Influence of pH on the Formation of Sulfate and Hydroxyl Radicals in the UV/Peroxymonosulfate System

The influence of pH on the degradation of refractory organics (benzoic acid, BA) in UV(254 nm)/Peroxymonosulfate (UV/PMS) system was investigated. The degradation of BA was significantly enhanced at the pH range of 8–11, which could not be explained only by the generally accepted theory that SO4 •‑...

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Published inEnvironmental science & technology Vol. 45; no. 21; pp. 9308 - 9314
Main Authors Guan, Ying-Hong, Ma, Jun, Li, Xu-Chun, Fang, Jing-Yun, Chen, Li-Wei
Format Journal Article
LanguageEnglish
Published Washington, DC American Chemical Society 01.11.2011
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Abstract The influence of pH on the degradation of refractory organics (benzoic acid, BA) in UV(254 nm)/Peroxymonosulfate (UV/PMS) system was investigated. The degradation of BA was significantly enhanced at the pH range of 8–11, which could not be explained only by the generally accepted theory that SO4 •‑ was converted to HO• at higher pH. A hypothesis was proposed that the rate of PMS photolysis into HO• and SO4 •‑ increased with pH. The hypothesis was evidenced by the measured increase of apparent-molar absorption coefficient of PMS (εPMS, 13.8–149.5 M–1·cm–1) and photolysis rate of PMS with pH, and further proved by the increased quasi-stationary concentrations of both HO• and SO4 •‑ at the pH range of 8–10. The formation of HO• and SO4 •‑ in the UV/PMS system was confirmed mainly from the cooperation of the photolysis of PMS, the decay of peroxomonosulfate radical (SO5 •‑) and the conversion of SO4 •‑ to HO• by simulation and experimental results. Additionally, the apparent quantum yield for SO4 •‑ in the UV/PMS system was calculated as 0.52 ± 0.01 at pH 7. The conclusions above as well as the general kinetic expressions given might provide some references for the UV/PMS applications.
AbstractList The influence of pH on the degradation of refractory organics (benzoic acid, BA) in UV(254 nm)/Peroxymonosulfate (UV/PMS) system was investigated. The degradation of BA was significantly enhanced at the pH range of 8-11, which could not be explained only by the generally accepted theory that ... was converted to ... at higher pH. A hypothesis was proposed that the rate of PMS photolysis into ... and ... increased with pH. The hypothesis was evidenced by the measured increase of apparent-molar absorption coefficient of PMS (..., 13.8-149.5 ...) and photolysis rate of PMS with pH, and further proved by the increased quasi-stationary concentrations of both ... and ... at the pH range of 8-10. The formation of ... and ... in the UV/PMS system was confirmed mainly from the cooperation of the photolysis of PMS, the decay of peroxomonosulfate radical (...) and the conversion of ... to ... by simulation and experimental results. Additionally, the apparent quantum yield for ... in the UV/PMS system was calculated as 0.52 ± 0.01 at pH 7. The conclusions above as well as the general kinetic expressions given might provide some references for the UV/PMS applications. (ProQuest: ... denotes formulae/symbols omitted.)
The influence of pH on the degradation of refractory organics (benzoic acid, BA) in UV(254 nm)/Peroxymonosulfate (UV/PMS) system was investigated. The degradation of BA was significantly enhanced at the pH range of 8–11, which could not be explained only by the generally accepted theory that SO4 •‑ was converted to HO• at higher pH. A hypothesis was proposed that the rate of PMS photolysis into HO• and SO4 •‑ increased with pH. The hypothesis was evidenced by the measured increase of apparent-molar absorption coefficient of PMS (εPMS, 13.8–149.5 M–1·cm–1) and photolysis rate of PMS with pH, and further proved by the increased quasi-stationary concentrations of both HO• and SO4 •‑ at the pH range of 8–10. The formation of HO• and SO4 •‑ in the UV/PMS system was confirmed mainly from the cooperation of the photolysis of PMS, the decay of peroxomonosulfate radical (SO5 •‑) and the conversion of SO4 •‑ to HO• by simulation and experimental results. Additionally, the apparent quantum yield for SO4 •‑ in the UV/PMS system was calculated as 0.52 ± 0.01 at pH 7. The conclusions above as well as the general kinetic expressions given might provide some references for the UV/PMS applications.
The influence of pH on the degradation of refractory organics (benzoic acid, BA) in UV(254 nm)/Peroxymonosulfate (UV/PMS) system was investigated. The degradation of BA was significantly enhanced at the pH range of 8-11, which could not be explained only by the generally accepted theory that SO(4)(•-) was converted to HO(•) at higher pH. A hypothesis was proposed that the rate of PMS photolysis into HO(•) and SO(4)(•-) increased with pH. The hypothesis was evidenced by the measured increase of apparent-molar absorption coefficient of PMS (ε(PMS), 13.8-149.5 M(-1)·cm(-1)) and photolysis rate of PMS with pH, and further proved by the increased quasi-stationary concentrations of both HO(•) and SO(4)(•-) at the pH range of 8-10. The formation of HO(•) and SO(4)(•-) in the UV/PMS system was confirmed mainly from the cooperation of the photolysis of PMS, the decay of peroxomonosulfate radical (SO(5)(•-)) and the conversion of SO(4)(•-) to HO(•) by simulation and experimental results. Additionally, the apparent quantum yield for SO(4)(•-) in the UV/PMS system was calculated as 0.52 ± 0.01 at pH 7. The conclusions above as well as the general kinetic expressions given might provide some references for the UV/PMS applications.
The influence of pH on the degradation of refractory organics (benzoic acid, BA) in UV(254 nm)/Peroxymonosulfate (UV/PMS) system was investigated. The degradation of BA was significantly enhanced at the pH range of 8-11, which could not be explained only by the generally accepted theory that SO(4)(•-) was converted to HO(•) at higher pH. A hypothesis was proposed that the rate of PMS photolysis into HO(•) and SO(4)(•-) increased with pH. The hypothesis was evidenced by the measured increase of apparent-molar absorption coefficient of PMS (ε(PMS), 13.8-149.5 M(-1)·cm(-1)) and photolysis rate of PMS with pH, and further proved by the increased quasi-stationary concentrations of both HO(•) and SO(4)(•-) at the pH range of 8-10. The formation of HO(•) and SO(4)(•-) in the UV/PMS system was confirmed mainly from the cooperation of the photolysis of PMS, the decay of peroxomonosulfate radical (SO(5)(•-)) and the conversion of SO(4)(•-) to HO(•) by simulation and experimental results. Additionally, the apparent quantum yield for SO(4)(•-) in the UV/PMS system was calculated as 0.52 ± 0.01 at pH 7. The conclusions above as well as the general kinetic expressions given might provide some references for the UV/PMS applications.The influence of pH on the degradation of refractory organics (benzoic acid, BA) in UV(254 nm)/Peroxymonosulfate (UV/PMS) system was investigated. The degradation of BA was significantly enhanced at the pH range of 8-11, which could not be explained only by the generally accepted theory that SO(4)(•-) was converted to HO(•) at higher pH. A hypothesis was proposed that the rate of PMS photolysis into HO(•) and SO(4)(•-) increased with pH. The hypothesis was evidenced by the measured increase of apparent-molar absorption coefficient of PMS (ε(PMS), 13.8-149.5 M(-1)·cm(-1)) and photolysis rate of PMS with pH, and further proved by the increased quasi-stationary concentrations of both HO(•) and SO(4)(•-) at the pH range of 8-10. The formation of HO(•) and SO(4)(•-) in the UV/PMS system was confirmed mainly from the cooperation of the photolysis of PMS, the decay of peroxomonosulfate radical (SO(5)(•-)) and the conversion of SO(4)(•-) to HO(•) by simulation and experimental results. Additionally, the apparent quantum yield for SO(4)(•-) in the UV/PMS system was calculated as 0.52 ± 0.01 at pH 7. The conclusions above as well as the general kinetic expressions given might provide some references for the UV/PMS applications.
Author Fang, Jing-Yun
Ma, Jun
Chen, Li-Wei
Guan, Ying-Hong
Li, Xu-Chun
AuthorAffiliation Harbin Institute of Technology
National Engineering Research Center of Urban Water Resources
State Key Laboratory of Urban Water Resource and Environment
AuthorAffiliation_xml – name: Harbin Institute of Technology
– name: State Key Laboratory of Urban Water Resource and Environment
– name: National Engineering Research Center of Urban Water Resources
Author_xml – sequence: 1
  givenname: Ying-Hong
  surname: Guan
  fullname: Guan, Ying-Hong
– sequence: 2
  givenname: Jun
  surname: Ma
  fullname: Ma, Jun
  email: majun@hit.edu.cn
– sequence: 3
  givenname: Xu-Chun
  surname: Li
  fullname: Li, Xu-Chun
– sequence: 4
  givenname: Jing-Yun
  surname: Fang
  fullname: Fang, Jing-Yun
– sequence: 5
  givenname: Li-Wei
  surname: Chen
  fullname: Chen, Li-Wei
BackLink http://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=24712146$$DView record in Pascal Francis
https://www.ncbi.nlm.nih.gov/pubmed/21999357$$D View this record in MEDLINE/PubMed
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Issue 21
Keywords Benzoic acid
Pollutant behavior
Sulfates
Pollution
Ultraviolet radiation
Carboxylic acid
Hydroxyl radicals
pH
Environment
Aromatic compound
Organic compounds
Photochemical degradation
Inorganic radical anion
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Snippet The influence of pH on the degradation of refractory organics (benzoic acid, BA) in UV(254 nm)/Peroxymonosulfate (UV/PMS) system was investigated. The...
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SubjectTerms Applied sciences
Biodegradation
Chemical compounds
Exact sciences and technology
Global environmental pollution
Hydrogen-Ion Concentration
Hydroxyl Radical - chemistry
Hypotheses
Kinetics
Peroxides - chemistry
Pollution
Remediation and Control Technologies
Simulation
Sulfates - chemistry
Ultraviolet Rays
Title Influence of pH on the Formation of Sulfate and Hydroxyl Radicals in the UV/Peroxymonosulfate System
URI http://dx.doi.org/10.1021/es2017363
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