Heterogeneous reaction of gaseous ozone with aqueous iodide in the presence of aqueous organic species

Sayaka Hayase; Akihiro Yabushita; Masahiro Kawasaki; Shinichi Enami; Michael R. Hoffmann; Agustín J. Colussi

doi:10.1021/jp101985f

Heterogeneous reaction of gaseous ozone with aqueous iodide in the presence of aqueous organic species

Sayaka Hayase, Akihiro Yabushita, Masahiro Kawasaki, Shinichi Enami, Michael R. Hoffmann, Agustín J. Colussi

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

45 Citations (Scopus)

Abstract

The fast reaction of gaseous ozone, O₃(g), with aqueous iodide, I^-(aq), was found to be affected by environmentally relevant cosolutes in experiments using cavity ring-down spectroscopy (CRDS) and electrospray ionization mass spectrometry (ESIMS) for the detection of gaseous and interfacial products, respectively. Iodine, I₂(g), and iodine monoxide radical, IO(g), product yields were suppressed in the presence of a few millimolar phenol (pK_a = 10.0), p-methoxyphenol (10.2), or p-cresol (10.3) at pH 3 but unaffected by salicylic acid (pKa₂ = 13.6), tert-butanol, n-butanol, or malonic acid. We infer that reactive anionic phenolates inhibit I₂(g) and IO(g) emissions by competing with I ^-(aq) for O₃(g) at the air/water interface. ESIMS product analysis supports this mechanism. Atmospheric implications are discussed.

Original language	English
Pages (from-to)	6016-6021
Number of pages	6
Journal	Journal of Physical Chemistry A
Volume	114
Issue number	19
DOIs	https://doi.org/10.1021/jp101985f
Publication status	Published - May 20 2010
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry

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10.1021/jp101985f

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title = "Heterogeneous reaction of gaseous ozone with aqueous iodide in the presence of aqueous organic species",

abstract = "The fast reaction of gaseous ozone, O3(g), with aqueous iodide, I-(aq), was found to be affected by environmentally relevant cosolutes in experiments using cavity ring-down spectroscopy (CRDS) and electrospray ionization mass spectrometry (ESIMS) for the detection of gaseous and interfacial products, respectively. Iodine, I2(g), and iodine monoxide radical, IO(g), product yields were suppressed in the presence of a few millimolar phenol (pKa = 10.0), p-methoxyphenol (10.2), or p-cresol (10.3) at pH 3 but unaffected by salicylic acid (pKa2 = 13.6), tert-butanol, n-butanol, or malonic acid. We infer that reactive anionic phenolates inhibit I2(g) and IO(g) emissions by competing with I -(aq) for O3(g) at the air/water interface. ESIMS product analysis supports this mechanism. Atmospheric implications are discussed.",

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AU - Hayase, Sayaka

AU - Yabushita, Akihiro

AU - Kawasaki, Masahiro

AU - Enami, Shinichi

AU - Hoffmann, Michael R.

AU - Colussi, Agustín J.

PY - 2010/5/20

Y1 - 2010/5/20

N2 - The fast reaction of gaseous ozone, O3(g), with aqueous iodide, I-(aq), was found to be affected by environmentally relevant cosolutes in experiments using cavity ring-down spectroscopy (CRDS) and electrospray ionization mass spectrometry (ESIMS) for the detection of gaseous and interfacial products, respectively. Iodine, I2(g), and iodine monoxide radical, IO(g), product yields were suppressed in the presence of a few millimolar phenol (pKa = 10.0), p-methoxyphenol (10.2), or p-cresol (10.3) at pH 3 but unaffected by salicylic acid (pKa2 = 13.6), tert-butanol, n-butanol, or malonic acid. We infer that reactive anionic phenolates inhibit I2(g) and IO(g) emissions by competing with I -(aq) for O3(g) at the air/water interface. ESIMS product analysis supports this mechanism. Atmospheric implications are discussed.

AB - The fast reaction of gaseous ozone, O3(g), with aqueous iodide, I-(aq), was found to be affected by environmentally relevant cosolutes in experiments using cavity ring-down spectroscopy (CRDS) and electrospray ionization mass spectrometry (ESIMS) for the detection of gaseous and interfacial products, respectively. Iodine, I2(g), and iodine monoxide radical, IO(g), product yields were suppressed in the presence of a few millimolar phenol (pKa = 10.0), p-methoxyphenol (10.2), or p-cresol (10.3) at pH 3 but unaffected by salicylic acid (pKa2 = 13.6), tert-butanol, n-butanol, or malonic acid. We infer that reactive anionic phenolates inhibit I2(g) and IO(g) emissions by competing with I -(aq) for O3(g) at the air/water interface. ESIMS product analysis supports this mechanism. Atmospheric implications are discussed.

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JO - Journal of Physical Chemistry A

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Heterogeneous reaction of gaseous ozone with aqueous iodide in the presence of aqueous organic species

Abstract

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