Center of Excellence for Functional Materials, Laboratory of Physical Chemistry at Åbo Akademi University, Porthansgatan 3-5, FI-20500 Åbo (Turku), Finland.
Adv Colloid Interface Sci. 2017 Sep;247:305-353. doi: 10.1016/j.cis.2017.07.010. Epub 2017 Jul 19.
Electron displacements may be considered as a general measure of semiconductor activity as well as of dipolar, acid-base and charge interactions. Electron transfers during reduction and oxidation reactions between dissolved cations and anions correspond to an extreme Lewis acid-base electron displacement. Brϕnsted proton release (protolysis) represents an extremely weakened hydrogen bond. The most common electrostatic (Born, PCM) and chemical (pK matching) models for electron and proton exchange between dissolved species are reviewed using aluminium species as examples. Dissolution of ions from solids (salts) may be considered as a reversed precipitation reaction. For partly covalent solids dissociation is dependent on electron or vacancy (hole) transfers to the solid which connects oxidation and reduction reactions to electron displacements in semiconductors. The electron exchange is characterized by Femi energy of semiconductors and of electrolytes. The standard reduction potential may thus be converted to Fermi energy of connected electrochemical cells. In disconnected particle suspensions (sols) the electron activity is a more appropriate parameter which may be converted both to standard reduction potential of ions and to Fermi energy of semiconductors. Dissolution of potential determining cations and anions and hydrolysis of surface sites determines the charging (electron transfer to/from surface) of solids. Both electrostatic (MUSIC) and chemical equilibrium constant models are available for Brϕnsted equilibrium of surface hydroxyls. Point of zero charge is a result of positive and negative charge matching and it represents the optimal condition for condensation of polynuclear species by olation and oxolation. The capability of partial charge (PCM) model to predict condensation is evaluated. Acidity (pH), composition and temperature dependence of aluminium species is illustrated by solubility limits of contributing species and by phase diagrams. Influence of ions on macroscopic suspension properties, such as wetting and electrophoretic mobility is evaluated with reference to point of zero charge and to isoelectric point. Restrictions to the use of zeta-potentials are related to the surface potential and particle size - Debye length ratios. Macroscopic settling (particle precipitation) and viscosity of suspensions (sols) are discussed with reference to Deryagin-Landau-Verwey-Overbeek (DLVO) model. The primary dependence on counterion valence is evaluated according to Schulz-Hardy approach. The secondary dependence on counterion hydration (Hofmeister or lyotropic effect) and ion association (Debye-Hückel limiting model) are discussed.
电子位移可以被视为半导体活性以及偶极子、酸碱和电荷相互作用的一般度量。溶解阳离子和阴离子之间的还原和氧化反应过程中的电子转移对应于极端路易斯酸碱电子位移。Brønsted 质子释放（质子化）代表一个极其弱化的氢键。使用铝物种作为示例，综述了溶解物种之间电子和质子交换的最常见静电（Born、PCM）和化学（pK 匹配）模型。从固体（盐）中溶解离子可被视为相反的沉淀反应。对于部分共价固体，离解取决于电子或空位（空穴）转移到固体，这将氧化还原反应与半导体中的电子位移联系起来。电子交换的特征是半导体和电解质的费米能。因此，标准还原电位可以转换为连接电化学电池的费米能。在不连续的颗粒悬浮液（溶胶）中，电子活度是一个更合适的参数，它可以同时转换为离子的标准还原电位和半导体的费米能。电位决定阳离子和阴离子的溶解和表面位点的水解决定了固体的充电（表面的电子转移）。表面羟基的 Brønsted 平衡既有静电（MUSIC）模型又有化学平衡常数模型。零电荷点是正电荷和负电荷匹配的结果，它代表了多核物种通过缩合和氧化缩合冷凝的最佳条件。部分电荷（PCM）模型预测冷凝的能力得到了评估。通过贡献物种的溶解度极限和相图来说明铝物种的酸度（pH）、组成和温度依赖性。参考零电荷点和等电点来评估离子对宏观悬浮液性质（例如润湿和电泳迁移率）的影响。对 ζ 电位的使用限制与表面电位和颗粒大小 - Debye 长度比有关。宏观沉降（颗粒沉淀）和悬浮液（溶胶）的粘度根据 Deryagin-Landau-Verwey-Overbeek (DLVO) 模型进行讨论。根据 Schulz-Hardy 方法评估了对反离子价的主要依赖性。讨论了对反离子水合（Hofmeister 或溶致效应）和离子缔合（Debye-Hückel 极限模型）的次要依赖性。
