Reaction Kinetics of NH 2 With H 2 CO and CH 3 CHO: Modeling Implications for NH 3 ‐Dual Fuel Blends

ABSTRACT Carbon‐free fuels like ammonia (NH 3 ) and hydrogen (H₂) offer significant potential in combating global warming by reducing greenhouse gas emissions and moving toward zero carbon emissions. Over the past few years, our research has focused on understanding the combustion behavior of carbon‐neutral and carbon‐free fuels. In particular, we have explored the combustion characteristics of NH 3 when blended with various hydrocarbons and oxygenates. Our investigation revealed that carbon‐nitrogen cross‐chemistry plays a crucial role in shaping the combustion properties of NH 3 ‐hydrocarbon/oxygenate blends. Specifically, the chemistry of amino (NH 2 ) radicals is vital in influencing the low‐temperature reactivity of these blends. Understanding the interactions between carbon and nitrogen is essential for optimizing combustion processes and improving the emissions profile of NH 3 ‐based fuels. Recognizing the significance of this cross‐chemistry, we investigated the reaction kinetics of NH 2 radicals with formaldehyde (H 2 CO) and acetaldehyde (CH 3 CHO) using high‐level ab initio and transition state theory calculations. We computed the potential energy profiles of these reactions at the CCSD(T)/CBS//M06‐2X/aug‐cc‐pVTZ level of theory to analyze the reactivity of NH 2 radicals at various C─H bond sites. The newly derived rate constants have proven to be highly sensitive for modeling the low‐temperature oxidation of NH 3 ‐dual fuel blends, significantly enhancing the predictive accuracy of our previously published kinetic models. This work offers valuable insights into the role of NH 2 radicals, thereby advancing the development of NH 3 ‐dual fuel systems.