The hydrolysis of chlorine nitrate on ice is autocatalytic

Franz M. Geiger; Charles D. Pibel; Janice M. Hicks

doi:10.1021/jp0101007

The hydrolysis of chlorine nitrate on ice is autocatalytic

Franz M. Geiger, Charles D. Pibel, Janice M. Hicks^*

^*Corresponding author for this work

Chemistry

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

17 Scopus citations

Abstract

A key chemical reaction in stratospheric ozone depletion is the reaction of chlorine nitrate (ClONO₂) with water. This reaction is known to be catalyzed in the presence of ice particles found in polar stratospheric clouds (PSCs). However, the mechanism and time scale of the reaction, and the role of the ice surface, are not well understood. This surface second harmonic generation study shows that the submonolayer ClONO₂ hydrolysis on basal ice (Ih) surfaces at 185 K occurs autocatalytically, with the product molecule HOCl acting as the autocatalyst. The other product, HNO₃, acts to delay the reaction. The hydrolysis reaction is surprisingly slow, with induction times that range from 100 to 1000 s, depending upon how much reactant is initially present. It is proposed that the ice surface serves as a reservoir, enabling the reaction to be acid catalyzed.

Original language	English (US)
Pages (from-to)	4940-4945
Number of pages	6
Journal	Journal of Physical Chemistry A
Volume	105
Issue number	20
DOIs	https://doi.org/10.1021/jp0101007
State	Published - May 24 2001

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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title = "The hydrolysis of chlorine nitrate on ice is autocatalytic",

abstract = "A key chemical reaction in stratospheric ozone depletion is the reaction of chlorine nitrate (ClONO2) with water. This reaction is known to be catalyzed in the presence of ice particles found in polar stratospheric clouds (PSCs). However, the mechanism and time scale of the reaction, and the role of the ice surface, are not well understood. This surface second harmonic generation study shows that the submonolayer ClONO2 hydrolysis on basal ice (Ih) surfaces at 185 K occurs autocatalytically, with the product molecule HOCl acting as the autocatalyst. The other product, HNO3, acts to delay the reaction. The hydrolysis reaction is surprisingly slow, with induction times that range from 100 to 1000 s, depending upon how much reactant is initially present. It is proposed that the ice surface serves as a reservoir, enabling the reaction to be acid catalyzed.",

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T1 - The hydrolysis of chlorine nitrate on ice is autocatalytic

AU - Geiger, Franz M.

AU - Pibel, Charles D.

AU - Hicks, Janice M.

PY - 2001/5/24

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N2 - A key chemical reaction in stratospheric ozone depletion is the reaction of chlorine nitrate (ClONO2) with water. This reaction is known to be catalyzed in the presence of ice particles found in polar stratospheric clouds (PSCs). However, the mechanism and time scale of the reaction, and the role of the ice surface, are not well understood. This surface second harmonic generation study shows that the submonolayer ClONO2 hydrolysis on basal ice (Ih) surfaces at 185 K occurs autocatalytically, with the product molecule HOCl acting as the autocatalyst. The other product, HNO3, acts to delay the reaction. The hydrolysis reaction is surprisingly slow, with induction times that range from 100 to 1000 s, depending upon how much reactant is initially present. It is proposed that the ice surface serves as a reservoir, enabling the reaction to be acid catalyzed.

AB - A key chemical reaction in stratospheric ozone depletion is the reaction of chlorine nitrate (ClONO2) with water. This reaction is known to be catalyzed in the presence of ice particles found in polar stratospheric clouds (PSCs). However, the mechanism and time scale of the reaction, and the role of the ice surface, are not well understood. This surface second harmonic generation study shows that the submonolayer ClONO2 hydrolysis on basal ice (Ih) surfaces at 185 K occurs autocatalytically, with the product molecule HOCl acting as the autocatalyst. The other product, HNO3, acts to delay the reaction. The hydrolysis reaction is surprisingly slow, with induction times that range from 100 to 1000 s, depending upon how much reactant is initially present. It is proposed that the ice surface serves as a reservoir, enabling the reaction to be acid catalyzed.

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The hydrolysis of chlorine nitrate on ice is autocatalytic

Abstract

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