Thermodynamic considerations in dibenzodioxin and dibenzofuran formation: Concentrations of chlorinated dioxins and furans in model fuel-rich combustion gases

A database for chlorinated dioxins (DBDs), with heats of formation derived by analogy with chlorination of quinone and benzene, has already been shown to predict relative isomer distributions nearer to those observed, and those predicted using MOPAC, than an earlier database due to Shaub. The model has been extended to obtain a similar database for chlorinated dibenzofurans (DBF's), and comparisons with observed isomer concentration distributions are illustrated. Calculations are carried out using the NPL MTDATA suite of programs. Isomer group values for the properties of the original compounds and each degree of chlorination have been derived, and the use of these values leads to a reduction in the data obtained in computations to more manageable proportions. The reduced database obtained is combined with other databases to carry out computer predictions for simulated chlorine-containing combustion gases. Data for inorganics substances and the simplest organic substances (methane. ethane and related species) are obtained from the SGTE database. More extensive data for aliphatic and aromatic hydrocarbons from various standard sources have been incorporated in an additional computational database. In order to examine the relative concentrations of DBFs and DBDs a database for chlorinated hydrocarbons has been established. Predictions for simulated fuel rich combustion products for the C, H, O, Cl system are presented.