The gas phase reaction between CO2 and lanthanide atoms. A test of a model for the isokinetic effect

Abstract

Using literature data on the gas phase reaction between free lanthanide atoms and carbon dioxide, we have found an isokinetic relation for seven of the twelve investigated elements with an isokinetic temperature, T iso , of 2500±330 K. This value is analyzed in the framework of the model of selective energy transfer, SET, indicating that metal-CO 2 complexes are formed as pre-reaction states. The result is in accordance with the fundamental concepts of SET.

Some tentative explanations for the enthalpy–entropy compensation effect in chemical kinetics: from experimental errors to the Hinshelwood-like model

“…The list of proposals considered hereafter does not try to be exhaustive, but only illustrative of the complexity of the problem analysed. Other plausible theoretical approximations have already been published by other authors [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21].…”

Isokinetic behaviour in gas phase catalytic haloarene hydrodehalogenation reactions: Mechanistic considerations

“…A further confirmation of the (pragmatic) value of the SET approach has recently been presented [27]. In treating the gas phase, non-catalytic reaction between carbon dioxide and free lanthanide atoms, the kinetics of which had been described by Campbell [28], it was demonstrated [27] that the isokinetic relation found for some of the lanthanide elements was described not by Eq. (2) that relates to condensed systems, but by the corresponding relation…”

“…the catalytic oxidation of propene and toluene [22], the catalytic hydrogenolysis of neopentane [23], a homogeneous non-catalytic (ligand substitution) reaction [24], the reaction of carbon dioxide at metal surfaces [25] and the hydrogenolysis of ethane [26]. A further confirmation of the (pragmatic) value of the SET approach has recently been presented [27]. In treating the gas phase, non-catalytic reaction between carbon dioxide and free lanthanide atoms, the kinetics of which had been described by Campbell [28], it was demonstrated [27] that the isokinetic relation found for some of the lanthanide elements was described not by Eq.…”

A SET Approach to the Interplay of Catalysts and Reactants

“…[23] for Nb. In a later paper, Larsson and Mascetti [24] also adapted this view to the lanthanides. Since Campbell et al [21] had obtained data characterizing the Arrhenius lines for the systems they investigated, it was easy to check on whether or not an isokinetic effect could be noted.…”