Física Aplicada I, Facultad de Ciencias, Universidad de Málaga, 29071 Málaga, Spain.
Institut für Weiche Materie und Funktionale Materialien, Helmholtz-Zentrum Berlin für Materialien und Energie, 14109 Berlin, Germany.
J Chem Phys. 2018 Feb 14;148(6):064705. doi: 10.1063/1.5016608.
Steric or attractive interactions among reactants or between reactants and inert crowders can substantially influence the total rate of a diffusion-influenced reaction in the liquid phase. However, the role of the product species, which has typically different physical properties than the reactant species, has been disregarded so far. Here we study the effects of reactant-product and product-product interactions as well as asymmetric diffusion properties on the rate of diffusion-controlled reactions in the classical Smoluchowski-setup for chemical transformations at a perfect catalytic sphere. For this, we solve the diffusion equation with appropriate boundary conditions coupled by a mean-field approach on the second virial level to account for the particle interactions. We find that all particle spatial distributions and the total rate can change significantly, depending on the diffusion and interaction properties of the accumulated products. Complex competing and self-regulating (homeostatic) or self-amplifying effects are observed for the system, leading to both decrease and increase in the rates, as the presence of interacting products feeds back to the reactant flux and thus the rate with which the products are generated.
反应物之间或反应物与惰性致孔剂之间的空间或吸引力相互作用会极大地影响液相中扩散控制反应的总速率。然而,迄今为止,产物物种的作用一直被忽视,而产物物种通常具有与反应物物种不同的物理性质。在这里,我们研究了反应物-产物和产物-产物相互作用以及不对称扩散特性对完美催化球上化学转化的经典 Smoluchowski 装置中扩散控制反应速率的影响。为此,我们通过平均场方法在第二维里水平上求解扩散方程,并结合适当的边界条件,以考虑粒子相互作用。我们发现,所有粒子的空间分布和总速率都可能发生显著变化,具体取决于积累产物的扩散和相互作用特性。系统中观察到复杂的竞争和自我调节(动态平衡)或自我放大效应,导致速率下降和上升,因为相互作用产物的存在反馈到反应物通量,从而影响产物生成的速率。