The reaction rate constant of chlorine nitrate hydrolysis

The first-order rate constant for the decomposition of chlorine nitrate (ClONO2) by water in a cyclic 1:3 complex at stratospheric temperatures is shown to be close to the values for the hydrolysis rate coefficient of chlorine nitrate on an ice surface determined in the laboratory. On the other hand the rate constants calculated for the cyclic 1:1 and 1:2 complexes are much lower than the experimental results. From the mechanistic point of view the reaction is found to be similar to a SN2 mechanism and coupled with water-mediated proton transfer in accordance with the intriguing findings of Bianco and Hynes R. Bianco, J. T. Hynes. J. Phys. Chem. A 1998, 102, 309-314]. The function of additional water molecules is to act as a catalyst, that is, to accelerate the hydrolysis process. Quantum-mechanical tunneling is negligible above 125 K in the 1:3 complex and above 175 K in the 1:2 complex. At temperatures below these limits all involved protons tunnel through the barrier at energies at least 5 kcalmol(-1) below the barrier-top in a concerted, but asynchronous manner.