The Atmosphere as a Chemical Reactor OutputsInputs Chemistry Radiation (energy) Biogeochemical Cycling.

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Presentation transcript:

The Atmosphere as a Chemical Reactor OutputsInputs Chemistry Radiation (energy) Biogeochemical Cycling

Temperature Structure of the Atmosphere from: composition/atmospheric_structure.jpg

Pressure Structure of the Atmosphere from:

Mixing Ratio vs. Concentration Mixing Ratio – the fraction of air by volume that is composed of a certain compound. –The fraction of N 2 is 0.80 or 80% –The fraction of N 2 O is 3.6x10 -7 or 3.6x10 -5 % or 360 ppbv. Concentration (number density) – number of molecules of a specified compound contained in a fixed volume. –[N 2 O] at 1010 mbar = 8.86x10 12 molecules/cm 3 –[N 2 O] at 500 mbar = 4.38x10 12 molecules/cm 3 The atmosphere has a density of 2.69x10 19 molecules/cm 3 at sea level

Chemical Composition of the Atmosphere CompoundMixing Ratio N2N O2O Ar CO 2 3.6x10 -4 Ne8x10 -6 He5.2x10 -6 CH 4 1.7x10 -6 Kr1.1x10 -6 H2H2 5.0x10 -7 N2ON2O3.6x10 -7 Xe9.0x10 -8 O3O3 1 – 10x10 -8 H2OH2O

Vertical Mixing of the Troposphere Boundary Layer – hours to days Free Troposphere – days to weeks Tropopause - years

Horizontal Mixing of the Troposphere from: Jacob

Horizontal Mixing of the Troposphere

Kinetics

Only true for elementary reactions!

Lifetime, Pseudo First Order First order reaction: Second order reaction:

Lifetime Some compounds have multiple sinks Methane chemical loss in troposphere by OH ≈ 12yrs physical deposition to the soil ≈ 100 yrs chemical loss in stratosphere ≈ 40 yrs Overall lifetime:

Rate Constants

J Values Photochemistry

Radical Chemistry Radicals do the work of the chemistry in the atmosphere. Produced by photochemical reactions and reactions by other radicals O( 3 P) is a bi-radical O( 1 D) is not a radical, but it is very reactive

The OH Radical

Production of OH Radical Assume steady-state for O( 1 D) ProductionLoss

Production of OH Radical Solve for [O( 1 D)] Substitute into the production of OH

Oxidation of CO

The Chemical Family NO x

Coupling of NO x and HO x NO slow fast

Sinks for NO x and HO x

O 3 Production

Oxidation of Formaldehyde Maximum O 3 production = 3 molecules (high NO x ) Maximum HO x production = 2 molecules (high NO x ) Minimum O 3 production = 0 molecules (low NO x ) Minimum HO x producion = -2 molecules (low NO x )

Oxidation of Methane Can oxidize NO to NO 2 just like HO 2 formaldehyde

O 3 Production by Methane High NO x (maximum O 3 and HO x production): Low NO x (minimum O 3 and HO x production):