New sonochemiluminescence involving solvated electron in Ce(III)/Ce(IV) solutions

The moving single-bubble sonoluminescence of Ce³⁺ in water and ethylene glycol solutions of CeCl₃ and (NH₄)₂Ce(NO₃)₆ was studied. As found, a significant part of intensity of the luminescence (100% with cerium concentration less than 10^–4 M) is due to the sonochemiluminescence. A key reaction of sonochemiluminescence is the Ce⁴⁺ reduction by a solvated (or hydrated in water) electron: Ce⁴⁺ + e_s (e_aq) → *Ce³⁺. Solvated electrons are formed in a solution via electrons ejection from a low-temperature plasma periodically generated in deformable moving bubble at acoustic vibrations. Reactions of heterolytic dissociation of solvents make up the source of electrons in the plasma. In aqueous CeCl₃ solutions, the Ce⁴⁺ ion is formed at the oxidation of Ce³⁺ by OH radical. The latter species originates from homolytic dissociation of water in the plasma of the bubble, also penetrating from the moving bubble into the solution. The sonochemiluminescence in cerium trichloride solutions are quenched by the Br⁻ (acceptor of OH) and H⁺ ions (acceptor of e_aq). In water and ethylene glycol solutions of (NH₄)₂Ce(NO₃)₆, the sonochemiluminescence also quenched by the H⁺ ion. The sonochemiluminescence in CeCl₃ solutions is registered at [Ce³⁺] ≥ 10^–5 M. Then the sonochemiluminescence intensity increases with the cerium ion concentration and reaches the saturation plateau at 10^–2 M. It was shown that sonophotoluminescence (re-emission of light of bubble plasma emitters by cerium ions) also contributes to the luminescence of Ce³⁺ in solutions with [Ce³⁺] ≥ 10^–4 M. If the cerium concentration is more than 10^–2 M, a third source contributes to luminescence, viz., the collisional excitation of Ce³⁺ ions penetrating into the moving bubble.