The surface and tribological chemistry of carbon tetrachloride on iron

The thermal decomposition of carbon tetrachloride on clean iron was studied in ultrahigh vacuum using molecular beam strategies, where it is found that carbon tetrachloride thermally decomposes on the surface to deposit iron and carbon with exactly identical kinetics as found at high pressures. No gas‐phase products are detected and the activation energy for the reaction (14.2 ± 0.5 kcal/mol) is in good agreement with the value measured at high pressures. Little carbon is detected on the surface using Auger spectroscopy following reaction and it is found that this diffuses into the surface much faster when formed from CCl4 than from CH2Cl2. This effect is ascribed to the effect of co‐adsorbed chlorine on the adsorbed carbon, which is proposed to decrease the activation energy for diffusion into the bulk of the sample. This effect explains the increased tendency for carbon tetrachloride to form carbides under extreme‐pressure tribological conditions.