CAJ | 학술논문

用密度泛函理论B3LYP方法对煤炭燃烧过程中N20的消除反应进行研究.选用6-311++G**和aug-cc-pVTZ基组.优化了反应通道上反应物、过渡态和产物的几何构型.预测了它们的热力学性质(总能量、焓、熵和吉布斯自由能)及其随温度的变化.预测N20+CO反应的活化能为200 kJ·mol-1,与实验值193±8 kJ·mol-1较一致.计算了500-1800 K温度范围的反应速率常数.在N20的分解中,N20与H和CN自由基的反应为动力学优先进行的反应,其活化能为50~55 kJ·tool-1.在B3LYP/aug-CC-pVTZ level水平下,N20+CN反应是热力学最有利的自发反应,其吉布斯自由能变化为-407 kJ·mol-1.
용밀도범함이론B3LYP방법대매탄연소과정중N20적소제반응진행연구.선용6-311++G**화aug-cc-pVTZ기조.우화료반응통도상반응물、과도태화산물적궤하구형.예측료타문적열역학성질(총능량、함、적화길포사자유능)급기수온도적변화.예측N20+CO반응적활화능위200 kJ·mol-1,여실험치193±8 kJ·mol-1교일치.계산료500-1800 K온도범위적반응속솔상수.재N20적분해중,N20여H화CN자유기적반응위동역학우선진행적반응,기활화능위50~55 kJ·tool-1.재B3LYP/aug-CC-pVTZ level수평하,N20+CN반응시열역학최유리적자발반응,기길포사자유능변화위-407 kJ·mol-1.
We have calculated the reactants,transition states and products of six reactions involving the N2O destruction under coal combustion.by using the DFT-B3LYP method with the 6-311++G** and aug-cc-pVTZ basis sets.Optimized structures were obtained.Thermodynamic property changes(total energy,enthalpy,entropy and Gibbs free energy)along the reaction paths,as well as their variations with temperatures,were predicted.The reactions of N20 with H and CN radicals are kinetically the leading roles in N20 destruction,with activation