Modulation of cationic surfactant micellization by imidazolium-based ionic liquids: A thermodynamic study

IF 1.6 4区 工程技术 Q3 CHEMISTRY, APPLIED
Álvaro Javier Patiño-Agudelo, Gabriel Max Dias Ferreira, Guilherme Max Dias Ferreira, Yara Luiza Coelho, Isabela A. Marques, Pedro dos Santos Moreau, Ruben Ramallo Ribera, Ana Clarissa dos Santos Pires, Luis Henrique Mendes da Silva
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Abstract

Understanding the modulation of ionic surfactant properties in the presence of ionic liquids (ILs) is fundamental for expanding the application of that class of compounds. Although the effect of ILs on the micellization process of anionic surfactant has gained broad attention, its effect on cationic surfactants aggregation processes has been underexplored. This work investigated the effect of 1-alkyl-3-methylimidazolium chlorides (CnmimCl, with n = 2 or 4) and NaCl on the micellization of alkylpyridinium chlorides (CnPyCl, with n = 12 or 16) cationic surfactants using Isothermal Titration Calorimetry (ITC) and electrical conductivity. The reduction in the critical micellar concentration (CMC) in the presence of the electrolytes depends similarly on the stoichiometry between the surfactant and the electrolyte in the solution before micellization, independent of the electrolyte nature. However, the more hydrophobic the ionic liquid and the surfactant, the more intense the effects of electrolyte concentration on the micellar dissociation degree (α) and the micellization parameters ( G mic o , H mic o , and T S mic o ). The presence of C2mimCl or C4mimCl made the micellization process of both surfactants more exothermic, associated mainly with the maximization of non-dispersive interactions among monomers within the micelles and reduction of repulsive electrostatic interactions among surfactant head groups. Additionally, kosmotropic effects and preferential solvation of the surfactant, more intense for C4mimCl, actuate at high concentrations of this ionic liquid, intensifying the decrease of H mic o . This underscores that, despite both the imidazolium cation and the surfactant being positively charged, dispersive interactions between them play an important role in efficiently modulating the aggregation process.

Abstract Image

咪唑基离子液体对阳离子表面活性剂胶束化的调节:热力学研究
了解离子液体存在时离子表面活性剂性质的调制是扩大该类化合物应用的基础。虽然il对阴离子表面活性剂胶束化过程的影响已引起广泛关注,但其对阳离子表面活性剂聚集过程的影响尚未得到充分研究。采用等温滴定量热法(ITC)和电导率法研究了1-烷基-3-甲基咪唑氯化物(CnmimCl, n = 2或4)和NaCl对n = 12或16的烷基吡啶氯化物(CnPyCl, n = 12或16)阳离子表面活性剂胶束化的影响。电解质存在时临界胶束浓度(CMC)的降低同样取决于胶束形成前溶液中表面活性剂和电解质之间的化学计量,而与电解质的性质无关。然而,离子液体和表面活性剂越疏水,电解质浓度对胶束解离度(α)和胶束参数(∆G mic o,∆H mic 0, T∆S mic 0)。C2mimCl或C4mimCl的存在使两种表面活性剂的胶束化过程更加放热,这主要与胶束内单体间的非色散相互作用最大化和表面活性剂头基间的排斥静电相互作用减少有关。此外,离子液体浓度高时,表面活性剂的亲宇宙效应和优先溶剂化作用(对C4mimCl更为强烈)加剧了∆H mic o的下降。这表明,尽管咪唑阳离子和表面活性剂都带正电,但它们之间的色散相互作用在有效调节聚集过程中起着重要作用。
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来源期刊
Journal of Surfactants and Detergents
Journal of Surfactants and Detergents 工程技术-工程:化工
CiteScore
3.80
自引率
6.20%
发文量
68
审稿时长
4 months
期刊介绍: Journal of Surfactants and Detergents, a journal of the American Oil Chemists’ Society (AOCS) publishes scientific contributions in the surfactants and detergents area. This includes the basic and applied science of petrochemical and oleochemical surfactants, the development and performance of surfactants in all applications, as well as the development and manufacture of detergent ingredients and their formulation into finished products.
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