Degrees of Rate Control at Non(pseudo)steady-State Conditions

Journal Article · 04 February 2020 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.9b04910 · OSTI ID:1658228

Foley, Brandon L. ^[1]; Bhan, Aditya  ^[2]

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1. University of Minnesota, Twin Cities, Minneapolis, MN (United States); University of Minnesota
2. University of Minnesota, Twin Cities, Minneapolis, MN (United States)

The degrees of rate control enable identification of rate-controlling transition states and species during (pseudo-)steady-state reaction. We demonstrate a method for identifying rate-controlling transition states and species at non-(pseudo-)steady-state conditions through modification of the definitions for degrees of rate control and sensitivities by superimposing the condition that time constants of the analytical rate function are kept constant when taking the partial derivatives of rate with respect to the rate constants/free energies. In conclusion, the utility of transient degrees of rate control is demonstrated for catalytic reaction networks to rationalize features of the transient rate including extrema and discontinuities.

• Research Organization: University of Minnesota, Minneapolis, MN (United States)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES)
• Grant/Contract Number: SC0019028
• OSTI ID: 1658228
• Journal Information: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 4 Vol. 10; ISSN 2155-5435
• Publisher: American Chemical Society (ACS)Copyright Statement
• Country of Publication: United States
• Language: English