Distinctive thermodynamic properties of solute–solvent hydrogen bonds in self‐associated solvents

Sedov, Igor A.

doi:10.1002/poc.2966

Cited by 11 publications

(3 citation statements)

References 32 publications

(38 reference statements)

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“…The values of Δ G HB as a function of temperature are plotted in Figure . In Table our results are compared at 298.15 K with the values proposed by Sedov et al, − which are based on a correlation involving experimental quantities such as Gibbs free energy of solvation. The values show that this model has a fair agreement with the experimentally obtained Gibbs energy of hydrogen bonding.…”

Section: Gibbs Energy Of Hydrogen Bondingmentioning

confidence: 89%

A New PC-SAFT Model for Pure Water, Water–Hydrocarbons, and Water–Oxygenates Systems and Subsequent Modeling of VLE, VLLE, and LLE

et al. 2016

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Accurate analytic thermodynamic modeling of water and its mixtures with hydrocarbon and oxygenates is difficult even with new and advanced equations of state such as the perturbed-chain statistical associating fluid theory (PC-SAFT). Several attempts have been made in the past by various authors to solve this issue. However, current models generally fail to describe simultaneously and accurately pure water properties (especially its liquid density) and liquid–liquid equilibria for mixtures involving water, hydrocarbons, and oxygenates. In the current work, this problem is dealt with by modification in the fundamental structure of the model. It was established that the temperature dependent diameter d(T) does not behave in the same way for water as it inscribed in the original model. Hence, a modification was proposed for d(T) of water in order to correctly represent the phase behavior of pure water and its mixtures with hydrocarbons and oxygenates. The deviations in saturated liquid densities and vapor pressure for pure water were reduced to 0.6% and 2.2%, respectively, in a large temperature range. The results for liquid–liquid equilibrium (LLE), vapor–liquid equilibrium (VLE) and vapor–liquid–liquid equilibrium (VLLE) of various water–hydrocarbons and oxygenates show the accuracy of this new model and its predictive capability when coupled with a group contribution approach. For certain oxygenated mixtures such as water with aldehydes, ketones, ethers, and esters a new contribution to the Helmholtz energy, known as the “non-additive hard sphere” contribution, was used. The cross-interaction parameters obtained for mixtures were validated qualitatively by calculating octanol/water partition coefficients and the Gibbs free energy of hydrogen bonding (ΔG HB). Results are found in good agreement with experimental data.

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Section: Gibbs Energy Of Hydrogen Bondingmentioning

confidence: 89%

A New PC-SAFT Model for Pure Water, Water–Hydrocarbons, and Water–Oxygenates Systems and Subsequent Modeling of VLE, VLLE, and LLE

et al. 2016

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“…Indeed, carbonyl and hydroxyl groups are common in biologically interesting molecules. Many experimental methods, including thermodynamics, − vibrational spectroscopy, − NMR, and molecular dynamics simulation , have been applied to analyze the structure and dynamics in this system. Marcus et al used the inverse Kirkwood–Buff integrals method, which provides detailed insight into the preferential solvation in many solute–solvent mixtures including the acetone/methanol mixture.…”

Section: Introductionmentioning

confidence: 99%

Inhomogeneous Distribution in Methanol/Acetone Mixture: Vibrational and NMR Spectroscopy Analysis

et al. 2014

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The main aim of this paper is to quantify the inhomogeneous distribution of the components of acetone/methanol mixture and to give detailed insight into the interplay between the dipole-dipole and hydrogen bonding interactions inducing this inhomogeneity. To this end, we used the concept of infrared excess molar absorption of a given vibrational mode as an observable which contains all the information on the collective interactions in the mixture. Indeed, the changes in the infrared excess molar absorption may be associated with the inhomogeneous distribution (clustering, self-association, or high-density domains) of the components and consequently with the interaction between the two components of the mixture. The results show that acetone molecules are not homogeneously distributed in the mixture, particularly in the mole fraction range of acetone between 0.05 and 0.55. The spectral signature of this inhomogeneity is associated with the appearance of a shoulder in the C═O and C-C stretching vibrational profiles of acetone. This inhomogeneity is driven by the prevalence of the dipole-dipole interactions over those of hydrogen bonding between acetone and methanol molecules. The inhomogeneous distribution of methanol molecules is found to occur in the mole fraction range of acetone between 0.55 and 1. In this case, the hydrogen bond interactions between methanol molecules prevail over those between methanol and acetone. However, the extent of this inhomogeneity is small compared with that of acetone in the low mole fraction range. The spectral signature of this inhomogeneity is not visible in the O-H stretching vibrational mode; however, a second peak appears as a shoulder of the C-O stretching vibrational mode in this range of acetone mole fraction.

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“…Another interesting aspect in the THF-rich system is that the water-water hydrogen bonding may compete with the water-THF hydrogen bonding, due to favorable energetics. [17,18] In order to understand the actual structures of THF-water complexes in the THF-rich system, the experimental spectral observations are important. With this aim, we investigate the structures of THF-water complexes in the THF-rich system by Raman measurements of binary solutions, focusing on the concentration range of 0.884 to 1 X THF , where X THF is the molar fraction of THF.…”

Section: Introductionmentioning

confidence: 99%

Raman spectra and structure of hydrogen‐bonded water oligomers in tetrahydrofuran–H₂O binary solutions

Raj

Chen

Wang

et al. 2022

J Raman Spectroscopy

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Raman spectra of hydrogen-bonded water oligomers have been resolved from concentration-dependent Raman spectra of tetrahydrofuran (THF)-water binary solutions with the use of multivariate curve resolution with alternating least-squares (MCR-ALS) analysis, assisted by hypothetical addition multivariate analysis with numerical differentiation (HAMAND) procedure. A total of 38 Raman spectra acquired in the broad spectral range of 700-3810 cm À1 were analyzed in a multistep procedure to explain the spectral variations in terms of four components: pure THF, Spectra A, Spectra B, and Spectra C. A fourcomponent MCR-ALS analysis was performed with initial guesses by HAMAND analysis to refine the spectral components and determine their concentration dependence. Of the MCR-ALS resolved three spectra, A was identified as THF(H 2 O), B as THF(H 2 O) 2 with two hydrogens attached to THF, and C as THF(H 2 O) n having two or more linearly hydrogen-bonded oligomers of water (n = 2-4). Observed spectral changes of the OH stretch vibrations of water and those of the C-C/C-O stretches of THF were well reproduced by quantum chemical calculations. Formation of hydrogen-bonded water oligomers in THF-water complexes has thus been revealed. The present study provides a new insight into the basics of hydrogen bonding formation in aqueous systems. It also provides experimental methodology for extracting concentration-dependent minor spectral components contained in complex condensed-phase Raman spectra.

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Distinctive thermodynamic properties of solute–solvent hydrogen bonds in self‐associated solvents

Cited by 11 publications

References 32 publications

A New PC-SAFT Model for Pure Water, Water–Hydrocarbons, and Water–Oxygenates Systems and Subsequent Modeling of VLE, VLLE, and LLE

A New PC-SAFT Model for Pure Water, Water–Hydrocarbons, and Water–Oxygenates Systems and Subsequent Modeling of VLE, VLLE, and LLE

Inhomogeneous Distribution in Methanol/Acetone Mixture: Vibrational and NMR Spectroscopy Analysis

Raman spectra and structure of hydrogen‐bonded water oligomers in tetrahydrofuran–H₂O binary solutions

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Distinctive thermodynamic properties of solute–solvent hydrogen bonds in self‐associated solvents

Cited by 11 publications

References 32 publications

A New PC-SAFT Model for Pure Water, Water–Hydrocarbons, and Water–Oxygenates Systems and Subsequent Modeling of VLE, VLLE, and LLE

A New PC-SAFT Model for Pure Water, Water–Hydrocarbons, and Water–Oxygenates Systems and Subsequent Modeling of VLE, VLLE, and LLE

Inhomogeneous Distribution in Methanol/Acetone Mixture: Vibrational and NMR Spectroscopy Analysis

Raman spectra and structure of hydrogen‐bonded water oligomers in tetrahydrofuran–H2O binary solutions

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Raman spectra and structure of hydrogen‐bonded water oligomers in tetrahydrofuran–H₂O binary solutions