Mechanochemical destruction of 4-bromochlorobenzene with CaO. Efficiency, kinetics, and mechanism

The degradation of 4-bromochlorobenzene (4-BCB) containing both chlorine and bromine by mechanochemical destruction (MCD) using CaO powder was investigated. The degradation efficiency of 4-BCB almost achieved 100% after 2 h milling. The debromination rate (0.41 h^–1) was higher than the dechlorination rate (0.31 h⁻¹) which can be ascribed to the lower dissociation energy of C–Br bond than that of C–Cl bond in 4-BCB. The kinetic analysis demonstrates that nucleation growth was the control step of dehalogenation reactions. Additionally, the dehalogenation efficiency increased with increasing rotate speed and milling ball weight. The XRD and FT-IR spectra analysis manifests that the CaO powder was transformed to CaCl₂, CaBr₂, Ca(OH)₂, and CaCO₃. The identification of intermediates and analysis of Raman spectra indicates that the 4-BCB degradation by MCD treatment using CaO powder may occur through three pathways: (a) breakup of the benzene ring to form small molecular halogenated hydrocarbons and mineralization to form CO₂ and H₂O in sequence, (b) dehalogenation reaction to form benzene and monohalogenobenzene and addition reaction of halogen radicals to form dihalogenobenzenes in sequence; (c) polymerization reaction to form biphenyl, halogenated biphenyl, and graphite.