Disclosed is a process for the manufacture of haloalkane compounds, and more particularly, an improved process for the manufacture of the compound 1,1,1,3,3-penta-chloropropane (HCC-240fa), which mitigates the formation of by-products from vinyl chloride (CH2═CHCl). The present invention is also useful in the manufacture of other haloalkane compounds such as HCC-250 and HCC-360. One embodiment of the invention comprises a method for mitigating 1,1,3,3,5,5-hexachloropentane and 1,1,1,3,5,5-hexachloropentane formation in the HCC-240fa manufacturing process, in which FeCl3, is introduced to a reactor only after the start-up phase has ended and a continuous operation has started. In a preferred embodiment, “pre-chelated” FeCl3, which is concentrated in a catalyst recovery column, is introduced to reactor after the continuous operation has started.
