Interpretation of rate optima vs reaction parameters in steady state catalytic kinetics: molecular aspects beyond concentration dependences

A1 Journal article (refereed)

Internal Authors/Editors

Publication Details

List of Authors: Dmitry Yu.Murzin
Publication year: 2017
Journal: Molecular Catalysis
Journal acronym: Mol. Catal.
Volume number: 433
Start page: 321
End page: 333
eISSN: 2468-8231


Steady state catalytic reactions often exhibit rate maxima not only as a
function of concentration, but also of other reaction parameters such
as solvent polarity, Hammett substitution constants or metal cluster
size. Analysis of several generic schemes operative in homogeneous and
heterogeneous catalysis and comprise linear steps was made showing that
kinetic expressions after incorporating dependence of rate constants on
abovementioned reaction parameters can be used to model experimental
data. Rate minima in steady state reactions depending on substituent
constants cannot be easily explained by single route conventional
mechanisms even after considering nonlinear steps. Such cases are
conventionally explained by a switch in reaction mechanisms. An
alternative developed in this study assumes presence of mechanistically
similar parallel routes involving at least two different catalytically
active species. The advanced model based on two step sequence is capable
of explaining concave upward Hammett plots.


Chemical Engineering

Last updated on 2019-18-08 at 05:38