Theoretical and Experimental Studies on the Reaction Mechanism of Cl2 + I2 = 2ICl

The gas phase reaction mechanism of Cl2 + I2 = 2ICl has been theoretically investigated by DFT method at the B3LYP/3-21G* level. Transition states of three reaction channels were consequently given. The results indicate that in the title reaction the least activation energy of bi-molecular reaction was smaller than the dissociation energies of I2 and Cl2, and thus the reaction mechanism was the course of molecule-molecule interaction at low reaction rate. If other factors such as illumination were taken into account, I2 could dissociate into I atoms and then react with Cl2, or Cl2 dissociates into Cl atoms and reacts with I2. These were photochemical reactions with high reaction speed. The theoretical results were further validated with absorbance measurement at 516 nm.