Year: 2025
Type: article
Abstract: The selective chlorination of ethane to 1,2-dichloroethane offers a promising route for upgrading ethane, yet its efficiency remains constrained by limited mechanistic insights into gas-phase chlorine-radical-mediated pathways, which govern target product selectivity and competing dehydrochlorination side reactions. This work systematically decouples the kinetics of ethane chlorination and chloroethane functionalization under varying Cl2 concentrations, revealing that chlorine radicals govern product distribution through thermodynamically favored pathways. This results in an interesting phenomenon whereby the product ratio between 1,1-C2H4Cl2 and 1,2-C2H4Cl2 maintains a constant 2:1 stoichiometry regardless of Cl2 concentration variation. A critical observation is that the rate of all chlorination steps remains independent of alkane concentrations, highlighting the dominant role of chlorine radicals in rate-determining steps. Furthermore, ethylene byproducts are demonstrated to originate from the dechlorination of chlorine-radical-induced 2-chloroethyl radicals derived from chloroethane, rather than the direct dehydrochlorination of chloroethane itself. These insights into the dual role of chlorine radicals—mediating both the chlorination and dehydrochlorination pathways—establish a foundational framework for integrating gas-phase radical chemistry with catalytic engineering strategies to suppress undesired side reactions and enable scalable, selective ethane chlorination.
Source: Molecules
Language: English
Subfield: Catalysis
Field: Chemical Engineering
Domain: Physical Sciences
Open Access status: gold
Estimated APC paid: $3,258
OpenAlex ID: W4409411508