Transfer chemical potentials solvation

Transfer chemical potentials solvation metal ions, 2,298 Transferrins, 2, 772 6, 669... 

Solubilities, in water, ethanol, and ethanol-water mixtures, have been reported for [Fe(phen)3]-(0104)2, [Fe(phen)3]2[Fe(CN)6], and [Fe(phen)3][Fe(phen)(CN)4]. Solubilities of salts of several iron(II) iiimine complexes have been measured in a range of binary aqueous solvent mixtures in order to estimate transfer chemical potentials and thus obtain quantitative data on solvation and an overall picture of how solvation is affected by the nature of the ligand and the nature of the mixed solvent medium. Table 8 acts as an index of reports of such data published since 1986 earlier data may be tracked through the references cited below Table 8, and through the review of the overall pattern for iron(II) and iron(III) complexes (cf. Figure 1 in Section 5.4.1.7 above) published recently. ... 

The structure of [Fe(MeCOCOCHCOMe)3] has been determined/ of [Fe(acac)]3 redetermined at 20K (Fe—0=1.977 to 2.004A).Iron(III) forms mainly 1 1 and 1 3 complexes with acetylacetone and with benzoylacetone in DMF their reduction has been monitored electrochem-ically. " Solubilities, and derived transfer chemical potentials, of [Fe(acac)3] in various binary aqueous solvent mixtures give a measure of preferential solvation. Rate constants have been determined, at 283 K, for formation of 2,4-octanedione and 2,4-nonanedione complexes of iron(III). ... 

EXAFS studies on tris-maltolatoiron(III) in the solid state and in solution, and on [Fe(Ll)3] hydrate, pave the way for detailed investigation of the hydration of complexes of this type in aqueous media.Solubilities and transfer chemical potentials have been determined for tris-maltolatoiron(III) in methanol-water, and for tris-etiwlmaltolatoiron(III) in alcohol-water mixtures and in isobutanol, 1-hexanol, and 1-octanol. Solubility maxima in mixed solvents, indicating synergic solvation, is relevant to trans-membrane transport of complexes of this type. Solubilities of tris-ethylmaltolatoiron(III) and of [Fe(Ll)3] have been determined in aqueous salt solutions (alkali halides NH4 and NR4 bromides). ... 

The solvation of clathrochelate iron(II) cyclohexanedione-1,2-dihydrazonate in methanol-water mixtures was studied in research reported in Ref. 184. The comparison of transfer chemical potentials (Fig. 41) illustrates the greater preference of the larger and more hydrophobic [Fe(cxcage)]-+ cation for methanol in a series of cage complexes. However, these complexes appear to exhibit somewhat less hydrophobic behaviour than their nonmacrocyclic analogs. 

This dependence is fundamental for electrochemistry, but its key role for liquid-liquid interfaces was first recognized by Koryta [1-5,35]. The standard transfer energy of an ion from the aqueous phase to the nonaqueous phase, AGf J, denoted in abbreviated form by the symbol A"G is the difference of standard chemical potential of standard chemical potentials of the ions, i.e., of the standard Gibbs energies of solvation in both phases. 

The elementary step of ion transfer is considered to take place between positions x and X2, and therefore the electrical potential drop affecting this transfer is Ao02- The ion transfer involves the renewal of the solvation shell. The change in standard chemical potential Ao f associated with this process takes place over very short distances in the interfacial region [51] and can be assumed to occur between positions X2 and x - Thus, the BV equation for the flux density /, of an ionic species i is [52]... 

The papers in the second section deal primarily with the liquid phase itself rather than with its equilibrium vapor. They cover effects of electrolytes on mixed solvents with respect to solubilities, solvation and liquid structure, distribution coefficients, chemical potentials, activity coefficients, work functions, heat capacities, heats of solution, volumes of transfer, free energies of transfer, electrical potentials, conductances, ionization constants, electrostatic theory, osmotic coefficients, acidity functions, viscosities, and related properties and behavior. 

Fig. 3.1. Schematic diagnam to illustrate the difference in the way potential electrolytes and true electrolytes dissolve to give ionb solutions (a) Oxalic acid (a potential electrolyte) undergoes a proton-transfer chemical reaction with waterto give rise to hydrogen ions and oxalate ions, (b) Sodium chloride (a true electrolyte) dissolves by the solvation of the Na and Cl bns in the crystal.

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