Maier J
Max-Planck-Institut fur Festkorperforschung, Stuttgart, Germany.
Chemistry. 2001 Nov 19;7(22):4762-70. doi: 10.1002/1521-3765(20011119)7:22<4762::aid-chem4762>3.0.co;2-f.
For the case of ionic crystals it is shown to be most straightforward and consistent to define acidity/basicity by the (electro-)chemical potential of the respective ion, in a similar fashion to the way that the Fermi level (i.e.. electrochemical potential of the electron) characterizes the redox state. The isomorphy is explicitly expressed by using the energy-level diagrams introduced for electrons in semiconductor physics. Without having to make further assumptions it is possible 1) to compare acidity/basicity between different solids, 2) to link internal and surface acidity/basicity, and 3) to establish acidity/basicity scales for ionic solids. The point defects are revealed to be the natural acidic and basic elementary centers, and associates between them to be the internal acids/bases exchanging these elementary centers. Even though acidity/basicity is an overall property of the solid, the number of point defects (if dilute) directly represents these properties in the same way as H+ or OH- accomplish this for aqueous solutions.
对于离子晶体的情况,与费米能级(即电子的电化学势)表征氧化还原状态的方式类似,通过相应离子的(电)化学势来定义酸度/碱度被证明是最直接且一致的。同构性通过使用半导体物理学中为电子引入的能级图来明确表示。无需进一步假设,就可以:1)比较不同固体之间的酸度/碱度;2)将内部酸度/碱度与表面酸度/碱度联系起来;3)建立离子固体的酸度/碱度标度。点缺陷被揭示为天然的酸性和碱性基本中心,它们之间的缔合体是交换这些基本中心的内部酸/碱。尽管酸度/碱度是固体的整体性质,但点缺陷的数量(如果是稀的)以与H⁺或OH⁻在水溶液中实现的方式相同,直接代表这些性质。