Fenton's reagent: Difference between revisions
→top: actually this whole sentence is pointless. Completely redundant, and contradictorilly over-specific compared to preceding one. |
Gave a more in-depth discussion to the effects of pH on the formation of radicals. Also gave input application of Fenton's reagent in the water science field. |
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{{NumBlk|:| 2 H<sub>2</sub>O<sub>2</sub> → HO• + HOO• + H<sub>2</sub>O|{{EquationRef|net reaction: 1+2}}}} |
{{NumBlk|:| 2 H<sub>2</sub>O<sub>2</sub> → HO• + HOO• + H<sub>2</sub>O|{{EquationRef|net reaction: 1+2}}}} |
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The [[free radical]]s generated by this process then engage in secondary reactions. For example, the hydroxyl is a powerful, non-selective oxidant.{{ |
The [[free radical]]s generated by this process then engage in secondary reactions. For example, the hydroxyl is a powerful, non-selective oxidant.<ref>{{Citation|last=Cai|first=Q. Q.|title=11 - Fenton- and ozone-based AOP processes for industrial effluent treatment|date=2021-01-01|url=https://www.sciencedirect.com/science/article/pii/B9780128210116000116|work=Advanced Oxidation Processes for Effluent Treatment Plants|pages=199–254|editor-last=Shah|editor-first=Maulin P.|publisher=Elsevier|language=en|doi=10.1016/b978-0-12-821011-6.00011-6|isbn=978-0-12-821011-6|access-date=2021-04-08|last2=Jothinathan|first2=L.|last3=Deng|first3=S. H.|last4=Ong|first4=S. L.|last5=Ng|first5=H. Y.|last6=Hu|first6=J. Y.}}</ref> Oxidation of an organic compound by Fenton's reagent is rapid and [[exothermic]] and results in the oxidation of contaminants to primarily carbon dioxide and water. |
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Reaction ({{EquationNote|1}}) was suggested by [[Fritz Haber|Haber]] and [[Joseph Joshua Weiss|Weiss]] in the 1930s as part of what would become the [[Haber–Weiss reaction]].<ref name="Haber_Weiss_1932">{{cite journal |author1=Haber, F. |author2=Weiss, J. | year = 1932 | title = Über die katalyse des hydroperoxydes | trans-title= On the catalysis of hydroperoxides | journal = [[Naturwissenschaften]] | doi = 10.1007/BF01504715|volume = 20|issue = 51|pages = 948–950|bibcode = 1932NW.....20..948H|s2cid=40200383 }}</ref> |
Reaction ({{EquationNote|1}}) was suggested by [[Fritz Haber|Haber]] and [[Joseph Joshua Weiss|Weiss]] in the 1930s as part of what would become the [[Haber–Weiss reaction]].<ref name="Haber_Weiss_1932">{{cite journal |author1=Haber, F. |author2=Weiss, J. | year = 1932 | title = Über die katalyse des hydroperoxydes | trans-title= On the catalysis of hydroperoxides | journal = [[Naturwissenschaften]] | doi = 10.1007/BF01504715|volume = 20|issue = 51|pages = 948–950|bibcode = 1932NW.....20..948H|s2cid=40200383 }}</ref> |
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{{NumBlk|:| C<sub>6</sub>H<sub>6</sub> + FeSO<sub>4</sub> + H<sub>2</sub>O<sub>2</sub> → C<sub>6</sub>H<sub>5</sub>OH|{{EquationRef|3}}}} |
{{NumBlk|:| C<sub>6</sub>H<sub>6</sub> + FeSO<sub>4</sub> + H<sub>2</sub>O<sub>2</sub> → C<sub>6</sub>H<sub>5</sub>OH|{{EquationRef|3}}}} |
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An example hydroxylation reaction involves the [[Organic redox reaction|oxidation]] of [[barbituric acid]] to [[alloxane]].<ref>{{cite journal |vauthors=Brömme HJ, Mörke W, Peschke E |title=Transformation of barbituric acid into alloxan by hydroxyl radicals: interaction with melatonin and with other hydroxyl radical scavengers |journal=J. Pineal Res. |volume=33 |issue=4 |pages=239–47 |date=November 2002 |pmid=12390507 |doi= 10.1034/j.1600-079X.2002.02936.x|s2cid=30242100 }}</ref> Another application of the reagent in organic synthesis is in [[coupling reaction]]s of alkanes. As an example [[Tert-Butanol|''tert''-butanol]] is dimerized with Fenton's reagent and [[sulfuric acid]] to 2,5-dimethyl-2,5-hexanediol.<ref>{{OrgSynth | collvol = 5 | collvolpages = 1026 | prep = cv5p1026 | title = α,α,α',α'-Tetramethyltetramethylene glycol | author = E. L. Jenner | year = 1973}}</ref> |
An example hydroxylation reaction involves the [[Organic redox reaction|oxidation]] of [[barbituric acid]] to [[alloxane]].<ref>{{cite journal |vauthors=Brömme HJ, Mörke W, Peschke E |title=Transformation of barbituric acid into alloxan by hydroxyl radicals: interaction with melatonin and with other hydroxyl radical scavengers |journal=J. Pineal Res. |volume=33 |issue=4 |pages=239–47 |date=November 2002 |pmid=12390507 |doi= 10.1034/j.1600-079X.2002.02936.x|s2cid=30242100 }}</ref> Another application of the reagent in organic synthesis is in [[coupling reaction]]s of alkanes. As an example [[Tert-Butanol|''tert''-butanol]] is dimerized with Fenton's reagent and [[sulfuric acid]] to 2,5-dimethyl-2,5-hexanediol.<ref>{{OrgSynth | collvol = 5 | collvolpages = 1026 | prep = cv5p1026 | title = α,α,α',α'-Tetramethyltetramethylene glycol | author = E. L. Jenner | year = 1973}}</ref> Fenton's reagent is also widely used in the field of environmental science for [[water purification]] and [[Environmental remediation|soil remediation]]. Various hazardous wastewater were reported to be effectively degraded through Fenton's reagent<ref>{{Cite journal|last=Cai|first=Q. Q.|last2=Lee|first2=B. C. Y.|last3=Ong|first3=S. L.|last4=Hu|first4=J. Y.|date=2021-02-15|title=Fluidized-bed Fenton technologies for recalcitrant industrial wastewater treatment–Recent advances, challenges and perspective|url=https://www.sciencedirect.com/science/article/pii/S0043135420312276|journal=Water Research|language=en|volume=190|pages=116692|doi=10.1016/j.watres.2020.116692|issn=0043-1354}}</ref> . |
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==Effect of pH on |
==Effect of pH on formation of free radicals== |
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pH affects the reaction rate due to a variety of different reasons. At a low pH, complexation of Fe<sup>2+</sup> also occurs, leading to lower availability of Fe<sup>2+</sup> to form [[Radicals|reactive oxidative species]] (OH•)<ref>{{Cite journal|last=Xu|first=Xiang-Rong|last2=Li|first2=Xiao-Yan|last3=Li|first3=Xiang-Zhong|last4=Li|first4=Hua-Bin|date=2009-08-05|title=Degradation of melatonin by UV, UV/H2O2, Fe2+/H2O2 and UV/Fe2+/H2O2 processes|url=https://www.sciencedirect.com/science/article/pii/S1383586609002202|journal=Separation and Purification Technology|language=en|volume=68|issue=2|pages=261–266|doi=10.1016/j.seppur.2009.05.013|issn=1383-5866}}</ref>. Lower pH also results in the scavenging of <sup>•</sup>OH by excess H<sup>+</sup> <ref>{{Cite journal|last=Tang|first=W. Z.|last2=Huang|first2=C. P.|date=1996-12-01|title=2,4-Dichlorophenol Oxidation Kinetics by Fenton's Reagent|url=https://www.tandfonline.com/doi/abs/10.1080/09593330.1996.9618465|journal=Environmental Technology|volume=17|issue=12|pages=1371–1378|doi=10.1080/09593330.1996.9618465|issn=0959-3330}}</ref>, hence reducing its reaction rate. Whereas at high pH, the reaction slows down due to precipitation of Fe(OH)<sub>3</sub>, lowering the concentration of the Fe<sup>3+</sup> species in solution.<ref>{{Cite journal|last=Cai|first=Q. Q.|last2=Lee|first2=B. C. Y.|last3=Ong|first3=S. L.|last4=Hu|first4=J. Y.|date=2021-02-15|title=Fluidized-bed Fenton technologies for recalcitrant industrial wastewater treatment–Recent advances, challenges and perspective|url=https://www.sciencedirect.com/science/article/pii/S0043135420312276|journal=Water Research|language=en|volume=190|pages=116692|doi=10.1016/j.watres.2020.116692|issn=0043-1354}}</ref> [[Solubility]] of iron species is directly governed by the solution's [[pH]]. Fe<sup>3+</sup> is about 100 times less soluble than Fe<sup>2+</sup> in natural water at near-neutral pH, the ferric ion concentration is the limiting factor for the reaction rate. Under high pH conditions, the stability of the H<sub>2</sub>O<sub>2</sub> is also affected, resulting in its self-decomposition <ref>{{Cite journal|last=Szpyrkowicz|first=Lidia|last2=Juzzolino|first2=Claudia|last3=Kaul|first3=Santosh N|date=2001-06|title=A Comparative study on oxidation of disperse dyes by electrochemical process, ozone, hypochlorite and fenton reagent|url=http://dx.doi.org/10.1016/s0043-1354(00)00487-5|journal=Water Research|volume=35|issue=9|pages=2129–2136|doi=10.1016/s0043-1354(00)00487-5|issn=0043-1354}}</ref>. Higher pH also decreased the redox potential of <sup>•</sup>OH thereby reducing its effectiveness. <ref>{{Cite journal|last=Velichkova|first=Filipa|last2=Delmas|first2=Henri|last3=Julcour|first3=Carine|last4=Koumanova|first4=Bogdana|date=2016-06-28|title=Heterogeneous fenton and photo-fenton oxidation for paracetamol removal using iron containing ZSM-5 zeolite as catalyst|url=http://dx.doi.org/10.1002/aic.15369|journal=AIChE Journal|volume=63|issue=2|pages=669–679|doi=10.1002/aic.15369|issn=0001-1541}}</ref> pH plays a crucial role in the formation of free radicals and hence the reaction performance. Thus ongoing research has been done to optimize pH and amongst other parameters for greater reaction rates.<ref>{{Cite journal|last=Cai|first=Qinqing|last2=Lee|first2=Brandon Chuan Yee|last3=Ong|first3=Say Leong|last4=Hu|first4=Jiangyong|date=2021-01-14|title=Application of a Multiobjective Artificial Neural Network (ANN) in Industrial Reverse Osmosis Concentrate Treatment with a Fluidized Bed Fenton Process: Performance Prediction and Process Optimization|url=https://doi.org/10.1021/acsestwater.0c00192|journal=ACS ES&T Water|doi=10.1021/acsestwater.0c00192}}</ref> |
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As the Fenton reaction depends on the simultaneous presence (in solution) of dissolved Fe<sup>2+</sup> and Fe<sup>3+</sup> ions, its kinetics are influenced by the respective [[solubility|solubilities]] of both species as a direct-function of the solution's [[pH]]. As Fe<sup>3+</sup> is about 100 times less soluble than Fe<sup>2+</sup> in natural water at near-neutral pH, the ferric ion concentration is the limiting factor for the reaction rate. The reaction only proceeds rapidly under acidic conditions. At high pH, under alkaline conditions, the reaction slows down due to precipitation of Fe(OH)<sub>3</sub>, lowering the concentration of the Fe<sup>3+</sup> species in solution. |
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{| class="wikitable" |
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|+Impacts of operation pH on reaction rate |
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! rowspan="2" |Low pH |
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|Formation of [Fe(H<sub>2</sub>O)<sub>6</sub>] <sup>2+</sup> complex, hence reducing Fe<sup>2+</sup> for radical generation |
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|Scavenging of <sup>•</sup>OH by excess H<sup>+</sup> |
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| rowspan="3" |'''High pH''' |
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|Lower redox potential of <sup>•</sup>OH |
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|Self-decomposition of H<sub>2</sub>O<sub>2</sub> due to decreased stability at high pH |
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|Precipitation of Fe(OH)<sub>3</sub> species in solution |
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==Biomedical implications== |
==Biomedical implications== |
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Revision as of 14:47, 8 April 2021
Fenton's reagent is a solution of hydrogen peroxide (H2O2) with ferrous iron (typically iron(II) sulfate, FeSO4) as a catalyst that is used to oxidize contaminants or waste waters. Fenton's reagent can be used to destroy organic compounds such as trichloroethylene (TCE) and tetrachloroethylene (perchloroethylene, PCE). It was developed in the 1890s by Henry John Horstman Fenton as an analytical reagent.[1][2][3]
Overview
Iron(II) is oxidized by hydrogen peroxide to iron(III), forming a hydroxyl radical and a hydroxide ion in the process. Iron(III) is then reduced back to iron(II) by another molecule of hydrogen peroxide, forming a hydroperoxyl radical and a proton. The net effect is a disproportionation of hydrogen peroxide to create two different oxygen-radical species, with water (H+ + OH−) as a byproduct.
| Fe2+ + H2O2 → Fe3+ + HO• + OH− | (1) |
| Fe3+ + H2O2 → Fe2+ + HOO• + H+ | (2) |
| 2 H2O2 → HO• + HOO• + H2O | (net reaction: 1+2) |
The free radicals generated by this process then engage in secondary reactions. For example, the hydroxyl is a powerful, non-selective oxidant.[4] Oxidation of an organic compound by Fenton's reagent is rapid and exothermic and results in the oxidation of contaminants to primarily carbon dioxide and water.
Reaction (1) was suggested by Haber and Weiss in the 1930s as part of what would become the Haber–Weiss reaction.[5]
Iron(II) sulfate is typically used as the iron catalyst. The exact mechanisms of the redox cycle are uncertain, and non-OH• oxidizing mechanisms of organic compounds have also been suggested.[citation needed] Therefore, it may be appropriate to broadly discuss Fenton chemistry rather than a specific Fenton reaction.
In the electro-Fenton process, hydrogen peroxide is produced in situ from the electrochemical reduction of oxygen.[6]
Fenton's reagent is also used in organic synthesis for the hydroxylation of arenes in a radical substitution reaction such as the classical conversion of benzene into phenol.
| C6H6 + FeSO4 + H2O2 → C6H5OH | (3) |
An example hydroxylation reaction involves the oxidation of barbituric acid to alloxane.[7] Another application of the reagent in organic synthesis is in coupling reactions of alkanes. As an example tert-butanol is dimerized with Fenton's reagent and sulfuric acid to 2,5-dimethyl-2,5-hexanediol.[8] Fenton's reagent is also widely used in the field of environmental science for water purification and soil remediation. Various hazardous wastewater were reported to be effectively degraded through Fenton's reagent[9] .
Effect of pH on formation of free radicals
pH affects the reaction rate due to a variety of different reasons. At a low pH, complexation of Fe2+ also occurs, leading to lower availability of Fe2+ to form reactive oxidative species (OH•)[10]. Lower pH also results in the scavenging of •OH by excess H+ [11], hence reducing its reaction rate. Whereas at high pH, the reaction slows down due to precipitation of Fe(OH)3, lowering the concentration of the Fe3+ species in solution.[12] Solubility of iron species is directly governed by the solution's pH. Fe3+ is about 100 times less soluble than Fe2+ in natural water at near-neutral pH, the ferric ion concentration is the limiting factor for the reaction rate. Under high pH conditions, the stability of the H2O2 is also affected, resulting in its self-decomposition [13]. Higher pH also decreased the redox potential of •OH thereby reducing its effectiveness. [14] pH plays a crucial role in the formation of free radicals and hence the reaction performance. Thus ongoing research has been done to optimize pH and amongst other parameters for greater reaction rates.[15]
| Low pH | Formation of [Fe(H2O)6] 2+ complex, hence reducing Fe2+ for radical generation |
|---|---|
| Scavenging of •OH by excess H+ | |
| High pH | Lower redox potential of •OH |
| Self-decomposition of H2O2 due to decreased stability at high pH | |
| Precipitation of Fe(OH)3 species in solution |
Biomedical implications
The Fenton reaction has different implications in biology because it involves the formation of free radicals by chemical species naturally present in the cell under in vivo conditions.[16] Transition-metal ions such as iron and copper can donate or accept free electrons via intracellular reactions and so contribute to the formation, or at the contrary to the scavenging, of free radicals. In oxygen respirating organisms, most of the intracellular iron is in the ferric (Fe3+) state[citation needed] and must therefore be reduced to the ferrous (Fe2+) form to take part in the Fenton reaction. Superoxide ions and transition metals act in a synergistic way in the appearance of free radical damages.[17] Therefore, although the clinical significance is still unclear, it is one of the viable reasons to avoid iron supplementation in patients with active infections, whereas other reasons include iron-mediated infections.[18]
See also
References
- ^ Koppenol, W.H. (1993). "The centennial of the Fenton reaction". Free Radical Biology and Medicine. 15 (6): 645–651. doi:10.1016/0891-5849(93)90168-T. ISSN 0891-5849. PMID 8138191.
- ^ Fenton H.J.H. (1894). "Oxidation of tartaric acid in presence of iron". J. Chem. Soc., Trans. 65 (65): 899–911. doi:10.1039/ct8946500899.
- ^ Hayyan M., Hashim M.A., AlNashef I.M., Superoxide ion: Generation and chemical implications. Chem. Rev., 2016, 116 (5), pp 3029–3085. DOI: 10.1021/acs.chemrev.5b00407
- ^ Cai, Q. Q.; Jothinathan, L.; Deng, S. H.; Ong, S. L.; Ng, H. Y.; Hu, J. Y. (2021-01-01), Shah, Maulin P. (ed.), "11 - Fenton- and ozone-based AOP processes for industrial effluent treatment", Advanced Oxidation Processes for Effluent Treatment Plants, Elsevier, pp. 199–254, doi:10.1016/b978-0-12-821011-6.00011-6, ISBN 978-0-12-821011-6, retrieved 2021-04-08
- ^ Haber, F.; Weiss, J. (1932). "Über die katalyse des hydroperoxydes" [On the catalysis of hydroperoxides]. Naturwissenschaften. 20 (51): 948–950. Bibcode:1932NW.....20..948H. doi:10.1007/BF01504715. S2CID 40200383.
- ^ Juan Casado; Jordi Fornaguera; Maria I. Galan (January 2005). "Mineralization of aromatics in water by sunlight-assisted electro-Fenton technology in a pilot reactor". Environ. Sci. Technol. 39 (6): 1843–47. Bibcode:2005EnST...39.1843C. doi:10.1021/es0498787. PMID 15819245.
- ^ Brömme HJ, Mörke W, Peschke E (November 2002). "Transformation of barbituric acid into alloxan by hydroxyl radicals: interaction with melatonin and with other hydroxyl radical scavengers". J. Pineal Res. 33 (4): 239–47. doi:10.1034/j.1600-079X.2002.02936.x. PMID 12390507. S2CID 30242100.
- ^ E. L. Jenner (1973). "α,α,α',α'-Tetramethyltetramethylene glycol". Organic Syntheses; Collected Volumes, vol. 5, p. 1026.
- ^ Cai, Q. Q.; Lee, B. C. Y.; Ong, S. L.; Hu, J. Y. (2021-02-15). "Fluidized-bed Fenton technologies for recalcitrant industrial wastewater treatment–Recent advances, challenges and perspective". Water Research. 190: 116692. doi:10.1016/j.watres.2020.116692. ISSN 0043-1354.
- ^ Xu, Xiang-Rong; Li, Xiao-Yan; Li, Xiang-Zhong; Li, Hua-Bin (2009-08-05). "Degradation of melatonin by UV, UV/H2O2, Fe2+/H2O2 and UV/Fe2+/H2O2 processes". Separation and Purification Technology. 68 (2): 261–266. doi:10.1016/j.seppur.2009.05.013. ISSN 1383-5866.
- ^ Tang, W. Z.; Huang, C. P. (1996-12-01). "2,4-Dichlorophenol Oxidation Kinetics by Fenton's Reagent". Environmental Technology. 17 (12): 1371–1378. doi:10.1080/09593330.1996.9618465. ISSN 0959-3330.
- ^ Cai, Q. Q.; Lee, B. C. Y.; Ong, S. L.; Hu, J. Y. (2021-02-15). "Fluidized-bed Fenton technologies for recalcitrant industrial wastewater treatment–Recent advances, challenges and perspective". Water Research. 190: 116692. doi:10.1016/j.watres.2020.116692. ISSN 0043-1354.
- ^ Szpyrkowicz, Lidia; Juzzolino, Claudia; Kaul, Santosh N (2001-06). "A Comparative study on oxidation of disperse dyes by electrochemical process, ozone, hypochlorite and fenton reagent". Water Research. 35 (9): 2129–2136. doi:10.1016/s0043-1354(00)00487-5. ISSN 0043-1354.
{{cite journal}}: Check date values in:|date=(help) - ^ Velichkova, Filipa; Delmas, Henri; Julcour, Carine; Koumanova, Bogdana (2016-06-28). "Heterogeneous fenton and photo-fenton oxidation for paracetamol removal using iron containing ZSM-5 zeolite as catalyst". AIChE Journal. 63 (2): 669–679. doi:10.1002/aic.15369. ISSN 0001-1541.
- ^ Cai, Qinqing; Lee, Brandon Chuan Yee; Ong, Say Leong; Hu, Jiangyong (2021-01-14). "Application of a Multiobjective Artificial Neural Network (ANN) in Industrial Reverse Osmosis Concentrate Treatment with a Fluidized Bed Fenton Process: Performance Prediction and Process Optimization". ACS ES&T Water. doi:10.1021/acsestwater.0c00192.
- ^ Matavos-Aramyan, S; Moussavi, M; Matavos-Aramyan, H; Roozkhosh, S (2017). "Cryptosporidium-contaminated water disinfection by a novel Fenton process". Free Radical Biology and Medicine. 106: 158–167. doi:10.1016/j.freeradbiomed.2017.02.030. PMID 28212822. S2CID 3918519.
- ^ Robbins & Cotran (2008). Pathologic basis of disease (7th ed.). Elsevier. p. 16. ISBN 9780808923022.
- ^ Lapointe, Marc (2004-01-01). "Iron supplementation in the intensive care unit: when, how much, and by what route?". Critical Care. 8 (2): S37–41. doi:10.1186/cc2825. ISSN 1364-8535. PMC 3226152. PMID 15196322.
{{cite journal}}: CS1 maint: unflagged free DOI (link)
Further reading
- Goldstein Sara; Meyerstein Dan; Czapski Gidon (1993). "The Fenton reagents". Free Radical Biology and Medicine. 15 (4): 435–445. doi:10.1016/0891-5849(93)90043-T. PMID 8225025.
- Barbusiński K. (2009). "Fenton Reaction – Controversy concerning the chemistry". Ecological Chemistry and Engineering, Vol 16, N° 3, pp. 347–358.
External links
- Reference Library Peroxide Applications
- Companies that use Fenton's Reagent for chemical remediation: ORIN