Reactions for the dechlorination or decomposition of polychlorinated dibenzo-p-dioxin (PCDD) and/or polychlorinated dibenzofuran (PCDF) were investigated thermodynamically, in order to develop techniques to prevent the release of PCDDs and PCDFs from municipal incinerators. The Gibbs energy of formation of PCDDs, PCDFs, and some organic compounds was calculated by using a computer program, which was based on statistical thermodynamics. It was found that CaO, Na2OSiG2, or 2Na20-Si02 would promote the dechlorination reaction of PCDDs and PCDFs by receiving chlorine atoms and that such organic materials as butane or butene would help the reaction by giving hydrogen in the reactions. The calculation showed that thermal decomposition of PCDDs or PCDFs would not proceed at temperatures below 1100 K. Some ways to prevent the release of PCDDs and PCDFs from municipal incinerators were discussed.
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