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voltage change is the same in our 2.5 M H2SO4 and 5 M HCl system, the charging reaction occurs much closer to the Cl2 evolution potential than previously thought. The electrolyte chemistry and Cl2 partial pressure also lower the potential of the Cl-/Cl2 reaction. Figure 3d shows the formal potential of Cl2 gas generation throughout the potential step experiment, as determined by the modified Nernst equation shown in Equation 4. 𝑒𝑞4. 𝐸#=1.359+0.0295𝑙𝑜𝑔?&!"# @14 (()$)# This equation considers the partial pressure of the Cl2 in the headspace as determined by the UGA output and the Cl- concentration in the solution, assumed to be constant at 5 M. When increasing the HCl concentration from 1 M to 5 M, there is a 40 mV reduction in the formal potential at any partial pressure of Cl2 above the solution (Figure S7). The standard 1.359 V reaction potential is for 1 M of Cl- in the solution, not the 5 M commonly found in MA electrolytes and used in this paper. Then we consider the low initial concentration of Cl2 measured in the posolyte headspace and the high concentration of Cl- in the electrolyte. According to Equation 4 and Figure S7, the formal potential of 2Cl-/Cl2 decreases significantly below a partial pressure of 0.1 atm. The observed PCl2 of ~0.012 atm at the beginning of the potential stepping experiment gives a formal potential of 1.257 V vs SHE for much of the test (Figure 3d), ~100 mV lower than the assumed standard potential. If the concentration of HCl in the electrolyte accounts for 40 mV of this 100 mV difference it can be inferred that the remaining 60 mV is from the low Cl2 partial pressure. The high Cl- concentration and low Cl2 partial pressure appear to reduce the gap between the posolyte charging and gas evolution reactions from 360 to 60 mV. Figures 2 and 3 show that 10PDF Image | Chlorine Gas Generation in Mixed-Acid Vanadium Redox
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