Research Group Electrochemical and Surface Engineering, Department of Electro Technique and Energy Technique, Vrije Universiteit Brussel, Brussels, Belgium.
J Sep Sci. 2009 Dec;32(23-24):4077-88. doi: 10.1002/jssc.200900458.
The band broadening that can be expected in perfectly ordered cylindrical pillar arrays has been calculated for a wide range of intra-particle diffusion coefficients (D(sz)) and zone retention factors (0<k''<10) using an in-house-developed computational fluid dynamics-algorithm. Both pressure-driven and electrically driven (PD and ED) flows are considered. In the case of a large intra-pillar diffusion coefficient (D(sz)/D(mol)=0.5), the minimal reduced plate height varies between h=0.8 (low k'') and h=1.2 (high k''), while the C-term range of the Van Deemter curve depends only slightly on k''. In the case of a small intra-pillar diffusion coefficient (D(sz)/D(mol)=0.1), h is nearly independent of k'' and approximately equals h(min)=1.1, while the C-term band broadening decreases strongly with increasing k''. The difference between ED and PD flows in perfectly ordered porous pillar arrays is much smaller than in packed beds, generally only 3% difference around the minimum of the plate-height curve and maximally 10% at high-reduced velocities. The generated data sets were also ideal to verify the accuracy of k'' and D(sz) dependency of the general plate height model of chromatography. Determining the values of the geometrical parameters appearing in the model through curve fitting, the average fitting error can be reduced to a value of about 1%.
使用内部开发的计算流体动力学算法，计算了在各种颗粒内扩散系数（D(sz)）和区保留因子（0<k''>10）下，完美有序圆柱柱阵列中可预期的带宽展宽。同时考虑了压力驱动和电驱动（PD 和 ED）流动。在柱内扩散系数较大的情况下（D(sz)/D(mol)=0.5），最小降低板高在 h=0.8（低 k''）和 h=1.2（高 k''>）之间变化，而 Van Deemter 曲线的 C 项范围仅略微取决于 k''>。在柱内扩散系数较小的情况下（D(sz)/D(mol)=0.1），h 几乎与 k''无关，大约等于 h(min)=1.1，而 C 项带宽展宽随着 k''>的增加而强烈减小。在完美有序多孔柱阵列中，ED 和 PD 流动之间的差异远小于填充床，通常在板高曲线的最小值周围只有 3%的差异，在高降低速度时最大为 10%。生成的数据集也非常适合验证色谱一般板高模型中 k''>和 D(sz)依赖性的准确性。通过曲线拟合确定模型中出现的几何参数的值，可以将平均拟合误差降低到约 1%。
