论文标题

电解质溶液中离子的部分渗透压

Partial osmotic pressures of ions in electrolyte solutions

论文作者

Warren, Patrick B.

论文摘要

对电解质溶液中离子的部分渗透压的概念进行了严格检查。原则上,可以通过引入溶剂可渗透的壁并测量每单位区域的力来定义这些定义,这肯定可以归因于单个离子。在这里,我证明,尽管总壁力平衡了机械平衡所要求的散装渗透压,但单个部分渗透压是按心脏的渗透压力取决于壁上的电气结构的外部动力学数量,因此它们类似于定义单个离子活性系数的尝试。还考虑了壁是只有一种离子的障碍的限制案例,并且双方都回收了经典的吉布斯 - 唐南膜平衡,从而提供了统一的处理。可以扩展该分析以说明大容量的电态如何受墙壁的性质和样品处理历史的影响,从而支持“ gibbs-guggenheim不确定性原理”(电气状态是不可估量的且通常意外确定的概念)。由于这种不确定性也赋予了单个离子活动,因此它对当前的IUPAC定义pH具有影响。

The concept of the partial osmotic pressure of ions in an electrolyte solution is critically examined. In principle these can be defined by introducing a solvent-permeable wall and measuring the force per unit area which can certainly be attributed to individual ions. Here I demonstrate that although the total wall force balances the bulk osmotic pressure as required by mechanical equilibrium, the individual partial osmotic pressures are extra-thermodynamic quantities dependent on the electrical structure at the wall, and as such they resemble attempts to define individual ion activity coefficients. The limiting case where the wall is a barrier to only one species of ion is also considered, and with ions on both sides the classic Gibbs-Donnan membrane equilibrium is recovered thus providing a unifying treatment. The analysis can be extended to illustrate how the electrical state of the bulk is affected by the nature of the walls and the sample handling history, thus supporting the 'Gibbs-Guggenheim uncertainty principle' (the notion that the electrical state is unmeasurable and usually accidentally determined). Since this uncertainty is conferred also onto individual ion activities, it has implications for the current (2002) IUPAC definition of pH.

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