Evolution of the Bromate Electrolyte Composition in the Course of Its Electroreduction inside a Membrane–Electrode Assembly with a Proton-Exchange Membrane
Abstract
:1. Introduction
2. Results and Discussion
2.1. Theoretical Analysis
2.1.1. Definitions and Balance Relations
or
2 cA = cH + cHSO4 + 2 cH2SO4 + ctot + ∑ xi ci + ∑ hi ci − 2 ∑ oi ci,
i.e., cHSO4 ≅ cA cH (Ka + cH)−1, cSO4 ≅ cA Ka (Ka + cH)−1,
or
cH(H2SO4) ≅ cH + ctot − [Br−] − [Br3−] − [Br5−] – [BrO−] – [BrO3−],
2.1.2. Thermodynamic Relations
2.1.3. Set of Equations
and
cH ≅ cH(H2SO4) − ctot + [Br−] + [Br3−] + [Br5−] + [BrO−] + [BrO3−],
2.2. General Shapes of Various Dependencies
2.3. Variation in Dissociation Degree of Sulfuric Acid
2.4. Effect of Added Acid Concentration for ctot = 0.1 M
2.5. Effect of Initial Bromate Concentration
3. Materials and Methods
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Appendix A
No. | Transformation | Equilibrium Relation | Value of Parameter |
---|---|---|---|
(A1) | Br2 + 2e− ⇄ 2Br− | 2 A (E − E1o) = log {Br2} − 2 log {Br−} | E1o = 1.0874 V [34] |
(A2) | HBrO + H+ + 2e− ⇄ Br− + H2O | 2 A (E − E2o) = log {HBrO} − pH − log {Br−} | E2o = 1.341 V [34] |
(A3) | BrO3− + 6H+ + 6e− ⇄ Br− + 3H2O | 6 A (E − E3o) = log {BrO3−} − 6 pH − log {Br−} E3o = E3bo + 14.0/A, E3bo for pH= 14 | E3bo = 0.584 V [34] E3o = 1.410 V |
(A4) | BrO4− + 8H+ + 8e− ⇄ Br− + 4H2O | 8 A (E − E4o) = log {BrO4−} − 8 pH − log {Br−} E4o = 0.75 E3o + 0.25 E8o | E4o = 1.520 V [34] |
(A5) | Br3− + 2e− ⇄ 3Br− | 2 A (E − E5o) = log {Br3−} − 3 log {Br−} | E5o = 1.0503 V [34] |
(A6) 1 | Br5− + 4e− ⇄ 5Br− | 4 A (E − E6o) = log {Br5−} − 5 log {Br−} 4 A (E1o − E6o) = log (K12 K11) = 1.44 | E6o = 1.066 V [11] |
(A7) | Br2liq + 2e− ⇄ Br2,sat + 2e− ⇄ 2Br−sat | 2 A (E − E7o) = −2 log {Br−}sat 2 A (E − E1o) = log {Br2}sat − 2 log {Br−}sat | E7o = 1.0652 V [34] {Br2}sat = 0.185 M [31] |
(A8) | BrO4− + 2H+ + 2e− ⇄ BrO3− + H2O | 2 A (E − E8o) = log {BrO4−} − 2 pH − log {BrO3−} | E8o = 1.853 V [34] |
(A9) | BrO− + H2O + 2e− ⇄ Br− + 2OH− | 2 A (E − E9o) = log {BrO−} − log {Br−} + 2 pOH | E9o = 0.766 V [34] |
(A10) 1 | BrO− + 2H+ + 2e− ⇄ Br− + H2O | 2 A (E − E10o) = log {BrO−} − log {Br−} –2 pH E10o − E9o = 14.0/A | E10o = 1.593 V |
(A11) | Br− + Br2 ⇄ Br3− | {Br3−} = K11 {Br−} {Br2}, log K11 = 2 A (E1o − E5o) | K11 = 17.9 [31] |
(A12) | Br3− + Br2 ⇄ Br5− | {Br5−} = K12 {Br3−} {Br2} = K12 K11 {Br−} {Br2}2 | K12 = 1.54 [31] |
(A13) 1,2 | Br2vap ⇄ Br2 | {Br2vap}sol = {Br2vap}Vgas/Vsol = K13 {Br2} {Br2vap} = Kvap {Br2}, K13 = Kvap Vgas/Vsol, | Kvap = 5.92·10−2 [35] |
(A14) 1 | BrO− + H+ ⇄ HBrO | {HBrO} = K14 {BrO−}, log K14 = −pH + 2 A (E10o − E2o) | log K14 = −pH + 8.5 [36] |
(A15) | Br2 + H2O ⇄ HBrO + Br− + H+ | {HBrO}{Br−} = K15 {Br2} log K15 = pH + 2 A (E1o − E2o) | log K15 = pH − 8.6 [36] 3 |
(A16) | Br2 + H2O ⇄ BrO− + Br− + 2H+ | {BrO−}{Br−} = K16 {Br2}, K16 = K15/K14 | log K16 = 2 pH − 17.1 [36] |
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i | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
---|---|---|---|---|---|---|---|---|---|
Br− | Br3− | Br5− | Br2 | HBrO | BrO− | BrO3− | Br2liq | Br2vap | |
ni | 1 | 3 | 5 | 2 | 1 | 1 | 1 | 2 | 2 |
xi | −1 | −1 | −1 | 0 | +1 | +1 | +5 | 0 | 0 |
hi | 0 | 0 | 0 | 0 | 1 | 0 | 0 | 0 | 0 |
oi | 0 | 0 | 0 | 0 | 1 | 1 | 3 | 0 | 0 |
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Konev, D.V.; Zader, P.A.; Vorotyntsev, M.A. Evolution of the Bromate Electrolyte Composition in the Course of Its Electroreduction inside a Membrane–Electrode Assembly with a Proton-Exchange Membrane. Int. J. Mol. Sci. 2023, 24, 15297. https://doi.org/10.3390/ijms242015297
Konev DV, Zader PA, Vorotyntsev MA. Evolution of the Bromate Electrolyte Composition in the Course of Its Electroreduction inside a Membrane–Electrode Assembly with a Proton-Exchange Membrane. International Journal of Molecular Sciences. 2023; 24(20):15297. https://doi.org/10.3390/ijms242015297
Chicago/Turabian StyleKonev, Dmitry V., Pavel A. Zader, and Mikhail A. Vorotyntsev. 2023. "Evolution of the Bromate Electrolyte Composition in the Course of Its Electroreduction inside a Membrane–Electrode Assembly with a Proton-Exchange Membrane" International Journal of Molecular Sciences 24, no. 20: 15297. https://doi.org/10.3390/ijms242015297