Prediction of viscosity of mixed electrolyte solutions based on the Eyring's absolute rate theory and the semi-ideal hydration model
Prediction of viscosity of mixed electrolyte solutions based on the Eyring's absolute rate theory and the semi-ideal hydration model
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DOI：
10.1016/s0013-4686(03)00226-3
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发表时间：
2003-06-15
影响因子：
6.6
通讯作者：
Lee, H
中科院分区：
文献类型：
--
作者：
Hu, YF;Lee, H
利用Eyring绝对速率理论和半理想水化模型，首次研究了等压平衡条件下电解质溶液粘度的混合行为。根据平均水化数的概念和离子物种的结构形成或结构破坏的性质，推导并讨论了流动的摩尔活化能变化与浓度的关系。将埃林理论和半理想水化模型耦合起来，得到了等压条件下电解质溶液粘度的非常简单的混合行为，从而得到了新的简单的粘度方程，该方程仅利用单一溶质溶液的信息就可以预测混合溶液。通过与15个体系的实验结果和文献报道的现有方程的比较，对新的方程进行了检验。目前的方程大大改进了预测，与实验结果的一致性总体上是很好的。研究了混合过程中的不同贡献对预测结果的影响。在等压条件下，只有利用二元溶液粘度的相加贡献才能很好地预测混合电解质溶液的粘度。在这个简单的加法方程中加入混合项，对主要由结构形成离子组成的混合溶液产生了更好的预测。密度项的加入对预测结果影响不大。(C)2003爱思唯尔科学有限公司。保留所有权利。
The mixing behavior of viscosities of electrolyte solutions under isopiestic equilibrium has been studied for the first time using the Eyring's absolute rate theory and the semi-ideal hydration model. The concentration dependence of the change in molar free energy of activation for flow has been formulated and discussed based on the concept of average hydration number and the structure-making or structure-breaking nature of the ion species. Coupling of the Erying's theory and the semi-ideal hydration model yields very simple mixing behavior of viscosities of electrolyte solutions under isopiestic conditions and thus yields new simple equations for viscosity, which can provide predictions for mixed solutions using only information on the single solute solutions. The new equations have been tested by comparisons with the experimental results for 15 systems and the existing equations reported in literature. The present equations improve the predictions considerably and the agreement with experimental results is in general quite good. The effect of different contributions accompanying the mixing process on the predicted results has been studied. The viscosities of the mixed electrolyte solutions can be well predicted only by using the additive contribution from the viscosities of binary solutions under isopiestic condition. The addition of the mixing term in this simple additive equation yields better predictions for mixed solutions mainly consisting of the structure-making ions. The inclusion of the density term has little effect on the predicted results. (C) 2003 Elsevier Science Ltd. All rights reserved.