National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230029, PR China.
J Phys Chem A. 2012 Sep 20;116(37):9238-44. doi: 10.1021/jp305885s. Epub 2012 Sep 11.
Pentanol is one of the promising "next generation" alcohol fuels with high energy density and low hygroscopicity. In the present work, dominant reaction channels of thermal decomposition of three isomers of pentanol: 1-pentanol, 2-methyl-1-butanol, and 3-methyl-1-butanol were investigated by CBS-QB3 calculations. Subsequently, the temperature- and pressure-dependent rate constants for these channels were computed by RRKM/master equation simulations. The difference between the thermal decomposition behavior of pentanol and butanol were discussed, while butanol as another potential alternative alcohol fuel has been extensively studied both experimentally and theoretically. Rate constants of barrierless bond dissociation reactions of pentanol isomers were treated by the variational transition state theory. The comparison between various channels revealed that the entropies of variational transition states significantly impact the rate constants of pentanol decomposition reactions. This work provides sound quality kinetic data for major decomposition channels of three pentanol isomers in the temperature range of 800-2000 K with pressure varying from 7.6 to 7.6 × 10(4) Torr, which might be valuable for developing detailed kinetic models for pentanol combustion.
戊醇是一种有前途的“下一代”酒精燃料，具有高能量密度和低吸湿性。在本工作中，通过 CBS-QB3 计算研究了三种戊醇异构体：1-戊醇、2-甲基-1-丁醇和 3-甲基-1-丁醇的热分解主要反应通道。随后，通过 RRKM/master 方程模拟计算了这些通道的温度和压力依赖的速率常数。讨论了戊醇和丁醇热分解行为的差异，而丁醇作为另一种有潜力的替代酒精燃料，已经在实验和理论上得到了广泛的研究。戊醇异构体无势垒键离解反应的速率常数采用变分过渡态理论处理。对各种通道的比较表明，变分过渡态的熵对戊醇分解反应的速率常数有显著影响。这项工作为三种戊醇异构体在 800-2000 K 温度范围内和 7.6-7.6×10(4)托压力范围内的主要分解通道提供了可靠的动力学数据，这对于开发戊醇燃烧的详细动力学模型可能是有价值的。
