How Acidic Is Carbonic Acid?

作者：Pines Dina; Ditkovich Julia; Mukra Tzach; Miller Yifat; Kiefer Philip M; Daschakraborty Snehasis; Hynes James T^*; Pines Ehud^*

来源：Journal of Physical Chemistry B, 2016, 120(9): 2440-2451.

DOI：10.1021/acs.jpcb.5b12428

Carbonic, lactic, and pyruvic acids have been generated in aqueous solution by the transient protonation of their corresponding conjugate bases by a tailor-made photo acid, the 6-hydroxy-1-sulfonate pyrene sodium salt molecule. A particular goal is to establish the pK(a) of carbonic acid H2CO3. The on-contact proton transfer (PT) reaction rate from the optically excited photoacid to the carboxylic bases was derived, with unprecedented precision, from time-correlated single photon-counting measurements of the fluorescence lifetime of the photoacid in the presence of the proton acceptors. The time-dependent diffusion-assisted PT rate was analyzed using the Szabo-Collins-Kimball equation with a radiation boundary condition. The on-contact PT rates were found to follow the acidity order of the carboxylic acids: the stronger was the acid, the slower was the PT reaction to its conjugate base. The plc of carbonic acid was found to be 3.49 +/- 0.05 using both the Marcus and Kiefer-Hynes free energy correlations. This establishes H2CO3 as being 0.37 pKa units stronger and about 1 pKa unit weaker, respectively, than the physiologically important lactic and pyruvic acids. The considerable acid strength of intact carbonic acid indicates that it is an important protonation agent under physiological conditions.

• 出版日期2016-3-10