Department of Chemistry, University of Tennessee, Knoxville, TN 37996-1600, USA.
J Chromatogr A. 2012 Aug 24;1252:56-66. doi: 10.1016/j.chroma.2012.05.080. Epub 2012 May 31.
As part of an investigation of the column-to-column repeatability of the efficiency of columns packed with sub-3μm shell particles, the parameters of the mass transfer kinetics of twelve columns packed with the same batch of 2.7μm Poroshell 120 EC-C(18) particles (Agilent Technologies, Little Fall, DE, USA) were sequentially measured, using columns provided by the manufacturers that were representative of the efficiency distribution given by the quality test control. The reduced longitudinal diffusion term (B) was measured using the peak parking (PP) method; the reduced solid-liquid mass transfer resistance term (C) was given by a combination of the PP results and the most accurate model of effective diffusion in ternary composite materials. The overall eddy diffusion term (A) was obtained by subtraction of these two HETP terms from the overall reduced HETP derived from the peak moments measured by numerical integration of the entire peak profiles. The results demonstrate that the dispersion of the column efficiencies is a result of the random nature of the packing process and the eddy diffusion term resulting from the lack of homogeneity of the column bed. At the highest reduced velocity achieved for small analytes, the relative standard deviations (RSD) of the eddy diffusion term for the 2.1mm I.D. columns were ca. 3 and 11% (with average values h(eddy)= 2.5 and 13.5) for naphthalene (k=3) and uracil (k=0), respectively. For the 4.6mm I.D. columns, these RSDs were 5 and 13%, respectively, with average values h(eddy)= 1.4 and 2.9. For insulin at reduced velocities as high as 160, the RSDs of the total reduced plate heights were 3 and 8% for the 2.1 and 4.6mm I.D. columns, respectively.
作为对柱效列(column-to-column repeatability)的柱间重复性进行调查的一部分,使用由制造商提供的、代表质量测试控制所给出的效率分布的代表性柱,依次测量了十二根装填相同批次 2.7μm Poroshell 120 EC-C(18) 颗粒(安捷伦科技,Little Fall,DE,美国)的柱的传质动力学参数。通过峰停驻(peak parking,PP)法测量了缩减的纵向扩散项(B);通过 PP 结果与三元复合材料中最准确的有效扩散模型的组合,给出了缩减的固液传质阻力项(C)。通过从通过数值积分测量整个峰形得到的总缩减 HETP 中减去这两个 HETP 项,得到了总涡流扩散项(A)。结果表明,柱效的分散是填充过程的随机性和柱床不均匀性导致涡流扩散项的结果。在小分析物达到的最高缩减速度下,2.1mm ID 柱的涡流扩散项的相对标准偏差(RSD)分别约为萘(k=3)和尿嘧啶(k=0)的 3%和 11%(平均涡流扩散项值 h(eddy)=2.5 和 13.5)。对于 4.6mm ID 柱,这些 RSD 分别为 5%和 13%,平均涡流扩散项值 h(eddy)=1.4 和 2.9。对于胰岛素在高达 160 的缩减速度下,2.1 和 4.6mm ID 柱的总缩减板高的 RSD 分别为 3%和 8%。