ON INFLUENCE OF H/D EXCHANGE ON SOLVENT ISOTOPE EFFECTS IN THERMODYNAMIC (ENTHALPIC) CHARACTERISTICS OF SOLVATION ...

ON INFLUENCE OF H/D EXCHANGE ON SOLVENT ISOTOPE EFFECTS IN THERMODYNAMIC (ENTHALPIC) CHARACTERISTICS OF SOLVATION OF PROTON-DONATING
NON-ELECTROLYTES
Some features of the solvent H/D-isotope effect method are discussed in the frame of development of ideas about the solvation mechanism including the structural and thermody-namic characteristics concept being proposed by G.A. Krestov and its followers. We have found it necessary to debate the possibility of employing the H2O-by-D2O isotope substitution for thermodynamic studying of binary aqueous systems containing a proton-donating organic non-electrolyte. In this regard, the two main aspects of the problem are discussed: (i) how the H-D exchange affects the thermodynamic (enthalpic) solvent isotope effects and (ii) how such effects dependent on the partial or complete pre-deuteration of a solute molecule. All potential-ly exchangeable protons (of N-H, O-H,) in heavy water are replaced by deuterons, but the fast exchange of D between D2O and the C-H (in methyl and methylen groups) does not occur. Herewith the extent to which proton-donor sites in complex molecules are stabilized by intra-molecular hydrogen bonding remains uncertain, making it difficult to assess details of H-D exchange mechanisms in the hydration process. It is important to note that the H-D-isotope exchange is accompanied by changes in the molecular composition both the solute and solvent (due to forming HDO) in the nearest environment. This affects the thermodynamic (mole-additive) parameters of solvation process in heavy water as well as the corresponding isotope effects. The problem can be partly overcome by using the deuterium-substitution in a solute molecule. In this case, the molar mass of each solution component does not change but we should not forget here on the effect of secondary H/D isotope substitution in the solute. From a purely thermodynamic view, we can focus only on the analysis of H/D isotope effects in char-acteristics of its sublimation or vaporization. Herewith H- and D-bonded systems have the same distinctions in the (zero-point) vibration energy as in individual components. It because the specified isotope effects can be rather directly related to the condensed-phase partition functions which may be written down under the assumption of isotope-independent potential energy surface (within the precision of Born-Oppenheimer “adiabatic” approximation).

Key words: aqueous non-electrolyte solution, solvent isotope effect, H-D exchange, solvation standard enthalpy

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