Singly Charged Ions and Molecular Mobility in Formic Acid at 298.15 K
DOI:
https://doi.org/10.15407/ujpe70.9.598Keywords:
formic acid, singly charged ions, diffusion, electrical conductivity, short-range solvation, negative solvationAbstract
The diffusion coefficients D0i and the diffusion displacement lengths d have been calculated for 16 singly charged ions H+, Li+, Na+, K+, NH+4, Me4N+, Et4N+, Pr4N+, Bu4N+, Pent4N+,Cl−, Br−, I−, ClO−4, BPh−4, and HCOO− from literature data on their limiting molar electrical conductivity at 298.15 K in formic acid. Based on the justified parameter d −ri, where ri is the ion radius, the negative (at d −ri < 0) or positive (at d −ri > 0) solvation is determined for each ion. Most ions, except H+ and HCOO−, are solvated positively. Unlike other ions, the negative solvation of the formate ion occurs due to the domination of intermolecular interactions over the ion-molecule interactions. For a proton, the negative solvation is caused by the prototropic transfer mechanism.
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