Oxidation of H2S with H2O2 in natural waters

Frank J Millero, A. LeFerriere, M. Fernandez, S. Hubinger, J. P. Hershey

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Abstract

The oxidation of H2S with H2O2 has been studied as a function of pH (2 - 13), temperature ( - 45°C), and ionic strength (0 - 6 m) in seawater and NaCl solutions. The rate constant, k (min-1 M-1), for the oxidation d[H2S](T)/dt = -k[H2S](T)[H2O2] at pH = 8 was found to be given by log k = 8.60 - 2052/T + 0.084I(1/2) in seawater and NaCl solutions (σ = 0.07). The energy of activation (ΔE = 39 ± 2 kJ mol-1) for the reaction was independent of ionic strength. The rate increased from pH = 2 to 8 due to the increased rate of oxidation of HS- compared to H2S. The rate constant for the oxidation of H2S was found to be zero at every temperature. The rate constant for the oxidation of HS- was found to be 12.0 ± 0.5, 36.2 ± 0.4, and 211 ± 5 min-a1 M-1, respectively, at 5, 25, and 45°C. The energy of activation (ΔE1 = 51 ± 3 kJ) for HS- was higher than the ΔE for the overall reaction due to the effect of temperature on K1, the dissociation constant of H2S. Above pH = 8.0, the rate slowly decreased in a near linear manner. The formation of HO2 -, which does not react easily with HS-, could be part of the cause of this decrease.

Original languageEnglish (US)
Pages (from-to)209-213
Number of pages5
JournalEnvironmental Science and Technology
Volume23
Issue number2
StatePublished - Feb 1989

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oxidation
Oxidation
Water
Rate constants
Ionic strength
Seawater
water
Chemical activation
seawater
temperature
Temperature
energy
rate

ASJC Scopus subject areas

  • Environmental Science(all)
  • Environmental Chemistry
  • Environmental Engineering

Cite this

Millero, F. J., LeFerriere, A., Fernandez, M., Hubinger, S., & Hershey, J. P. (1989). Oxidation of H2S with H2O2 in natural waters. Environmental Science and Technology, 23(2), 209-213.

Oxidation of H2S with H2O2 in natural waters. / Millero, Frank J; LeFerriere, A.; Fernandez, M.; Hubinger, S.; Hershey, J. P.

In: Environmental Science and Technology, Vol. 23, No. 2, 02.1989, p. 209-213.

Research output: Contribution to journalArticle

Millero, FJ, LeFerriere, A, Fernandez, M, Hubinger, S & Hershey, JP 1989, 'Oxidation of H2S with H2O2 in natural waters', Environmental Science and Technology, vol. 23, no. 2, pp. 209-213.
Millero FJ, LeFerriere A, Fernandez M, Hubinger S, Hershey JP. Oxidation of H2S with H2O2 in natural waters. Environmental Science and Technology. 1989 Feb;23(2):209-213.
Millero, Frank J ; LeFerriere, A. ; Fernandez, M. ; Hubinger, S. ; Hershey, J. P. / Oxidation of H2S with H2O2 in natural waters. In: Environmental Science and Technology. 1989 ; Vol. 23, No. 2. pp. 209-213.
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