Studies on the formation of Graphite-Ferric Chloride complexes: Kinetics of Formation

Abstract

A study has been made of the kinetics of the diffusion of anhydrous FeC1, in graphite. I t was found that this process can be represented for stages between 50 and 100 per cent. saturation of the graphite and at temperatures in the range 200 to 360 OC by a relation of the type

δc/δt = D(δ²c/δr² + δc/δ/r),

providing the diffusion coefficient D is assigned several values for concentrations of occluded FeCl₃ above and below a critical concentration. The value of the latter was found to be about two-thirds the saturation concentration of FeCl₃ in graphite, this value apparently being the point at which open hexagonal packing of intercalated ferric ions is complete and a closer hexagonal packing commences. Values of the activation energies of occlusion for concentrations above and below two-thirds saturation were found from the relations of corresponding values of diffusion coefficients to temper- ature. The small difference between these activation energies which were of the order of 2 to 3 kcal is attributed to a cancelling of effects, thus the energy necessary to separate carbon lamellae in early stages of occlusion is offset in later stages by hindrance imposed on diffusing molecules by those already occluded. Reduction of particle size of graphite accelerated the occlusion of FeCl₃.