Compensation of Isotope Effects at the Near Solvation of Singly Charged Ions in Light and Heavy Waters
Keywords: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, 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.
V.I. Bulavin, I.M. V'yunyk, Ya.I. Lazareva. Diffusion and microscopic characteristics of singly charged ion transfer in extremely diluted aqueous solutions. Ukr. J. Phys. 62, 769 (2017).
O.Ya. Samoilov. Structure of Aqueous Electrolyte Solutions and the Hydration of Ions (Consultants Bureau, 1965).
V.I. Bulavin, I.M. V'yunyk, V.O. Minakov. Diffusion and microscopic characteristics of the length, time, and rate of translational displacement of singly charged ions in extremely dilute solutions in formamide. In: Abstracts of the XI All-Ukrainian Scientific Conference of Students and Postgraduates "Chemical Karazin Readings-2019" (V.N. Karazin Kharkiv National University, 2019), p. 27 (in Ukrainian).
V.I. Bulavin, I.M. V'yunnik, V.O. Minakov. The near solvation of singly charged ions in solvents with a spatial network of H-bonds at 298.15 K. In: Abstracts of the XX Ukrainian Conference on Neorganic Chemistry (LIRA, 2018), p. 161.
G.A. Krestov, V.I. Vinogradov, Yu.M. Kessler et al. Modern Problems of Solution Chemistry (Nauka, 1986) (in Russian).
V.I. Bulavin, I.N. V'yunyk, A.V. Kramarenko, A.I. Rusynov, V.A. Minakov. Near solvation of tetraalkylammonium ions in ethylene glycol and water. Visn. Nats. Tekhn. Univ. KhPI Ser. Khim. Khim. Tekhn. Ekolog. No. 2, 63 (2019) (in Ukrainian).
Y. Marcus. Are ionic Stokes radii of any use? J. Solut. Chem. 41, 2082 (2012).
Y. Marcus. Ions in Solution and Their Solvation (John Wiley and Sons, 2015).
R.P. Bell. The Proton in Chemistry (Springer, 1973).
M. Rodnikova. Spatial network of hydrogen bonds in liquids and solutions. In: Selected Proceedings of the IV International Congress "Weak and superweak fields and measurements in biology and medicine" (2006), pp. 100-108 (in Russian).
G.A. Krestov. Thermodynamics of Ionic Processes in Solutions (Khimiya, 1984) (in Russian).
Yu.V. Yergin, L.I. Kostrova. Magnetochemical study of the solvation of alkali metal halide ions in monohydric alcohols. Zhurn. Strukt. Khim. 11, 762 (1970) (in Russian).
O.Ya. Samoilov, P.S. Yastremsky. Change in ion solvation when switching from solutions in H2O to solutions in D2O. Zhurn. Strukt. Khim. 12, 379 (1971) (in Russian).
O.Ya. Samoilov. K osnovam kineticheskoj teorii gidrofobnoj gidratacii v razbavlennech vodnyh rastvorach. Zhurn. Fiz. Khim. 52, 1857 (1978) (in Russian).
C.G. Swain, D.F. Evans. Conductance of ions in light and heavy water at 25 ∘C. J. Am. Chem. Soc. 88, 383 (1966).
D.F. Evans, R.L. Kay. The conductance behavior of the symmetrical tetraalkylammonium halides in aqueous solution at 25 ∘C and 10 ∘C. J. Phys. Chem. 70, 366 (1966).
T.L. Broadwater, R.L. Kay. The temperature coefficient of conductance for the alkali metal, halide, tetraalkylammonium, halate, and perhalate ions in D2O. J. Solut. Chem. 4, 745 (1975).
I.B. Rabinovich. Influence of Isotopy on the Physicochemical Properties of Liquids (Springer, 1970).
V.A. Rabinovich, Z.Ya. Khavin. Brief Chemical Handbook (Khimiya, 1978) (in Russian).
Y. Tada, M. Ueno, N. Tsuchihashi, K. Shimizu. Pressure and temperature effects on the excess deuteron and proton conductance. J. Solut. Chem. 21, 971 (1992).
D.K. Chatterjee, B.K. Seal. Viscosity B-coefficients of sodium salts of some orthosubstituted benzoic acids in relation to hydrogen bonding and electronegativity. Indian Acad. Sci. Chem. Sci. 104, 409 (1992).
M.I. Shakhparonov. Introduction to the Molecular Theory of Solutions (Gostekhizdat, 1956) (in Russian).
G.N. Zatsepina. Physical Properties and Structure of Water (Mosk. Gos. Univ., 1998) (in Russian).
K. Yoshida, C. Wakai, N. Matubayasi, M. Nakahara. A new high-temperature multinuclear-magnetic-resonance probe and the self-diffusion of light and heavy water in suband supercritical conditions. J. Chem. Phys. 123, 164506 (2005).
M.I. Shakhparonov. Introduction to Modern Solution Theory (Vysshaya Shkola, 1976) (in Russian).
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