title: Application of the compensated Arrhenius formalism to explain the dielectric constant dependence of rates for Menschutkin reactions.
abstract: The dependence of the reaction rate on solvent dielectric constant is examined for the reaction of trihexylamine with 1-bromohexane in a series of 2-ketones over the temperature range 25-80 °C. The rate constant data are analyzed using the compensated Arrhenius formalism (CAF), where the rate constant assumes an Arrhenius-like equation that also contains a dielectric constant dependence in the exponential prefactor. The CAF activation energies are substantially higher than those obtained using the simple Arrhenius equation. A master curve of the data is observed by plotting the prefactors against the solvent dielectric constant. The master curve shows that the reaction rate has a weak dependence on dielectric constant for values approximately less than 10 and increases more rapidly for dielectric constant values greater than 10.
authors.affiliation: Department of Chemistry and Biochemistry, University of Oklahoma , Norman, Oklahoma 73019, United States.
authors.forename: Matt
authors.initials: M
authors.lastname: Petrowsky
authors.forename: Daniel T
authors.initials: DT
authors.lastname: Glatzhofer
authors.forename: Roger
authors.initials: R
authors.lastname: Frech