Abstract
Dodecane was efficiently chlorinated at a porous carbon anode in an electrolytic cell containing a 20% hydrochloric acid electrolyte. The dodecane flowed continuously through the porous anode, and chlorinated products were continuously withdrawn. Voltametric studies on small‐scale electrodes indicated that the reaction mechanism involves chlorine evolution followed by a chlorination reaction which takes place in a thin film adhering to the electrode. The distribution of products, i.e., the ratio of monochlorododecanes to dichlorododecanes produced were correlated on the basis of a calculated statistical distribution assuming a free radical mechanism. The pronounced deviations from this statistical distribution at low current densities are explained on the basis of a competing reaction which involves the diffusion of free radical inhibitors into the reaction film.
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