Hydrogen Isotope Exchange of Chlorinated Ethylenes in Aqueous Solution

Possibly a Termolecular Liquid Phase Reaction

Mario Gabričević, G. Lente, I. Fábián

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

This work reports an experimental study of the hydrogen/deuterium exchange in the basic aqueous solutions of trichloroethylene, trans-1,2-dichloroethylene, and cis-1,2-dichloroethylene using 1H NMR as a monitoring method. 1,1-Dichlorethylene was also investigated but found not to exchange hydrogen isotopes with water. The kinetics of isotope exchange features two different pathways, the first is first order with respect to hydroxide ion, whereas the second is second order. The first pathway is interpreted as a straightforward bimolecular reaction between chloroethylene and hydroxide ion, which leads to the deprotonation of chloroethylene. The second pathway involves a transition state with the association of one molecule of the chloroethylene and two hydroxide ions. It is shown that the second pathway could involve the formation of a precursor complex composed of one chloroethylene molecule and one hydroxide ion, but a direct termolecular elementary reaction is also feasible, which is shown by deriving a theoretical highest limit for the rate constants of termolecular reactions in solution.

Original languageEnglish
Pages (from-to)12627-12634
Number of pages8
JournalJournal of Physical Chemistry A
Volume119
Issue number51
DOIs
Publication statusPublished - Dec 24 2015

Fingerprint

Ethylenes
chloroethylene
Vinyl Chloride
hydrogen isotopes
Isotopes
hydroxides
Hydrogen
Ion exchange
liquid phases
ethylene
aqueous solutions
Liquids
ions
trichloroethylene
Trichloroethylene
Deprotonation
Molecules
Deuterium
molecules
deuterium

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Hydrogen Isotope Exchange of Chlorinated Ethylenes in Aqueous Solution : Possibly a Termolecular Liquid Phase Reaction. / Gabričević, Mario; Lente, G.; Fábián, I.

In: Journal of Physical Chemistry A, Vol. 119, No. 51, 24.12.2015, p. 12627-12634.

Research output: Contribution to journalArticle

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