{"title":"从多层准化学模型看非离子液体界面的热力学性质和结构","authors":"","doi":"10.1016/j.molliq.2024.126229","DOIUrl":null,"url":null,"abstract":"<div><div>The interfacial properties and structure of nonuniform fluids containing complex chainlike molecules and associating species are very much needed in a variety of different fields, including enhanced oil recovery, drug delivery, pharmacy, cosmetics, food processing, etc.</div><div>Recently, we described the Multilayer Quasichemical Model (MQuM) of a nonuniform fluid that provides a remarkably detailed structural information, including the local concentration and orientation of functional groups of the molecules, the orientation profiles of the chemical bonds in molecular chains and the orientation profiles of the hydrogen bonds in the mixture.</div><div>In this work, we focus on the description of thermodynamic properties with the aid of MQuM, including the interfacial tension and the profiles of normal and transverse pressures. Before proceeding to more complex systems, a test is performed through comparison with the previously known results from the Scheutjens-Fleer theory for the planar liquid–vapor interface and spherical droplet in one-component fluid of nonpolar monomeric molecules. The model is applied then for planar interfaces between the liquid phases in mixtures of water with n-alkanes of different chain length and for spherical drops in model systems that contain an associating solvent, a nonpolar chain and a nonionic amphiphile. Our theoretical results are compared with experiment, predictions from iSAFT and MD simulation data from the literature. For the spherical droplets, we discuss the model description of the dependence of the interfacial tension on the curvature and estimate the Tolman length. For the planar interface between the equilibrium liquid phases in water – n-alkane mixtures, the interfacial tensions predicted from the model are in good agreement with experiment.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":null,"pages":null},"PeriodicalIF":5.3000,"publicationDate":"2024-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Thermodynamic properties and structure of interfacial boundaries in nonionic fluids from the multilayer quasichemical model\",\"authors\":\"\",\"doi\":\"10.1016/j.molliq.2024.126229\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The interfacial properties and structure of nonuniform fluids containing complex chainlike molecules and associating species are very much needed in a variety of different fields, including enhanced oil recovery, drug delivery, pharmacy, cosmetics, food processing, etc.</div><div>Recently, we described the Multilayer Quasichemical Model (MQuM) of a nonuniform fluid that provides a remarkably detailed structural information, including the local concentration and orientation of functional groups of the molecules, the orientation profiles of the chemical bonds in molecular chains and the orientation profiles of the hydrogen bonds in the mixture.</div><div>In this work, we focus on the description of thermodynamic properties with the aid of MQuM, including the interfacial tension and the profiles of normal and transverse pressures. Before proceeding to more complex systems, a test is performed through comparison with the previously known results from the Scheutjens-Fleer theory for the planar liquid–vapor interface and spherical droplet in one-component fluid of nonpolar monomeric molecules. The model is applied then for planar interfaces between the liquid phases in mixtures of water with n-alkanes of different chain length and for spherical drops in model systems that contain an associating solvent, a nonpolar chain and a nonionic amphiphile. Our theoretical results are compared with experiment, predictions from iSAFT and MD simulation data from the literature. For the spherical droplets, we discuss the model description of the dependence of the interfacial tension on the curvature and estimate the Tolman length. For the planar interface between the equilibrium liquid phases in water – n-alkane mixtures, the interfacial tensions predicted from the model are in good agreement with experiment.</div></div>\",\"PeriodicalId\":371,\"journal\":{\"name\":\"Journal of Molecular Liquids\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.3000,\"publicationDate\":\"2024-10-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Molecular Liquids\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0167732224022888\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Molecular Liquids","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0167732224022888","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Thermodynamic properties and structure of interfacial boundaries in nonionic fluids from the multilayer quasichemical model
The interfacial properties and structure of nonuniform fluids containing complex chainlike molecules and associating species are very much needed in a variety of different fields, including enhanced oil recovery, drug delivery, pharmacy, cosmetics, food processing, etc.
Recently, we described the Multilayer Quasichemical Model (MQuM) of a nonuniform fluid that provides a remarkably detailed structural information, including the local concentration and orientation of functional groups of the molecules, the orientation profiles of the chemical bonds in molecular chains and the orientation profiles of the hydrogen bonds in the mixture.
In this work, we focus on the description of thermodynamic properties with the aid of MQuM, including the interfacial tension and the profiles of normal and transverse pressures. Before proceeding to more complex systems, a test is performed through comparison with the previously known results from the Scheutjens-Fleer theory for the planar liquid–vapor interface and spherical droplet in one-component fluid of nonpolar monomeric molecules. The model is applied then for planar interfaces between the liquid phases in mixtures of water with n-alkanes of different chain length and for spherical drops in model systems that contain an associating solvent, a nonpolar chain and a nonionic amphiphile. Our theoretical results are compared with experiment, predictions from iSAFT and MD simulation data from the literature. For the spherical droplets, we discuss the model description of the dependence of the interfacial tension on the curvature and estimate the Tolman length. For the planar interface between the equilibrium liquid phases in water – n-alkane mixtures, the interfacial tensions predicted from the model are in good agreement with experiment.
期刊介绍:
The journal includes papers in the following areas:
– Simple organic liquids and mixtures
– Ionic liquids
– Surfactant solutions (including micelles and vesicles) and liquid interfaces
– Colloidal solutions and nanoparticles
– Thermotropic and lyotropic liquid crystals
– Ferrofluids
– Water, aqueous solutions and other hydrogen-bonded liquids
– Lubricants, polymer solutions and melts
– Molten metals and salts
– Phase transitions and critical phenomena in liquids and confined fluids
– Self assembly in complex liquids.– Biomolecules in solution
The emphasis is on the molecular (or microscopic) understanding of particular liquids or liquid systems, especially concerning structure, dynamics and intermolecular forces. The experimental techniques used may include:
– Conventional spectroscopy (mid-IR and far-IR, Raman, NMR, etc.)
– Non-linear optics and time resolved spectroscopy (psec, fsec, asec, ISRS, etc.)
– Light scattering (Rayleigh, Brillouin, PCS, etc.)
– Dielectric relaxation
– X-ray and neutron scattering and diffraction.
Experimental studies, computer simulations (MD or MC) and analytical theory will be considered for publication; papers just reporting experimental results that do not contribute to the understanding of the fundamentals of molecular and ionic liquids will not be accepted. Only papers of a non-routine nature and advancing the field will be considered for publication.