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  4. Heterogeneous Chemistry of Cl2O and HOCl on Frozen Natural Sea Salt, Recrystallized Sea Salt, KCl and NaCl Solutions at 200 and 215 K
 
research article

Heterogeneous Chemistry of Cl2O and HOCl on Frozen Natural Sea Salt, Recrystallized Sea Salt, KCl and NaCl Solutions at 200 and 215 K

Pratte, Pascal
•
Rossi, Michel J.  
2010
Zeitschrift Fur Physikalische Chemie-International Journal Of Research In Physical Chemistry & Chemical Physics

The HOCl heterogeneous reaction on frozen natural (NSS) and recrystallized (RSS) sea salt KCl and NaCl solutions was studied using a low pressure flow reactor in order to measure the uptake coefficient gamma and products of reaction The HOCl sample used in these experiments always contained up to 25% Cl2O which was also studied separately as a pure gas in order to understand the heterogeneous chemistry of both gases By performing HOCl uptake on frozen NSS solution at 200 K and a gas phase residence time of (1 6 +/- 0 6) s we obtained a steady state uptake coefficient gamma(HOCl) (on NSS) = (2 5 +/- 0 7) X 10(-3) and gamma(Cl2O on NSS) = (2 8 +/- 0 8) X 10(-3) On frozen KCl solution at 200 K we obtain gamma(HOCl on KCl) = (2 8 +/- 1 3) X 10(-3) identical to NSS and gamma(Cl2O on) (KCl) = (4 6 +/- 0 8) X 10(-4) The main product formed during the uptake, on frozen NSS solution is Cl-2 which is sustained for at least one hour In contrast only a transient Cl-2 flow (pulse) decreasing on the time scale of 100 s was observed on frozen KCl (NaCl) solution 25 +/- 10 % of the HOCl taken up on all chloride containing frozen substrates at 200 K react to produce Cl-2 at high HOCl concentration (4 5 X 10(11) molecule cm(-3)) and at a residence time of 1 6 s in comparison with twice that for Cl2O For smaller concentrations such as [HOCl] = 3 7 X 10(10) molecule cm(-3) and/or a shorter residence time (0 137 +/- 0 004s) HOCl uptake did not generate Cl-2 in contrast to Cl2O A single Br-2 burst event was monitored when a Cl2O or HOCl/Cl2O mixture is taken up on fresh frozen NSS solution during the first uptake at 200 K Further Cl2O or HOCl/Cl2O uptake on the same sample even after annealing at 240 K does not show an additional Br-2 pulse This Br-2 release may be significant in the autocatalytic ozone destruction mechanism in the troposphere during polar sunrise Some of the atmospheric implications of the present results are highlighted with emphasis on the preequilibrium Cl2O(ads) + H2O(ice) reversible arrow 2 HOCl(ads) between adsorbed HOCl and Cl2O with the latter being the gateway to reactive uptake of HOCl at low temperatures

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Type
research article
DOI
10.1524/zpch.2010.6144
Web of Science ID

WOS:000285161400011

Author(s)
Pratte, Pascal
Rossi, Michel J.  
Date Issued

2010

Publisher

Oldenbourg Wissenschaftsverlag GmbH, De Gruyter

Published in
Zeitschrift Fur Physikalische Chemie-International Journal Of Research In Physical Chemistry & Chemical Physics
Volume

224

Start page

1119

End page

1150

Subjects

Heterogeneous Chemistry

•

Sea Salt

•

Cl2O

•

HOCl

•

Arctic Boundary-Layer

•

Polar Sunrise

•

Ultraviolet-Spectrum

•

Equilibrium-Constant

•

Ozone Destruction

•

Ice Surfaces

•

Ab-Initio

•

Temperature

•

Kinetics

•

Bromine

Note

National Licences

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LPAS  
Available on Infoscience
December 16, 2011
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/74888
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