Diffusion and Microscopic Characteristics of Singly Charged Ion Transfer in Extremely Diluted Aqueous Solutions
Keywords:singly charged ions, diffusion, electric conductivity, Stokes radius, negative solvation
Diffusion coefficients and microscopic characteristics of the length ( ¯d), time, and rate of ion diffusion displacement have been calculated for 19 singly charged ions (Li+, Na+, K+, Rb+, Cs+, F−, Cl−, Br−, I−, NO−3 , CNS−, ClO−4 , NH+4 , Me4N+, Et4N+, Pr4N+, Bu4N+, Pent4N+, and BPh−4 ) in water at temperatures from 273.15 to 473.15 K. The calculations are based on the literature data concerning the limiting molar electric conductivity of those ions. The analysis of the data obtained shows that the length of the ion diffusion displacement ¯d correlates with the type of ion solvation. If the average value ¯d exceeds the crystallographic (structural) radius ri of an ion, the latter is solvated positively. However, if ¯d is less than ri, the ion solvation is negative.
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