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Determination of the Effective Hydrodynamic Radii of Small Molecules by Viscometry

机译:粘度测定法测定小分子的有效流体力学半径

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摘要

The effective hydrodynamic radii of small uncharged molecules in dilute aqueous solution were determined using Einstein's classical theory of viscosity. The radii thus obtained are those of a hypothetical sphere whose hydrodynamic behavior is the same as that of the solute molecule plus that water of hydration which is too firmly bound to partake in the viscous shearing process. The results obtained compare favorably with radii determined from molecular models constructed in accordance with atomic dimensions compiled by Pauling. Although the application of the Einstein theory to molecules whose size is comparable to that of water represents a considerable extrapolation, the results suggest that this deviation from the assumptions of the theory, in the case of the molecules studied, is of second order importance. Employing the viscometric radii, we have formulated an empirical correction of the Stokes-Einstein diffusion equation. This correction is similar in form to those previously proposed by Cunningham (22) and Millikan (21) and is of particular significance when the solute molecule is comparable in size to the discontinuities of the surrounding medium. The molecular radii of a number of small organic molecules obtained by means of the corrected Stokes-Einstein equation do not differ significantly from the radii obtained from molecular models of these compounds.
机译:使用爱因斯坦经典的粘度理论确定稀水溶液中不带电小分子的有效流体力学半径。如此获得的半径是假想球体的半径,该球体的流体力学行为与溶质分子的流体力学行为相同,再加上水合水,水合水太牢固地结合在一起,无法参与粘性剪切过程。获得的结果与根据Pauling编制的根据原子尺寸构建的分子模型确定的半径相比具有优势。尽管将爱因斯坦理论应用于大小可与水相比的分子代表了相当大的推断,但结果表明,在所研究的分子的情况下,这种偏离理论假设的假设具有二阶重要性。利用粘度半径,我们制定了斯托克斯-爱因斯坦扩散方程的经验校正。这种校正的形式与Cunningham(22)和Millikan(21)先前提出的校正类似,当溶质分子的大小与周围介质的不连续性相当时,这种校正特别重要。通过校正的斯托克斯-爱因斯坦方程获得的许多小有机分子的分子半径与从这些化合物的分子模型获得的半径没有显着差异。

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