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Influence of pH on the Formation of Sulfate and Hydroxyl Radicals in the UV/Peroxymonosulfate System
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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Buxton, G. V., Greenstock, C. L., Helman, W. P., & Ross, A. B. (1988) · Journal of Physical and Chemical Reference Data · doi:10.1063/1.555805 · Cited by 12,332
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Metadata
- Authors
- Guan, Y.-H., Ma, J., Li, X.-C., Fang, J.-Y., & Chen, L.-W.
- Venue
- Environmental Science & Technology
- Publisher
- American Chemical Society (ACS)
- 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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- Guan, Y.-H., Ma, J., Li, X.-C., Fang, J.-Y., & Chen, L.-W. (2011). Influence of pH on the Formation of Sulfate and Hydroxyl Radicals in the UV/Peroxymonosulfate System. Environmental Science & Technology. https://doi.org/10.1021/es2017363
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