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爱因斯坦黏度方程的另一种解释能够准确描述亲水溶质在高浓度下的行为。

A different interpretation of Einstein's viscosity equation provides accurate representations of the behavior of hydrophilic solutes to high concentrations.

机构信息

Department of Chemistry and Biochemistry, Long Island University, University Plaza, Brooklyn, New York 11201, USA.

出版信息

J Phys Chem B. 2012 Aug 23;116(33):10055-69. doi: 10.1021/jp306248a. Epub 2012 Aug 10.

Abstract

Viscosities of aqueous solutions of many highly soluble hydrophilic solutes with hydroxyl and amino groups are examined with a focus on improving the concentration range over which Einstein's relationship between solution viscosity and solute volume, V, is applicable accurately. V is the hydrodynamic effective volume of the solute, including any water strongly bound to it and acting as a single entity with it. The widespread practice is to relate the relative viscosity of solute to solvent, η/η(0), to V/V(tot), where V(tot) is the total volume of the solution. For solutions that are not infinitely dilute, it is shown that the volume ratio must be expressed as V/V(0), where V(0) = V(tot) - V. V(0) is the volume of water not bound to the solute, the "free" water solvent. At infinite dilution, V/V(0) = V/V(tot). For the solutions examined, the proportionality constant between the relative viscosity and volume ratio is shown to be 2.9, rather than the 2.5 commonly used. To understand the phenomena relating to viscosity, the hydrodynamic effective volume of water is important. It is estimated to be between 54 and 85 cm(3). With the above interpretations of Einstein's equation, which are consistent with his stated reasoning, the relation between the viscosity and volume ratio remains accurate to much higher concentrations than those attainable with any of the other relations examined that express the volume ratio as V/V(tot).

摘要

考察了许多具有羟基和氨基的高度水溶性亲水性溶质在水溶液中的粘度,重点是改进爱因斯坦关于溶液粘度与溶质体积 V 之间关系的适用浓度范围,使该关系能够更准确地适用。V 是溶质的流体力学有效体积,包括与之强烈结合的任何水,并与它作为一个整体一起作用。目前广泛采用的做法是将溶质相对于溶剂的相对粘度η/η(0)与 V/V(tot)相关联,其中 V(tot)是溶液的总体积。对于非无限稀释的溶液,表明体积比必须表示为 V/V(0),其中 V(0)=V(tot)-V。V(0)是不与溶质结合的水的体积,即“自由”水溶剂。在无限稀释时,V/V(0)=V/V(tot)。对于所考察的溶液,相对粘度与体积比之间的比例常数被证明是 2.9,而不是常用的 2.5。为了理解与粘度相关的现象,水的流体力学有效体积很重要。它估计在 54 到 85cm(3)之间。通过对爱因斯坦方程的上述解释,这些解释与他的陈述推理一致,使得粘度与体积比之间的关系在比任何其他所考察的以 V/V(tot)表示体积比的关系更能达到更高的浓度下仍然保持准确。

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