Dissociation Constants of Perchloric and Sulfuric Acids in Aqueous Solution

The Journal of Physical Chemistry. B
Alexander V LevanovValery V Lunin

Abstract

The experimental dissociation constants of strong acids are notoriously ill-defined, and it is necessary to rely on theoretical methods for their evaluation. We present a methodology for the theoretical evaluation of the dissociation constants, and the values of Ka for perchloric and sulfuric acids have been estimated. It has been shown that the acid dissociation constant Ka can be expressed as a product of two terms, Ka = Ka' × fHA∞, where Ka' is the apparent dissociation constant and fHA∞ is the infinite dilution activity coefficient of undissociated molecule of acid in liquid solution. The values of Ka' can be computed from readily available reference data. The limiting activity coefficients fHA∞ for strong acids can be determined by theoretical methods only. The following estimate for the limiting activity coefficients of perchloric and sulfuric acids has been obtained, -2.5 < log10  fHA∞ < -1.3. The ranges of values of the dissociation constants of HClO4 and H2SO4 at 25 °C have been determined; log10  Ka(HClO4) = 10.8-12.3; log10  Ka1(H2SO4) = 4.5-8.6.

References

Nov 19, 2005·The Journal of Chemical Physics·Patrick AyottePatrick Marchand
Apr 10, 2013·Biochimica Et Biophysica Acta·James T MuckermanYuko Wasada-Tsutsui
Nov 18, 2015·Journal of Chemical Theory and Computation·A KlamtJ Palomar
Feb 16, 2016·The Journal of Physical Chemistry. B·Junming Ho, Mehmed Z Ertem
Apr 27, 2016·The Journal of Physical Chemistry. a·Aleksander TrummalIvo Leito

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Citations

Oct 26, 2018·The Journal of Physical Chemistry. a·Daniel MausGregor Jung

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