concentration of the autocatalytic product and temperature through buoyancy terms proportional to, respectively, a solutal R(C) and a thermal R(T) Rayleigh number. We show that exothermic fronts can exhibit new types of dynamics in the presence of convection with regard to the isothermal system. In the cooperative case (R(C) and R(T) are of the same sign), the dynamics asymptotes to one vortex surrounding, deforming, and accelerating the front much like in the isothermal case. However, persistent local stratification of heavy zones over light ones can be observed at the rear of the front when the Lewis number Le (ratio of thermal diffusivity over molecular diffusion) is nonzero. When the solutal and thermal effects are antagonistic (R(C) and R(T) of opposite sign), temporal oscillations of the concentration, temperature, and velocity fields can, in some cases, be observed in a reference frame moving with the front. The various dynamical regimes are discussed as a function of R(C), R(T), and Le.

Influence of thermal effects on buoyancy-driven convection around autocatalytic chemical fronts propagating horizontally.

The spatiotemporal dynamics of vertical autocatalytic fronts traveling horizontally in thin solution layers closed to the air can be influenced by buoyancy-driven convection induced by density gradients across the front. We perform here a combined experimental and theoretical study of the competition between solutal and thermal effects on such convection. Experimentally, we focus on the antagonistic chlorite-tetrathionate reaction for which solutal and thermal contributions to the density jump across the front have opposite signs. We show that in isothermal conditions the heavier products sink below the lighter reactants, providing an asymptotic constant finger shape deformation of the front by convection. When thermal effects are present, the hotter products, on the contrary, climb above the reactants for strongly exothermic conditions. These various observations as well as the influence of the relative weight of the solutal and thermal effects and of the thickness of the solution layer on the dynamics are discussed in terms of a two-dimensional reaction-diffusion-convection model parametrized by a solutal R(C) and a thermal R(T) Rayleigh number.

Dynamics of A + B --> C reaction fronts in the presence of buoyancy-driven convection.

The dynamics of A+B-->C fronts in horizontal solution layers can be influenced by buoyancy-driven convection as soon as the densities of A, B, and C are not all identical. Such convective motions can lead to front propagation even in the case of equal diffusion coefficients and initial concentration of reactants for which reaction-diffusion (RD) scalings predict a nonmoving front. We show theoretically that the dynamics in the presence of convection can in that case be predicted solely on the basis of the knowledge of the one-dimensional RD density profile across the front.