Compensation of Isotope Effects at the Near Solvation of Singly Charged Ions in Light and Heavy Waters
DOI:
https://doi.org/10.15407/ujpe67.7.527Keywords:
solvent isotope effect, singly charged ions, diffusion, electrical conductivity, short-range solvation, negative solvationAbstract
The diffusion coefficients Di0 and the microscopic characteristics of the diffusional displacement length d, time т, and velocity V of 18 singly charged ions (Li+, Na+, K+, Cs+, Me4N+, Et4N+, Pr4N+, Bu4N+, F-, Cl-, Br-, I-, ClO-3 , ClO-4 , BrO-3, IO-3 , IO-4 , and OBz-) in heavy and light waters at temperatures of 283.15 and 298.15 K have been calculated on the basis of literature data concerning the limiting molar electric conductivity of those ions. Using the proposed parameter (d-ri), where ri is the structural radius of an ion, the type of the solvation of those ions is determined: it is positive, if (d - ri) > 0, and negative, if (d - ri) < 0. The solvent isotope effects (SIEs) – namely, the variations of the ion diffusion coefficient, D0iH/D0iD, the length, dH/dD, time, тH/тD, and velocity, VH/VD, of the translational ion displacement, and the solvent viscosity, nD0/nH0, as a result of the substitution H → D in H2O – are calculated and analyzed. It is found that, in the case of SIE, the deviation of D0iH/D0iD or VH/VD from 1 can be up to 25.0–25.9%, whereas, for the near solvation SIE, the deviation of dH/dD from 1 is an order of magnitude lower. These facts are explained on the basis of a derived equation, where the SIE dH/dD is the product of the inverse SIEs nD0/nH0 and D0iH/D0iD. The low dH/dD-values are obtained due to the opposite effect of the indicated factors, which points to the compensation of the intermolecular and ion-molecular interactions. Hence, since those interactions govern the near solvation of singly charged ions in H2O and D2O, the results obtained testify to a significant solvent effect on this process.
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