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Atmospheric Chemistry Atmospheric Chemistry John Lee Grenfell Technische Universität Berlin Atmospheres and Habitability (Earthlike) Atmospheres: -support complex life (respiration) -stabilise temperature -maintain liquid water -we can measure their spectra hence life-signs Modern Atmospheric Composition CO2 Modern Atmospheric Composition O2 CO2 N2 CO2 N2 CO2 Modern Atmospheric Composition O2 CO2 N2 CO2 N2 P 93bar 1bar 6mb 1.5bar surface CO2 Tsurface 735K 288K 220K 94K Early Earth Atmospheric Compositions Magma Hadean Archaean Proterozoic Snowball CO2 Early Earth Atmospheric Compositions Magma Hadean Archaean Proterozoic Snowball Silicate CO2 CO2 N2 N2 Steam H2ON2 O2 O2 CO2 Additional terrestrial-type atmospheres Jurassic Earth Early Mars Early Venus Jungleworld Desertworld Waterworld Superearth Modern Atmospheric Composition Today we will talk about these CO2 Reading List Yuk Yung (Caltech) and William DeMore “Photochemistry of Planetary Atmospheres” Richard P. Wayne (Oxford) “Chemistry of Atmospheres” T. Gredel and Paul Crutzen (Mainz) “Chemie der Atmosphäre” Processes influencing Photochemistry Photons Protection Delivery Escape Clouds Photochemistry Surface OCEAN Biology Volcanism Some fundamentals… ALKALI METALS The Periodic Table NOBLE GASES One outer electron Increasing atomic number 8 outer electrons: reactive Rows called PERIODS unreactive GROUPS: similar Halogens chemical C, Si etc. have 4 outer electrons properties SO CAN FORM STABLE CHAINS Chemical Structure and Reactivity s and p orbitals d orbitals The Aufbau Method works OK for the first 18 elements EIGHT ELECTRON STABILITY RULE Neon 1s2 2s2 2p6 Argon 1s2 2s2 2p6 3s2 3p6 USEFUL FOR UNDERSTANDING CHEMICAL PROPERTIES Electrons in Oxygen Rules Pauli exclusion principle (01,2 electrons per orbital, with different different spins) Hund’s Rules highest orbital fills SINGLY with same spin Electrons in Oxygen USEFUL FOR UNDERSTANDING CHEMICAL PROPERTIES Pauli exclusion principle (01,2 electrons perRules orbital, with different different spins) highest orbital fills SINGLY Hund’s Rules with same spin TWO Ways to form Chemical Bonds… COVALENT BOND IONIC BOND Covalent bonds can be….. Non-polar (hydrophobic) Polar Molecular Orbitals electrons and nucleii interact in two ways – in-phase and out of phase Molecular Orbitals Useful to predict properties of molecules such as O , H O electrons and nucleii interact in 2 2 ways – in-phase and out of phase two EQUILIBRIUM CHEMISTRY Consider the general reaction: αA+ βB σS+ τT At equilibrium: Rate forward = Rate backwards Now, applying law of mass action: Reaction Rate = Rate Constant (k) * Concentrations α β σ τ i.e. kforward[A] [B] = kbackwards[S] [T] Equilibrium constant, K = (kforward/ kbackwards) i.e. K = [S]σ[T]τ / [A]α[B]β It can be shown that: ΔG = -RT(lnK) Note: at equilibrium, all species are present in a mixture determined by K EQUILIBRIUM CHEMISTRY Consider the general reaction: αA+ βB σS+ τT UCH ST At equilibrium: M FA Rate forward = RateW backwardsW Now, applyingHO law ofHO mass action: Reaction Rate = RateS Constant (k) * Concentrations i.e. k Y[A]α[B]β = k [S]σ[T]τ forward SAY backwards SA T Equilibrium constant, K = (kforward/ kbackwards) NLY i.e.NO K = [S]σ[T]τ / [A]α[B]β O It canES be shown that: ΔG = -RT(lnK) Note: atDO equilibrium, all species are present in a mixture determined by K REACTION KINETICS – How fast? Energy (photon, cosmic ray, thermal) e.g. O2 HOW FAST depends on: Initial Concentration (C) AND Reaction Rate Constant (k) e.g. d(O2)/dt = -k [O2] Chemical Kinetics Generally, three types of reactions: A Æ Products 1st order A + B Æ C + D 2nd order A + B + M Æ AB + M 3rd order M = “third-body” = any species needed to carry away excess vibrational energy Rates (mostly) depend on Temperature: Arrhenius Equation Svante Arrhenius Rate constant, K=Aexp(-Eact/kT) (1859-1927) K = rate constant A = pre-exponential constant Eact = activation energy Rates (mostly) depend on Temperature: Arrhenius Equation Svante Arrhenius Rate constant, K=Aexp(-Eact/kT) (1859-1927) K = rate constant A = pre-exponential constant Eact = activation energy Why is there an activation energy? Why is there an activation energy? H C H H H O-H H . H C H H-O-H C H H H H O-H METHANE Why is there an activation energy? H C H H energy needed to break H O-H bonds and to overcome electron-electron repulsion H . H C H H-O-H C H H H H O-H METHANE H C H H H O-H energy emitted via newly-formed bond(s) H . H C H H-O-H C H H H H O-H METHANE How strong are common molecules in Earth’s atmosphere? Molecule Bond Strength (eV) Nitric Acid (HNO3)2.2Weak molecules Nitrogen dioxide (NO2) 3.2 Broken in visible light Hydrogen (H2)4.5 Methane (CH4)4.6Medium-strength Ammonia (NH3) 4.7 Broken in UV Oxygen (O2)5.2 Water (H2O) 5.2 Carbon Dioxide (CO2)5.5 Nitrogen (N2) 9.8 Strong molecules Carbon monoxide (CO) 11.1 Broken in EUV SUMMARY EQUILIBRIUM CHEMISTRY FAVOURED AT VERY HIGH T, P (e.g. deep under the Earth, on Venus’ surface, deep in Jupiter and Saturn) All substances present as a mixture governed by ΔG NON-EQUILIBRIUM CHEMISTRY e.g. photochemistry in Earth’s atmosphere Species react and are removed to form products EQUILIBRIUM THEORY PREDICTS ONLY FINAL COMPOSITION NOT HOW LONG IT TAKES TO BE REACHED - FOR THE RATES WE NEED “REACTION KINETICS” Thermodynamic Equilibrium in Troposphere Non-Thermodynamic Equilibrium (“Photochemical”) Photochemical Processes Absorption AB+hvÆAB* Ionisation AB*ÆAB+ + e- Quenching AB*+MÆAB+M Dissociation AB*ÆA+B Reaction AB*+C Æ Products Luminescence AB*ÆAB + hv Photolysis AB + hvÆ A + B Photolysis AB + hv Æ A + B Photolysis Rate = σ (λ,T) φ (λ) Φ dλ σ (λ,T) Absorption Cross-Section φ (λ) Quantum yield Φ Actinic Flux dλ Wavelength interval Photolysis Rate = σ (λ,T) φ (λ) Φ dλ (1) Absorption Cross Section, σ (λ,T) 2 σ = Π (rm) CROSS SECTIONAL AREA σ is the AREA presented by a particular molecule to a flux of photons Photolysis Rate = σ(λ,T)φ(l)Φ dλ (2) Quantum Yield, φ (λ) φ(λ) = Number of molecules reacting per total photons absorbed. Values range from 0.0 to 1.0 Photolysis Rate = σ(λ,T)φ(l)Φ dλ Actinic Flux (Φ ) Total photons available to at a point in the atmosphere - integral of spectral radiance (J m-2 s-1) over 3D space Heterogeneous Chemistry Gas-phase Solid or liquid phase Particle (e.g. dust, pollen, seasalt) Aerosol (e.g. sulphate, cloud droplet) Heterogeneous Chemistry Gas-phase ADSORBS Solid or liquid phase Particle (e.g. dust, pollen, seasalt) Aerosol (e.g. sulphate, cloud droplet) Heterogeneous Chemistry Gas-phase ADSORBS Solid or liquid phase Particle (e.g. dust, pollen, seasalt) Aerosol (e.g. sulphate, cloud droplet) Heterogeneous Chemistry Gas-phase ADSORBS Solid or liquid phase Chemisorption -chemical bonds Physisorption Particle (e.g. dust, pollen, seasalt) -Van der Waal Bonds Aerosol (e.g. sulphate, cloud droplet) Heterogeneous Chemistry Some adsobed species can move along surface Particle (e.g. dust, pollen, seasalt) Aerosol (e.g. sulphate, cloud droplet) Heterogeneous Chemistry Adsorbed species react with surface or with other gas-phase molecules to form products which are desorbed Particle (e.g. dust, pollen, seasalt) Aerosol (e.g. sulphate, cloud droplet) Heterogeneous Chemistry Adsorbed species react with surface or with other gas-phase molecules to form products which are desorbed Particle (e.g. dust, pollen, seasalt) Aerosol (e.g. sulphate, cloud droplet) Heterogeneous Reaction Rates Rate of Adsorption = kads[X(g)] 2 Kads = f( γ ν (πrx )Νx ) γ = sticking coefficient (0Æ1) ν = molecular velocity 2 (πrx ) particle area Νx = number density in gas-phase Atmospheric Regions “Thermos”=heat Heating (oxygen absorption) “Mesos”=middle Cooling (adiabatic expansion) “Strato”=layered Heating (ozone Ozone layer absorption) “Tropo”=turning Cooling (adiabatic expansion) Earth’s Atmospheric Composition Why so much N2 and O2? Original (primary) atmosphere: H2, He, H2O and CO2 Then, H2 and He LOST via escape CO2 dissolved in rain to form carbonates in rocks So, N2 (from volcanoes) came to dominate why nitrogen? -volatile, unreactive, stable to photolysis O2 was input by PHOTOSYNTHESIS Oxygen (O2) and Ozone (O3) O=O 1.207 A Oxygen Ozone Good biomarkers (indicators of life) O3 produced mainly from O2, O2 from life Ozone comes from oxygen…so study the Oxygen Cycle 3.8x1019 mol O (atm) (0.5%) O2 in 2 (Lasaga and Ohmoto, 2002) Photochemistry (~91% from oceans, Holland 2006) 6CO2+6H2O+energy Respiration ~ balances ÆC6H12O6+6O2 Photosynthesis Burial removes organics – leads to increase in O2 MOST O2 STORED IN ROCKS e.g. Zahnle and Catling (2003) quantify the cycle Photochemistry of Biomarkers on Earth Biomarker Source Sink O2 + O + (N2)ÆO3 Catalytic cycles O3 LIFE spectrum FROM OXYGEN Denitrifying N O bacteria Photolysis 2 LIFE FROM BACTERIA 1D Ozone (O3) Photochemistry 50km chlorine cycles 40km Chapman Ozone (from O2 + hν) 30km faster at high hν 20km FROM nitrogen and LIFE hydrogen cycles 10km Smog Ozone e.g. from pollution volume mixing ratio ~9x10-6 Stratospheric Tropospheric column=90% column=10% Pole North photolysis 2 from tropics to pole Daily variation in the tropics via O Tropospheric chemistry (photolysis): 0.1-1.0ppm transported formed (HOx) cycles important in mesosphere Ozone c o x x x x n t r o l (O ) ClO , NO , , HO , Bad ozone: Hydrocarbons, NOx, UV (smog) Ozone D y n a m i c a l Chemical control Chemical 2D Ozone Photochemistry on Earth Pole South N2O comes from bacteria as by-product of the NITROGEN CYCLE Nitrogen Cycle N (g) 2 N2, N2O, energy fixation denitrification nitrification N2O comes from bacteria as by-product of the NITROGEN CYCLE Nitrogen Cycle N (g) 2 N2, N2O, energy fixation denitrification nitrification biological N2O sources on Earth about one billion times stronger than non-biological (photochemistry) Why is there an ozone “layer”? Ozone formed from oxygen and UV Ozone formation is a trade-off of two opposing factors Low in atmosphere -->lots of O2 but little UV High in atmosphere-->lots of UV, but little O2 -leads to peak at 30km in ozone Problem: Chapman scheme overestimates observed ozone by a factor 2-3 Solution: Add catalytic cycles, which destroy ozone: X+O3-->XO+O2 XO+O-->X+O2 ---------------------- Overall: O3+O-->2O2 X= catalyst e.g.
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