Novel valence states of thallium as studied by pulse radiolysis

Abstract

The absorption spectra of Tl²⁺ and Tl₂⁺ in aqueous solutions have been obtained using the technique of pulse radiolysis. The formation and reactions of the species have been studied under a variety of conditions, and rate constants for the following reactions have been obtained: OH + Tl⁺→ OH^–+ Tl²⁺(7·6 ± 1)× 10⁹ l. mole^–1 sec.^–1, 2 Tl²⁺→ Tl⁺+ Tl³⁺(2·3 ± 0·8)× 10⁹ l. mole^–1 sec.^–1 at zero ionic strength, Tl²⁺+ HO₂→ Tl⁺+ H⁺+ O₂(2·5 ± 1)× 10⁹ l. mole^–1 sec.^–1, Tl²⁺+ H₂O₂→ Tl⁺+ H⁺+ HO₂(2·8 ± 0·8)× 10⁷ l. mole^–1 sec.^–1 Tl + Tl⁺⇌ Tl₂⁺K₆=k_F/k_B= 2·3 × 10³ l. mole^–1 Tl₂⁺+ Tl²⁺→ 3 Tl⁺(4·4 ± 0·9)× 10⁹ l. mole^–1 sec.^–1 at zero ionic strength