Direct and indirect effects in pulse irradiated concentrated aqueous solutions of chloride and sulfate ions

Kim, Kang‐Jin; Hamill, William H.

doi:10.1021/j100562a003

Cited by 38 publications

(29 citation statements)

References 5 publications

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“…In a previous study, the rate constant for the forward reac- [Buxton et al, 1999b] has confirmed earlier studies [Kim and Hamill, 1976;Neta and Huie, 1986] that indicate that the correct rate constant for this reaction is much higher than the values obtained…”

Section: ! Comparison With Prior Kinetics Resultssupporting

confidence: 84%

Equilibrium constant of the reaction ·OH + HNO₃ ⇆ H₂O + NO₃. in aqueous solution

Poskrebyshev¹,

Neta²,

Huie³

2001

J. Geophys. Res.

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Section: ! Comparison With Prior Kinetics Resultssupporting

confidence: 84%

Equilibrium constant of the reaction ·OH + HNO₃ ⇆ H₂O + NO₃. in aqueous solution

Poskrebyshev¹,

Neta²,

Huie³

2001

J. Geophys. Res.

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“…In addition to the yields of the radicals SOn', SO3', and OH from (R 1 ), the relative importance of subsequent reactions of these radicals must be known quantitatively in order to assess the efficiency of the free radical chain mechanism as an oxidation pathway for S IV in clouds. In the case of SOn', the reaction reported in the literature [Heckel et al, 1966;Dogliotti and Hayon, 1967a, b;Kraljic, 1970;Hayon et al, 1972;Redpath and Willson, 1975;Chawla and Fessenden, 1975;Kim and Hamill, 1976; Maruthamuthu and Neta, 1978;Eibenberger et al, 1978;Huie and Neta, 1987]. However, the study reported here employed much lower concentrations of SOn' and other reactive radicals than all previous direct studies, thus minimizing potential interferences from fast radical-radical side reactions.…”

Section: Introductionmentioning

confidence: 80%

Kinetics of aqueous phase reactions of the SO₄⁻radical with potential importance in cloud chemistry

Wine¹,

Tang²,

Thorn³

et al. 1989

J. Geophys. Res.

123

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A laser flash photolysis/long path absorption technique has been employed to study at 298 K the kinetics of aqueous phase reactions of the SO4− radical with a number of species commonly found in cloud water. Much lower radical concentrations were employed than in all previous direct studies of SO4− reaction kinetics. In the zero ionic strength limit, rate coefficients for SO4− reactions with the anions HSO3−, Cl−, NO2−, HCOO−, and CH3COO− are found to be 7.5 × 108, 2.6 × 108, 9.8 × 108, 1.1 × 108, and 3.7 × 106 M−1 s−1, respectively. Rate coefficients for SO4− reactions with the neutral species H2O2, CH3OH, HCOOH, and CH3COOH are found to be 1.2 × 107, 8.8 × 106, 4.6 × 105, and 1.4 × 104 M−1 s−1, respectively. For many of the reactions studied, agreement with previously reported rate data is poor. Of particular importance for cloud chemistry is the fact that the SO4− + HSO3− reaction proceeds more slowly than previously believed, while the SO4− + Cl− reaction is somewhat faster than previously thought. Incorporation of these results into cloud chemistry models should reduce the calculated efficiency of free radical chain reactions as an oxidation mechanism for S IV.

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“…Radiation effects in chloride brines are therefore of fundamental importance for the safety of a final disposal. The radiolysis of highly concentrated chloride solutions (NaCl, MgCl 2 and LiCl) was previously investigated [3][4][5][6][7][8]. Using pulse radiolysis it was found that the Cl 2 − radical anions are formed in acidic solutions as a consequence of the following reversible reactions: yield of different radiolytic products formed by γ -radiolysis from NaCl brines at ambient temperature and dose rates betweeen 0.1 and 1 kGy/h were determined [9,10].…”

Section: Introductionmentioning

confidence: 99%

Radiation-chemical effects in the near-field of a final disposal site: role of bromine on the radiolytic processes in NaCl-solutions

Ершов¹,

Kelm²,

Janata³

et al. 2002

Radiochimica Acta

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Chloride / Bromide / Aqueous solution / Pulse radiolysis / Oxidation / Radical anions / EquilibriumSummary. The oxidation of Br − by Cl 2 − is investigated by gamma pulse radiolysis in aqueous solutions of NaCl and NaBr. Depending on the ratio of the concentration of Br − to Cl − , the main product being observed is either Cl 2 − , ClBr − or Br 2 − . The mixed radical anion ClBr − exhibits a broad absorption band at 350 nm with ε 350 = 9300 dm 3 mol −1 cm −1 . The rate constants of the equilibrium Cl 2 − + Br − ⇔ ClBr − + Cl − are determined to be k f = 4 × 10 9 dm 3 mol −1 s −1 and k b = 1.1 × 10 2 dm 3 mol −1 s −1 . The formation of the Cl 3 − (λ max = 220 nm), Cl 2 Br − (λ max = 230 nm) and ClBr 2 − (λ max = 245 nm) ions in the radiation-chemical oxidation of Cl − and Br − ions in an aqueous solution was observed by pulse radiolysis, and its mechanisms of appearance and the equilibrium constants were determined.

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Direct and indirect effects in pulse irradiated concentrated aqueous solutions of chloride and sulfate ions

Cited by 38 publications

References 5 publications

Equilibrium constant of the reaction ·OH + HNO₃ ⇆ H₂O + NO₃. in aqueous solution

Equilibrium constant of the reaction ·OH + HNO₃ ⇆ H₂O + NO₃. in aqueous solution

Kinetics of aqueous phase reactions of the SO₄⁻radical with potential importance in cloud chemistry

Radiation-chemical effects in the near-field of a final disposal site: role of bromine on the radiolytic processes in NaCl-solutions

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Direct and indirect effects in pulse irradiated concentrated aqueous solutions of chloride and sulfate ions

Cited by 38 publications

References 5 publications

Equilibrium constant of the reaction ·OH + HNO3 ⇆ H2O + NO3. in aqueous solution

Equilibrium constant of the reaction ·OH + HNO3 ⇆ H2O + NO3. in aqueous solution

Kinetics of aqueous phase reactions of the SO4−radical with potential importance in cloud chemistry

Radiation-chemical effects in the near-field of a final disposal site: role of bromine on the radiolytic processes in NaCl-solutions

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Equilibrium constant of the reaction ·OH + HNO₃ ⇆ H₂O + NO₃. in aqueous solution

Equilibrium constant of the reaction ·OH + HNO₃ ⇆ H₂O + NO₃. in aqueous solution

Kinetics of aqueous phase reactions of the SO₄⁻radical with potential importance in cloud chemistry