Brønsted-Evans-Polanyi relation of multistep reactions and volcano curve in heterogeneous catalysis

Journal of Physical Chemistry C

Volumn 112, Issue 5, 2008, Pages 1308-1311

  Cheng, Jun ^a   Hu, P ^a   Ellis, Peter ^b   French, Sam ^b   Kelly, Gordon ^b   Lok, C Martin ^b  

^a QUEEN'S UNIVERSITY BELFAST   (United Kingdom)

^b JOHNSON MATTHEY TECHNOLOGY CENTRE   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ASSOCIATION REACTIONS; DESORPTION; KINETICS;

KINETIC ANALYSIS; VOLCANO CURVES;

CATALYSIS;

EID: 39649098709     PISSN: 19327447     EISSN: 19327455     Source Type: Journal    
DOI: 10.1021/jp711191j     Document Type: Article

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26. It should be noted that there are some negative barriers because the molecule in the gas phase was selected as an IS. There are good reasons for choosing this reference state: (i) In a typical molecular dissociation reaction, there are two elementary steps; molecular adsorption and the dissociation of the adsorbed molecule. The molecular adsorption step and its reverse step (the molecular desorption) can usually reach quasi-equilibrium. Then the state of the molecule in the gas phase is kinetically equivalent to the state of the adsorbed molecule on the surface, (ii) The advantage of taking the molecule in the gas phase as a reference state is that this state is the same for the molecule to dissociate on different metal surfaces. Thus, one can readily obtain trends of molecular dissociation on different surfaces.