Peroxyacyl nitrates

Peroxyacyl nitrates

Peroxyacyl nitrates, or PANs, are powerful respiratory and eye irritants present in photochemical smog. They are formed from a peroxyacyl radical and nitrogen dioxide, for example peroxyacetyl nitrate, CH3COOONO2:

Hydrocarbons + O2 + NO2 + light → CH3COOONO2

The general equation is;

CxHyO3 + NO2 → CxHyO3NO2

PANs are both toxic and irritating, as they dissolve more readily in water than ozone. At concentrations of only a few parts per billion they cause eye irritation. At higher concentrations they cause extensive damage to vegetation.Both PANs and their chlorinated derivates are said to be mutagenic, as they can be a factor causing skin cancer.

PANs are secondary pollutants, which means they are not directly emitted as exhaust from power plants or internal combustion engines, but they are formed from other pollutants by chemical reactions in the atmosphere. Free radical reactions catalyzed by ultraviolet light from the sun oxidize unburned hydrocarbons to aldehydes, ketones, and dicarbonyl compounds, whose secondary reactions create peroxyacyl radicals, which combine with nitrogen dioxide to form peroxyacyl nitrates.

The most common peroxyacyl radical is peroxyacetyl, which can be formed from the free radical oxidation of acetaldehyde, various ketones, or the photolysis of dicarbonyl compunds such as methylglyoxal or diacetyl.

Since they dissociate quite slowly in the atmosphere into radicals and NO2, PANs are able to transport these unstable compounds far away from the urban and industrial origin. This is important for tropospheric ozone production as PANs transport NOx to regions where it can more efficiently produce ozone.

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