from first principles PP-I-1

PL-2Thermodynamics of Operating Catalyst: Some Approaches and FindingsParmon V.N.Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russiaparmon@catalysis.ruIn contrast to chemical kinetics, thermodynamics is so far not very actively used fordescribing the state and behavior of operating heterogeneous catalysts. The reason is indeedthe non-equilibrium state of operating catalysts that does not allow common equilibriumthermodynamics to be used. In the last decade, however, there was a progress inunderstanding how the approaches of non-equilibrium thermodynamics could be applied tooperating catalysts.The presentation gives few examples of such applications. There are, first of all, explanationof superlow temperature of melting nanoparticles of metal catalysts active in carbon nanofiberproduction, semiquantitative description of the size effect for at least metal catalysts,possibility to couple or even convert direction of undesirable processes with the desirableones, as well as ideas about possibility to change the stationary phase state of the operatingcatalytically active components via controlling the composition of the surrounding reactivemixture. It is also shown that a quite typical situation for catalytic processes is notcoincidence of the rate-controlling step and the “bottle neck” (limiting step) of the overallprocess.References:Valentin Parmon, Thermodynamics of Non-Equilibrium Processes for Chemists with a ParticularApplication to Catalysis, Elsevier, 2010, 340 p.8