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

By W G Frankenberg

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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. Some information comes from the absolute values of heats of chemisorption of oxygen when the adsorption is studied under different conditions. /mole. One cannot perhaps state unequivocally that these two widely different heats represent intrinsically different modes of oxygen chemisorption (because there may be a strong dependence of the heat of adsorption on coverage), but the result is certainly suggestive.

26 F. S. STONE It is interesting to remark that the concept of two different forms of oxygen chemisorption on zinc oxide has recently received support froin a quite independent type of experimental study. 96 is critically dependent on the temperature a t which oxygen has been adsorbed. The signal (studied a t 24’) was quenched very much more effectively by chemisorption a t 25” than by chemisorption a t 400”. Kokes goes on to show that the dependence of the signal on coverage is consistent with a chemisorption a t 25” which withdraws electrons and is of the O&,) type, but a t 400’ a type of chemisorption is present which removes interstitial zinc, thus confirming in a very large measure the conclusions drawn earlier from the studies of kinetics.

These observations provided very important background to the developments described in Sections II,B and II,D, where the hypothesis of a common COa complex, capable of being prepared by various routes and active as an intermediate in the catalytic reaction, was put forward. 7. Resistance changes during the reaction between carbon monoxide and oxygen on cuprous oxide at 20". The conductivity method offers considerable scope for analysis of the kinetics of adsorption and desorption, particularly of oxygen, and Gray and his co-authors (56-59) have made this the main theme of several of their publications.

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