Near Solvation of Tetraalkylammon Ions in Ethylene Glycol and in Water

Компенсація Ізотопних Ефектів При Ближній Сольватації Однозарядних Іонів У Легкій Та Важкій Воді

“…When calculating the SIE values, the required parameters of ions in light water were taken from works [1,6].…”

“…The validity of the choice of the difference (𝑑 − 𝑟 𝑖 ) as a measure of the ionic influence on the mobility of the closest solvent molecules (the measure of near solvation) was demonstrated in work [6], where we used a friction coefficient independent of the nature of the force acting on the particle. In work [6], it was also shown that the difference (𝑑 − 𝑟 𝑖 ) follows from the difference between the total, 𝜁, and viscous, 𝜁 𝜈 , friction coefficients, which are characterized by the quantities 𝑑 and 𝑟 𝑖 , respectively. The parameter 𝑑 is considered by us [1,3,4,6] as a characteristic microscopic length of some discrete displacement between two equilibrium positions that an ion passes during a characteristic time 𝜏 .…”

“…In work [6], it was also shown that the difference (𝑑 − 𝑟 𝑖 ) follows from the difference between the total, 𝜁, and viscous, 𝜁 𝜈 , friction coefficients, which are characterized by the quantities 𝑑 and 𝑟 𝑖 , respectively. The parameter 𝑑 is considered by us [1,3,4,6] as a characteristic microscopic length of some discrete displacement between two equilibrium positions that an ion passes during a characteristic time 𝜏 . The structural radius of the ion 𝑟 𝑖 was considered as its inherent and constant [7] characteristic, which quantitatively takes into account its behavior in the continuum approximation.…”

“…It was interesting to apply the approach developed in works [1,3,4,6] to determine the microscopic characteristics of translational displacement (MCTDs) -𝑑, 𝜏 , 𝑉 , and (𝑑−𝑟 𝑖 ) -for singly charged ions in heavy water, which is an isotopically substituted liquid solvent with respect to light water. The phenomenon of isotopic substitution of a certain element in a compound by its isotope, which is known as the isotope effect [5,9], is quite interesting and examined for various properties.…”

“…It is restricted with respect to ions and temperature, sometimes being contradictory. The application of the approach developed in works [1,6] to study the influence of singly charged ions of various nature on the mobil- ity of D 2 O molecules made it possible to explain the weak solvent isotope effect (SIE) at the near solvation and its variability owing to the compensation of the I-M and M-M interactions in the solutions of singly charged ions, when changing from light to heavy water. The ratios between the calculated parameters in the H 2 O and D 2 O cases were used as the corresponding SIE magnitudes.…”