Ys. Ho et al., CALORIMETRIC STUDY ON INTERACTION OF DIOXYGEN WITH ALUMINA-SUPPORTED PALLADIUM, Journal of molecular catalysis. A, Chemical, 112(2), 1996, pp. 287-294
Pd/Al2O3 samples of various palladium loadings were prepared with the
incipient-wetness method. With an increase in the palladium loading, t
he average diameter (d) of palladium crystallites on these samples was
estimated from chemisorption of hydrogen to vary from 10 to 80 Angstr
om. Also, the phenomena of oxidizing these dispersed palladium crystal
lites with dioxygen were studied by a simultaneous TG-DSC instrument.
The extent of oxidation was found to increase in three steps with temp
erature: adsorption on the surface of Pd crystallites at ambient or lo
wer temperatures, penetration of oxygen into the sublayer when raising
the temperature over 300 K, and formation of palladium oxide structur
e at 800 K. The heat evolved during oxygen adsorption on palladium cry
stallites depended on their average diameter (d) and displayed a relat
ionship of - Q(ad) [kJ (mol O-2)(-1)] = 373 - 14d (nm). Evolved heat u
pon palladium oxidation decreased with the extent of oxidation (N-O/N-
Pd ratio in the product). Upon the complete oxidation at 800 K, a diam
eter independent Delta(f)H(298)degrees(PdO) of - 187 +/- 2 kJ (mol O-2
)(-1) was subsequently obtained. This value differs significantly from
the literature Delta H(298)degrees(PdO) values (- 220 kJ (mol O-2)(-1
)) obtained from the Clausius-Clapeyron equation. The discrepancy shou
ld have resulted from a partial desorption of oxygen from PdO during m
easurement.