A molecular parameter to scale the Gibbs free energies of adsorption and micellization for nonionic surfactants
A molecular parameter to scale the Gibbs free energies of adsorption and micellization for nonionic surfactants
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用于衡量非离子表面活性剂吸附和胶束化吉布斯自由能的分子参数
DOI：
10.1016/j.colsurfa.2020.125622
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Alvarez, Nicolas J.
中科院分区：
文献类型：
--
作者：
Hinton, Zachary R.;Alvarez, Nicolas J.
界面热力学界长期以来的目标是根据分子参数确定吸附和胶束的自由能。历史上，对于一类常见的非离子表面活性剂，已经提出了乙二醇基团数量和/或碳数量与热力学参数之间的相关性，例如临界胶束浓度（CMC），平衡常数(K)和最大表面浓度（Γ∞）。然而，到目前为止，还没有这样的相关性能够捕获大量的热动力参数数据集。本文从分子参数的角度提出了非离子型表面活性剂的临界胶束浓度和吸附等温线参数的函数形式。对文献进行了广泛的回顾，以产生广泛的碳、热、热化学的界面热力学参数。这些数据用于参数化和验证分子模型。更具体地说，我们结合了众所周知的CMC和K对碳数N C的线性依赖，以及对亲水性-亲脂性平衡（HLB）的理论依赖，表示为y phob，它能够将所有实验数据压缩到主曲线上。由此产生的自由能模型代表了第一个成功的现象学理论，它能够崩溃广泛的表面活性剂的实验数据。此外，所提出的胶束和吸附的自由能模型能够预测空气-水界面上的最大表面浓度，从而提供了吸附物理和自组装之间的联系。这一理论是通过化学设计实现界面热力学工程的一步，它使预测新型表面活性剂的界面性质无需外推。此外，本文还总结了多年来对表面活性剂结构性质关系的实验和理论认识，并定量地解释了其界面热力学的许多假设。
A long standing goal in the interfacial thermodynamics community is free energies of adsorption and micellization in terms of molecular parameters. Historically, correlations for C i E j's, a common class of nonionic surfactants, have been proposed between the number of ethylene glycol groups and/or the number of carbons and thermodynamic parameters, such as the critical micelle concentration (CMC), the equilibrium constant (K), and the maximum surface concentration (Γ∞). However, no such correlations to date are capable of capturing a large dataset of C i E j thermodynamic parameters. In this paper we propose the functional form of the critical micelle concentration and adsorption isotherm parameters in terms of molecular parameters for nonionic, C i E j surfactant chemistry. An extensive review of the literature is performed to generate interfacial thermodynamic parameters for a wide-range of C i E j chemistries. The data are used to parameterize and validate the molecular models. More specifically, we combine the well known linear dependence of CMC and K on the number of carbons, N C, with the theorized dependence on hydrophilic-lipophilic balance (HLB), represented as y phob, which is capable of collapsing all experimental data onto mastercurves. The resulting free energy models represent the first successful phenomenological theory which is able to collapse a broad range of experimental data for C i E j surfactants. Furthermore, the proposed models for the free energies of micellization and adsorption are capable of predicting the maximum surface concentration of C i E j surfactants at the air–water interface, thus providing a link between the physics of adsorption and self-assembly. This theory is a step towards engineering interfacial thermodynamics by chemical design which enables prediction of interfacial properties of novel surfactants without extrapolation. In addition, this paper summarizes the many years of experimental and theoretical understanding of surfactant structure property relationships for C i E j's and the resulting theory quantitatively explains many hypotheses about their interfacial thermodynamics.
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影响因子：
1.4
作者：
L. Caseli;D. Masui;R. P. Furriel;F. A. Leone;M. D. Zaniquelli
通讯作者：
L. Caseli;D. Masui;R. P. Furriel;F. A. Leone;M. D. Zaniquelli
表面活性环氧乙烷加合物
DOI：
10.1016/c2013-0-05512-0
发表时间：
2013
期刊：
Kolloid-Zeitschrift und Zeitschrift für Polymere
影响因子：
--
作者：
N. Schönfeldt
通讯作者：
N. Schönfeldt
表面活性剂和固体颗粒的亲水亲油平衡：物理化学方面和应用
DOI：
10.1016/s1383-7303(00)x8012-x
发表时间：
2000
期刊：
The Journal of Physical Chemistry
影响因子：
--
作者：
P. M. Krugli︠a︡kov
通讯作者：
P. M. Krugli︠a︡kov
第四部分：一些聚乙二醇单己醚在二元和三元体系中的临界胶束浓度☆
DOI：
10.1016/0095-8522(62)90020-x
发表时间：
1962
期刊：
Journal of Colloid Science
影响因子：
--
作者：
B. Mulley;A. Metcalf
通讯作者：
A. Metcalf
DOI：
10.1016/0095-8522(64)90014-5
发表时间：
1964
期刊：
Journal of Colloid Science
影响因子：
--
作者：
J. E. Carless;R. Challis;B. Mulley
通讯作者：
B. Mulley