He Wei, Chen Kaixuan, Yue Minghang, Zhang Lidong
Guangxi Key Laboratory of Ocean Engineering Equipment and Technology, Qinzhou 535011, P.R. China.
Key Laboratory of Beibu Gulf Offshore Engineering Equipment and Technology, Beibu Gulf University, Education Department of Guangxi Zhuang Autonomous Region, Qinzhou 535011, P.R. China.
ACS Omega. 2023 Feb 28;8(10):9385-9393. doi: 10.1021/acsomega.2c08047. eCollection 2023 Mar 14.
Linear ethers are promising biomass fuels with high volume energy density and high cetane number that may be used directly as alternative fuels or fuel additives in internal combustion engines. In this work, the first O addition reaction of the di--propyl ether radical was investigated using high-level quantum chemical calculations combined with the Rice-Ramsperger-Kassel-Marcus theory to solve the master equation. The potential energy surfaces of di--propyl ether radicals (CHO) with O were constructed at the QCISD(T)/CBS//M062X/6-311++G() level, and the rate constants were calculated for the pressure range of 0.1-100 atm and the temperature range of 300-1500 K and fitted by a modified Arrhenius formula. The calculations show that the consumption of di--propyl ether peroxyl radicals (CHO) via the five-membered ring or six-membered ring transition-state reaction channel is most favorable. In addition, the low-temperature oxidation experiments of di--propyl ether were validated based on the calculations of the current work, and the results showed that the calculations were a good predictor of the experimental results.
