Absolute rates of the carbon‐carbon dioxide reaction

The etch‐decoration transmission electron microscopy technique was used to measure the turnover frequencies of the C‐CO₂ reaction in the temperature range 600–900°C. The absolute rate constants of the elementary rate steps were determined, and were in reasonably good agreement with statistical theories. The rates on monolayer steps of graphite were higher than those on multilayer steps by approximately four orders of magnitude at 800°C, because the CO bond in the reaction intermediate is stronger by about 9 kcal/mol on the monolayer steps. The rates of vacancy formation in the lattice were also determined. The vacancies are formed by atomic oxygen dissociated from CO₂.