Boreskov molecularity

The Catalysis of Isotopic Exchange in Molecular Oxygen G. K. Boreskov... 

It is important to remember that if the Horiuti Boreskov relationship is vahd at any concentrations of external reactants, then both of the formal molecularities of the stepwise reaction remain constant as well. Note also that in most cases, the Horiuti Boreskov relationship may not be vaftd for the stationary occurrence of stepwise reactions with transformations that are nonlinear in respect to the intermediates. The formal moleculari ties of the entire stepwise process in such cases may change upon variations in the concentrations of the external reactants. 

The failure of the Horiuti Boreskov relationship and the possibility of changing the formal molecularities of a stepwise reaction can be demon strated in the following simple example. Let us consider a stepwise process... 

G.K. Boreskov, Zhumal Pizicheskoi Khimii, Relationship between the Molecularity and Activation Energy of a Reaction in its Forward and Backward Direction, 19 (1 2) (1945) 92 95 (in Russian). 

The comparison with the activity with respect to the hydrogen oxidation is particularly reliable since this reaction was studied by Popovsky and Boreskov 36) on the same samples of oxides isotopic exchange in molecular oxygen had been investigated in other work (5). 

Anshiz AG, Sokolovskii VD, Boreskov GK, Boronin AI. (1977). Participation of Molecular-Oxygen in Formation of Complete Oxidation-Products Via a Concerted... 

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