Miura Toshiaki, Seki Kazuhiko
National Institute of Advanced Industrial Science and Technology (AIST) , AIST Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan.
J Phys Chem B. 2015 Aug 27;119(34):10954-61. doi: 10.1021/acs.jpcb.5b00580. Epub 2015 May 21.
When the kinetics of adsorption is influenced by the diffusive flow of solutes, the solute concentration at the surface is influenced by the surface coverage of solutes, which is given by the Langmuir-Hinshelwood adsorption equation. The diffusion equation with the boundary condition given by the Langmuir-Hinshelwood adsorption equation leads to the nonlinear integro-differential equation for the surface coverage. In this paper, we solved the nonlinear integro-differential equation using the Grünwald-Letnikov formula developed to solve fractional kinetics. Guided by the numerical results, analytical expressions for the upper and lower bounds of the exact numerical results were obtained. The upper and lower bounds were close to the exact numerical results in the diffusion- and reaction-controlled limits, respectively. We examined the validity of the two simple analytical expressions obtained in the diffusion-controlled limit. The results were generalized to include the effect of dispersive diffusion. We also investigated the effect of molecular rearrangement of anisotropic molecules on surface coverage.
当吸附动力学受溶质扩散流影响时,表面溶质浓度受溶质表面覆盖度影响,该覆盖度由朗缪尔 - 欣谢尔伍德吸附方程给出。具有朗缪尔 - 欣谢尔伍德吸附方程所给边界条件的扩散方程会导出关于表面覆盖度的非线性积分 - 微分方程。在本文中,我们使用为求解分数动力学而发展的 Grünwald - Letnikov 公式求解了该非线性积分 - 微分方程。在数值结果的指导下,得到了精确数值结果上下界的解析表达式。上下界分别在扩散控制和反应控制极限下接近精确数值结果。我们检验了在扩散控制极限下得到的两个简单解析表达式的有效性。结果被推广以包括弥散扩散的影响。我们还研究了各向异性分子的分子重排对表面覆盖度的影响。