Leffler-Grunwald operator

The observed solvent effect can be expressed quantitatively with the aid of the Leffler-Grunwald operator 5m introduced in Chapter 7. For rate constant k measured in medium M we have, from transition state theory, k = (kT//i)exp ( —AGm// T) and similarly for rate constant ko measured in a reference solvent. Combining these two expressions gives... [Pg.386]

Linear free energy relationship (LFER) — For various series of similar chemical reactions it has been empirically found that linear relationships hold between the series of free energies (-> Gibbs energy) of activation AG and the series of the standard free energies of reactions AGf, i.e., between the series of log fc (k -rate constants) and log K (Kt - equilibrium constants) (z labels the compounds of a series). Such relations correlate the - kinetics and -> thermodynamics of these reactions, and thus they are of fundamental importance. The LFER s can be formulated with the so-called Leffler-Grunwald operator dR ... [Pg.402]

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