Abstract: | Rates of thermal gas‐phase elimination of eleven 2‐aryloxyacetic acid have been measured over a 45°C temperature range for each compound. Hammett correlation of the present kinetic data with the literature σ0 values of the given substituents gave a reaction ρ constant of 0.69 at 600 K; this is more than that for the gas‐phase elimination parameter of 2‐aryloxypropanoic acid (ρ = 0.26) and consistent with a transition state with some charge separation, suggesting a partial formation of carbocation. The implications of this observation for the thermal gas‐phase elimination of α‐aryloxycarboxylic acids are considered. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 612–616, 2001 |