E.10.

2 Outline the formation of secondary pollutants in photochemical smog

PHOTOCHEMICAL SMOG
Modern smog are caused by traffic exhaust fumes Produced by series of free radical reactions due to interaction between: sunlight nitrogen monoxide volatile organic compounds(VOC) produced from car exhausts

Production of Nitrogen Monoxide

Formed by direct combination of nitrogen and oxygen at high Temperature of the internal combustion engine:

Production of Nitrogen Dioxide

Secondary pollutant formed by direct oxidation of nitrogen monoxide by oxygen
+

The photochemical reactions begin with absorption of light by secondary nitrogen dioxide as primary pollutant nitrogen monoxide is oxidized Nitrogen dioxide is broken up by sunlight

+ .

PRODUCTION OF OZONE
Reactive oxygen atom reacts with molecular oxygen to produce ozone

+
Dangerous pollutant. Causes shortness of breath, irritation of throat, eyes and nose

Production of hydrocarbon radicals

VOC from unburnt petroleum products are also emitted as primary pollutants from car exhausts

When oxygen atoms remove a hydrogen atom from alkane, alkyl radicals and hydroxyl radicals are produced

+ +

 The hydroxyl radicals react with alkane molecules to produce further alkyl radicals

+ +
Which reacts with oxygen molecule to produce peroxy radicals

Production of aldehydes
The peroxy radicals produced can react with nitrogen monoxide to produce nitrogen dioxide:
+ . . +

The radicals then react with oxygen to form aldehydes:

+ +

Production of nitric acid

Nitric acid is formed by combination of hydroxyl radicals with nitrogen dioxide

Production of peroxyacylnitrates (PANs)

Secondary pollutant which has serious effect on health Produced by series of further sequence of free radical reactions Hydroxyl free radicals remove a hydrogen atom from an aldehyde:

+ +

 The resulting free radicals then react with an oxygen molecule to produce a peroxide

 The resulting free radicals then react with nitrogen monoxide molecule in a termination step to produce relatively stable PAN