Letellier Pierre, Turmine Mireille
Laboratoire Interfaces et Systèmes Electrochimiques, UPMC Université Paris 06, UMR 8235, Sorbonne Universités , F-75005, Paris, France.
J Phys Chem B. 2015 Mar 12;119(10):4143-54. doi: 10.1021/jp512576y. Epub 2015 Mar 3.
This work is a discussion on the applicability of the Gibbs-Duhem relationship. We show that it does not exist in the nonextensive thermodynamic approaches. To illustrate this, we have chosen to present the properties of three surfactants (dodecyltrimethylammonium bromide (DTABr), sodium dodecyl sulfate (SDS), sodium decanoate (NaDec) in aqueous solutions at 298 K) whose behavior after the micellization threshold can be described by the rules of the nonextensive thermodynamics. We show that the Gibbs-Duhem relationship does not apply to these systems and we propose to formalize the deviation from this law. The consequences of this study are discussed for the different approaches that involve the use of Gibbs-Duhem relation in the case of micellized solutions. In particular, the applicability of the Gibbs relation which links surface tension and the chemical potentials of solutes is considered. More generally, this study warns against the blind application of the Gibbs-Duhem (or Gibbs) relation, to any system.
这项工作是关于吉布斯-杜亥姆关系适用性的讨论。我们表明，它在非广延热力学方法中并不存在。为了说明这一点，我们选择展示三种表面活性剂（298 K下十二烷基三甲基溴化铵（DTABr）、十二烷基硫酸钠（SDS）、癸酸钠（NaDec）在水溶液中的性质），其胶束化阈值后的行为可以用非广延热力学规则来描述。我们表明吉布斯-杜亥姆关系不适用于这些体系，并且我们提议将与该定律的偏差形式化。针对在胶束化溶液情况下涉及使用吉布斯-杜亥姆关系的不同方法，讨论了这项研究的结果。特别地，考虑了将表面张力与溶质化学势联系起来的吉布斯关系的适用性。更一般地说，这项研究告诫人们不要盲目地将吉布斯-杜亥姆（或吉布斯）关系应用于任何体系。
