Air Pollution Chemistry.ppt

Air Pollution Chemistry Introduction Air Pollutants Carbon monoxide (CO) - Primary Sulfur dioxide (SO2) - Primary Nitrogen dioxide (NO2) - Primary and Secondary Ozone (O3) - Secondary Particulate matter 10 um in diameter (PM10) - Primary and Secondary Atmospheric Processes Emission Dispersion Wind Inversion Transport Transformation Deposition Hydrocarbon Combustion Ideally Fuel + Air = Products HC+O2 = CO2+H2O Too Simple Methane (CH4) Combustion CH4 +O2+Inert (N2 or Ar) Requires over 170 reactions and over 30 compounds If add NOx chemistry Requires over 275 reactions and over 45 compounds Incomplete Combustion Intermediate Compound Emissions Formaldehyde and Acetylene More toxic or reactive Precursors to secondary pollutants (e.g., ozone and particulate) Oxygenated Compounds Ethers -- R-O-R CH3-O-C(CH3)3 = MTBE Multifunctional Carbonyls More than one oxygenated functional group on same molecule Ambient HC Concentrations Ambient Concentrations of HC Species Outline Ozone Formation Hydrocarbon Reactivity Particulate Matter Formation Conclusions Nitrogen Cycle Only a few minutes per cycle: O + O2 + M O3 + M (fast) M is the “third body”, primarily N2 and O2 NO2 + hv NO + O (k1) hv is ultraviolet radiation O3 + NO NO2 + O2 (k3) ozone “scavenging” reaction NO2 Photolysis Rates forJune 12 and December 12 Photostationary State [O3] = {k1 / k3} . {[NO2] / [NO]} NOx emissions 90% NO. [O3] = {10} . {1 / 10} [O3] = 1 ppb Fast Radical Transfer Reaction Oxidizes NO to NO2, allowing O3 to build up. RO2 + NO RO + NO2 R is any hydrocarbon fragment. 100’s of hydrocarbons 1000’s of reactions Takes hours to affect PSS. Hydrocarbon Oxidation Cycle The hydroxyl radical begins cycle, OH + HCHO H2O + HCO HCO + O2 HO2 + CO HO2 + NO NO2 + OH and is returned at end of cycle. Sources of Radicals Formaldehyde photolysis HCHO + hv + O2 HO2 + HCO Ozone photolysis O3 + hv + H20