Reactions of ligands from BT(B)P family with solvated electrons and benzophenone ketyl radicals in 1-octanol solutions. Pulse radiolysis study

Abstract

Pulse radiolysis involving reactions of solvated electrons and benzophenone ketyl radicals in 1-octanol with selected compounds from bis-triazinyl pyridines and bis-triazinyl bipyridines, BT(B)P family, developed for extraction of trivalent actinides have been studied. The designated ligands were: 2,6-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzo-[1,2,4]triazin-3-yl)pyridine, 6,6′-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzo-[1,2,4-]triazin-3-yl)-[2,2′]bipyridine, 6,6′-bis(5,6-diethyl-[1,2,4]triazin-3-yl)-[2,2′]bipyridine and 6,6′-bis(5,6-dipentyl-[1,2,4]triazin-3-yl)-[2,2′]bipyridine. Reactions of the ligands with solvated electrons in 1-octanol are fast. The rate constants were determined as equal to: $$ k_{{{\text{CyMe}}_{4} {\text{BTP}}}} . $$ = (2.4 ± 0.2) × 109 dm3 mol−1 s−1, $$ k_{{{\text{CyMe}}_{ 4} {\text{BTBP}}}} $$ = (1.7 ± 0.3) × 109 dm3 mol−1 s−1, $$ k_{{{\text{C}}_{ 2} {\text{BTBP}}}} $$ = (1.3 ± 0.3) × 109 dm3 mol−1 s−1 and $$ k_{{{\text{C}}_{ 5} {\text{BTBP}}}} $$ = (1.7 ± 0.3) × 109 dm3 mol−1 s−1. Reactions of the ligands with benzophenone ketyl radicals are much slower and the measured rate constants were as follows: $$ k_{{{\text{CyMe}}_{ 4} {\text{BTP}}}} $$ = 6.7 × 107 dm3 mol−1 s−1 and $$ k_{{{\text{CyMe}}_{ 4} {\text{BTBP}}}} $$ = 3.2 × 107 dm3 mol−1 s−1.