NDLI: Ions in Aqueous Acetic Acid Mixtures: Solvent Reorganization around Protons and Gibbs Energies of Transfer from Water

Content Provider	Springer Nature Link
Author	Wells, Cecil F.
Copyright Year	2000
Abstract	The photo-absorbing, basic sensor, 4-nitroaniline, has been used to determine theequilibrium constant for solvent reorganization around the proton in mixtures ofvarying composition of water with acetic acid. In all the mixtures used, theself-ionization of the acetic acid was suppressed. In contrast to mixtures of waterwith the related ethanol or acetone, this equilibrium is shifted more toward thewater-solvated species as the mole fraction x $_{2}$ of the cosolvent increases. TheGibbs energy of transfer of protons from water into the mixture ΔG $^{o}$ $_{ t }$(H$^{+}$) can bederived with the aid of this equilibrium constant for the solvent reorganization.Using ΔG $^{o}$ $_{ t }$(H$^{+}$), ΔG $^{o}$ $_{ t }$(i) for i denoting anions and other cations can be evaluated.In comparison the ΔG $^{o}$ $_{ t }$(i) for cations have lower negative values than when eitherethanol or acetone is added to water. Correspondingly, for halide anions, thepositive ΔG $^{o}$ $_{ t }$(i) with added acetic acid are rather less than is found with eitherethanol or acetone added. The influence on the ion-solvent interaction of bothelectron withdrawing hydroxy and carbonyl groups in acetic acid may beresponsible for this. Although ΔG $^{o}$ $_{ t }$(i) for C10$^{−}$ $_{4}$ and Re0$^{−}$ $_{4}$ are also positive, both picrateions and OH$^{−}$ give negative values with acetic acid added to water. With picrateions, the hydrophobic effect of the carbon ring produces stabilization in themixture relative to water. With OH$^{−}$, complete conversion to acetate anionsoccurs. As is found with other cosolvents, the contribution of the charge onacetate anion to ΔG $^{o}$ $_{ t }$(CH$_{3}$COO$^{−}$) is found to increase as x $_{2}$ rises. The aciddissociation constant K $_{ a }$ for acetic acid is found to decrease slowly as x $_{2}$ rises to0.5, followed by a rapid decrease for x $_{2}$ greater than 0.7 where dimerization ofacetic acid occurs.
Starting Page	271
Ending Page	287
Page Count	17
File Format	PDF
ISSN	00959782
Journal	Journal of Solution Chemistry
Volume Number	29
Issue Number	3
e-ISSN	15728927
Language	English
Publisher	Kluwer Academic Publishers-Plenum Publishers
Publisher Date	2000-01-01
Publisher Place	New York
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Inorganic Chemistry Physical Chemistry Industrial Chemistry/Chemical Engineering Condensed Matter
Content Type	Text
Resource Type	Article
Subject	Biochemistry Molecular Biology Biophysics Physical and Theoretical Chemistry

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