Photo(solar)-Activated Hypochlorite Treatment: Radicals Analysis Using a Validated Model and Assessment of Efficiency in Organic Pollutants Degradation
Abstract
:1. Introduction
2. Experimental and Modeling Package
2.1. Reagents and Setup Specifications
2.2. Kinetic Model, Simulator, and Computational Approach
2.3. Reactive Species Contribution
3. Results and Discussion
3.1. Validated RhB Degradation Kinetics Using Scavenger Tests
3.2. Determination of Unknown Rate Constants
3.3. Concentration Profiles of ClO−, Reactive Species and Degradation Products
3.3.1. Control Conditions (without Scavengers)
3.3.2. UVsolar/ClO−/TBA and UVsolar/ClO−/BA Systems
3.4. Analysis of Initial Hypochlorite Dosage
3.4.1. RhB and Hypochlorite Decay
3.4.2. ROS and RCS Evolutions
3.4.3. Products and Reactive Species Contribution
3.5. Analysis of Solution Temperature Impact
4. Conclusions
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
References
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Name | Reaction | Rate Constant | Ref. | |
---|---|---|---|---|
R1 | ClO− photolysis Rxns | ClO− O●− + Cl● | (0.028–2.67) × 10−4 s−1 | This study |
R2 | ClO− O(3P) + Cl− | (1.88–2.46) × 10−5 s−1 | This study | |
R3 | ClO− O(1D) + Cl− | 0 s−1 | This study | |
R4 | O(1D)/O(3P) Rxns | O(1D) + H2O → 2●OH | 1.2 × 1011 M−1s−1 | [5] |
R5 | O(3P) + O2 → O3 | 4.0 × 109 M−1s−1 | [5] | |
R6 | O(3P) + ClO− → ClO2− | 9.4 × 109 M−1s−1 | [5] | |
R7 | O(3P) + H2O2 → ●OH + HO2● | 1.6 × 109 M−1s−1 | [5] | |
R8 | O(3P) + HO2− → ●OH + O2●− | 5.3 × 109 M−1s−1 | [5] | |
R9 | O(3P) + OH− → HO2− | 4.2 × 108 M−1s−1 | [5] | |
R10 | O3 → O2 + O(3P) | 4.5 × 10−6 s−1 | [5] | |
R11 | Speciations Rxns | HOCl → H+ + ClO− | 1.41 × 103 s−1 | [5] |
R12 | H+ + ClO− → HOCl | 5.0 × 1010 M−1s−1 | [33] | |
R13 | HOCl + Cl− → Cl2 + H2O | 0.182 M−1s−1 | [5] | |
R14 | Cl2 + H2O → HOCl + Cl− + H+ | 0.27 M−1s | [14] | |
R15 | HOCl + Cl− → Cl2OH− | 1.5 × 104 M−1s−1 | [5] | |
R16 | Cl2 + OH− → HOCl + Cl− | 1.0 × 109 M−1s−1 | [5] | |
R17 | HCl → H+ + Cl− | 8.6 × 1016 s−1 | [14] | |
R18 | H+ + Cl− → HCl | 5.0 × 1010 M−1s−1 | [14] | |
R19 | H2O2 → H+ + HO2− | 0.13 s−1 | [33] | |
R20 | H+ + HO2− → H2O2 | 5.0 × 1010 M−1s−1 | [33] | |
R21 | H2O → H+ + OH− | 0.001 s−1 | [14] | |
R22 | H+ + OH− → H2O | 1.0 × 1011 M−1s−1 | [14] | |
R23 | ●OH Rxns | ●OH + HOCl → ClO● + H2O | 2.0 × 109 M−1s−1 | [34] |
R24 | 2●OH → H2O2 | 5.5 × 109 M−1s−1 | [34] | |
R25 | ●OH + ClO● → ClO2− + H+ | 1.0 × 109 M−1s−1 | [5] | |
R26 | ●OH + H2O2 → HO2● + H2O | 2.7 × 107 M−1s−1 | [33] | |
R27 | ●OH + O2●− → O2 + OH− | 7.0 × 109 M−1s−1 | [14] | |
R28 | ●OH + Cl− → Cl● + OH− | 1.1 × 109 M−1s−1 | [5] | |
R29 | ●OH + Cl2●− → HOCl + Cl− | 1.0 × 109 M−1s−1 | [5,14] | |
R30 | ●OH + ClO− → ClO● + OH− | 8.8 × 109 M−1s−1 | [14] | |
R31 | ●OH + HO2● → O2 + H2O | 6.6 × 109 M−1s−1 | [5,14] | |
R32 | ●OH + Cl− → HOCl●− | 4.3 × 109 M−1s−1 | [14] | |
R33 | ●OH + ClO2− → OH− + ClO2● | 4.5 × 109 M−1s−1 | [5] | |
R34 | ●OH + ClO3− → ClO3● + OH− | 1.0 × 106 M−1s−1 | [5] | |
R35 | ●OH + HO2− → HO2● + OH− | 7.5 × 109 M−1s−1 | [33] | |
R36 | ●OH + HO2− → H2O + O2●− | 7.05 × 109 M−1s−1 | [33] | |
R37 | ●OH + OH− → O●− + H2O | 1.25 × 1010 M−1s−1 | [5] | |
R38 | ●OH + O●− → HO2− | 2.0 × 1010 M−1s−1 | [5] | |
R39 | ●OH + ClO2● → ClO3− + H+ | 4.0 × 109 M−1s−1 | [5] | |
R40 | ●OH + O3●− → HO2● + O2●− | 8.5 × 109 M−1s−1 | [5] | |
R41 | ●OH + O3 → O2 + HO2● | 1.05 × 108 M−1s−1 | [5] | |
R42 | Cl● Rxns | 2Cl● → Cl2. | 8.8.8 × 107 M−1s−1 | [5,14] |
R43 | Cl● + HOCl → Cl− + ClO● + H+ | 3.0 × 109 M−1s−1 | [35] | |
R44 | Cl● + ClO− → Cl− + ClO● | 8.3 × 109 M−1s−1 | [35] | |
R45 | Cl● + Cl2 → Cl3● | 5.3 × 108 M−1s−1 | [5] | |
R46 | Cl● + H2O → HOCl●− + H+ | 2.05 × 105 M−1s−1 | [5] | |
R47 | Cl● + Cl− → Cl2●− | 8.5 × 109 M−1s−1 | [14] | |
R48 | Cl● + OH− → HOCl●− | 1.8 × 1010 M−1s−1 | [14] | |
R49 | Cl● + H2O2 → HO2● + Cl− + H+ | 2.0 × 109 M−1s−1 | [14] | |
R50 | Cl● + ClO3− → Prod_1 | 1.0 × 106 M−1s−1 | [5] | |
R51 | Cl● + ClO2● → Prod_2 | 1.0 × 109 M−1s−1 | [5] | |
R52 | Cl● + Cl2●− → Cl2 + Cl− | 2.1 × 109 M−1s−1 | [5] | |
R53 | Cl● + ClO2− → ClO2● + Cl− | 7.0 × 109 M−1s−1 | [5] | |
R54 | Cl2●− Rxns | 2Cl2●− → Cl2 + 2Cl− | 8.0 × 108 M−1s−1 | [5] |
R55 | Cl2●− + H2O → HOCl●− + Cl− + H+ | 1.3 × 103 M−1s−1 | [5] | |
R56 | Cl2●− + OH− → HOCl●− + Cl− | 4.5 × 107 M−1s−1 | [5] | |
R57 | Cl2●− + ClO− → ClO● + 2Cl− | 2.9 × 108 M−1s−1 | [5] | |
R58 | Cl2●− + O2●− → O2 + 2Cl− | 2.0 × 109 M−1s−1 | [5,14] | |
R59 | Cl2●− + HO2● → O2 + 2Cl− + H+ | 3.0 × 109 M−1s−1 | [14] | |
R60 | Cl2●− + H2O2 → HO2● + 2Cl− + H+ | 1.4 × 105 M−1s−1 | [5] | |
R61 | Cl2●− → Cl● + Cl− | 6.0 × 104 s−1 | [5] | |
R62 | Cl2●− + ClO2● → Prod_3 | 1.0 × 109 M−1s−1 | [5] | |
R63 | ClO● Rxns | 2ClO● → Cl2O2 | 2.5 × 109 M−1s−1 | [36] |
R64 | Cl2O2 + H2O → HOCl + ClO2− + H+ | 4.5 × 107 M−1s−1 | [36] | |
R65 | Cl2O2 + OH− → ClO− + ClO2− + H+ | 2.5 × 109 M−1s−1 | [36] | |
R66 | ClO● + ClO2− → ClO2● + ClO− | 9.4 × 108 M−1s−1 | [5] | |
R67 | Ozone Rxns | O3 + OH− → O2 + HO2− | 48 M−1s−1 | [6] |
R68 | O3 + HO2− → O3●− + HO2● | 5.5 × 106 M−1s−1 | [5] | |
R69 | O3 + HO2● → H+ + O2 + O3●− | 1.6 × 109 M−1s−1 | [5] | |
R70 | O3 + ClO− → 2O2 + Cl− | 110 M−1s−1 | [5] | |
R71 | O3 + ClO− → O2 + ClO2− | 30 M−1s−1 | [5] | |
R72 | O3 + Cl− → O2 + ClO− | 0.0016 M−1s−1 | [5] | |
R73 | O3 + H2O2 → O2 + ●OH + HO2● | 0.0272 M−1s−1 | [5] | |
R74 | O3 + HO2− → O2 + ●OH + O2●− | 5.5 × 106 M−1s−1 | [5] | |
R75 | O3 + Cl2●− → Prod_4 | 9.0 × 107 M−1s−1 | [5] | |
R76 | O3 + O2●− → O2 + O3●− | 1.55 × 109 M−1s−1 | [5] | |
R77 | O3 + ClO2● → O2 + ClO3● | 1230 M−1s−1 | [5] | |
R78 | O3 + ClO3− → Prod_5 | 0.0001 M−1s−1 | [5] | |
R79 | O3 + H+ → Prod_6 | 0.0004 M−1s−1 | [5] | |
R80 | O3 + ClO2− → O3●− + ClO2● | 2.01 × 106 M−1s−1 | [5] | |
R81 | ROS Rxns | H2O2 + Cl2 → 2HCl + O2 | 1.3 × 104 M−1s−1 | [5] |
R82 | H2O2 + HOCl → HCl + H2O + O2 | 1.1 × 104 M−1s−1 | [5] | |
R83 | H2O2 + ClO− → Cl− + H2O + O2 | 1.7 × 105 M−1s−1 | [5] | |
R84 | H2O2 + HO2● → O2 + ●OH + H2O | 3 M−1s−1 | [5] | |
R85 | H2O2 + O2●− → O2 + ●OH + OH− | 0.13 M−1s−1 | [5] | |
R86 | H2O2 + O●− → O2●− + H2O | 4.0 × 108 M−1s−1 | [5] | |
R87 | HO2− + O●− → HO2● + 2OH- | 5.0 × 108 M−1s−1 | [5] | |
R88 | HO2− + O●− → ●OH + O2●− | 4.0 × 108 M−1s−1 | [5] | |
R89 | HO2− + ClO2● → HO2● + ClO2- | 9.57 × 104 M−1s−1 | [5] | |
R90 | HO2● + HOCl → Cl● + OH− + O2 + H+ | 7.5 × 106 M−1s−1 | [5] | |
R91 | HO2● + Cl2 → Cl2●− + H+ + O2 | 1.0 × 109 M−1s−1 | [5] | |
R92 | HO2● → H+ + O2●− | 1.6 × 105 M−1s−1 | [5] | |
R93 | HO2● + O2●− → H2O2 + O2 + OH- | 7.9 × 107 M−1s−1 | [5] | |
R94 | HO2● + O2●− → HO2− + O2 | 9.7 × 107 M−1s−1 | [5] | |
R95 | 2 HO2● → H2O2 + O2 | 8.3 × 105 M−1s−1 | [5] | |
R96 | HO2● + ClO2● → Prod_7 | 1.0 × 106 M−1s−1 | [5] | |
R97 | O2●− + HOCl → Cl● + OH− + O2 | 7.5 × 106 M−1s−1 | [5] | |
R98 | O2●− + HOCl → Cl− + ●OH + O2 | 7.5 × 106 M−1s−1 | [5] | |
R99 | O2●− + ClO− → Cl● + 2 OH− + O2 | 2.0 × 108 M−1s−1 | [5] | |
R100 | O2●− + Cl2 → Cl2●− + O2 | 1.0 × 109 M−1s−1 | [5] | |
R101 | O2●− + O●− → 2OH− + O2 | 6.0 × 108 M−1s−1 | [5] | |
R102 | O2●− + Cl− → Prod_8 | 140 M−1s−1 | [5] | |
R103 | O2●− + ClO2● → O2 + ClO2- | 3.15 × 109 M−1s−1 | [5] | |
R104 | O2●− + ClO2− → Prod_9 | 40 M−1s−1 | [5] | |
R105 | O2●− + H+ → HO2● | 5.0 × 1010 M−1s−1 | [33] | |
R106 | O2●− + ClO3− → Prod_10 | 3.2 × 103 M−1s−1 | [5] | |
R107 | O3●− → O2 + O●− | 3.2 × 103 s−1 | [5,6] | |
R108 | O3●− + ClO● → ClO− + O3 | 1.0 × 109 M−1s−1 | [5] | |
R109 | O3●− + H+ → O2 + ●OH | 9.0 × 1010 M−1s−1 | [5] | |
R110 | O3●− + O●− → 2O2●− | 7.0 × 108 M−1s−1 | [5] | |
R111 | O3●− + ClO2● → O2 + ClO3− | 1.8 × 105 M−1s−1 | [5] | |
R112 | 2O3●− → Prod_11 | 9.0 × 108 M−1s−1 | [5] | |
R113 | O3●− + ClO2● → ClO2− + O3 | 3.15 × 109 M−1s−1 | [5] | |
R114 | O●− + ClO− + H2O → ClO● + 2OH− | 2.3 × 108 M−1s−1 | [5] | |
R115 | O●− + H2O → ●OH + OH− | 1.8 × 106 M−1s−1 | [14] | |
R116 | O●− + O2 → O3●− | 3.5 × 109 M−1s−1 | [5] | |
R117 | O●− + ClO2− → OH− + ClO2● | 1.95 × 108 M−1s−1 | [5] | |
R118 | 2O●− → O22 − | 4.65 × 109 M−1s−1 | [5] | |
R119 | O●− + ClO2● → ClO3− | 2.7 × 109 M−1s−1 | [5] | |
R120 | Other RCS Rxns | HOCl●− → Cl− + ●OH | 6.1 × 109 M−1s−1 | [37] |
R121 | HOCl●− + H+ → Cl● + H2O | 2.1 × 1010 M−1s−1 | [5] | |
R122 | HOCl●− + Cl− → Cl2●− + OH− | 1.0 × 104 M−1s−1 | [5] | |
R123 | ClO2● → Cl● + O2 | 6.7 × 109 M−1s−1 | [5] | |
R124 | Pollutants Rxns | P + ●OH → Prod_●OH | 2.5 × 1010 M−1s−1 | [33] |
R125 | P + O●− → Prod_O●− | 4.8 × 109 M−1s−1 | This study | |
R126 | P + O3 → Prod_O3 | 2450 M−1s−1 | [38] | |
R127 | P + Cl● → Prod_Cl● | 1.45 × 109 M−1s−1 | This study | |
R128 | P + ClO● → Prod_ClO● | 8.70 × 104 M−1s−1 | This study | |
R129 | P + Cl2●− → Prod_Cl2●− | 2.50 × 107 M−1s−1 | This study | |
R130 | P + HOCl●− → Prod_HOCl●− | 4.10 × 104 M−1s−1 | This study | |
R131 | P + HO2● → Prod_HO2● | 7.30 × 105 M−1s−1 | This study | |
R132 | P + O2●− → Prod_O2●− | 3.60 × 104 M−1s−1 | This study | |
R133 | P + O(3P) → Prod_O(3P) | 0.40 M−1s−1 | This study | |
R134 | TBA Rxns | TBA + Cl● → Prod_Cl●-TBA | 3 × 108 M−1s−1 | [39] |
R135 | TBA + ClO● → Prod_ClO●-TBA | 1.30 × 107 M−1s−1 | [39] | |
R136 | TBA + Cl2●− → Prod_Cl2●−-TBA | 700 M−1s−1 | [39] | |
R137 | TBA + ●OH → Prod_●OH-TBA | 3.80 × 108 M−1s−1 | [40] | |
R138 | TBA + O3 → Prod_O3-TBA | 0.003 M−1s−1 | [41] | |
R139 | TBA + O●− → Prod_O●−-TBA | 5 × 108 M−1s−1 | ||
R140 | BA Rxns | BA + Cl● → Prod_Cl●-BA | 1.8 × 1010 M−1s−1 | [39] |
R141 | BA + ClO● → Prod_ClO●-BA | <3 × 106 M−1s−1 | [42] | |
R142 | BA + Cl2●− → Prod_Cl2●−-BA | 2 × 106 M−1s−1 | [5] | |
R143 | BA + ●OH → Prod_●OH-BA | 5.27 × 109 M−1s−1 | [5] | |
R144 | BA + O●− → Prod_O●−-BA | 4 × 107 M−1s−1 | [5] |
Species | Rate (M/s) | Contribution (%) |
---|---|---|
[ClO−]₀ = 1000 µM | ||
RhB | 2.89 × 10−6 | |
Prod_Cl• | 1.93 × 10−8 | 0.67 |
Prod_•OH | 1.94 × 10−6 | 67.01 |
Prod_O•− | 6.05 × 10−8 | 2.09 |
Prod_ClO• | 8.58 × 10−7 | 29.63 |
Prod_O₃ | 1.75 × 10−8 | 0.60 |
[ClO−]₀ = 500 µM | ||
RhB | 1.25 × 10−6 | |
Prod_Cl• | 4.61 × 10−9 | 0.37 |
Prod_•OH | 7.84 × 10−7 | 62.78 |
Prod_O•− | 2.12 × 10−8 | 1.70 |
Prod_ClO• | 3.69 × 10−7 | 29.54 |
Prod_O₃ | 7.00 × 10−8 | 5.61 |
[ClO−]₀ = 300 µM | ||
RhB | 2.70 × 10−7 | |
Prod_Cl• | 5.60 × 10−10 | 0.21 |
Prod_•OH | 1.31 × 10−7 | 48.43 |
Prod_O•− | 3.32 × 10−9 | 1.23 |
Prod_ClO• | 9.16 × 10−8 | 33.93 |
Prod_O₃ | 4.38 × 10−8 | 16.21 |
Species | Rate (M/s) | Contribution (%) |
---|---|---|
Temp. 25 °C | ||
RhB | 2.89 × 10−6 | |
Prod_Cl• | 1.93 × 10−8 | 0.67 |
Prod_•OH | 1.94 × 10−6 | 67.01 |
Prod_O•− | 6.05 × 10−8 | 2.09 |
Prod_ClO• | 8.58 × 10−7 | 29.63 |
Prod_O₃ | 1.75 × 10−8 | 0.60 |
Temp. 35 °C | ||
RhB | 3.35 × 10−6 | |
Prod_Cl• | 2.27 × 10−8 | 0.68 |
Prod_•OH | 2.32 × 10−6 | 69.25 |
Prod_O•− | 7.25 × 10−8 | 2.16 |
Prod_ClO• | 9.18 × 10−7 | 27.39 |
Prod_O₃ | 1.72 × 10−8 | 0.51 |
Temp. 45 °C | ||
RhB | 4.58 × 10−6 | |
Prod_Cl• | 3.18 × 10−8 | 0.69 |
Prod_•OH | 3.38 × 10−6 | 73.77 |
Prod_O•− | 1.06 × 10−7 | 2.31 |
Prod_ClO• | 1.03 × 10−6 | 22.50 |
Prod_O₃ | 3.33 × 10−8 | 0.73 |
Temp. 55 °C | ||
RhB | 5.87 × 10−6 | |
Prod_Cl• | 4.07 × 10−8 | 0.69 |
Prod_•OH | 4.55 × 10−6 | 77.54 |
Prod_O•− | 1.43 × 10−7 | 2.44 |
Prod_ClO• | 1.03 × 10−6 | 17.53 |
Prod_O₃ | 3.50 × 10−8 | 0.60 |
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Amichi, H.; Merouani, S.; Dehane, A.; Bouchoucha, H.; Hamdaoui, O. Photo(solar)-Activated Hypochlorite Treatment: Radicals Analysis Using a Validated Model and Assessment of Efficiency in Organic Pollutants Degradation. Processes 2024, 12, 1853. https://doi.org/10.3390/pr12091853
Amichi H, Merouani S, Dehane A, Bouchoucha H, Hamdaoui O. Photo(solar)-Activated Hypochlorite Treatment: Radicals Analysis Using a Validated Model and Assessment of Efficiency in Organic Pollutants Degradation. Processes. 2024; 12(9):1853. https://doi.org/10.3390/pr12091853
Chicago/Turabian StyleAmichi, Hayet, Slimane Merouani, Aissa Dehane, Hana Bouchoucha, and Oualid Hamdaoui. 2024. "Photo(solar)-Activated Hypochlorite Treatment: Radicals Analysis Using a Validated Model and Assessment of Efficiency in Organic Pollutants Degradation" Processes 12, no. 9: 1853. https://doi.org/10.3390/pr12091853