STANDARD THERMODYNAMICS OF TRANSFER - USES AND MISUSES
STANDARD THERMODYNAMICS OF TRANSFER - USES AND MISUSES
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DOI：
10.1021/j100496a008
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发表时间：
1978-01-01
影响因子：
--
通讯作者：
BENNAIM, A
中科院分区：
文献类型：
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作者：
BENNAIM, A
从热力学和统计力学两方面讨论了溶质a在两种溶剂a和b之间的标准自由转移能。结果表明，单凭热力学不能用来选择“最佳”标准量，而统计力学可以帮助做出这样的选择。结果表明，用数字密度（或摩尔浓度）标度计算A的标准自由能µ^具有以下优点：(1)它是最简单和最不模糊的量；(2)是直接探测两种溶剂相对于溶质A的溶剂化性质差异的量；(3)它可以在任何溶液中使用，不需要改变符号，不一定是稀溶液，甚至包括纯a；(4)通过简单的热力学操作，可以得到同一过程的熵、焓、体积变化等。所有这些量都有类似于自由能变化的优点。由于这种特殊选择标准量的优点，我们建议将标准热力学传递量的使用“标准化”，并将其称为局部标准量。指出了对其他标准量的一些常见误解和误解。
The standard free energy of transfer of a solute A between two solvents a and b is discussed atboth a thermodynamic and a statistical mechanical level. It is shown that whereas thermodynamics alone cannot be used to choose the “best” standard quantity, statistical mechanics can help to make such a choice. It is shown that µ^, the standard free energy of transferring A, computed by the use of the number density (or molarity) scale, has the following advantages:(1) it is the simplest and least ambiguous quantity;(2) it is the quantity that directly probes the differencein the solvation properties of the two solvents with respect to the solute A;(3) it can be used, without any change of notation, in any solution, not necessarily a dilute one, and including even pure A;(4) by straightforward thermodynamic manipulations one obtains the entropy, enthalpy, volume changes, etc. for the same process. All of these quantities have advantages similar to the ones indicated for the free energychange. Because of the advantages of this particular choice of standard quantities, we propose to “standardize” the use of the standard thermodynamic quantities of transfer and refer to them as the local-standard quantities. Some common misconceptions and misinterpretations of other standard quantities are indicated.