As ketene is a crucial intermediate for the high-temperature combustion of oxygenated hydrocarbons in general, an in-depth understanding of its chemistry is a fundamental requirement for the kinetic modeling of bio-based fuels. To gain a profound insight into the decomposition of ketene and subsequent reaction pathways high level ab initio methods were used. DSD-PBEP86/cc-pVTZ level of theory was applied for the geometries and frequencies, while single-point energies were determined at the CCSDT-1a level of theory extrapolated to the basis set limit. The reaction rate parameters for 38 reactions involved in the ketene chemistry including C1 to C4 species like acetylene, ethylene, propyne and allene were computed. For a total of 16 species, the thermochemistry were updated. The calculated rate parameters and the two new species cyclopropenone and 1,4-dioxo-1,3-butadiene were used to update the AramcoMech 3.0 base mechanism, which was then validated against speciation measurements during ketene pyrolysis. A reaction pathway analysis was performed to find the most prominent reactions at the investigated conditions and to discuss the simulation results. A significant improvement in the model’s prediction capability was found when applying the newly calculated reaction rate parameter and thermochemical data.

由于乙烯酮通常是氧化碳氢化合物高温燃烧的关键中间体，因此深入了解其化学性质是生物基燃料动力学建模的基本要求。深入了解乙烯酮的分解以及后续的反应途径，从头开始方法被使用。DSD-PBEP86 / cc-pVTZ理论水平适用于几何形状和频率，而单点能量是在CCSDT-1a理论水平确定的，外推至基本设定极限。计算了涉及乙烯酮化学反应的38个反应的反应速率参数，这些反应包括乙炔，乙烯，丙炔和丙二烯等C1至C4物种。对于总共16种，热化学进行了更新。计算的速率参数和两个新物种环丙烯酮和1,4-二氧代-1,3-丁二烯被用于更新AramcoMech 3.0的基本机理，然后针对乙烯酮热解过程中的形态测量进行了验证。进行了反应途径分析，以发现所研究条件下最突出的反应并讨论模拟结果。