AbstractThe pyrolysis kinetics of several ethyl esters with polar substituents at the acyl carbon have been studied in the temperature range of 319.8–400.0°C and pressure range of 50.5–178.0 torr. These eliminations are homogeneous, unimolecular, and follow a first‐order rate law. The rate coefficients are given by the Arrhenius equations: for ethyl glycolate, logk1(s−1) = (12.75 ± 0.30) – (201.4 ± 3.8) kJ/mol/2.303RT; for ethyl cyanoacetate, logk1(s−1) = (12.19 ± 0.18) – (191.8 ± 2.1) kJ/mol/2.303RT; for ethyl dichloroacetate, logk1(s−1) = (12.62 ± 0.36) – (193.9 ± 4.3) kJ/mol/2.303RT; for ethyl trichloroacetate, logk1(s−1) = (12.27 ± 0.09) – (185.1 ± 1.0) kJ/mol/2.303RT. The results of the present work together with those reported recently in the literature give an approximate linear correlation when plotting logk/k0vs. σ* values (ρ* = 0.315 ± 0.004,r= 0.976, and intercept = 0.032 ± 0.006 at 400°C). This linear relationship indicates that the polar substituents affect the rate of elimination by electronic factors. The greater the electronegative nature of the polar substituent, the faster is the pyrolysis rate. The alkyl substituents yield, within experimental error, similar values in rates which makes difficult an adequate