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Kinetics and general reaction rule for hydrogen atom abstraction reactions from C4-C10 alcohols by a hydroxyl radical
Ying Huo1, Yachao Chang1, Ming Jia1
1Key Laboratory of Ocean Energy Utilization and Energy Conservation of Ministry of Education, Dalian University of Technology, Dalian, Liaoning 116024, P. R. China. jiaming@dlut.edu.cn.
Abstract:
This study establishes a generalized reaction rule for hydrogen atom (H) abstraction from C4-C10 1-alcohols by hydroxyl radicals (HO˙), overcoming the fundamental limitations of bond dissociation energy (BDE) models. Through systematic kinetics analysis, this study reveals that hydrogen atoms on OH-proximal carbons (C1-C4) exhibit alcohol-specific asymmetric reactivity, starkly deviating from n-alkane behavior, whereas distal carbons (>C4) show convergence. Crucially, hydrogen bonding leads to distinct kinetics for OS (opposite-side, relative to the hydroxyl group) and SS (same-side, relative to the hydroxyl group) pathways by modulating the transition state geometries and energy barriers. By incorporating these asymmetric reactivities and secondary electronic effects, a chain-length-independent rate rule is established that categorizes ten unique reaction channels with unified kinetic parameters. Validated by high-precision ONIOM-based energy calculations against CCSD(T)/CBS benchmarks, this rule enables accurate mechanistic extrapolation for long-chain alcohol combustion. The work provides a fundamental framework for refining kinetic models of oxygenated fuels and advancing energy technologies.
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