A kinetic and product study of the hydrolysis of ClONO2 on type Ia polar stratospheric cloud materials at 185 K

Stephen B. Barone, Mark Andrew Zondlo, Margaret A. Tolbert

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Abstract

A Knudsen cell reactor equipped with FTIR reflection-absorption spectroscopy (FTIR-RAS) has been used to study the hydrolysis of chlorine nitrate (ClONO2) on thin nitric acid trihydrate (NAT) and nitric acid dihydrate (NAD) films. The reaction efficiencies and condensed-phase products have been measured for a variety of water partial pressures at 185 K. The reaction efficiencies for ClONO2 hydrolysis on NAT and NAD were of similar magnitude and increased from γ = 0.0004 to γ= 0.007 as the water partial pressure was increased from 5 × 10-6 to 1.4 × 10-4 Torr. Although these values agree well with literature values at 90% relative humidity, significant differences are observed at lower relative humidities. Using our results at 185 K along with previous studies at 191 and 202 K, we suggest that this reaction may have a temperature dependence that is not currently addressed in atmospheric models. In the condensed phase, we observed the water dependence by the formation of progressively water-rich surface layers. The amount of water incorporated onto the NAT and NAD films increased with increasing relative humidity, suggesting that ClONO2 hydrolysis occurs most efficiently on a water-rich hydrate surface. For water saturation ratios S ≥ 1.5, nucleation and growth of crystalline ice was observed to occur in the aqueous HNO3 surface layer on top of the reactant NAD and NAT films.

Original languageEnglish (US)
Pages (from-to)8643-8652
Number of pages10
JournalJournal of Physical Chemistry A
Volume101
Issue number46
DOIs
StatePublished - Nov 13 1997

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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