Reaction Mechanism of the Reduction of Ozone on Graphite

The kinetics of the ozonation of graphite with different particle sizes (106 μm, G₁₀₆; 6.20 μm, G_6.2) was studied at several temperatures under a flow of O₃ diluted in O₂. The reaction was first-order with respect to graphite and to the consumption of ozone. X-ray photoelectron spectrum (XPS) showed that the reactions occurring in the solid under steady-state conditions maintain the original stoichiometry, as predicted by the postulated mechanism for SO₂. The deoxygenation reaction occurred along with the ozonation reaction at 100 °C. The rate of oxygen elimination in the flow system has the same rate-determining kinetic barrier as ozone insertion. Ozonation and deoxygenation reactions are sequentially related. Ozonation occurs with the insertion of O₃, forming a 1,2,3-trioxolane followed by an oxygen transfer that produces a peroxide valence tautomer in equilibrium with 1,3-dicarbonyl, [peroxide ↔ dicarbonyl], and an oxirene that eliminates atomic oxygen. The decarboxylation reaction was studied at 600 °C from the ozonated G₁₀₆ (ΔG^≠ = 83.60 ± 0.08 kcal·mol^-1). Total decarboxylation at 600 °C matched the number of moles of CO₂ removed and the oxygen content after ozonation, showing that the reduction of ozone on graphite was essentially a clean reduction with no secondary oxidations. When ozonized graphite was heated to 600 °C, only [peroxide ↔ dicarbonyl] species remained in the matrix. The peroxide tautomer isomerized to dioxirane and eliminated CO₂ as a dioxicarbene. Total deoxygenation of decarboxylated graphite G₁₀₆ was obtained by pyrolysis. There was residual oxygen that arose from the atomic oxygen eliminated from the oxirene, intercalated in graphite layers, and formed basal epoxy groups. Also, incoming O atoms reacted with the intercalated O atoms to produce O₂ molecules. Thermal annealing deintercalated molecular oxygen (600-900 °C).