_{3}CHO, C

_{2}H

_{3}F, CH

_{4}, CO, C

_{2}H

_{4}, and C

_{2}H

_{6}. The unimolecular eliminations of HF and H

_{2}O are found to be the major channels through which 2-fluoroethanol decomposes under these conditions. The rate constant for HF elimination is found to be 10

^{13.17±0.33}exp[−(59.5 ± 1.7)/(

*RT*)] s

^{-1}, and the rate constant for H

_{2}O elimination is found to be 10

^{14.30±0.34}exp[−(69.7 ± 1.7)/(

*RT*)] s

^{-1}, where the activation energies are given in kcal mol

^{-1}. The CH

_{3}CHO produced by HF elimination through the vinyl alcohol intermediate is chemically active and decomposes leading to CH

_{4}and CH

_{3}CH

_{3}products. The production of ethylene could not be explained from the CH

_{3}CHO pyrolysis mechanism. It is most likely formed directly from the reactant through HOF elimination or by radical processes beginning with C−O bond dissociation. Ab initio (Hartree−Fock [HF] and second-order Møller−Plesset perturbation theory [MP2]) and density functional theory [DFT] calculations have been carried out to find the transition state and activation barrier for HF and H

_{2}O elimination reactions. The HF calculations overestimate the barrier by 18 kcal mol

^{-1}for HF elimination and 22 kcal mol

^{-1}for H

_{2}O elimination, and including electron correlation improves the agreement. In particular, DFT predictions for activation energies for HF and H

_{2}O elimination reactions are within 1 kcal mol

^{-1}of the experimental values.