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On the Mechanisms of Ionic Reactions at the Highly Charged Interface

高电荷界面离子反应机理的研究

基本信息

批准号：
08454237
负责人：
MIYAJIMA Tohru
金额：
$ 0.7万
依托单位：
KYUSHU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1997
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08454237/
关键词：
Polyelectrolytes Ion-Exchange Complexation equilibria Hydrophobicity Hydrophilicity 触媒ドナン平衡

项目摘要

Any ionic reactions of charged macromolecules (linear-, cross-linked linear polymers, and ionic micelles, etc.) , whether they are positively or negatively charged, can be analyzed by assuming a two-phase property of polyion/supporting electrolyte systems. In this reserch project, novel analytical treatments of the equilibria of ionic reactions in polyion systems have been examined. Acid-dissociation and metal complexation properties of weakly acidic polyelectrolytes (polyacrylic acid and polymethacrylic acid) and the conjugate acids of weakly besic polyelectrolytes (poly (N-vinylimidazole) and polyallylamine) , have been analyzed in a unified manner. High sensitivity of the equilibria to the added salt concentration levels was interpreted by a Donnan-based concept. By the use of the non-ideality terms of the acid-dissociation equilibria of the polyacids, the electrostatic effect on the metal complexation equilibria of the charged polymer systems has been evaluated correctly, which made possible to extract the intrinsic formation constants of the metal complexes formed at the polymer surface. This "phase-separation" concept in polyion systems has also been applied to the quantification of "polyelectrolyte eatalysis" . Acceleration of Fe^<2+>/ [Co (NH_3) _5Cl] ^<2+> electron transfer reaction with the addition of strongly acidic polyions, polyvinylsulfonate ions, has been examined. Polyelectrolyte phase volume needed to interpret the reaction acceleration was consistent with the value calculated by the use of counterion binding equilibrium data. Pronounced hydrophobic interaction between counterions and charged polymer sites has been revealed for small anion-positively charged polymer systems. Complexation behavior of Co^<2+>/SCN^- in the presence of polyvinylbenzyltrimethylammonium ions has been investigated. It has been indicated that the hydrophobic interaction is greatly affected by the hydrophobic nature of supporting anions.

任何带电的大分子(线性、交联线性聚合物和离子胶束等)的离子反应，无论它们是带正电荷还是带负电荷，都可以通过假设聚离子/支持电解质体系的两相性质来分析。在这个研究项目中，我们研究了多离子体系中离子反应平衡的新的分析处理方法。统一分析了弱酸性聚电解质(聚丙烯酸和聚甲基丙烯酸)和弱碱性聚电解质(聚N-乙烯基咪唑和聚烯丙基胺)的酸解离和金属络合性质。基于Donnan的概念解释了平衡对添加的盐浓度水平的高度敏感性。利用多酸酸解离平衡的非理想项，正确地评价了静电对带电聚合物体系金属络合平衡的影响，从而可以提取在聚合物表面形成的金属络合物的本征形成常数。聚离子体系中的这种“相分离”概念也被应用于“聚电解质催化”的量化。研究了强酸性多离子聚乙烯磺酸盐对Fe~(2+)~(2+)&gt~(2+)/[Co(NH_3)_5Cl]~(2+)的电子转移反应的加速作用。解释反应加速所需的聚电解质相体积与利用反离子结合平衡数据计算的值一致。对于小的阴离子-正电荷聚合物体系，反离子和带电聚合物之间的疏水相互作用已经被揭示出来。研究了在聚乙烯基苄基三甲基铵离子存在下，Co~(2+)和Gt~(2+)/SCN~(2-)的络合行为。研究表明，载体阴离子的疏水性质对疏水相互作用有很大影响。