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Slope of free energy plots in chemical kinetics
Abstract
In current electron-transfer theory, an activation free energy term, ΔF*, depends in a simple way on the “standard” free energy of reaction, ΔF^0’, in the prevailing medium. Namely, ΔF* = (1/4)λ[1 + (ΔF^0’/λ)]^2, apart from small work terms; λ/4 is ΔF_0*, the value of ΔF* at (ΔF^0’ = 0; and λ obeys a simple additivity property. As an exploratory step an equation of the same functional form is applied in the present paper to data on Brønsted slopes of 16 proton- and atom-transfer reaction series. Thereby, the instantaneous slope of a ΔF* vs. ΔF^0’ plot is calculated to be (1/2)[1 + (ΔF^0’/4 ΔF_0*)]. Thus far the experimental results are consistent with this equation, but more data are needed. Other applications of the ΔF* equation, including one to the kinetic isotope effect, are also discussed. A rather approximate derivation of the above equation for atom and other transfers was given in an earlier paper of this series.
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Cited by
Excited-state proton transfer reactions I. Fundamentals and intermolecular reactions
Arnaut, L. G., & Formosinho, S. J. (1993) · Journal of Photochemistry and Photobiology A: Chemistry · doi:10.1016/1010-6030(93)80157-5 · Cited by 561
Plata, R. E., & Singleton, D. A. (2015) · Journal of the American Chemical Society · doi:10.1021/ja5111392 · Cited by 445
Real-Time Observation of Carbonic Acid Formation in Aqueous Solution
Adamczyk, K., Prémont-Schwarz, M., Pines, D., Pines, E., & Nibbering, E. T. J. (2009) · Science · doi:10.1126/science.1180060 · Cited by 315
Enzymatic mechanisms for catalysis of enolization: ketosteroid isomerase
Pollack, R. M. (2004) · Bioorganic Chemistry · doi:10.1016/j.bioorg.2004.06.005 · Cited by 110
Metadata
- Authors
- Cohen, A. O., & Marcus, R. A.
- Venue
- The Journal of Physical Chemistry
- Publisher
- American Chemical Society (ACS)
- Published
- 1968-11
- Volume
- 72
- Issue
- 12
- Pages
- 4249-4256
- ISSN
- 0022-3654 (ISSN-L)
- 1541-5740
- OpenAlex
- W113405576
- Cited by
- 232
- References
- 0
- FWCI
- 1.03
- Type
- journal article
- Language
- en
- Open access
- closed
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- Cohen, A. O., & Marcus, R. A. (1968). Slope of free energy plots in chemical kinetics. The Journal of Physical Chemistry. https://doi.org/10.1021/j100858a052
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