Environment of Earth

September 16, 2009

CHLORINE CHEMISTRY OF STRATOSPHERE

Filed under: Atmospheric chemistry — gargpk @ 2:30 pm
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Chief natural source of chlorine in atmosphere is probably methyl chloride from marine algae but it accounts for only 25% of the chlorine currently being transported across tropopause into the stratosphere. Other natural sources adding minor amounts are HCl acid from volcanoes and chlorine from sea sprays. In the past few decades, chlorofluorocarbons (mostly CFCl3 i.e. Feron-11) and CF2Cl2 i.e. Feron-12) added to the atmosphere by human activities have become chief source of stratospheric chlorine. Ammonium perchlorate-aluminium solid rocket propellents are another anthropogenic source of atmospheric chlorine. These compounds absorb UV radiation in the range of 190 to 220 nm resulting in their photodissociation:

CH3Cl + hv —–> CH3 + Cl

CFCl3 + hv ——> CFCl2 + Cl

CF2Cl2 + hv —–> CF2Cl + Cl

Free Cl atoms in stratosphere may undergo various reaction cycles:

1. Reaction with ozone: Free chlorine atoms in stratosphere react with ozone in catalytic manner and cause depletion of ozone:

Cl + O3 —–> ClO + O2

ClO produced may react with nitrogen compounds:

ClO + NO —–> Cl + NO2

ClO + NO2 + M ——–> ClNO3 + M

ClNO3 may be decomposed by UV radiation or by reaction with atomic oxygen:

ClNO3 + hv —–> ClO + NO2

ClNO3 + O —-> O2 + ClO + NO

Reactions of ClO with NO or NO2 are important because they effectively remove N- and Cl- species involved in ozone destroying cycles.

2. Reaction with methane and hydrogen: Free Cl may also react with CH4 or H2:

Cl + CH4 —–> HCl + CH3

Cl + H2 ——> HCl + H

Some of the HCl may react with OH radical in stratosphere:

OH + HCl —–> H2O + Cl

However, most of the HCl moves down to tropopause and is removed with rainfall as HCl acid.

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