The H‐Abstraction Reactions of n‐Hexanol by Ḣ, ĊH₃, ȮH and HȮ₂ Radicals: Theoretical Calculations and Kinetic Modeling Study

Due to the limitations of comprehensive experimental and theoretical research, rate coefficients are commonly derived through analogies with alcohols or estimations based on alkane data. Consequently, this paper delves into the critical H‐abstraction reactions involving n ‐hexanol and radicals (Ḣ, HȮ 2 , ȮH and ĊH 3 ), serving as foundational steps in the combustion mechanism. Rate coefficients are determined using traditional and variational transition state theory combined with Eckart tunneling correction. Emphasis on H‐abstraction from C α is evident in branching ratios for n ‐hexanol + Ḣ/HȮ 2 /ĊH 3 systems, while the dominant reaction for n ‐hexanol + ȮH system shifts from C ε above 330 K to C β below 330 K. The total H‐abstraction rate coefficient for n ‐hexanol + ȮH is calculated as k OH = 12.76 × T 3.62 × exp. (472.81/T) (cm 3 mol −1 s −1 ), with the CBS‐QB3 level reproducing experimental data commendably. Furthermore, the kinetics model proposed by Togbé et al. is refined through updated rate coefficients, validated against ignition delay times, showcasing notable agreement with experimental data. Reaction path and sensitivity analyses provide insights into crucial reactions and corresponding fuel consumption paths during n ‐hexanol oxidation.