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Study of redox flow battery systems for residential applications Figure 4.3 shows an experimental plot of a charged electrolyte from negative tank titrated with KMnO4 where it is possible to detect the oxidation of V2+, V3+ and VO2+ ions through the equivalence points EP1, EP2 and EP3, respectively, (when the mole number of a specific vanadium ion is equal to the mole number of KMnO4) at different potentials. 1300 1100 900 700 500 300 100 -100 -300 Volume (KMnO4) (mL) Measured value (mV) V2+ Equivalence Point (EP1) V3+ Equivalence Point (EP1) V4+ Equivalence Point (EP3) Figure 4.3 - Example of a titration curve of sample V6T1ChaCy1211116 (charged negative tank) with 0.10 M KMnO4. The reduction reaction of KMnO4 and V2+ ion can be described as [69, 70]: 21.4649 mL; 1021 mV 12.8818 mL; 675 mV 4.5795 mL; 266 mV 0 5 10 15 20 25 MnO4- + 8H+ + 5e- Mn2+ + 4H2O V3+ + e- V2+ Thus, global reaction for V2+ ion oxidation with KMnO4 comes: MnO4- + 5V2+ + 8H+ Mn2+ + 5V3+ + 4H2O 𝐸°Mn7+/Mn2+ = 1.510 V 𝐸°V3+/V2+ = −0.255 V 𝐸° = 1.765V Where the standard potential of the global reaction was determined by using Equation (4.1). 𝐸° = 𝐸°Mn7+/Mn2+ − 𝐸°V3+/V2+ = 1.510 − (−0.255) = 1.765 V (4.1) The reduction reactions of V3+ and VO2+ are [69, 70]: VO2+ + 2H+ + e- V3+ + H2O 𝐸°V4+/V3+ = 0.337 V VO2+ + 2H+ + e- VO2+ + H2O 𝐸°V5+/V4+ = 1.000 V Therefore, the global reactions for V3+ and VO2+ ions oxidation with potassium permanganate are: MnO4- + 5V3+ + H2O Mn2+ + 5VO2+ + 2H+ 𝐸° = 1.173V Chapter 4: Methods and materials 23 Measured potential (mV)PDF Image | Tubular Vanadium Air Redox‐flow battery
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