By W G Frankenberg

ISBN-10: 0080565174

ISBN-13: 9780080565170

ISBN-10: 0120078139

ISBN-13: 9780120078134

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Knowing from the first increments the heat of formation of the complex and knowing the standard heat of formation of COZ,the sudden fall in heat to be expected when reaction (4) takes over from reaction (5) can be calculated. /mole, in good agreement with the experimental value. Turning to nickel oxide, the thermochemical data of Tables I1 and I V show that the oxidation via the C03 complex should be more difficult than on cuprous oxide or cobaltous oxide. The various reaction paths are shown schematically in Fig.

For formaldehyde formation C2H4(,) 2 0 ( a d a ) = 2CHz0(ads),the heat is about 100 kcal. Thus one may judge that one molecule is often reacting with two atoms of adsorbed oxygen in the initial increments, but with later increments t,he main reaction is with single atoms to give adsorbed acetaldehyde or ethylene oxide. + IV. The Emergence and Significance of the Electronic Factor A. SEMICONDUCTIVITY CHANGESDUI~ING CHEMISORPTION The equilibrium nonstoichiometry of oxides a s a function of oxygen pressure at high temperatures can be conveniently studied by measurcmcnts of their semiconductivity, a method much exploited by Wagner arid his co-workers (39) in the nineteen-thirties, and inasmuch as chemisorption of oxygen and other gases is held to involve electron transfer and the formation of ions the same method should be applicable to studies of adsorption and catalysis, even a t low temperatures.

STONE The distinctions most easily drawn are those between physically and chemically adsorbed oxygen. Beebe and Dowden (44) showed that this could be achieved calorimetrically. With chromia a t - 183", a slow liberation of heat without any further uptake of oxygen gave evidence of the transformation from the physically adsorbed to a chemisorbed state. /mole. /mole) has been observed calorimetrically with uranium dioxide a t - 183" by Ferguson and McConnell (45). We are more concerned in this review with distinctions between the various chemisorbed states of oxygen.

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Advances in Catalysis and Related Subjects, Volume 13 by W G Frankenberg

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