Transmission infrared spectroscopy was used to monitor CClx(a) interme
diate surface species formed during the decomposition of CCl4 on high
surface area calcium oxide. Carbon tetrachloride was adsorbed on calci
um oxide at 113 K. During CCl4 desorption, additional infrared bands a
t 801, 787, 775, 765, and 751 cm(-1) were observed in the temperature
range 110-250 K. These bands, which disappeared in the temperature ran
ge 150-250 K, were attributed to the formation and depletion of CClx(a
) species as C-Cl bonds are broken and Ca-Cl bonds are formed on the C
aO surface. Carbon tetrachloride (C-13 labeled) was employed to prove
that the infrared bands of the surface intermediates were due to C-CI
vibrational modes. To compare carbon tetrachloride decomposition on di
fferent types of calcium oxides, both autoclave prepared (nanoscale pa
rticles) and conventionally prepared CaO were investigated.