Decoupling the Arrhenius equation via mechanochemistry

Abstract

We identified three different energetic regions that we believe are defining characteristics of most, if not all mechanochemical reactions. For a given ball mill's region, activation energy determines whether a reaction is energetically easy (Region I), challenging (Region II), or forbidden (Region III). In Region II, yield depends exponentially on oscillation frequency. Modifications granted control of the locations of Regions I, II, and III.

Thermal and Mechanical Stability of Immobilized Candida antarctica Lipase B: an Approximation to Mechanochemical Energetics in Enzyme Catalysis.

“…Indeed, temperature analysis during mechanochemical reactions as well as the energy transfer mechanisms from the milling‐jar and balls to the reactants are cutting‐edge topics in the study of mechanochemical transformations . In this context, the enantiopreference of a biocatalyst ( E ) in an enzymatic resolution is a temperature dependent process .…”

“…Indeed, temperature analysis during mechanochemical reactions as well as the energy transfer mechanisms from the milling-jar and balls to the reactants are cutting-edge topics in the study of mechanochemical transformations. [43][44][45] In this context, the enantiopreference of a biocatalyst (E) in an enzymatic resolution is a temperature dependent process. [46] Thus, an adequate assessment of a stereoselective reaction performed under conventional heating and stirring conditions vis-a-vis mechanical activation could lead to an estimation of the approximate temperature range for the process and could help to clarify the extend of inactivation due to mechanical stress.…”

Recent Advances in Mechanochemical Organic Synthesis

“…Some cycloaddition reactions were carried out in ball mill for the first time. A mechanistic study of Diels-Alder reactions of selected anthracenes by Arrhenius kinetics was reported by Andersen and Mack [70]. The array of 1,3-dipolar cycloaddition reactions is recently extended with nitrones [71] and nitrile oxides [72].…”

Oxidative Mechanochemistry: Direct, Room‐Temperature, Solvent‐Free Conversion of Palladium and Gold Metals into Soluble Salts and Coordination Complexes

“…Crystallization from water gave crystals of K 2 PdCl 4 , which was identified by comparison of the measured crystallographic unit cell to that of the published one (see the Supporting Information). Milder milling using Teflon jars enabled the observation of X‐ray reflections of K 2 PdCl 4 in the diffraction pattern of the crude mixture. Similar results were obtained with NH 4 Cl as the halide source, and subsequent solution 15 N NMR analysis revealed the presence of a single type of nitrogen center, which was consistent with NH 4 + ions and the absence of ammine complexes (see the Supporting Information).…”