Unveiling mechanochemistry: Kinematic-kinetic approach for the prediction of mechanically induced reactions

Abstract

Mechanochemistry has attracted a lot of attention over the last few decades with a rapid growth in the number of publications due to its unique features. However, very little is known about how mechanical energy is converted into chemical energy. Most of the published works using mechanochemistry neglect the required attention to the experimental parameters and their effect over the resulting products, what makes extremely difficult to reproduce the results from lab to lab. Moreover, if it is taken into consideration the broad range of experimental conditions used in different studies, it is quite difficult to compare results and set optimum conditions. As a result, mechanochemistry is generally viewed as a "black box". The aim of this work is to provide some insight into mechanochemistry. Thus, a simple kinematic-kinetic approach that allows the full parametrization of mechanically induced reactions is proposed. In an analogous way to thermally activated process, it is shown that kinetic modeling can serve to parametrize and model mechanically induced reactions as a function of the milling parameters with great reliability, thereby gaining prediction capability. As a way of example, this methodology has been applied for the first time to the mechanochemical reaction of Co and Sb to form CoSb3, a skutterudite-type thermoelectric material. Moreover, the universality of this methodology has also been validated with data from the literature. A key feature of the proposed kinematickinetic approach is that it can be extrapolated to other mechanically induced reactions, either inorganic or organic.

The mechanochemical synthesis of polymers

“…• The milling parameters play a major role in enabling and controlling mechanochemical reactions. 56,58–60…”

Controlling Nonlinear Dynamics of Milling Bodies in Mechanochemical Devices Driven by Pendular Forcing

“…On the basis of these first results, we check the existence of a guiding criterion to predict the typology of dynamical regimes on the basis of the relative size of the reactor and the milling body. This represents a contribution on the way towards a unifying parametrization of mechanochemical devices, which could help the reproducibility and the scaling-up of the results of mechanical processing, which are carried out in a plethora of different experimental conditions (Gil-González et al, 2021). We finally investigate systematically the effect of an asymmetric forcing on the milling body dynamics.…”

Elucidation of the Diels–Alder Reaction Kinetics between Diphenylfulvene and Maleimide by Mechanochemistry and in Solution

“…They are supported by dislocation and phonon and short-live-active center theories. − In-situ analyses by X-ray powder diffraction and Raman spectroscopy have allowed a complete quantification of the kinetics to understand the chemo-mechanical reactivity . It has also been reported by us and others that some reactions follow zero-order kinetics. − In recent years, different phenomenological models have been applied to ball mill reactions to describe the apparent kinetics of mechanochemical transformations. , In their principles these approaches take into account the very efficient stirring of the powder in the milling vessel leading to a global chemical homogeneity. However, depending on the critical loading conditions (CLCs), the activation of the transformation occurs in a small fraction of the powder which is trapped in the colliding zone of the milling media.…”