Acta Phys. -Chim. Sin. ›› 1994, Vol. 10 ›› Issue (11): 1004-1008.doi: 10.3866/PKU.WHXB19941108

• ARTICLE • Previous Articles     Next Articles

A Theoretical Study on the Thermo Decomposition of HNCO to HNCNH and CO2

Zhang Shao-Wen, Fu Xiao-Yuan   

  1. Department of Chemistry,Beijing Normal University,Beijing 100875
  • Received:1993-10-13 Revised:1993-11-27 Published:1994-11-15
  • Contact: Fu Xiao-Yuan


 Ab initio RHF/3-21G method has been employed to study the mechanism of the bimolecular thermolysis of HNCO. The results show that this reaction is a stepwise reaction. The first step is the dimerization of HNCO to form a four-membered ring intermediate, the second step is the dissociation of the intermediate to form the products HNCNH and CO2. The calculated activation barrier for the steps are 172.55kJ•mol-1 and 83.68kJ•mol-1, respectively. It can be seen that the first step is the rate determining step, its barrier is in good agreement with experimental data (activation energy: 176.40±16.30 kJ•mol-1). The second step is a fast step, the four-membered ring intermediate can not stay as a final product. The reaction can be described as a stepwise non-synchronous reaction.

Key words: HNCO, Thermolysis mechanism, Ab initio method