Quantum Chemical Investigation of Perchloric Acid Decomposition Releasing Oxygen.

The primary objectives of this study are to identify the initiation steps of perchloric acid (HClO4) decomposition and to validate and provide insights into the reaction pathways of O2 formation. To this end, we have performed quantum chemical calculations using the Gaussian 09 program package to identify new reaction pathways and species formed during decomposition. The thermodynamic quantities of the species, such as Gibbs free energy and enthalpy, are calculated using a double-hybrid density functional theory method, B2PLYP, with Jensen's basis set, aug-pc2. For heavy atoms, such as chlorine, the basis set is augmented by adding 2 d functions with a stride factor of 2.5. To incorporate the solvation effect, the conductor-like polarizable continuum model, which is an implicit solvation model, is used. Numerical simulations using a control-volume analysis of an experiment are also performed using the proposed mechanism. In these simulations, rates of the reactions are calculated using transition state theory, incorporating diffusion effects on the rate constants. In order to consider the nonideal behavior of a concentrated HClO4 solution, activity coefficients are used to calculate the effective concentration of acid in solution. The activity coefficient of HClO4 plays a critical role in the calculation of the induction period involved in the HClO4 decomposition. A comparison of numerically predicted O2 evolution and duration of the induction period with experimental data shows that the numerical simulation using the proposed mechanism predicts both the three-stage decomposition characteristics and the induction period observed during HClO4 decomposition, thus validating the proposed mechanism.