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Evaluation of Hydration Enthalpies of Monatomic Cations by Considering Both Long-Range and Short-Range Interactions.

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Title: Evaluation of Hydration Enthalpies of Monatomic Cations by Considering Both Long-Range and Short-Range Interactions.
Authors: Ichieda, N.1, Kasuno, M.1, Banu, K.1, Kihara, S.1, Nakamatsu, H.1
Source: Journal of Physical Chemistry A. Sep2003, Vol. 107 Issue 38, p7597. 7p.
Subjects: Enthalpy, Hydration, Cations, Thermodynamics
Abstract: The standard hydration enthalpy, ΔH°hyd, of a monatomic cation was calculated as the sum of (1) the enthalpy due to the long-range interaction between a hydrated ion and bulk water, ΔH°LR, (2) the enthalpy due to the short-range interaction between the ion and water molecules in the first hydration shell, ΔH°SR, and (3) the enthalpy due to the ligand field stabilization of an ion, ΔH°LF, which arises for a transition-metal ion. ΔH°LR was estimated on the basis of the Born theory assuming the radius of the hydrated ion as the interatomic distance between the ion and the oxygen atom of a water molecule in the first hydration shell, rM-O, determined experimentally. ΔH°SR was evaluated on the basis of the donor-acceptor interaction between an ion and a water molecule coordinating to the ion, which was evaluated by the molecular orbital calculation of a monohydrated cluster of an ion combined with the Mulliken population analysis. ΔH°LF was calculated on the basis of the crystal field theory. Hydration enthalpies of 48 monatomic cations thus calculated agreed well with those observed experimentally. [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
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Abstract:The standard hydration enthalpy, ΔH°hyd, of a monatomic cation was calculated as the sum of (1) the enthalpy due to the long-range interaction between a hydrated ion and bulk water, ΔH°LR, (2) the enthalpy due to the short-range interaction between the ion and water molecules in the first hydration shell, ΔH°SR, and (3) the enthalpy due to the ligand field stabilization of an ion, ΔH°LF, which arises for a transition-metal ion. ΔH°LR was estimated on the basis of the Born theory assuming the radius of the hydrated ion as the interatomic distance between the ion and the oxygen atom of a water molecule in the first hydration shell, rM-O, determined experimentally. ΔH°SR was evaluated on the basis of the donor-acceptor interaction between an ion and a water molecule coordinating to the ion, which was evaluated by the molecular orbital calculation of a monohydrated cluster of an ion combined with the Mulliken population analysis. ΔH°LF was calculated on the basis of the crystal field theory. Hydration enthalpies of 48 monatomic cations thus calculated agreed well with those observed experimentally. [ABSTRACT FROM AUTHOR]
ISSN:10895639
DOI:10.1021/jp0348171