Zheng Changluo, Yan Tong, Yan Jia, Ao Chengcheng, Zhang Lidong, Lei Lili, Wang Pan
School of Automotive and Traffic Engineering, Jiangsu University, Zhenjiang 212013, China.
National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230026, China.
J Phys Chem A. 2024 Sep 5;128(35):7429-7439. doi: 10.1021/acs.jpca.4c03385. Epub 2024 Aug 22.
2-Pentanone is a significant carbon-neutral fuel. To better understand 2-pentanone combustion, the CCSD(T)/CBS method was used to calculate the potential energy surfaces (PES) for H-abstraction, isomerization, and β-scission reactions of 2-pentanone. Rate constants for the above reactions were calculated by the MESS employing conventional transition state theory (CTST) at 300-2000 K. The findings reveal adherence to the Evans-Polanyi principle in the H-abstraction reactions of 2-pentanone by H atoms. Specifically, the 2-site shows more competitive kinetics due to having the lowest energy barrier of 7.8 kcal/mol. The 4-position has the highest energy barrier, making the reaction difficult to occur. In the subsequent reactions, the breaking of C-H bonds is most competitive at low temperatures. In particular, the H transfer from INT1 to INT3 has a potential well height of 24.8 kcal/mol. The β-scission reactions become the main pathway for the depletion of pentanone radicals with increasing temperature. This study significantly extends the kinetic parameters of 2-pentanone combustion over a wide range of temperatures and pressures, which is expected to contribute to the development of 2-pentanone combustion models.
2-戊酮是一种重要的碳中性燃料。为了更好地理解2-戊酮的燃烧过程，采用CCSD(T)/CBS方法计算了2-戊酮的氢提取、异构化和β-断裂反应的势能面（PES）。利用传统过渡态理论（CTST），通过MESS在300-2000K温度范围内计算了上述反应的速率常数。研究结果表明，2-戊酮与氢原子的氢提取反应遵循埃文斯-波拉尼原理。具体来说，2号位由于具有7.8千卡/摩尔的最低能垒，表现出更具竞争力的动力学。4号位具有最高的能垒，使得反应难以发生。在后续反应中，C-H键的断裂在低温下最具竞争力。特别是，从INT1到INT3的氢转移具有24.8千卡/摩尔的势阱高度。随着温度升高，β-断裂反应成为戊酮自由基消耗的主要途径。本研究显著扩展了2-戊酮在广泛温度和压力范围内的燃烧动力学参数，有望为2-戊酮燃烧模型的发展做出贡献。
