Formation and decay of the biphenyl cation radical in aqueous acidic solution

Sehested, Κ.; Hart, Edwin J.

doi:10.1021/j100583a005

Cited by 61 publications

(35 citation statements)

References 6 publications

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“…The second order rate constant for the reaction between biphenyl and HNO 2 was then determined to be 9.5×10 9 L·mol −1 ·s -1 , which was in good agreement with (0.9±0.1)×10 10 L·mol −1 ·s −1 reported by Sehested et al [7] and (1.04 ± 0.05)×10 10 L·mol −1 ·s −1 given by Chen et al [8] using pulse radiolysis.…”

Section: The Transient Absorbance Spectra Recorded After Laser Photolsupporting

confidence: 85%

“…The spectrum recorded 0.5 μs after laser pulse exhibited major peaks centered at 310 and 360 nm, respectively. Both their absorption positions and peaks were identical to that of Bp-OH adduct acquired by Sehested et al [7] and Chen et al [8] through pulse radiolysis study.…”

Section: Laser Flash Photolysis Apparatus and Experimental Methodssupporting

confidence: 78%

“…Bp-OH adduct was observed to proceed bimolecular decay in the pulse radiolysis studies performed by Sehested et al [7] and Chen et al [8] . It took several milliseconds for Bp-OH adduct to vanish while Bp-OH adduct decayed on a time scale of merely tens of microseconds in this research work.…”

Section: The Fate Of Bp-oh Adductmentioning

confidence: 96%

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Mechanism study on the reactions between biphenyl and HNO2 initiated by 355 nm irradiation in aqueous phase

Huang

Zhang

et al. 2007

SCI CHINA SER B

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The reactions taking place in the mixed solution of biphenyl and nitrous acid after it was exposed to UV irradiation were studied in this research work. The transient species were identified with the nanosecond transient spectroscopic technique, and the final products were ascertained by GC-MS analysis. It was shown that the OH radical, generated by the direct photolysis of nitrous acid, would attack biphenyl molecule to form Bp-OH adduct with a rate constant of 9.5×10 9 L·mol −1 ·s −1 . The Bp-OH adduct could either react with H + or be oxidized by nitrous acid to form nitrosobiphenol. The reactions between biphenyl and nitrous acid under UV irradiation in atmospheric aqueous phase were therefore suggested to be one promising source of nitrocompounds in the environment.biphenyl, nitrous acid, laser flash photolysis, Bp-OH adduct, nitrosobiphenolAs the parent molecule of polychlorinated biphenyls (PCBs), biphenyl was one kind of important organic pollutant in the environment. The biphenyl in the environment came mainly from the manufacture and utilization of insulating liquids, plasticizing agents, antiseptic substances, dyes, organic heat carriers and high-energy fuels in the chemical and medical industry. In addition, the dechlorination process of PCBs under sunlight is regarded as another source of biphenyl in the environment [1,2] . What are the sinks of biphenyl in the atmosphere? Hitherto, most literature were limited to the elimination of biphenyl in the gas phase [3,4] . Rare research work reported its conversion pathway in the atmospheric condensed phase, such as cloud, fog, dew, and the surface water of aerosol and so on.With the increasing release of NO x , N-containing compounds, e.g., NO, NO 2 , HNO 2 , and HNO 3 , were also recognized as main contaminants in the atmosphere. Atmospheric aqueous phase was recognized as an important reservoir of NO 2 −

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Section: The Transient Absorbance Spectra Recorded After Laser Photolsupporting

confidence: 85%

Section: Laser Flash Photolysis Apparatus and Experimental Methodssupporting

confidence: 78%

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Mechanism study on the reactions between biphenyl and HNO2 initiated by 355 nm irradiation in aqueous phase

Huang

Zhang

et al. 2007

SCI CHINA SER B

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“…Excellent agreement between both sets of data gave k(es-+ B) = 2.2 + 0.2 x 10" M-' sf' which can be compared with values of 8 x 101° and 1.2 x 101° M-' s-' determined with NH, (38) and water (39) respectively.…”

Section: Methodsmentioning

confidence: 56%

“…Absolute values of 1.9 and Substituting the values for E, , , and Avl12 3.1 x 104 M-' cm-' have been reported for deduced above gives f = 0.58. Assuming the the 400 nm band in water (39) and NH, (38), spectrum is described by a Gaussian-Lorenztian respectively. These differ considerably from shape function (44) and then correcting for the that assumed in this and previous work (14) on internal field of the solvent (16) gives a comthe basis of conventional spectrophotometric parable value f = 0.61.…”

Section: Methodsmentioning

confidence: 99%

Pulse radiolytic formation of solvated electrons in hydrazine

Seddon¹,

Fletcher²,

Sopchyshyn³

1976

Can. J. Chem.

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The spectrum and yield of solvated electrons in anhydrous hydrazine have been investigated by pulse radiolysis. At room temperature the optical absorption band has a maximum at 1.22 eV (1015 nm) with a molar extinction coefficient of 2.2 ± 0.1 × 104 M−1 cm−1 and a temperature coefficient of 1.5 × 10−3 eV deg−1 from 7–45 °C. The oscillator strength is estimated to be 0.6. The optical transition energy is in reasonable agreement with an empirical correlation of solvent properties proposed by Freeman provided that only the polarisability of the nitrogen lone-pair electrons contribute to Emax. Comparisons are made with liquid amides which also have lone-pair polarisable groups and with water and liquid ammonia which have physical properties very similar to hydrazine. Electron yields increase from [Formula: see text] in pure hydrazine to 2.65 + 0.15 in basic solutions containing ≥0.1 M sodium hydrazide.

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Pulse Radiolysis and Electron Spin Resonance Studies on the Formation of Phenoxyl Radicals by Reaction of OH Radicals with Methoxylated Phenols and Hydroxybenzoic Acids

O’Neill¹,

Steenken²

1977

Ber Bunsenges Phys Chem

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OH radicals react with methoxylated phenols and methoxylated hydroxybenzoic acids by addition to the aromatic ring to yield hydroxycyclohexadienyl radicals (OH adducts) (k = (1—2) · 1010 M−1 s−1). With respect to the sites of attachment, OH shows a preference for ring positions activated by the electron donating OH or OCH3 groups. Only those hydroxycyclohexadienyl radicals which are produced by addition of OH to ring positions not occupied by methoxyl groups yield phenoxyl type radicals. Formation of phenoxyl radicals is enhanced in the presence of acid or base. Acid catalysis of phenoxyl formation is suggested to proceed via cationic intermediates similar to those proposed for formation of radical cations. In alkaline solution, OH− is eliminated from deprotonated hydroxycyclohexadienyl radicals to yield phenoxyl radicals (k > 106 s−1).—The phenoxyl radicals undergo reaction with a) each other (2k ∼ 1 · 109 M−1 s−1), b) OH adducts (k ∼ 1.3 · 109 M−1 s−1), and c) H adducts (k ∼ 4 · 109 M−1 s−1). The absorption maxima of the isomeric methoxyphenoxyl radicals are blue‐shifted relative to those of radical cations from structurally analogous di‐ and trimethoxybenzenes.

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Formation and decay of the biphenyl cation radical in aqueous acidic solution

Cited by 61 publications

References 6 publications

Mechanism study on the reactions between biphenyl and HNO2 initiated by 355 nm irradiation in aqueous phase

Mechanism study on the reactions between biphenyl and HNO2 initiated by 355 nm irradiation in aqueous phase

Pulse radiolytic formation of solvated electrons in hydrazine

Pulse Radiolysis and Electron Spin Resonance Studies on the Formation of Phenoxyl Radicals by Reaction of OH Radicals with Methoxylated Phenols and Hydroxybenzoic Acids

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