链状聚电解质由于是长链大分子又有很高的电荷密度,其溶液即使在极低的浓度下仍具有很强的负偏差,与Debye-Huckel理论预测的结果相去甚远。工程上使用的Manning模型认为聚离子的电荷密度有一临界值,当超过临界值时,反离子即凝聚在聚离子表面使其实际电荷密度降至临界值。Nagvekar等在该模型的基础上引入NRTL方程,以计及短程相互作用的贡献。Manning等的方法虽然有一定的物理意义,但临界值的确定缺乏可靠的根据。 Due to the high charge density of long chain macromolecules, the chain polyelectrolytes have very strong negative deviations even at very low concentrations, far from the predictions of Debye-Huckel theory. The Manning model used in engineering considers that the charge density of polyion has a critical value. When it exceeds the critical value, the counterion condenses on the polyion surface to reduce its actual charge density to a critical value. Based on this model, Nagvekar et al. Introduced the NRTL equation to account for the contribution of short-range interactions. Although Manning et al. Have certain physical meanings, the determination of the critical value lacks a reliable basis.