Ion‐Pair Theory of Concentrated Electrolytes. I. Basic Concepts
Ion‐Pair Theory of Concentrated Electrolytes. I. Basic Concepts
复制标题
DOI：
10.1063/1.1669709
复制
发表时间：
1968-05
影响因子：
4.4
通讯作者：
F. Stillinger;R. Lovett
中科院分区：
文献类型：
--
作者：
F. Stillinger;R. Lovett
对称“原始模型”电解质的统计热力学是以所有离子都唯一配对的方式制定的。所得到的“极性分子”流体的行为可以方便地由波长依赖的介电常数e（k）来描述。导出了关于e（k）的一个严格的柯克伍德型公式。由于离子-大气平均电荷密度可以从e（k）获得，因此该介电函数用于构建电解质自由能表达式[等式10]。(50)]，以及建立一个精确的二阶矩条件的离子气氛[方程。（73）]。从后者可以证明，对于直径为a的刚性球形离子，当κa > 61 / 2（κ− 1 =德拜长度）时，离子大气必然具有不均匀的电荷符号。
The statistical thermodynamics of symmetrical “primitive‐model” electrolytes is formulated in such a way that all ions are uniquely paired. The behavior of the resulting fluid of “polar molecules” may conveniently be described by a wavelength‐dependent dielectric constant e(k). A rigorous formula of the Kirkwood type for e(k) is derived. Since ion‐atmosphere mean charge densities may be obtained from e(k), this dielectric function is utilized in construction of an electrolyte free‐energy expression [Eq. (50)], as well as to establish an exact second‐moment condition on the ion atmospheres [Eq. (73)]. From the latter it is demonstrated that for rigid spherical ions of diameter a, the ion atmospheres necessarily each have nonuniform charge sign when κa > 61 / 2 (κ− 1 = Debye length).