Abstract
AbstractIn this paper Campbell's degree of rate control is extended to introduce the concepts of degree of kinetic rate control, degree of kinetic selectivity control, degree of thermodynamic rate control and degree of thermodynamic selectivity control. It is demonstrated by applying hypothetical but realistic kinetic models of varying complexity that the new methods offers a rigorous framework to analyze the importance of kinetic and thermodynamic parameters i.e. establishing the critical parameters of the kinetic model. The methods are general and can be applied to complex reaction networks with multiple overall reactions not only in heterogeneous catalysis but for all sorts of chemical kinetic models.
Highlights
Microkinetic modeling has become an important tool in bridging the gap between experimental and theoretical surface science and heterogeneous catalysis at industrial relevant conditions [1,2,3,4,5,6,7] and references therein.In microkinetic modeling the outcome of one or multiple overall reactions is modeled as a consequence of a detailed reaction mechanism
We have found that the sum rule apply for all steadystate kinetic models investigated in the present paper including complex reaction networks with multiple overall reactions
This is similar to the previous findings applying the degree of kinetic and thermodynamic rate control where the stability of A* is critical and the degree of rate control showed that step 1 is rate limiting and inhibiting
Summary
Microkinetic modeling has become an important tool in bridging the gap between experimental and theoretical surface science and heterogeneous catalysis at industrial relevant conditions [1,2,3,4,5,6,7] and references therein. The challenge in analyzing microkinetic models is to accurately pin point these rate-controlling reaction steps and intermediates. Obtaining this information, is pivotal in order to identify which knob to turn in order to design the optimal catalyst. A general concept of rate-control has been formulated by the authors [8] in which it is possible to pin point exactly which key transition states and key reaction intermediates are important by making small changes to their energies and determining the sensitivity of the net reaction rate to these changes (see [9,10,11]).
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