Computational Evidence Suggests That 1-Chloroethanol May Be an Intermediate in the Thermal Decomposition of 2-Chloroethanol into Acetaldehyde and HCl

The Journal of Physical Chemistry. a
Zoi SaltaVincenzo Barone

Abstract

The dehalogenation of 2-chloroethanol (2ClEtOH) in the gas phase with and without the participation of catalytic water molecules has been investigated using methods rooted into the density functional theory. The well-known HCl elimination leading to vinyl alcohol (VA) was compared to the alternative elimination route toward oxirane and shown to be kinetically and thermodynamically more favorable. However, the isomerization of VA to acetaldehyde in the gas phase, in the absence of water, was shown to be kinetically and thermodynamically less favorable than the recombination of VA and HCl to form the isomeric 1-chloroethanol (1ClEtOH) species. At the ωB97X-D/cc-pVTZ level of calculation, this species is more stable than 2ClEtOH by about 6 kcal mol-1 at 298 K, and the reaction barrier for VA to 1ClEtOH is 23 kcal mol-1 versus 55 kcal mol-1 for the direct transformation of VA to acetaldehyde. In a successive step, 1ClEtOH can decompose directly to acetaldehyde and HCl with a lower barrier (29 kcal mol-1) than that of VA to the same products (55 kcal mol-1). The calculations were repeated using a single ancillary water molecule (W) in the complexes 2ClEtOH_W and 1ClEtOH_W. The latter adduct is now more stable than 2ClEtOH_W by about...Continue Reading

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