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Chapter 2
Environmental Chemistry
Chuyang Y. Tang
tangc@[Link]
2859 1976
Expected learning outcomes for Chapter 1
• Stoichiometry
• Oxygen demand
• Chemical equilibrium
• Reactor quotient (Q) and equilibrium constant (K)
• P notation: pX = -log10(X)
• Chemical speciation
• Solubility
• Henry’ law
• Nuclear chemistry
• Radioactive decay and half life
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Stoichiometry
• Balancing chemical reactions
CH4 + O2 CO2 + H2O
• Atomic weight
• C = 12 g/mol; H = 1 g/mol; O = 16 g/mol
• Molecular weight
• CH4: 12 + 1 x 4 = 16 g/mol; O2:32 g/mol; CO2 = 44 g/mol; H2O = 18 g/mol
CH4 + 2O2 CO2 + 2H2O
1 mol 2 mol 1 mol 2 mol
16 g 64 g 44 g 36 g
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Stoichiometry
Ex. 2.3 Carbon emissions from natural gas
Energy content of methane = 39,000 kJ/m3 (@STP);
Worldwide energy production from burning methane: 10.9 x 10 16 kJ/yr.
??? Emission rate of CO2
moles of methane = (10.9 x 1016 kJ/yr) / (39,000 kJ/m3) / 0.0224 m3
= 12.5 x 1013 mol/yr
CH4 + 2O2 CO2 + 2H2O
12.5 x 1013 mol/yr 12.5 x 1013 mol/yr
CO2 emission = 12.5 x 1013 mol/yr x 44g/mol = 5.5 x 1015 g/yr = 5.5 x 109 tonne/yr
Carbon emission = 5.5 x 109 x 12/44 = 1.5 x 109 tonne/yr = 1.5Gtonne/yr
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Stoichiometry
Ex. 2.2 Theoretical oxygen demand
A wastewater contains 1.67 mM glucose (C6H12O6). Find the amount of
oxygen required to fully oxidize glucose.
C6H12O6 + 6O2 6CO2 + 6H2O
1 6
1.67 mM 1.67 x 6 = 10 mM
Theoretical oxygen demand = 10 x 10-3 mol/l x 32 g/mol = 320 x 10-3 g/l
= 320 mg/l
Or simply, 10 mM x 32 mg/mmol = 320 mg/l
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Oxygen demand
- amount of oxygen required to oxidize organic matter
• Theoretical oxygen demand
• Calculated based on stoichiometry
• Requires the knowledge of molecular formula
• Biochemical oxygen demand (BOD)
• Oxygen required to biologically remove a (organic) pollutant
• Chemical oxygen demand (COD)
• Oxygen required to chemically oxidize a (organic) pollutant
• Theoretical oxygen demand > COD > BOD
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Enthalpy in chemical systems
U1 U2
Q
U1 + Q = U2 + W H > 0 endothermic (absorb heat)
Q = U2 – U1 + P(V2 – V1 ) H < 0 exothermic (release heat)
Or Q = (U2 + PV2) – (U1 - PV1 )
Define H = U + PV (enthalpy)
Q = H = H2 – H1 (heat of reaction)
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Enthalpy in chemical systems
Ex. 2.4 Heat of combustion of methane
Table 2.1 standard enthalpies (H2980 , 1 atm and 25 C)
CH4 + 2O2 CO2 + 2H2O (l)
(-74.9) 2 x 0 (-393.5) 2 x (-285.8)
(-393.5) + 2 x (-285.8) - (-74.9) - 2 x 0
= -890.2 kJ/mol of CH4
(negative sign means heat is released)
Higher heating value (HHV): water – liquid
= 890.2 kJ/mol of CH4
Lower heating value (LHV): water – vapor
= HHV – heat needed for evaporation
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(see Ex. 2.5)
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Enthalpy in chemical systems
Tips for ozone
Ex. 2.5 Photolysis of ozone Stratospheric ozone:
Protecting earth by absorbing UV light
(more discussion in Chapter 8)
O3 + h (photon) O2 + O
(142.9) (0) (247.5) Ground-level ozone:
An air pollutant
(more discussion in Chapter 6
H0 = 247.5 – 142.9 = + 104.6 kJ/mol
(+ sign means energy needs to be absorbed to realize the reaction)
Each ozone molecule absorb energy from one photon,
Minimum energy for photon = 104,600 J/(6.02 x 1023) = 1.74 x 10-19 J
E = h and = c/ = hc/E
= (6.6 x 10-34 J.s) x (3 x 108 m/s) / (1.74 x 10-19 J) = 1.13 x 10-6 m = 1.13 µm
Limitations
Chemical equilibria Reactions are not always at equilibrium
Some slow reactions
A general chemical reaction
c d
Q
[ C] [ D ]
aA bB cC dD K
[A]a [B]b
Notes:
1. K is the equilibrium constant
Q = K, reaction at equilibrium
Q < K, reaction proceeds forward
Q > K, reaction proceeds backward
2. Concentration in M. Pure solid or pure liquid, activity = 1.
Acidity constant: Ka
Solubility product: Ksp or Ks
Henry’s constant: KH 10
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Chemical equilibria p notation
pH = -log10[H+]
- acid-base equilibria pC = -log10C
[H ][A ] pKa = -log10Ka
HA H A Ka …
[HA] pX= -log10X
For acetic acid (CH3COOH or HAc),
CH3COOH = CH3COO- + H+ (Ka = 10-4.76)
[H ][CH 3COO ]
Ka
[CH 3COOH]
[CH 3COO ] K
a
[CH 3COOH] [H ]
pH
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Chemical equilibria
- pH scale [OH-] = Kw/[H+] = 10-14 /[H+]
p notation
pH = -log10[H+]
[Link]
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Chemical equilibria
- acid-base equilibria Table 6.2
p notation
pH = -log10[H+]
pC = -log10C
pKa = -log10Ka
…
pX= -log10X
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Chemical equilibria
- acid-base equilibria
Ex. 2.8 Disinfection
Hypochlorous acid (HOCl) is a much stronger disinfectant than hypochlorite (OCl-).
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Chemical equilibria
- Solubility product
Solid (s) aA bB K sp [A]a [B]b
Ex. 2.9 Fluoride solubility
CaF2 (s) = Ca2+ + 2F- (Ksp = 3 x 10-11)
c 2c
[Ca2+][F-]2 = 3 x 10-11
c (2c)2 = 3 x 10-11
c = 2 x 10-4 M (or 7.6 mg/l)
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Chemical equilibria
- Gas liquid partitioning (solubility of gas)
Henry’s Law [X] K H Px Where
[X] is the concentration of dissolved gas;
Px is the partial pressure of the gas
Ex. 2.10 Oxygen solubility
KH = 0.00126 mol/[Link] at 25 C
At ground level, partial pressure of oxygen is 0.21 atm
[O2] = 0.00126 x 0.21 = 2.65 x 10-4 mol/l 8.5 mg/l
Atmospheric pressure decreases at higher elevation:
P = P0 – 1.15 x 10-4 H
At higher elevation, solubility of oxygen will be significantly decreased.
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Read Ex. 2.11
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Chemical equilibria
- Carbonate system
Air-water equilibrium
CO2 (g) + H2O = H2CO3 (aq) [H2CO3] = KHPCO2 (KH = 0.0334 mol/[Link])
Acid-base equilibrium
H2CO3 = H+ + HCO3- K1 = [H+][HCO3-]/[H2CO3] = 4.47 x 10-7 (pK1 = 6.35)
HCO3- = H+ + CO32- K2 = [H+][CO32-]/[HCO3-] = 4.68 x 10-11 (pK2 = 10.33)
Liquid-solid equilibrium
CaCO3 (s) = Ca2+ + CO32- Ksp = [Ca2+][CO32-] = 4.57 x 10-9
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Chemical equilibria
- pH of rain Air-water equilibrium
[H2CO3] = KHPCO2 = 0.0334 x 390 x 10-6 = 1.3 x 10-5 M
Acid-base equilibrium
CO2 = 390 ppm [HCO3-] = [H2CO3]x(K1/[H+])
[CO32-] = [HCO3-]x(K2/[H+])
[OH-] = Kw/[H+] = 10-14 /[H+]
H+ , OH- Charge balance
H2CO3 , HCO3- , [H+] = [HCO3-] + 2[CO32-] + [OH-]
CO32-
[H+] = [H2CO3]x(K1/[H+])
[H+] = (K1[H2CO3])0.5 = (4.47 x 10-7 x 1.3 x 10-5) = 2.42 x 10-6 M
pH = 5.62
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Chemical equilibria
- Acid rain
CO2 = 390 ppm
SO2 (later oxidized to SO3)
NOx
H+ , OH- SO3 + H2O H2SO4 SO42- + 2H+
H2CO3 , HCO3- ,
CO32- , SO42-
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Chemical equilibria
- Ocean as a CO2 sink
CO2
H2CO3
←→ HCO3- + H+
←→ CO32- + 2H+ Ocean acidification
CaCO3 (s)
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Nuclear chemistry
Radioactive decay and half life
Uranium isotopes (U-235 and U-238)
92 U 2
Pu 235
239 4
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Mass number (#protons + #neutrons) 90
38 Sr 9039Y
Alpha particle: 2-protons, 2-neutron particle
235 238
92 U 92 U Beta particle: electron
Gamma: electromagnetic radiation (photon
particles)
Atomic number (number
of protons) Half life t1/2: time required for half of the
atoms to decay
Radiation unit: curie (Ci) (100 50 25 12.5 …)
(1 Ci = 3.7 x 1010 radioactive decay per second)
Readings and practice questions
• Readings
• Essential reading: Sec 2.2, 2.3, 2.4, 2.5, 2.6 (first 3 pages)
• Practice questions
• Q2.1, 2.20, 2.29, 2.30, 2.35
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