The thermal decomposition of aromatic compounds - II. Dichlorobenzenes

A kinetic study of the thermal decomposition of the dichlorobenzenes shows that the three isomers behave similarly. The compounds differ strikingly from chlorobenzene, inasmuch as the rate of decomposition is not reduced by nitric oxide or ammonia. Other kinetic features suggest that the reaction is unimolecular, and that chain processes do not occur to an appreciable extent. The main gaseous decomposition product is hydrogen chloride, and nearly all the combined chlorine can be accounted for as this product. Very small amounts of gaseous hydrogen are also found, but the balance of the combined hydrogen remains in the carbon deposited on the walls of the reaction vessel; this carbonaceous deposit is of similar composition and structure to that formed from chlorobenzene. Comparison of the thermal stabilities of benzene, chlorobenzene and the dichlorobenzenes shows that the stability is dependent on the extent of substitution of the aromatic ring but is little influenced by the relative positions of the substituents. The increased rate of decomposition caused by a second chlorine atom is evidently due to its ability to facilitate a molecular reaction, which apparently operates to the complete exclusion of chain processes.