The carbon formation/gasification equilibrium on silica-supported nick
el and nickel-copper catalysts in CO + CO2 gas mixtures and the steady
state kinetics of carbon formation from CO on the same catalysts were
studied in a thermogravimetric flow system. The equilibrium gas compo
sition was found to be the same for the nickel and the nickel-copper c
atalysts except at the highest copper concentrations (greater-than-or-
equal-to 25 at.%), where larger deviations from graphite equilibrium w
ere found at the lowest temperature (673 K). The deviations at equilib
rium of the free energy, DELTAG(c), from the value calculated for grap
hite equilibrium were larger than found previously for carbon formatio
n in CH4 + H-2 gas mixtures. The steady-state kinetic results have bee
n modelled by using a simple Langmuir model with one type of sites. In
contrast to some previous studies of carbon formation from CO the pre
sent kinetic results are well described by a model in which the surfac
e reaction of two CO molecules to form carbon and CO2 is the rate-limi
ting step at temperatures below about 680 K and CO pressures in the ra
nge 15-50 kPa. At higher temperatures and pressures, the experimental
rates fall below the model rates, probably due to diffusion limitation
s and to the partial coverage of the active surface by graphitic carbo
n. The conflict whereby a model with CO dissociation as the rate-limit
ing step gives a better description of the results of some previous ki
netic studies of carbon formation from CO is suggested to be resolved
by assuming that the latter model is valid when the CO pressure is low
or when the gas contains CO2. (C) 1994 Academic Press, Inc.