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By Frederick Winthrop Faxon

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Solvation Numbers 31 Brownian motion. Accordingly, the primary solvation number is a definite quantity, while the "secondary solvation" caused by electrostatic interaction beyond the first solvation shell depends on the type of property observed. Various methods have been suggested for the determination of primary solvation numbers. 10 (a) The isotope dilution technique. This method was applied 92 to the study of the exchange of methanol between solvated cations and the solvent. The conditions required for the sucess ofthe method are that the solvated cation be a specific entity distinguishable from the solvent and that the exchange be not yet complete at the time ofisotopic sampling.

MIXED SOLVENTS Most of the work on mixed solvents has been concerned with aqueous-organic solvents, with emphasis on changes in thermodynamic behavior of electrolytes with decreasing water content of the mixed solvent. Equilibrium properties of mixed solvents will be considered in terms of the thermodynamic properties of transfer. Go and in water wGo. Thus, (58) actually characterizes the change in solvation during transfer from one solvent to another, as we have previously seen. 220 31 61 90 125 197 267 328 378 434 492 546 612 679 737 792 835 890 948 1002 1172 1302 67 118 174 213 293 373 451 530 608 704 787 871 958 1043 1125 1214 73 146 203 260 365 471 575 676 775 888 986 1096 1188 1282 26 66 102 138 226 316 413 520 625 738 863 1005 1158 172 327 465 583 799 975 1143 1304 1447 110 195 290 389 717 873 1105 1325 1558 192 306 411 512 709 902 1084 1282 1488 1674 1852 2012 2269 2339 2492 2654 2812 2923 Ionic Solvation in Nonaqueous and Mixed Solvents 38 dH~" entropy dS~" and volume d V~, of transfer may be similarly defined.

Assuming the additivity of molar refractions, the solvated molar refraction was calculated and it was shown 151 that the refractive index of the solvated complex is independent of concentration. The polarizability of solvated ions could be calculated, as well as the electronic contribution to the molar polarization of the solvated salt. Actually, the same model has been inherently used for the ion in the development of electrolyte theories and has properties independent of the concentration, which point to its usefulness as a working entity.

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