Basic Physical Chemistry

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)

Chemical Kinetics Chemical Kinetics (cont.)

• Reaction rates aA + bB + … gG + hH + … , k (rate coef)
-1/a d[A]/dt = -1/b d[B]/dt = … = 1/g d[G]/dt = 1/h d[H]/dt
• Rate law: reaction rate = k[A]m[B]n…
• First order reaction: A ! B -d[A]/dt = k [A]
• Second order reaction: A + A ! B -d[A]/dt = k [A]2
A + B ! C -d[A]/dt = k [A][B]
• Third order reaction: A + B + C ! D - d[A]/dt=k
[A][B][C]
• Chemical mechanism
• Concept of rate limiting step
• Reaction rates and equilibria: A + B ! AB, kf AB ! A + B, kr
At equilibrium kf [A][B] = kr[AB] , so kf/kr = [AB]/([A][B]) = Keq
• What determines the rate constant of bimolecular reactions?
! Upper limit from collision theory: k = 2 ×10-10 cm3 molec-1 s-1 (room T.)
! Most reactions slower: energy barrier, geometry, temperature
Insert figure 3.2
• Arrhenius’ relation: k = A exp -Ea
RT

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 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

Solution chemistry and aqueous equilibria Acids and bases

• Solubility. Henry’s law H2O(l) H+(aq) + OH-(aq), Kw= [H+][OH-]= 10-14 M2, pH = -log[H+]
Cg = kHpg
Neutral solution: [H+] = [OH-] (pH = 7)

• 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]

Base = proton acceptors A-(aq) + H2O(aq) HA(aq) + OH-(aq)

Kb = [HA][OH-]/[A-]

Acids and bases (cont.) Oxidation-reduction reactions

• Electron transfer
• Buffers • Oxidation = loss of electron Cu(s) ! Cu2+(aq) + 2e-
• Mass balance and charge balance relations
• Reduction = gain of electron 2 Ag+(aq) + 2e- ! 2 Ag(s)
HA(aq) + H2O(l) H3O+(aq) + A-(aq), Ka
2H2O(l) H3O+(aq) + OH-(aq)
• Redox reaction: Cu(s) + 2 Ag+(aq) ! Cu2+(aq) + 2 Ag(s)
Ka = [HA]/[H3O+][A-]
reductant oxidant
Kw = [H3O+][OH-] • Oxidation numbers (H = +1 ; O = -2)
[HA]initial = [HA] + [OH-]
HSO3 (aq) + H2O(l) ! HSO4-(aq) + 2H+(aq)+2e-
-
[H3O+] = [OH-]+ [A-]
2Fe3+(aq) + 2e- ! 2 Fe2+(aq)
S(IV) ! S(VI) oxidation number increases: oxidation reaction
Fe(III) ! Fe(II) oxidation number decreases: reduction reaction
• Balancing oxidation-reduction reactions. CO2 + H2O ! C6H12O6

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 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

Cu2+ + 2e-!Cu E0red=0.34V Photolysis rate:

Cu2+ + Zn !Cu + Zn2+ d[AB]/dt = -J [AB], with J = photolytic rate constant
Cu2+/Cu E0= 0.34 V E0= E0oxid + E0red= 0.34+0.76=1.1V

Photochemistry (cont.)

• A gas molecule will absorb radiation at a given

wavelength only if the energy can be used to increase
the internal energy level of a molecule

• Rotational transitions ! far IR ( >20 µm)

• Vibrational transitions ! Near IR (20 – 0.7 µm)
• Electronic transitions ! UV radiation (<0.4 µm)