Иваново, Ивановская область, Россия
Иваново, Ивановская область, Россия
УДК 544.332 Теплота (энтальпия) химических процессов. Изменение энтальпии в химической реакции (^ДH). Аддитивность теплот реакций. Закон Гесса *
УДК 544.582.6 Изотопные эффекты
УДК 546.212.027 Тяжелая вода D2O
Based on the analysis of thermochemical data on the study of solvation of H2O and D2O molecules and the state of them in aprotic dipolar organic media, being available in the literature including the results of own calorimetric measurements by the authors, three groups of solvents were identified in the given review. They differ in the nature of specific interaction with water H/D isotopologues. The first group consists of moderately electron-donating tetrahydrofuran (THF), para-dioxane (DO), and acetone (Ac), solvents whose hydrogen-bonds with the solute water are not much inferior in energy to those being formed between H2O or D2O molecules. The effects of heterocomponent H(D)-bond formation in the solvents of second group consisting of the predominantly electron-accepting propylene carbonate (PC), acetonitrile (AN), and nitromethane (NM) are largely caused by the availability of their donor-acceptor centers to interact with water isotopologue molecules. In this sense, PC corresponds in overall to the solvents from first group, while steric inconsistencies for the interaction of AN and, especially, NM with H2O or D2O molecules decrease appreciably the hydrogen-bonding contribution to forming the water-containing “solvation complex”. The process of solvation of H2O or D2O molecules in solvents of the third group, namely, in N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), hexamethylphosphotriamide (HMPT), and dimethylsulphoxide (DMSO), where electron-donating abilities are higher than that of water, on the contrary, is accompanied by the formation of energetically more stable heterocomponent H- or D-bonds, compared to those existing in the “unary” aqueous medium. It was found that D2O‒H2O isotope effects (IE) in the standard molar enthalpy of water solvation are in rather good correlation with the energy of hydrogen bonding between H2O and an aprotic dipolar solvent. The specified enthalpy-isotope effects of solvation are also correlated in overall with the half-sum of donor and acceptor numbers (according to Gutmann) relating to the aprotic dipolar organic media being compared. The possibility of plotting the correct dependence of IE in the standard molar enthalpy of water solvation in amides on the solvent structuredness parameter (according to Ohtaki) was illustrated, too.
water H/D isotopologues, aprotic dipolar organic solvents, standard molar enthalpies of dissolution and solvation, isotope effects, hydrogen-bonding, donor-acceptor properties
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