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Mechanistic interpretation of orders in catalyst greater than one

Nature Reviews Chemistry volume 7, pages 26–34 (2023)Cite this article

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Abstract

Orders in catalyst greater than one can be attributed to several different reaction mechanisms. Differentiating among these possibilities requires careful analysis of their rate laws, rational experiment design and accurate measurement of the progress of the reactions. We have compiled the most popular mechanisms proposed for reactions with an order in catalyst greater than one and derived their steady-state rate laws. We have analysed the rate laws and proposed experiments to discern between mechanisms. Finally, we have examined 100 case studies that showcase good practices to propose robust mechanisms and to avoid common pitfalls.

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Fig. 1: Scenarios responsible for the order in catalyst greater than one.
Fig. 2: Differentiating between inhibition mechanisms.
Fig. 3: Differentiating mechanisms M3 (off-cycle dimerization) and M1 (complete catalyst inhibition).
Fig. 4: The use of uncorrected rates measured at different concentrations of reactants can lead to errors in the determined order of reaction in catalyst.
Fig. 5: Popular methods used to estimate the order of reaction in catalyst.
Fig. 6: Plots of ro against \({[{\rm{cat}}]}_{{\rm{T}}}^{{\rm{\alpha }}}\) can be misleading.
Fig. 7: The fitting of non-perfectly aligned log–log data results in an incorrect estimation of the order in catalyst.

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Data availability

Fitting results are available in the Supplementary Information.

Change history

  • 09 January 2023

    In the version of this article initially published, the Supplementary information, “Fitting results” were missing and are now included in the online version of the article.

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Acknowledgements

We thank many colleagues for useful and inspiring discussions over the years, especially Prof. Donna Blackmond, Prof. Alan Armstrong, Prof. Igor Larrosa, Prof. Jason Hein and Dr. David Sale. We also thank all the authors of the case studies analysed in the Supplementary Information for the data reported. We acknowledge funding from the EPSRC projects EP/S005315/1, EP/R513131/1 and EP/T030666/1.

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  1. These authors contributed equally: Carla Alamillo-Ferrer, George Hutchinson.

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  1. Department of Chemistry, The University of Manchester, Manchester, UK

    Carla Alamillo-Ferrer, George Hutchinson & Jordi Burés

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  1. Carla Alamillo-Ferrer
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  2. George Hutchinson
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J.B. conceived the Review and wrote the manuscript. C.A.-F. and G.H. analysed the data and wrote the Supplementary Information.

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Correspondence to Jordi Burés.

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Alamillo-Ferrer, C., Hutchinson, G. & Burés, J. Mechanistic interpretation of orders in catalyst greater than one. Nat Rev Chem 7, 26–34 (2023). https://doi.org/10.1038/s41570-022-00447-w

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