Preferential solvation and elasticity of the hydrogen bonds network in tertiary butyl alcohol–water mixture

Киселев, М. Г.; Ivlev, D. V.; Puhovski, Yurii P.; Kerdcharoen, Teerakiat

doi:10.1016/j.cplett.2003.08.082

Cited by 16 publications

(13 citation statements)

References 21 publications

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“…Earlier the structure of (water + tert-butanol) mixture was studied with numerical methods, viz with Monte Carlo (MC) method at x 2 = 0.005 by Nakanishi et al [50], with molecular dynamic (MD) simulations at x 2 = 0.032 by Tanaka et al [51,52], at x 2 = 0.02 and 0.08 by Kusalik et al [53], and at x 2 = 0.05 to 0.07 by Kiselev et al [54]. In works of Bowron et al [55][56][57] with hydrogen/deuterium isotopic substitution neutron diffraction technique and applying empirical potential structure refinement (EPSR) calculations the mixtures with compositions of x 2 = 0.057; 0.107, and 0.167 at 298 K were investigated, moreover the composition with x 2 = 0.057 was studied at 338 K also.…”

Section: Tablementioning

confidence: 99%

Densities and volume properties of (water+tert-butanol) over the temperature range of (274.15 to 348.15)K at pressure of 0.1MPa

Egorov

Makarov

2011

The Journal of Chemical Thermodynamics

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Section: Tablementioning

confidence: 99%

Densities and volume properties of (water+tert-butanol) over the temperature range of (274.15 to 348.15)K at pressure of 0.1MPa

Egorov

Makarov

2011

The Journal of Chemical Thermodynamics

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“…The majority of them are performed in a rather limited (although some are broader) concentration range [44,[46][47][48], but we could not find a structural study of aqueous TBA that would really closely combine the x-ray scattering experiment and theory across the whole concentration range. Both experimental [47,49] and simulation studies [6,7,46,[50][51][52][53][54][55][56][57][58] show that mixtures of TBA and water are homogeneous on the mesoscopic scale [44,59], while on the microscopic scale heterogeneities can be observed -a feature strongly dependent on the composition of the solution. Such heterogeneities are associated with the formation of discrete local TBA-rich and water-rich regions, whose effective sizes and structure remain unclear.…”

Section: Introductionmentioning

confidence: 99%

Structural, rheological and dynamic aspects of hydrogen-bonding molecular liquids: Aqueous solutions of hydrotropic tert-butyl alcohol

Cerar

Jamnik

Pethes

et al. 2020

Journal of Colloid and Interface Science

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Hypothesis: The structural details, viscosity trends and dynamic phenomena in t-butanol/water solutions are closely related on the molecular scales across the entire composition range. Utilizing the experimental small-and wide-angle x-ray scattering (SWAXS) method, molecular dynamics (MD) simulations and the 'complemented-system approach' method developed in our group it is possible to comprehensively describe the structure-viscosity-dynamics relationship in such structurally versatile hydrogen-bonded molecular liquids, as well as in similar, self-assembling systems with pronounced molecular and supramolecular structures at the intra-, inter-, and supra-molecular scales. Experiments: The SWAXS and x-ray diffraction experiments and MD simulations were performed for aqueous t-butanol solutions at 25 °C. Literature viscosity and self-diffusion data were also used. Findings: The interpretive power of the proposed scheme was demonstrated by the extensive and diverse results obtained for aqueous t-butanol solutions across the whole concentration range. Four composition ranges with qualitatively different structures and viscosity trends were revealed. The experimental and calculated zero-shear viscosities and molecular self-diffusion coefficients were successfully related to the corresponding structural details. The hydrogen bonds 2 that were, along with hydrophobic effects, recognized as the most important driving force for the formation of t-butanol aggregates, show intriguing lifetime trends and thermodynamic properties of their formation. Binary System.Recently, attention has turned to substances with small molecules exhibiting only a weak amphiphilic character that are sometimes addressed as 'amphiphilic solvents' or 'solvosurfactants' [9, 10]. They can be seen as liquids exhibiting the properties of surfactants, such as 3 surface activity, self-assembly in water, co-micellization, etc. The term 'hydrotrope' is also very commonly used, even though, as reviewed by Kunz et al. [11], it comprises a broader range of amphiphilic compounds [12][13][14]. Their ternary systems are often called 'surfactant-free microemulsions' [15] or 'detergentless microemulsions' [16]. More recently Zemb et al.proposed the term 'ultraflexible microemulsions' [17], as such systems exhibit low bending rigidities.The binary aqueous solutions of such substances are especially interesting due to their strong non-ideal behavior, e.g., in terms of their viscosity, partial molar volume, excess thermodynamic properties, compressibility, and sound-attenuation coefficient [18][19][20][21][22][23]. Such behavior arises because the hydrophilic part of the molecule forms strong hydrogen-bonds (HBs) with water, while the hydrophobic part introduces a perturbation to the water's hydrogen-bonded structure and induces cooperative ordering, stemming from the hydrophobic hydration effects.However, a full understanding of the hydration structure of such systems and their non-ideal behavior is still incomplete.In our recent research we have strived to learn m...

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“…At the same time, they also noted structural ordering of the surrounding water structure. Several other simulation studies [44][45][46] revealed the self-association of TBA molecules in their binary mixture. Lee and Vegt [47] proposed a modified force field for TBA in aqueous solution, in order to have a better approximation of the KirkwoodBuff integrals and made detailed analysis of the structural aspects, again asserting the presence of TBA selfaggregates.…”

Section: Introductionmentioning

confidence: 99%

“…Indeed, several simulation studies [42][43][44][45][46][47][48][49][50] have been performed on this important binary mixture, at different concentrations and using different force fields. Early in the 1990's, Tanaka and Nakanishi [42] performed simulations on this system and noted self-aggregation of TBA molecules at mole fraction 0.17.…”

Section: Introductionmentioning

confidence: 99%

Fluctuating micro-heterogeneity in water–tert-butyl alcohol mixtures and lambda-type divergence of the mean cluster size with phase transition-like multiple anomalies

Banerjee

Furtado

Bagchi

2014

The Journal of Chemical Physics

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Water-tert-butyl alcohol (TBA) binary mixture exhibits a large number of thermodynamic and dynamic anomalies. These anomalies are observed at surprisingly low TBA mole fraction, with xTBA ≈ 0.03 − 0.07. We demonstrate here that the origin of the anomalies lies in the local structural changes that occur due to self-aggregation of TBA molecules. We observe a percolation transition of the TBA molecules at xTBA ≈ 0.05. We note that "islands" of TBA clusters form even below this mole fraction, while a large spanning cluster emerges above that mole fraction. At this percolation threshold, we observe a lambda-type divergence in the fluctuation of the size of the largest TBA cluster, reminiscent of a critical point. Alongside, the structure of water is also perturbed, albeit weakly, by the aggregation of TBA molecules. There is a monotonic decrease in the tetrahedral order parameter of water, while the dipole moment correlation shows a weak non-linearity. Interestingly, water molecules themselves exhibit a reverse percolation transition at higher TBA concentration, xTBA ≈ 0.45, where large spanning water clusters now break-up into small clusters. This is accompanied by significant divergence of the fluctuations in the size of largest water cluster. This second transition gives rise to another set of anomalies around. Both the percolation transitions can be regarded as manifestations of Janus effect at small molecular level.

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Preferential solvation and elasticity of the hydrogen bonds network in tertiary butyl alcohol–water mixture

Cited by 16 publications

References 21 publications

Densities and volume properties of (water+tert-butanol) over the temperature range of (274.15 to 348.15)K at pressure of 0.1MPa

Densities and volume properties of (water+tert-butanol) over the temperature range of (274.15 to 348.15)K at pressure of 0.1MPa

Structural, rheological and dynamic aspects of hydrogen-bonding molecular liquids: Aqueous solutions of hydrotropic tert-butyl alcohol

Fluctuating micro-heterogeneity in water–tert-butyl alcohol mixtures and lambda-type divergence of the mean cluster size with phase transition-like multiple anomalies

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