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    Feedback Kinetics in Mechanochemistry: The Importance of Cohesive States.

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    Publication date
    2017-11-27
    Author
    Hutchings, B.P.
    Crawford, Deborah E.
    Gao, L.
    Hu, P.
    James, S.L.
    Keyword
    Feedback cycles
    Kinetics
    Mechanochemistry
    Solid-state reactions
    Sustainable chemistry
    Peer-Reviewed
    Yes
    
    Metadata
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    Abstract
    Although mechanochemical synthesis is becoming more widely applied and even commercialised, greater basic understanding is needed if the field is to progress on less of a trial‐and‐error basis. We report that a mechanochemical reaction in a ball mill exhibits unusual sigmoidal feedback kinetics that differ dramatically from the simple first‐order kinetics for the same reaction in solution. An induction period is followed by a rapid increase in reaction rate before the rate decreases again as the reaction goes to completion. The origin of these unusual kinetics is found to be a feedback cycle involving both chemical and mechanical factors. During the reaction the physical form of the reaction mixture changes from a powder to a cohesive rubber‐like state, and this results in the observed reaction rate increase. The study reveals that non‐obvious and dynamic rheological changes in the reaction mixture must be appreciated to understand how mechanochemical reactions progress.
    URI
    http://hdl.handle.net/10454/17635
    Version
    No full-text in the repository
    Citation
    Hutchings BP, Crawford DE, Gao L et al (2017) Feedback Kinetics in Mechanochemistry: The Importance of Cohesive States. Angewandte Chemie - International Edition. 56(48): 15252-15256.
    Link to publisher’s version
    https://doi.org/10.1002/anie.201706723
    Type
    Article
    Collections
    Engineering and Informatics Publications

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