title: Towards the experimental decomposition rate of carbonic acid (H2CO3) in aqueous solution.
abstract: Dry carbonic acid has recently been shown to be kinetically stable even at room temperature. Addition of water molecules reduces this stability significantly, and the decomposition (H2CO3 + nH2O --> (n+1)H2O + CO2) is extremely accelerated for n = 1, 2, 3. By including two water molecules, a reaction rate that is a factor of 3000 below the experimental one (10 s(-1)) at room temperature was found. In order to further remove the gap between experiment and theory, we increased the number of water molecules involved to 3 and took into consideration different mechanisms for thorough elucidation of the reaction. A mechanism whereby the reaction proceedes via a six-membered transition state turns out to be the most efficient one over the whole examined temperature range. The determined reaction rates approach experimental values in aqueous solution reasonably well; most especially, a significant increase in the rates in comparison to the decomposition reaction with fewer water molecules is found. Further agreement with experiment is found in the kinetic isotope effects (KIE) for the deuterated species. For water-free carbonic acid, the KIE (i.e., kH2CO3/kD2CO3) for the decomposition reaction is predicted to be 220 at 300 K, whereas it amounts to 2.2-3.0 for the investigated mechanisms including three water molecules. This result is therefore reasonably close to the experimental value of 2 (at 300 K). These KIEs are in much better accordance with the experiment than the KIE for decomposition with fewer water entities.
authors.affiliation: Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck, Austria.
authors.forename: Christofer S
authors.initials: CS
authors.lastname: Tautermann
authors.forename: Andreas F
authors.initials: AF
authors.lastname: Voegele
authors.forename: Thomas
authors.initials: T
authors.lastname: Loerting
authors.forename: Ingrid
authors.initials: I
authors.lastname: Kohl
authors.forename: Andreas
authors.initials: A
authors.lastname: Hallbrucker
authors.forename: Erwin
authors.initials: E
authors.lastname: Mayer
authors.forename: Klaus R
authors.initials: KR
authors.lastname: Liedl
mesh_terms: D002255:Carbonic Acid / Q000737:chemistry*; D002384:Catalysis; D055598:Chemical Phenomena; D002627:Chemistry, Physical; D003903:Deuterium / Q000737:chemistry; D007700:Kinetics; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D011522:Protons; D013696:Temperature; D014867:Water / Q000737:chemistry*
chemical_list: D011522:Protons; D014867:Water; D002255:Carbonic Acid; D003903:Deuterium