Quantum chemical modeling of the structure formation and proton transfer in 2-hydroxybenzenesulfonic, 4-hydroxy-1,3-benzenedisulfonic, and 1,3-benzenedisulfonic acids

Abstract

Hydrate clusters of 2-hydroxybenzenesulfonic and 1,3-benzenedisulfonic acids were calculated in terms of the density functional theory (DFT) by the B3LYP/6-31G** method. The process of water adsorption on the crystal surface of 4-hydroxy-1,3-benzenedisulfonic acid dihydrate was simulated using the generalized gradient approximation (DFT/PBE) and periodic boundary conditions. For the model system (OHC6H4SO3 −)·H5O2 +, the activation barriers for the proton transfer were calculated depending on the distance between the O atoms and the deviation of the proton from the O...O bond line. The presence of one H2O molecule per SO3H group is energetically most favorable for the formation of clusters of 1,3-benzenedisulfonic acid containing a stoichiometric amount of water. The simulation of the hydration of 4-hydroxy-1,3-benzenedisulfonic acid dihydrate (OHC6H3(SO3H)2·2 H2O + n H2O, n = 1–3) showed that the superstoichiometric H2O molecule is adsorbed on the crystal surface of this dihydrate with energy release of 0.75–0.95 eV. The position of this water molecule is less favorable in the bulk than on the surface.