Compensation of Isotope Effects at the Near Solvation of Singly Charged Ions in Light and Heavy Waters


  • V.I. Bulavin National Technical University “Kharkiv Polytechnic Institute”
  • I.N. Vyunnik V.N. Karazin National University of Kharkiv



solvent isotope effect, singly charged ions, diffusion, electrical conductivity, short-range solvation, negative solvation


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, тHD, 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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How to Cite

Bulavin, V., & Vyunnik, I. (2022). Compensation of Isotope Effects at the Near Solvation of Singly Charged Ions in Light and Heavy Waters. Ukrainian Journal of Physics, 67(7), 527.



Physics of liquids and liquid systems, biophysics and medical physics