The Rationale of Trouton's Rule and of the Trouton-Hildebrand-Everett Rule

Logan, S. R.

doi:10.1515/zna-1996-1215

Cited by 5 publications

(2 citation statements)

References 3 publications

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“…Spectroscopic evidence for translational motion in liquids has been observed for mixtures of rare gases and H 2 in Ar, where the rotational and translational signals from H 2 can be clearly separated. , The idea of an effective volume in which a molecule in a liquid can move has also been used to provide a statistical–mechanical basis for Trouton’s rule. − We build upon this idea of the solute moving in an effective volume to approximate S t in solution.…”

Section: Theorymentioning

confidence: 99%

Solvation Entropy Made Simple

Garza

2019

J. Chem. Theory Comput.

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The entropies of molecules in solution are routinely calculated using gas phase formulae. It is assumed that, because implicit solvation models are fitted to reproduce free energies, this is sufficient for modeling reactions in solution. However, this procedure exaggerates entropic effects in processes that change molecularity. Here, computationally efficient (i.e., having similar cost as gas phase entropy calculations) approximations for determining solvation entropy are proposed to address this issue. The S ω , S , and S α models are nonempirical and rely only on physical arguments and elementary properties of the medium (e.g., density and relative permittivity). For all three methods, average errors as compared to experiment are within chemical accuracy for 110 solvation entropies, 11 activation entropies in solution, and 32 vaporization enthalpies. The models also make predictions regarding microscopic and bulk properties of liquids which prove to be accurate. These results imply that ∆H sol and ∆S sol can be described separately and with less reliance on parametrization by a combination of the methods presented here with existing, reparametrized implicit solvation models.

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Section: Theorymentioning

confidence: 99%

Solvation Entropy Made Simple

Garza

2019

J. Chem. Theory Comput.

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“…According to the Trouton rule 26,27 and its modifications, [139][140][141][142][143][144][145] the entropy difference between the gas phase and solution is ca. 21.0 cal mol À1 K À1 for most organic materials, which is expressed in modern terms as follows 146 DH vap…”

Section: Entropy Correction In the Solution Systemmentioning

confidence: 99%