Apparent Stoichiometry of Water in Proton Hydration and Proton Dehydration Reactions in CH3CN/H2O Solutions

作者：Kalish Noa Ben Menachem; Shandalov Elisabetha; Kharlanov Vladimir; Pines Dina; Pines Ehud^*

来源：Journal of Physical Chemistry A, 2011, 115(16): 4063-4075.

DOI：10.1021/jp110873t

Gradual solvation of protons by water is observed in liquids by mixing strong mineral acids with various amounts of water in acetonitrile solutions, a process which prey:Motes rapid dissociation of the acids in these solutions. The stoichiometry of the reaction XH+ + n(H2O) = X + (H2O)(n)H+ was studied for strong mineral acids (negatively charged X, X = ClO(4) over bar, C (l) over bar, B (r) over bar, (I) over bar, CF3SO(3) over bar) and for strong cationic acids (uncharged X, X = R*NH2, H2O). We have found by direct quantitative analysis preference of n = 2 over n = 1 for both groups cif proton transfer reactions at relatively low water concentrations in acetonitrile. At high water concentrations, we have found that larger water solvates must also be involved in the solvation of the proton while the spectral features already observed for n = 2, H+(H2O)(2), remain almost unchanged at large n values up to at least 10 M of water.

• 出版日期2011-4-28