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Chemical Equilibrium
for the Atmospheric Sciences
1. Chemical Equilibrium • Equilibrium constants
2. Chemical Thermodynamics
NO2 + NO3 N2O5 , Keq = [N2O5]/([NO2][NO3])
3. Chemical Kinetics aA + bB + … gG + hH + …, Keq = [G]g[H]h…
4. Solution Chemistry and Aqueous Equilibria [A]a[B]b…
5. Acids and Bases • Reaction quotient ( not in equilibrium)
6. Oxidation-Reduction Reactions Q = [G]g[H]h… if Q < Keq , then (forward)
7. Photochemistry [A]a[B]b… if Q > Keq , then (backward)
• Le Châtelier’s principle
perturbance of a system at equilibrium ! minimize effect
of perturbance
Chemical Thermodynamics
• Enthalpies of reactions and formation
• A chemical reaction generally starts off fast, slows with time, and
finally ceases K = A exp - ∆H0rx , ∆ H0rx = molar standard enthalpy (heat)
RT of reaction
• The equilibrium constant for a chemical reaction is independent
of the exact mechanism of the reaction, the rate at which the aA + bB + … gG + hH + …
equilibrium is approached, or the direction from which the ∆H0rx = [g∆H0f(G) + h∆H0f(H)+…] – [a∆H0f(A) + b∆H0f(B)+ …]
equilibrium is approached ∆H0rx < 0 : heat released (exothermic) spontaneous
∆H0rx > 0 : heat absorbed (endothermic)
• Only for reactions in which the number of molecules of gaseous
reactants is different from the number of molecules of gaseous • Gibbs-Helmholtz equation:
products does a volume change remove the system from Equilibrium:
∆G = ∆H0rx -T ∆S ≤ 0
equilibrium. dg=0
• Free energy change and equilibrium constant:
∆G0T = -R T ln Kp (1 atm)
1
Chemical Kinetics (cont.)
• Lifetimes, half-lifes: d[A]/dt = -k [A] • A piece of paper can remain in contact with air indefinitely without
!Lifetime (residence time): τ = 1/k (time it takes to reach 1/e of initial any observable reaction, but it reacts as soon as it is touched with a
concentration) flame
!Half life: t1/2 = ln(2)/k (time it takes to reach 1/2 of initial
concentration) • Increasing pressure generally decreases the rates of chemical
reactions of solids (or liquids) that produce gases
FI
• Increasing pressure always increases the rates of reactions of gases
M
• Gases the have small residence times in the atmosphere tend to
have large spatial variabilities
FO
τ = M/F o
• Dissolution Acidic solution: [H+] > [OH-] (pH<7). HCl(aq) ! H+(aq) + Cl-(aq)
– Strong electrolyte: HCl(g) ! H+(aq) + Cl-(aq)
Basic solution: [H+] < [OH-] (pH>7). NaOH ! Na+(aq) + OH-(aq)
– Weak electrolyte: CH3COOH(l) H+(aq) + CH3COO-(aq)
Acids = protons donors HA(aq) + H2O(l) H3O+(aq) + A-(aq)
– Equilibrium constant Ksp = [H+][CH3COO-]/[CH3COOH] Ka = [H3O+][A-]/[HA]
2
Oxidation-reduction reactions (cont.) Photochemistry
• Half-reactions in electrochemical cells • Photochemical reactions
• Strengths of oxidants and reductants AB + hν ! AB* ! AB + hν luminescence
– Standard cell potential E0cell Planck constant ! AB + M quenching
frequency
– Standard half-cell potential: wrt H2(g) ! 2H+(aq) + 2e- ! A+B photodissociation
– Table of electrode potential: Reduced form will react
spontaneously with oxidized form below
Quantum yield, φ probability that a pathway will occur
Zn2+/Zn E0= -0.763 V Zn ! Zn + 2e- E oxid=0.76V
2+ 0
Photochemistry (cont.)