Quantitative analysis for the enhancement of hydroxyl radical generation by phenols during ozonation of water

Sang Kuk Han, Kazuhiro Ichikawa, Hideo Utsumi

    Research output: Contribution to journalArticle

    48 Citations (Scopus)

    Abstract

    Generation of hydroxyl radical, one of the major reactive species in the ozonation of water, was directly and quantitatively measured with the combination technique of spin-trapping, stopped flow and electron spin resonance (ESR) spectroscopy. Hydroxyl radical in ozonated water was trapped with 5,5-dimethyl-pyrrolidine-1-oxyl (DMPO) as a stable radical, DMPO-OH, and the amount of DMPO-OH was quantitatively measured with an ESR spectrometer. The ESR signal of DMPO-OH increased linearly with increasing ozone and 1 M ozone produced 0.011 M DMPO-OH, if one molecule of ozone produces one molecule of .OH. The kinetics of DMPO:OH generation was determined with a stopped-flow/ESR method and analyzed by two different methods. The logarithmic plot of the initial velocity of DMPO-OH generation vs the ozone concentration gave a linear relationship, which was expressed as v0 (M s-1) = 8.7 x 101 x [O3 (M)]2.25. The rate constant of DMPO-OH generation, 8.7 x 101 M-1.25 s-1, is close to the reaction constant of ozone with an hydroxide ion. The decomposition rate of ozone to .OH was estimated to be 0.026 s-1 at 40 μM aqueous ozone from the semilogarithmic plot of the amount of DMPO-OH against reaction time. The presence of phenol derivatives increased both the generation rate and the final amount of DMPO-OH in a dose dependent manner. The enhancing effect of phenols on .OH generation was also analyzed with the above two methods, the decomposition of ozone and the generation of DMPO-OH. The effect depended on the kind, position and number of substituents of phenol. The chlorine substitution of phenol had a more enhancing effect than that of methyl substitution and the ortho-substitution by chlorine showed a stronger enhancement. 2,4-Dichlorophenol showed the strongest enhancing effect on .OH generation among phenols examined, followed by 2-chlorophenol.

    Original languageEnglish
    Pages (from-to)3261-3266
    Number of pages6
    JournalWater Research
    Volume32
    Issue number11
    DOIs
    Publication statusPublished - Nov 1 1998

    Fingerprint

    Ozonization
    hydroxyl radical
    Ozone
    quantitative analysis
    Phenols
    phenol
    ozone
    electron spin resonance
    Chemical analysis
    Water
    Paramagnetic resonance
    water
    substitution
    Substitution reactions
    Chlorine
    chlorine
    Rate constants
    decomposition
    Electron spin resonance spectroscopy
    Decomposition

    All Science Journal Classification (ASJC) codes

    • Ecological Modelling
    • Water Science and Technology
    • Waste Management and Disposal
    • Pollution

    Cite this

    Quantitative analysis for the enhancement of hydroxyl radical generation by phenols during ozonation of water. / Han, Sang Kuk; Ichikawa, Kazuhiro; Utsumi, Hideo.

    In: Water Research, Vol. 32, No. 11, 01.11.1998, p. 3261-3266.

    Research output: Contribution to journalArticle

    Han, Sang Kuk ; Ichikawa, Kazuhiro ; Utsumi, Hideo. / Quantitative analysis for the enhancement of hydroxyl radical generation by phenols during ozonation of water. In: Water Research. 1998 ; Vol. 32, No. 11. pp. 3261-3266.
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    abstract = "Generation of hydroxyl radical, one of the major reactive species in the ozonation of water, was directly and quantitatively measured with the combination technique of spin-trapping, stopped flow and electron spin resonance (ESR) spectroscopy. Hydroxyl radical in ozonated water was trapped with 5,5-dimethyl-pyrrolidine-1-oxyl (DMPO) as a stable radical, DMPO-OH, and the amount of DMPO-OH was quantitatively measured with an ESR spectrometer. The ESR signal of DMPO-OH increased linearly with increasing ozone and 1 M ozone produced 0.011 M DMPO-OH, if one molecule of ozone produces one molecule of .OH. The kinetics of DMPO:OH generation was determined with a stopped-flow/ESR method and analyzed by two different methods. The logarithmic plot of the initial velocity of DMPO-OH generation vs the ozone concentration gave a linear relationship, which was expressed as v0 (M s-1) = 8.7 x 101 x [O3 (M)]2.25. The rate constant of DMPO-OH generation, 8.7 x 101 M-1.25 s-1, is close to the reaction constant of ozone with an hydroxide ion. The decomposition rate of ozone to .OH was estimated to be 0.026 s-1 at 40 μM aqueous ozone from the semilogarithmic plot of the amount of DMPO-OH against reaction time. The presence of phenol derivatives increased both the generation rate and the final amount of DMPO-OH in a dose dependent manner. The enhancing effect of phenols on .OH generation was also analyzed with the above two methods, the decomposition of ozone and the generation of DMPO-OH. The effect depended on the kind, position and number of substituents of phenol. The chlorine substitution of phenol had a more enhancing effect than that of methyl substitution and the ortho-substitution by chlorine showed a stronger enhancement. 2,4-Dichlorophenol showed the strongest enhancing effect on .OH generation among phenols examined, followed by 2-chlorophenol.",
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