Acid rain
Hydrologic cycle
Evaporation
Transpiration
Condensation
Precipitation
Processes that
cycle water
between air and
earth surface
pH value of pure water
K w  [ H  ][OH  ]


 log K w   log[ H ]  log[ OH ]
pK w  pH  pOH
In pure water, autoionization is the only source of
ions, therefore:
[ H  ]  [OH  ]  10 7 M
pH  7
A pH of 7 defines neutrality, pH<7 means acidic and
pH>7 is basic.
Acid rain
• Rainwater has a pH of 5.7 if CO2 is the only species
that affects its acidity.
• When additional acidic species are present at
appreciable levels as a result of man-made activities,
pH of rain water becomes lower than 5.7. Acid
rain.
• H2SO4 and HNO3 are the major contributors to acid
rain.
pH of acid rain
H2SO4 and HNO3 are the major contributors to acid rain.
Sources for H2SO4 and HNO3 in the air
• Both substances are formed in the air
– Precursor to H2SO4: SO2
– Precursor to HNO3: NO2
• Concentrations of the precursors SO2 and NO2
are greatly increased by man-made activities,
especially fossil fuel combustion.
Formation of sulfuric acid from SO2
Gas-phase
SO2 + . OH + M  HSO3. + M
HSO3. + O2  HO2. + SO3
SO3 + H2O + M  H2SO4 + M
(fast)
(fast)
Aqueous phase (cloud and rain)
Dissolved SO2 is oxidized to sulfate by O3 and/or H2O2
–O3 (dominant pathway when pH>5)
–H2O2 (dominant pathway when pH<5)
–Organic peroxides
–O2 catalyzed by iron and manganese
Role of NH3 in acid rain
• Ammonia dissolved in rainwater scavenges H+:
– NH3 (aq) + H+ = NH4+
• Ammonia input lowers the acidity in rain.
Ion
H+(pH)
SO42NO3HCO3NH4+
Rural New York
(meq/l)
46 (4.34)
45
25
0.1
8.3
Southwest Minnesota
(meq/l)
0.5 (6.31)
46
24
10
38
The larger input of NH3 in MN is responsible for the lower
rain acidity than in NY.
Production of NH3
• Animal waste,
• ammonification of humus followed by
emission from soils
• losses of NH3-based fertilizers from soils
• industrial emissions.
Acid Rain: Cross-boundary Pollution
A large portion of SO2 and NO2 produced in
one country is exported to others by prevailing
surface winds.
Effects of acid rain
• Acidification of surface water (lakes, rivers, etc), and
subsequent damage to aquatic ecosystems.
– kills aquatic plants, fish and microorganisms in lakes and
streams by releasing ions of Al, Pb, Hg and Cd from soils
and sediments.
• Damage to forests and vegetation
– Weakens or kills trees, especially conifers at high
elevations;
– Makes trees more susceptible to diseases, insects, and
fungi and mosses that thrive under acidic conditions;
– Stunts growth of crops such as tomatoes, soybeans,
carrots, and cotton
Acid rain has scarred the pine forest at Clingman’s Dove in the
Smoky Mountain
Effects of acid rain (Continued)
• Damage of materials and structures
– building materials, statues, metals, cars.
– CaCO3 + H2SO4--> CaSO4 + CO2 + H2O
– CaSO4 occupies more volume than CaCO3 and is more
soluble than CaCO3.
• Harm to human beings
– irritation to eyes, inflammation of lung tissue, respiratory
illness, etc.