PROCESSES OCCURRING DURING PHOTOLYSIS OF VITREOUS SOLUTIONS OF CHLORINE IN HYDROCHLORIC-ACID AT 77-K

Optical spectroscopy was used to study the photolysis by 365-nm light of solutions of chlorine in a matrix of a vitreous aqueous HCl solutio n (congruent-to 10 M) at 77 K. A scheme of the reactions occurring dur ing the photolysis is presented. The scheme includes a photochemical r eaction of formation of Cl2- radical-anion pairs, a step of free-valen ce migration, consisting of a sequence of photodecomposition reactions of the Cl2- radical anion and stabilization of the Cl atom formed dur ing the photodecomposition by the "nonparent" Cl- anion, and reactions of chain termination of the photochemical chain process, consisting o f reactions of recombination of the Cl atom with the Cl2- radical anio n or stabilization of the Cl atom by a Cl2- molecule or Cl3- anion.