Dechlorination of lindane, dieldrin, tetrachloroethane, trichloroethene, and PVC in subcritical water.

Pure water has been used to dechlorinate aliphatic organics without the need for catalysts or other additives. Dehydrohalogenation (loss of HCI with the formation of a double bond) occurred at temperatures as low as 105-200 degrees C for 1,1,2,2-tetrachloroethane, lindane (1,2,3,4,5,6-hexachlorocyclohexane, gamma-isomer), and dieldrin (1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4a,5,6,7,8,8a-octahydro-endo, exo-1,4:5,8-dimethanonaphthalene). Complete loss of the parent compounds was achieved in less than 1 h at 150, 200, and 300 degrees C for 1,1,2,2-tetrachloroethane, lindane, and dieldrin, respectively. The initial dechlorination of lindane had an activation energy of 84 kJ mol(-1) with an Arrhenius pre-exponential factor of 1.5 x 10(6) s(-1). Dehydrohalogenation of lindane formed trichlorobenzenes, followed by subsequent hydrolysis and hydride/chloride exchange to form chlorophenols, lower chlorobenzenes, and phenol as the major final product. Reaction of poly(vinyl chloride) at 300 degrees C for 1 h formed aromatic hydrocarbons ranging from benzene to anthracene and a char residue with a ca. 1:1 carbon-to-hydrogen ratio (mol/mol). The residue contained <1 wt % of chlorine compared to 57 wt % chlorine in the original polymer. All compounds tested yielded chloride ion as the major product (at higher temperatures), indicating that complete dechlorination of some aliphatic organochlorines may be feasible.