Proton-donating power of 100% perchloric acid: An MP2 study |
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Authors: | V N Solkan V B Kazanskii |
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Institution: | 1.Zelinsky Institute of Organic Chemistry,Russian Academy of Sciences,Moscow,Russia |
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Abstract: | The ab initio quantum chemical method MP2 with a 6-311++G(d, p) basis set is used to calculate the energy of gas-phase solvation of the H2Cl4+ cation and Cl4− anion by one perchloric acid molecule. The energy of additional solvation of the resulting complexes by liquid perchloric
acid is estimated within the continuum model of solvation by the PCM method, with the acid modeled as a continuum with a large
dielectric constant of ɛ = 115. The calculated data have provided an almost quantitative estimate for the energy of selfionization
of 100% liquid perchloric acid. The similarly calculated energy of solvation of protons by 100% perchloric acid is 30.7 kcal/mol
lower than the heat of hydration of protons in aqueous solution. This result explains the fact that anhydrous perchloric acid
exhibits the properties of a superacid. |
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