Nonlinear Physical Chemistry Unit and Center for Nonlinear Phenomena and Complex Systems, CP 231, Faculté des Sciences, Université Libre de Bruxelles, Brussels 1050, Belgium.
J Chem Phys. 2009 Nov 14;131(18):184701. doi: 10.1063/1.3258277.
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.
放热化学反应前沿处浓度和温度的空间变化可以引发浮力驱动对流。我们在此理论研究了在放热自催化反应、扩散和浮力驱动流之间的这种耦合作用下,当放热自催化前沿垂直于重力场在薄溶液层中传播时产生的时空动力学。为此,我们通过与浓度的演化方程耦合的不可压缩 Stokes 方程,数值积分了自催化产物和温度的浮力项分别正比于溶质 R(C)和热 R(T)瑞利数。我们表明,与等温系统相比,对流存在时放热前沿会表现出新型动力学。在协同情况下(R(C)和 R(T)的符号相同),动力学渐近于一个围绕、变形和加速前沿的旋涡,就像在等温情况下一样。然而,当刘易斯数 Le(热扩散率与分子扩散率之比)不为零时,在前缘后方可以观察到较重区域对较轻区域的持续局部分层。当溶质和热效应相反时(R(C)和 R(T)的符号相反),在与前沿一起移动的参考系中,在某些情况下可以观察到浓度、温度和速度场的时间振荡。讨论了各种动力学状态作为 R(C)、R(T)和 Le 的函数。