A method to determine the Gibbs energy of specific interactions in solutions. Hydrogen bonding of proton donating solutes in basic solvents

Sedov, Igor A.

doi:10.1016/j.fluid.2008.10.015

Cited by 14 publications

(4 citation statements)

References 33 publications

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“…For the systems with specific interactions, one can find $\Delta _{{\mathop{\rm int}} ({\rm sp})} G^{{\rm A/S}}$ using it together with Eqn (3b). In this manner, we calculated the Gibbs energies of specific interactions of some proton donors dissolved in basic solvents 26. Most of the values were found to be close to the Gibbs energies of 1:1 complexation in tetrachloromethane.…”

Section: Methodsmentioning

confidence: 87%

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Gibbs energy of cooperative hydrogen‐bonding interactions in aqueous solutions of amines and pyridines

Solomonov

Akhmadiyarov

2009

J of Physical Organic Chem

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A method to determine the Gibbs energy of specific (hydrogen bonding) interactions of a solute with water is proposed. The energies of hydrogen bonding in bulk water are very difficult to determine by any method. The Gibbs energy of hydration of substances forming hydrogen bonds with water is considered as the sum of contributions due to non-specific interactions, the hydrophobic effect, and specific interactions. The first two terms were found to be rather accurately described by empirical equations. The Gibbs energies of hydrogen bonding of aliphatic amines and pyridines in bulk water are determined, and the results are compared with the energies of their complexes with one molecule of water. The cooperativity of hydrogen bonding is proved in aqueous solutions of amines and pyridines. To use our equations, experimental values of the Gibbs energies of solvation in 'standard' solvents need to be known. The Gibbs energies of solvation of ten amines and pyridines in dimethyl sulfoxide are determined experimentally using chromatographic head space analysis. The tendencies observed for the series of amines and pyridines are in agreement with other studies.

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Section: Methodsmentioning

confidence: 87%

“…For some compounds, a correct model can be difficult to find (as for water, ammonia, and other simple solutes). In recent works of our group, new methods to determine the enthalpies25 and the Gibbs energies of specific interactions26 in non‐aqueous solvents without using model solutes have been proposed.…”

Section: Introductionmentioning

confidence: 99%

Gibbs energy of cooperative hydrogen‐bonding interactions in aqueous solutions of amines and pyridines

Solomonov

Akhmadiyarov

2009

J of Physical Organic Chem

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“…The number of bonds that are reorganized is not the same in different systems: it is determined at least by the number of protonaccepting and -donating sites in both the solute and solvent molecules. The total contribution of these processes to the Gibbs energy of solvation is what we call the Gibbs specific-interaction energy of solute A in solvent S [Δ int(sp) G A/S ], 5 which reflects the change in Gibbs energy during the transfer of solute from its nonhydrogen-bonded state in solution into the equilibrium mixture of solute-solvent complexes with various structures. The magnitude of Δ int(sp) G A/S determines the hydrogen-bonding-induced changes in solute reactivity.…”

Section: ' Introductionmentioning

confidence: 99%

Determining the Gibbs Energies of Hydrogen-Bonding Interactions of Proton-Accepting Solutes in Aqueous Solutions from Thermodynamic Data at 298 K with Regard to the Hydrophobic Effect

Sedov

Solomonov

2011

J. Chem. Eng. Data

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Reaction rate and equilibrium constants in aqueous solutions are affected by the strength of hydrogen bonds formed between dissolved species and water molecules. Thermodynamic functions of hydrogen bonding with bulk water cannot be measured directly using spectroscopic methods, but the contribution of hydrogen-bonding processes to the thermodynamic functions of hydration may be determined using some model of aqueous solutions. We determined the Gibbs energies of hydrogenbonding interactions in water for various simple proton-accepting organic molecules on the basis of two different models that allow the contributions of nonspecific van der Waals interactions and the hydrophobic effect to be quantified. It is shown that hydrogen bonding with bulk water may be stronger than with a single water molecule. The influence of solute structure on the Gibbs energy of hydrogen-bonding interactions is discussed.

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“…For applications, it is more important to consider hydrogen bonds between a solute and solvent, which have a large impact on solute reactivity and other physico‐chemical properties. We have shown that the values of thermodynamic functions for equimolar complexes with solvents having a single basic or acidic center are close to those for the same complex in inert medium. However, the equations and data obtained for bimolecular complexes in inert medium may become useless when one considers the complexes formed by solutes with hydrogen‐bonded multimers of self‐associated solvents.…”

Section: Introductionmentioning

confidence: 68%

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

Sedov

2012

J of Physical Organic Chem

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Solute-solvent hydrogen bonding affects reactivity and other properties of dissolved species. In self-associated media, because of cooperativity and solvent reorganization, the thermodynamic functions of solute bonding with bulk solvent can be different from those of bimolecular solute-solvent complexes. Using available experimental data on the Gibbs free energies of solvation in aliphatic alcohols and water, we have determined the energies of solute-solvent hydrogen bonding for various proton accepting solutes. We show that the increase in the strength of hydrogen bonds because of the cooperative effect is strong for bonding with bulk water and significantly less so with bulk aliphatic alcohols. The hydrogen bonding Gibbs free energies for the same solute with bulk water and alcohol are correlated, but they correlate poorly with the energies of formation of the corresponding bimolecular solute-solvent complexes. Thus, the traditional hydrogen bond basicity scales, based on data for bimolecular complexes, do not correctly describe the thermodynamics of hydrogen bonding with self-associated solvents. Our results may help to define a separate solute basicity scale for associated media.

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A method to determine the Gibbs energy of specific interactions in solutions. Hydrogen bonding of proton donating solutes in basic solvents

Cited by 14 publications

References 33 publications

Gibbs energy of cooperative hydrogen‐bonding interactions in aqueous solutions of amines and pyridines

Gibbs energy of cooperative hydrogen‐bonding interactions in aqueous solutions of amines and pyridines

Determining the Gibbs Energies of Hydrogen-Bonding Interactions of Proton-Accepting Solutes in Aqueous Solutions from Thermodynamic Data at 298 K with Regard to the Hydrophobic Effect

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

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