含酯基Gemini表面活性剂在有机醇-水体系中的胶束热力学及聚集行为

引用本文: 张婷, 沈杰. 含酯基Gemini表面活性剂在有机醇-水体系中的胶束热力学及聚集行为[J]. 物理化学学报, 2017, 33(4): 795-802. doi: 10.3866/PKU.WHXB201612202 shu

Citation: ZHANG Ting, SHEN Jie. Aggregation Properties and Thermodynamics of Micellization of Gemini Surfactants with Diester and Rigid Spacers in Organic Alcohol-Water Mixed Media[J]. Acta Physico-Chimica Sinica, 2017, 33(4): 795-802. doi: 10.3866/PKU.WHXB201612202 shu

含酯基Gemini表面活性剂在有机醇-水体系中的胶束热力学及聚集行为

张婷 ,
沈杰

安徽科技学院化学与材料工程学院, 安徽凤阳 233100
基金项目:
安徽省教育厅自然科学基金重点项目（KJ2016A184）和安徽科技学院重点学科项目（AKZDXK2015A01）资助

摘要: 采用电导法研究了不同温度下含酯基Gemini 表面活性剂在纯水和在质量分数为10%的甲醇-水（MAWR），乙二醇-水（EG-WR），丙三醇-水（GL-WR）四种体系中的集聚行为和胶束热力学；聚集行为参数包括临界胶束浓度（cmc）和抗衡离子的解离程度（α）以及胶束的热力学参数，包括标准吉布斯自由能（ΔG_m^o）、吉布斯迁移自由能（ΔG_trans^o）、吉布斯烷基链胶束化自由能（ΔG_tail^o）、标准焓变（ΔH_m^o）和标准熵变（ΔSom），均被计算和讨论。研究表明在所有的研究体系中，cmc值随着疏水链的增加而减小，随着加入的醇结构中羟基数目的增加而增大，随温度的升高先变小，后变大呈U字形；胶束化过程都是自发进行的，并且在293.15 K下，胶束化过程是吸热的，在293.15 K上，胶束化过程是放热的；通过稳态荧光光谱法研究了表面活性剂在纯水、有机醇-水混合溶液中的微极性，结果表明，在相同溶剂中，随着烷基链长度的增加，溶液微环境的疏水性越强；对于相同的Gemini 表面活性剂，随着加入含羟基数目越多的醇，其微环境的疏水性越强。并研究了Gemini表面活性剂在混合体系中形成胶束过程的焓-熵补偿曲线。

关键词:

English

Aggregation Properties and Thermodynamics of Micellization of Gemini Surfactants with Diester and Rigid Spacers in Organic Alcohol-Water Mixed Media

ZHANG Ting ,
SHEN Jie

School of Chemistry and Material Engineering, Anhui Science and Technology University, Fengyang 233100, Anhui Province, P. R. China
Received Date: 30 October 2016
Revised Date: 19 December 2016
Available Online: 20 December 2016
Fund Project:
The project was supported by the Natural Science Foundation of Anhui Province, China (KJ2016A184) and Research Funds of Anhui Science and Technology University, China (AKZDXK2015A01).

Abstract: The aggregation behavior and thermodynamics of micellization for three Gemini surfactants with diester and rigid spacers in pure water and 10% (mass fraction) organic alcohol-water co-solvents (MA-WR, EG-WR and GL-WR) across a range of temperatures from 283.15 to 308.15 K were investigated by electrical conductivity measurements. The aggregation behavior parameters, including critical micelle concentration (cmc), degree of counter ion dissociation (α), and the thermodynamic parameters of micellization including standard Gibbs energy (ΔG_m^o), Gibbs energy of transfer (ΔG_trans^o), Gibbs energy of micellization per alkyl tail (ΔG_tail^o), standard enthalpy (ΔH_m^o), and standard entropy (ΔS_m^o) were calculated and discussed. Gemini surfactants with longer hydrophobic chain length have a lower cmc value, which was found to increase with the increasing number of hydroxyl groups of the alcohol in the organic mixed solvent. The temperature dependence of the cmc value for the Gemini surfactants was U-shaped in all the investigated systems. The micellization process is spontaneous, is endothermic at temperatures below 293.15 K, and becomes exothermic at temperatures above 293.15 K. The micropolarity of the Gemini surfactants in pure water and organic alcohol-water co-solvents were evaluated by steady-state fluorescence spectroscopy. The results showed that the hydrophobicity of the microenvironment for Gemini surfactant solutions becomes stronger with the increasing chain length of the surfactants and the number of hydroxyl groups of the alcohol in the organic mixed solvents. The compensation between the enthalpy and entropy for micellization of all the three gemini surfactants were observed in all the studied mixed media.

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含酯基Gemini表面活性剂在有机醇-水体系中的胶束热力学及聚集行为

English

Aggregation Properties and Thermodynamics of Micellization of Gemini Surfactants with Diester and Rigid Spacers in Organic Alcohol-Water Mixed Media

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

含酯基Gemini表面活性剂在有机醇-水体系中的胶束热力学及聚集行为

English

Aggregation Properties and Thermodynamics of Micellization of Gemini Surfactants with Diester and Rigid Spacers in Organic Alcohol-Water Mixed Media

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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