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

Guan, Ying-Hong, Ma, Jun, Li, Xu-Chun, Fang, Jing-Yun, Chen, Li-Wei·2011·Environmental Science & Technology

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 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.

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Metadata

Authors
Guan, Y.-H., Ma, J., Li, X.-C., Fang, J.-Y., & Chen, L.-W.
Venue
Environmental Science & Technology
Published
2011-10-14
Volume
45
Issue
21
Pages
9308-9314
ISSN
  • 0013-936X (ISSN-L)
  • 1520-5851
OpenAlex
W2060044938
Cited by
1,338
References
1
FWCI
16.02
Type
journal article
Language
en
Open access
closed

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