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Review of the molar heats of chemisorption and chemabsorption by crystalline oxides and the surface “homogeneity versus heterogeneity” problem

Review of the molar heats of chemisorption and chemabsorption by crystalline oxides and the surface “homogeneity versus heterogeneity” problem

ISSN:1388-6150
2012年第108卷第2期

To obtain a solution of the surface “homogeneity versus heterogeneity” problem, the results of microcalorimetric measurements of the dependences of the molar heats of chemisorption and chemabsorption of different gases on the amounts of chemisorbed or chemabsorbed gases in more than 20 gas/metal-oxide systems, in which the molar chemisorption heats are coverage-independent over rather wide ranges of the surface coverages, are presented. In order to approach the states of the metal oxide samples to those in real catalytic processes catalyzed by these oxides, the coverage dependences of the heats of chemisorption of gases at the samples were measured for a number of gas/metal-oxide systems against the chemisorbed amounts of not only the gas under study but also of another gas chemisorbed previously. The calorimetric data-set is supplemented with data obtained by other methods capable of helping to solve the surface “homogeneity versus heterogeneity” problem. These data are discussed together with the data on chemisorption in more than 40 gas/metal systems for which homogeneity of the surfaces was stated in our previous review. The entire set of the measurements was published for several decades by about 40 different composite authors. The chemisorption and chemabsorption mechanisms are discussed. It is concluded that thermally stabilized powder metal and metal oxide surfaces are homogeneous relative to the chemical ability of their atoms in chemisorption and catalytic processes in line with Langmuir’s opinion and the band theory of solids.

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ISSN:1388-6150
2012年第108卷第2期

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