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AbstractAbstract
[en] In a recent H2O-D2O molar volume isotope effect study on the alkali metal halide solutions, individual ionic standard partial molar volume contributions (V-barion0(H2O)-V-barion0(D2O)=ΔV-barion0(H-D)) have been derived, dependent only on the chosen (Pauling) ionic radii, rion. It has been concluded that the isotope effect of the cations (except for Li+) and that of the chloride anion exhibit a linear function of 1/rion, with ΔV-barion0(H-D) vanishing when 1/rion approaches zero. On the other hand, the directly measurable hydrodynamic 'cosphere' volumes of the ions, V-barcosph0, derived from the kinetic ionic (Stokes) radii, show a similar pattern, here also the cationic and anionic rion relations cross or meet at V-barcosph0(Cs+)≅V-barcosph0(Cl-). Because both ΔV-barion0(H-D)andV-barcosph0 originate in the hydration volumes of the ions, (V-barhydr0=V-barion0-V-barintr0) determined by electrostriction, this rion pattern of the V-barhydr0 (ion) provides an 'extra-thermodynamic' assumption to evaluate the individual cationic and anionic molar volume contributions in normal water solution. As a basis for the evaluation, this rion pattern is applied to the conventional cationic and anionic V-barhydr0 (ion) values (related toV-barion0(H+,aq.)=0cm3.mol-1), calculated from literature V-barion0 data, assuming that the V-barintr0 (ion) = V-barcryst0 (ion). To adjust the V-barhydr0(Cl-) to the V-barhydr0(Na+,K+,Rb+,Cs+)versus rion relation at T = 298.15 K, the conventional anionic V-barhydr0 (ion) data have to be increased, the cations have to be decreased by 4.2 cm3 . mol-1. Similar adjustments at five different temperatures between T = (273 and 323) K, result in V-barion0(H+,aq.)=-(4.2±0.2)cm3.mol-1 at T = 298.15 K, with an increment of -0.02 cm3 . K-1 . mol-1. Related to these parameters, relations of V-barion0versus temperature for the alkali metal and halide ions were calculated. The cationic and anionic V-barhydr0 (ion) values, when related to V-barion0(H+,aq.)=-4.2cm3.mol-1, show strong rion correlation with V-barcosph0, their ratio versus rion offers a linear equation to compare the influence of the ions on the solvent structure on a well defined 'quantitative' scale. The value of the derived V-barion0(H+,aq.), while being consistent with that widely accepted ca. - (5 ± 2) cm3 . mol-1, has a higher precision with a reasonable basis of the applied 'extra-thermodynamic' assumption. It can serve to verify other partitioning procedures used in non-aqueous solvents
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S0021-9614(08)00014-1; Available from http://dx.doi.org/10.1016/j.jct.2008.01.030; Copyright (c) 2008 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
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Journal Article
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ALKALI METAL COMPOUNDS, CHARGED PARTICLES, CHLORIDES, CHLORINE COMPOUNDS, DEUTERIUM COMPOUNDS, DISPERSIONS, HALIDES, HALOGEN COMPOUNDS, HOMOGENEOUS MIXTURES, HYDROGEN COMPOUNDS, IONS, LITHIUM COMPOUNDS, LITHIUM HALIDES, MIXTURES, OXYGEN COMPOUNDS, POTASSIUM COMPOUNDS, RUBIDIUM COMPOUNDS, SODIUM COMPOUNDS, SOLUTIONS, SOLVATION, SOLVENTS, WATER
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