Transference of Water to the Nitrobenzene Phase for the Extraction of Tris(1,10-phenanthroline)iron (II) and Tris(2,2′-bipyridine)iron(II) Chelate Salts

Yamamoto, Yuroku; Tarumoto, Tsunehiko; Tarui, Takao

doi:10.1246/bcsj.46.1466

Cited by 21 publications

(12 citation statements)

References 2 publications

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“…and Iwachido and co-workers − employed the Karl Fischer method to determine hydration numbers of alkali and alkaline earth metal ions in nitrobenzene (NB). Some inorganic anions (Cl - , Br - , I - , SCN - , ClO 4 - , and NO 3 - ) have also been found to coextract water into NB. − Similar phenomena have further been observed in solvents other than NB (e.g., 1,1- and 1,2- dichloroethane, 4-methyl-2-pentanone, chloroform, NB−benzene mixtures). − If these observations are valid, we should reconsider the previous theories of of transfer of ions between mutually saturated solvents in which the hydration of ions in O is not properly taken into account. The purpose of this study is to reaffirm the hydration of ions in NB and determine accurate hydration numbers for a variety of common ions.…”

Section: Introductionmentioning

confidence: 75%

Hydration of Ions in Organic Solvent and Its Significance in the Gibbs Energy of Ion Transfer between Two Immiscible Liquids

1997

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Various kinds of cations (alkali and alkaline earth metal ions, Me4N+, Et4N+, n-Bu4N+, and tetraphenylarsonium ion) and anions (halide ions, SCN-, ClO4 -, NO3 -, and tetraphenylborate ion) have been extracted from water to nitrobenzene (NB) using several extractants: viz. tetraphenylborate and dipicrylaminate for the cations; n-Bu4N+, n-Pen4N+, n-Hep4N+, and tris(1,10-phenanthroline)iron(II) for the anions. The determination of water content in NB by means of the Karl Fischer method has confirmed that some water molecules are coextracted by hydrophilic inorganic cations and anions. Accurate numbers (n) of the coextracted water molecules per ion have been established. On the basis of these findings, a new model has been proposed for a better understanding of the Gibbs energy of ion transfer at the organic solvent/water interface. If hydrated radii of ions evaluated from n are used, conventional (Born-type) electrostatic solvation models are invalid. A new approach recognizing short-range ion−solvent interactions (e.g. hydrogen bonds) has given a better account of for the hydrated ions.

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Section: Introductionmentioning

confidence: 75%

Hydration of Ions in Organic Solvent and Its Significance in the Gibbs Energy of Ion Transfer between Two Immiscible Liquids

1997

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“…In such a medium hydrophilic ions such as alkali and alkaline earth metal ions are preferentially solvated by water. Although this phenomenon has become apparent since at latest 1968 by the Karl Fischer method − or NMR, almost all theories of ignored this matter. In the preceding study we have determined accurate hydration numbers of a variety of common ions in NB and then have proposed a new model for of hydrophilic ions.…”

Section: Introductionmentioning

confidence: 99%

Non-Bornian Theory of the Gibbs Energy of Ion Transfer between Two Immiscible Liquids

1998

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A non-Bornian theory has been proposed for the standard Gibbs free energy (∆G°t r ,OfW) of ion transfer at the organic solvent (O)/water (W) interface. In this theory the ionic charge (z)-dependent term of ∆G°t r ,OfW , which has so far been considered as describing electrostatic (i.e., long-range) ion-solvent interactions, is treated as describing the specific (short-range) interactions. A quantum chemical consideration has shown that the short-range interaction energy can be given by a quadratic function of the surface field strength (E) of an ion. In the present theory it should also be noted that a hydrophilic ion, being preferentially hydrated in the O phase, is assumed to transfer across the interface as the hydrated ion. The new, non-Bornian theory has been applied to 34 ions in the nitrobenzene (NB)/W system. In the data analyses the ions have been classified into five groups, including hydrated cations, nonhydrated cations, hydrated anions, nonhydrated anions, and polyoxometalate anions (nonhydrated), where "hydrated" or "nonhydrated" means that the ion is associated with some water molecules in NB or not. Regression analyses have shown that in accord with the theory, the z-dependent term of ∆G°t r ,OfW can be given by a quadratic function of E for each group of ions. Furthermore, the present theory has been found to be useful for the prediction of ∆G°t r ,OfW for some hydrophilic ions.

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“…So if a value larger than 1/2 is used, the triple ion contribution discussed later becomes smaller. iodide ion into NB.45, 46 The organic solvents used here dissolve only a small amount of water (below 0.01 mol fraction in most solvents). So it is unlikely that the dissolved water has a significant effect on the solvent nature, as seen by the viscosities.…”

Section: Discussionmentioning

confidence: 99%

Solute-solvent interactions in ion-pair extraction of tetraalkylammonium iodides. 1. A new approach to the extraction constant

Iwamoto¹,

Ito²,

Yamamoto³

1981

J. Phys. Chem.

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Transference of Water to the Nitrobenzene Phase for the Extraction of Tris(1,10-phenanthroline)iron (II) and Tris(2,2′-bipyridine)iron(II) Chelate Salts

Cited by 21 publications

References 2 publications

Hydration of Ions in Organic Solvent and Its Significance in the Gibbs Energy of Ion Transfer between Two Immiscible Liquids

Hydration of Ions in Organic Solvent and Its Significance in the Gibbs Energy of Ion Transfer between Two Immiscible Liquids

Non-Bornian Theory of the Gibbs Energy of Ion Transfer between Two Immiscible Liquids

Solute-solvent interactions in ion-pair extraction of tetraalkylammonium iodides. 1. A new approach to the extraction constant

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