NOx reduction by reburning: theoretical study of the branching ratio of the HCCO+NO reaction

The product distribution of the HCCO + NO reaction is examined í theoretically over an extended temperature range, using RRKM-master equation analyses incorporating the effect of internal rotations on the state densities. The potential energy surface was characterized at the B3LYP-DFT/6-311++G(d,p) and CCSD(T)/6-31G(d,p) levels of theory, combined with high-level single point CCSD(T)/6-311++G(2d,p) calculations. The only reaction products of importance were found to be HCNO+CO and HCN+CO2, where the predicted CO2 yield can be expressed as α(T)=0.0652+0.220exp(−T/917.9 K), for T=300–2500 K. The predicted product distribution is in agreement with the available experimental values.