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Issue 8, 2017
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Decoupling the Arrhenius equation via mechanochemistry

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Mechanochemistry continues to reveal new possibilities in chemistry including the opportunity for “greening” reactions. Nevertheless, a clear understanding of the energetic transformations within mechanochemical systems remains elusive. We employed a uniquely modified ball mill and strategically chosen Diels–Alder reactions to evaluate the role of several ball-milling variables. This revealed three different energetic regions that we believe are defining characteristics of most, if not all, mechanochemical reactors. Relative to the locations of a given ball mill's regions, activation energy determines whether a reaction is energetically easy (Region I), challenging (Region II), or unreasonable (Region III) in a given timeframe. It is in Region II, that great sensitivity to mechanochemical conditions such as vial material and oscillation frequency emerge. Our unique modifications granted control of reaction vessel temperature, which in turn allowed control of the locations of Regions I, II, and III for our mill. Taken together, these results suggest envisioning vibratory mills (and likely other mechanochemical methodologies) as molecular-collision facilitating devices that act upon molecules occupying a thermally-derived energy distribution. This unifies ball-milling energetics with solution-reaction energetics via a common tie to the Arrhenius equation, but gives mechanochemistry the unique opportunity to influence either half of the equation. In light of this, we discuss a strategy for translating solvent-based reaction conditions to ball milling conditions. Lastly, we posit that the extra control via frequency factor grants mechanochemistry the potential for greater selectivity than conventional solution reactions.

Graphical abstract: Decoupling the Arrhenius equation via mechanochemistry

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Publication details

The article was received on 05 Feb 2017, accepted on 28 May 2017 and first published on 30 May 2017

Article type: Edge Article
DOI: 10.1039/C7SC00538E
Citation: Chem. Sci., 2017,8, 5447-5453
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    Decoupling the Arrhenius equation via mechanochemistry

    J. M. Andersen and J. Mack, Chem. Sci., 2017, 8, 5447
    DOI: 10.1039/C7SC00538E

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