Homogeneous electron-transfer reaction between anionic species of anthraquinone derivatives and molecular oxygen in acetonitrile solutions: Electrochemical properties of disperse red 60
| Autor: | Pablo D. Astudillo-Sánchez, Magali Salas-Reyes, Roberto Flores-Moreno, Gilberto Rocha-Ortiz, Malcolm E. Tessensohn, Richard D. Webster |
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| Rok vydání: | 2020 |
| Předmět: |
General Chemical Engineering
Inorganic chemistry 02 engineering and technology 010402 general chemistry 021001 nanoscience & nanotechnology Electrochemistry 01 natural sciences 0104 chemical sciences Quinone chemistry.chemical_compound Electron transfer chemistry Molecule Bulk electrolysis Cyclic voltammetry 0210 nano-technology Acetonitrile Equilibrium constant |
| Zdroj: | Electrochimica Acta. 354:136601 |
| ISSN: | 0013-4686 |
| DOI: | 10.1016/j.electacta.2020.136601 |
| Popis: | In this work, the voltammetric behaviour of disperse red 60 (DR60) in acetonitrile solutions in the presence of water and dioxygen (O2) is reported for the first time. DR60 can be reduced in two one-electron steps to form first the anion radical and then the dianion. The first reduction process of DR60 is affected by the water content of the acetonitrile, with digital simulations of the cyclic voltammetric waves supporting interactions between the radical anion and water molecules. Additionally, the presence of O2 modifies the first voltammetric process of DR60, suggesting the occurrence of homogeneous electron transfer reaction between anion radicals of DR60 and O2. Furthermore, the water content of the acetonitrile also affects the reduction wave of O2, with digital simulations supporting the occurrence of two association steps with the superoxide intermediate. The homogeneous electron transfer reaction between the quinone and oxygen species was also examined by reacting bulk electrolyzed solutions containing the anions of DR60 and O2 with neutral species of O2 and DR60, respectively, and recording the variation in the colour of the electrolyzed solutions. An equilibrium constant value was obtained from the difference between the formal reduction potentials of DR60 and O2 (−0.9955 and −0.9770, respectively, both vs. Ag in CH3CN with 0.5 M n-Bu4NPF6), indicating the direction of the homogenous electron transfer reaction (Keq = 2.013). Similarly, to confirm the occurrence of the homogeneous electron transfer reaction between O2 and another quinone based molecule, cyclic voltammetry and bulk electrolysis experiments were carried out on 9,10-anthraquinone (AQ), and its equilibrium constant value was also obtained (Keq = 4.392). |
| Databáze: | OpenAIRE |
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