On the photochemistry of aqueous nitrate solutions excited in the 195-nm band

Uri Shuali; Michael Ottolenghi; Joseph Rabani; Ziva Yelin

doi:10.1021/j100844a052

On the photochemistry of aqueous nitrate solutions excited in the 195-nm band

Uri Shuali^*, Michael Ottolenghi, Joseph Rabani, Ziva Yelin

^*Corresponding author for this work

Institute of Chemistry

Research output: Contribution to journal › Article › peer-review

70 Scopus citations

Abstract

The photochemistry of aqueous nitrate solutions excited in the high-energy (195-nm) ππ* band of the ion is investigated using steady-state and flash-irradiation techniques. The formation of hydroxyl radicals is demonstrated by observing the absorption of characteristic transients formed by the reaction of OH (or O^-) with CO₃^2-, CNS^-, and O₂. The formation of pernitrite is also investigated and found to be unaffected by [NO₂^-], [NO₃^-], [O₂], and [CH₃CH₂OH]. The flash technique enables the determination of the dissociation constant of pernitrous acid, yielding pK_a = 6.0 ± 0.3. A third photochemical path, the evolution of O₂ and the stoichiometric formation of NO₂^-, is also investigated. The effect of various solutes on the yields of molecular oxygen is analyzed. The results appear to be inconsistent with a mechanism involving intermediate oxygen atoms.

Original language	English
Pages (from-to)	3445-3451
Number of pages	7
Journal	Journal of Physical Chemistry
Volume	73
Issue number	10
DOIs	https://doi.org/10.1021/j100844a052
State	Published - 1969

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title = "On the photochemistry of aqueous nitrate solutions excited in the 195-nm band",

abstract = "The photochemistry of aqueous nitrate solutions excited in the high-energy (195-nm) ππ* band of the ion is investigated using steady-state and flash-irradiation techniques. The formation of hydroxyl radicals is demonstrated by observing the absorption of characteristic transients formed by the reaction of OH (or O-) with CO32-, CNS-, and O2. The formation of pernitrite is also investigated and found to be unaffected by [NO2-], [NO3-], [O2], and [CH3CH2OH]. The flash technique enables the determination of the dissociation constant of pernitrous acid, yielding pKa = 6.0 ± 0.3. A third photochemical path, the evolution of O2 and the stoichiometric formation of NO2-, is also investigated. The effect of various solutes on the yields of molecular oxygen is analyzed. The results appear to be inconsistent with a mechanism involving intermediate oxygen atoms.",

author = "Uri Shuali and Michael Ottolenghi and Joseph Rabani and Ziva Yelin",

year = "1969",

doi = "10.1021/j100844a052",

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journal = "Journal of Physical Chemistry",

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T1 - On the photochemistry of aqueous nitrate solutions excited in the 195-nm band

AU - Shuali, Uri

AU - Ottolenghi, Michael

AU - Rabani, Joseph

AU - Yelin, Ziva

PY - 1969

Y1 - 1969

N2 - The photochemistry of aqueous nitrate solutions excited in the high-energy (195-nm) ππ* band of the ion is investigated using steady-state and flash-irradiation techniques. The formation of hydroxyl radicals is demonstrated by observing the absorption of characteristic transients formed by the reaction of OH (or O-) with CO32-, CNS-, and O2. The formation of pernitrite is also investigated and found to be unaffected by [NO2-], [NO3-], [O2], and [CH3CH2OH]. The flash technique enables the determination of the dissociation constant of pernitrous acid, yielding pKa = 6.0 ± 0.3. A third photochemical path, the evolution of O2 and the stoichiometric formation of NO2-, is also investigated. The effect of various solutes on the yields of molecular oxygen is analyzed. The results appear to be inconsistent with a mechanism involving intermediate oxygen atoms.

AB - The photochemistry of aqueous nitrate solutions excited in the high-energy (195-nm) ππ* band of the ion is investigated using steady-state and flash-irradiation techniques. The formation of hydroxyl radicals is demonstrated by observing the absorption of characteristic transients formed by the reaction of OH (or O-) with CO32-, CNS-, and O2. The formation of pernitrite is also investigated and found to be unaffected by [NO2-], [NO3-], [O2], and [CH3CH2OH]. The flash technique enables the determination of the dissociation constant of pernitrous acid, yielding pKa = 6.0 ± 0.3. A third photochemical path, the evolution of O2 and the stoichiometric formation of NO2-, is also investigated. The effect of various solutes on the yields of molecular oxygen is analyzed. The results appear to be inconsistent with a mechanism involving intermediate oxygen atoms.

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On the photochemistry of aqueous nitrate solutions excited in the 195-nm band

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