Studies of radial distribution function and second virial coefficient for surfactant decyltrimethylammonium bromide in aqueous solutions at 298.15 K: Evidence for cation–cation hydrophobic interactions effect
Excess internal pressure of solution and excess partial molar volume of solute data embedded in the parameter reversible isothermal work (W) have been used to calculate the ion–ion pair correlation functions (gij(r), r being distance) and the thermodynamic properties of aqueous solutions of decyltri...
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| Format: | Article |
| Language: | English |
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Elsevier
2022-08-01
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| Series: | Chemical Thermodynamics and Thermal Analysis |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2667312622000281 |
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| author | Preeti A. Tomar Vasim R. Shaikh Kesharsingh J. Patil |
| author_facet | Preeti A. Tomar Vasim R. Shaikh Kesharsingh J. Patil |
| author_sort | Preeti A. Tomar |
| collection | DOAJ |
| description | Excess internal pressure of solution and excess partial molar volume of solute data embedded in the parameter reversible isothermal work (W) have been used to calculate the ion–ion pair correlation functions (gij(r), r being distance) and the thermodynamic properties of aqueous solutions of decyltrimethylammonium bromide (C10TAB) in concentration range 0.01 – 0.14 mol∙kg–1. It is observed that gij(r) exhibits a peak at critical micelle concentration (cmc), while the virial coefficient term (gij(r) – 1) also goes through a maximum. Using Friedman's methodology and McMillan–Mayer theory of solutions, these results have been examined. With the help of concept of Gurney cosphere around the ions, the overlap of solvation shells (water molecules) as the concentration of ions increases have been used to probe water– structure effects as water–structure making/breaking. Coefficients Aij are estimated (Coulombic term, a core repulsive term, a cavity formation term and overlap of cosphere term) at various concentrations of ionic surfactant and at a radial distance of 20 Å for a micellar entity. Further analysis indicates that gij parameter (that is, representing cation–cation interaction g++) dominate over g+– (representing ion–solvent interaction) in solution phase. Thus for a self–assembly process (formation of micelle with aggregation number) in a solution phase is being characterized by a peak in gij(r) function at cmc and aggregation number of ≈ 38, area under the peak, while the virial coefficient variation indicates a dominance of cation–cation interaction and cosphere water–structural effects. It is emphasized that the approach adopted by us to use excess PV work to estimate gij(r) is better to understand the thermodynamic process involved in self–assemblies and micelle formation. |
| first_indexed | 2024-12-10T18:14:17Z |
| format | Article |
| id | doaj.art-5920434d2a4b4d75a9922a196f9b86d5 |
| institution | Directory Open Access Journal |
| issn | 2667-3126 |
| language | English |
| last_indexed | 2024-12-10T18:14:17Z |
| publishDate | 2022-08-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Chemical Thermodynamics and Thermal Analysis |
| spelling | doaj.art-5920434d2a4b4d75a9922a196f9b86d52022-12-22T01:38:22ZengElsevierChemical Thermodynamics and Thermal Analysis2667-31262022-08-017100062Studies of radial distribution function and second virial coefficient for surfactant decyltrimethylammonium bromide in aqueous solutions at 298.15 K: Evidence for cation–cation hydrophobic interactions effectPreeti A. Tomar0Vasim R. Shaikh1Kesharsingh J. Patil2JSPM's Rajarshi Shahu College of Engineering, Pune, 411027, Maharashtra, IndiaSchool of Chemical Sciences, K. C. E. Society's Moolji Jaitha College (Autonomous), Jalgaon, 425001, Maharashtra, IndiaSchool of Chemical Sciences, Kavayitri Bahinabai Chaudhari North Maharashtra University, Jalgaon, 425001, Maharashtra, India; Corresponding author.Excess internal pressure of solution and excess partial molar volume of solute data embedded in the parameter reversible isothermal work (W) have been used to calculate the ion–ion pair correlation functions (gij(r), r being distance) and the thermodynamic properties of aqueous solutions of decyltrimethylammonium bromide (C10TAB) in concentration range 0.01 – 0.14 mol∙kg–1. It is observed that gij(r) exhibits a peak at critical micelle concentration (cmc), while the virial coefficient term (gij(r) – 1) also goes through a maximum. Using Friedman's methodology and McMillan–Mayer theory of solutions, these results have been examined. With the help of concept of Gurney cosphere around the ions, the overlap of solvation shells (water molecules) as the concentration of ions increases have been used to probe water– structure effects as water–structure making/breaking. Coefficients Aij are estimated (Coulombic term, a core repulsive term, a cavity formation term and overlap of cosphere term) at various concentrations of ionic surfactant and at a radial distance of 20 Å for a micellar entity. Further analysis indicates that gij parameter (that is, representing cation–cation interaction g++) dominate over g+– (representing ion–solvent interaction) in solution phase. Thus for a self–assembly process (formation of micelle with aggregation number) in a solution phase is being characterized by a peak in gij(r) function at cmc and aggregation number of ≈ 38, area under the peak, while the virial coefficient variation indicates a dominance of cation–cation interaction and cosphere water–structural effects. It is emphasized that the approach adopted by us to use excess PV work to estimate gij(r) is better to understand the thermodynamic process involved in self–assemblies and micelle formation.http://www.sciencedirect.com/science/article/pii/S2667312622000281Ionic salvationIon–ion pair correlation functionVirial equationGurney overlap effectsCation–cation interactionsSelf–assembly at critical micelle concentration |
| spellingShingle | Preeti A. Tomar Vasim R. Shaikh Kesharsingh J. Patil Studies of radial distribution function and second virial coefficient for surfactant decyltrimethylammonium bromide in aqueous solutions at 298.15 K: Evidence for cation–cation hydrophobic interactions effect Chemical Thermodynamics and Thermal Analysis Ionic salvation Ion–ion pair correlation function Virial equation Gurney overlap effects Cation–cation interactions Self–assembly at critical micelle concentration |
| title | Studies of radial distribution function and second virial coefficient for surfactant decyltrimethylammonium bromide in aqueous solutions at 298.15 K: Evidence for cation–cation hydrophobic interactions effect |
| title_full | Studies of radial distribution function and second virial coefficient for surfactant decyltrimethylammonium bromide in aqueous solutions at 298.15 K: Evidence for cation–cation hydrophobic interactions effect |
| title_fullStr | Studies of radial distribution function and second virial coefficient for surfactant decyltrimethylammonium bromide in aqueous solutions at 298.15 K: Evidence for cation–cation hydrophobic interactions effect |
| title_full_unstemmed | Studies of radial distribution function and second virial coefficient for surfactant decyltrimethylammonium bromide in aqueous solutions at 298.15 K: Evidence for cation–cation hydrophobic interactions effect |
| title_short | Studies of radial distribution function and second virial coefficient for surfactant decyltrimethylammonium bromide in aqueous solutions at 298.15 K: Evidence for cation–cation hydrophobic interactions effect |
| title_sort | studies of radial distribution function and second virial coefficient for surfactant decyltrimethylammonium bromide in aqueous solutions at 298 15 k evidence for cation cation hydrophobic interactions effect |
| topic | Ionic salvation Ion–ion pair correlation function Virial equation Gurney overlap effects Cation–cation interactions Self–assembly at critical micelle concentration |
| url | http://www.sciencedirect.com/science/article/pii/S2667312622000281 |
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