The gas-phase chlorination of ethane has been studied experimentally and by simulation of tile corresponding gas-phase reaction scheme. In addition, some key reactions in ethane chlorination have been studied in detail by quantum chemical methods. Experimental results indicate that the chlorination reactivity of C2H6-xClx decreases with increasing x and, further, that 1,1-dichloroethane is the preferred dichlorination product. The preference for 1,1-dichloroethane over 1,2-dichloroethane at higher temperatures has been ascribed to the 1,2-dichloroethane precursor radical decomposing into ethene and a chlorine atom. General agreement was found between experiments, kinetic simulation (with rate constants from the NIST database), and quantum chemical calculations for ethane chlorination.