Kinetics of azobenzene nitrene oxidation by molecular oxygen in glassy propylene carbonate

J Chem Phys. 2011 Dec 28;135(24):244504. doi: 10.1063/1.3671637.

Abstract

The kinetics of azobenzene nitrene oxidation by molecular oxygen dissolved in a matrix was studied in glassy propylene carbonate. The reaction was carried out in excess oxygen within its concentration range 0.008 to 0.048 M. The oxidation kinetics, controlled by oxygen diffusion, is not described by the exponential function. A specific reaction rate decreases in the course of the process. The higher the oxygen concentration in the matrix, the sharper is the decrease in the reaction rate. It is shown that at all concentrations, the oxidation kinetics is described in the framework of the model of heterogeneous matrix with a characteristic size of heterogeneities of 1.5 nm and a dispersion of the activation energy of oxygen molecule jump of 4 kJ/mol. The reaction radius is about 0.5 nm.