Table of Contents
Laser Chemistry
Volume 10, Issue 3, Pages 185-195
http://dx.doi.org/10.1155/1990/89853

Infrared Laser Photochemistry of Trans-1, 2-Dichloroethylene. Evidence For A CI Atom Chain Reaction

Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis 55455, MN, USA

Received 1 May 1989; Accepted 10 September 1989

Copyright © 1990 Hindawi Publishing Corporation. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

The TEA-CO2 laser induced reaction of trans-l,2-dichloroethylene (TDCE) was investigated at 925 cm-1. The laser radiation was focused to yield beam waist fluences of approximately 125 J cm-2. The major reaction product was cis-1, 2-dichloroethylene (CDCE), with a few per cent of chloroacetylene, and minor amounts of acetylene, dichloroacetylene, chloroethylene and an unidentified C4 compound also being formed. The reaction of pure TDCE was studied as a function of number of laser pulses and total pressure (0.02 to 5 torr). Some experiments were also done with added ethane (20%) and propane (2%). Evidence was obtained that the formation of the cis isomer occurs via two mechanisms, (1) a unimolecular isomerization, and (2) a CI atom chain reaction. The results are consistent with laser induced decomposition of TDCE occurring through the three lowest energy channels: unimolecular structural isomerization (57.4 kcal/mol); molecular HCI elimination (69 kcal/mol); and C-CI bond scission (89 kcal/mol).