Environmental Chemistry:

Air Pollution

OH + CO → CO2 + H

The Atmospheric pressure

99.8% below 50Km
P = P0 EXP ( - Mgh / RT )

90% below 16 Km
 Transportation and pollution

Typical Car Emissions in g per kM

1966 Today

HC 6.58 0.199

CO 52.17 2.29

Nox 2.55 0.149

What happens to CO, NOx and HC ?

 Defining
Atmospheric
height:
50kM

Earth

13000kM / 50kM = 260

99.8% below
50kM
 The atmospheric mass
Pressure = Force / Area

= Mass x Acceleration / Area

Mass = Pressure x Area / Acceleration

= P x 4π R2 / g

= (105 Pa ) ( 5x1014 m2 ) / (9.8m.s-2 )

= 5.2x1018 Kg
The atmospheric T and P
P = P0 EXP ( - Mgh / RT )

(275K, 50Km)
99.8% below 50Km

(215K, 12Km)
90% below 16 Km
 The atmospheric composition / units

Bond E = 941kJ/mol
Bond E = 495kJ/mol

What about OH, O, OOH, NO, NO2, Cl, NO3 , HCO etc ?
Solar radiation breaking bonds : O2 + hʋ (≤ 242nm ) → O + O

Bond dissociation energy of O2 is 495 KJ / mol.

Calculate λ of photon with enough energy to dissociate O2

λ of Photon required for dissociating O2 :

 Free Radicals in the
atmosphere

H; O; O2; OH; OOH; NO; NO2;

NO3; CH3O; CH3OO; HCO etc

Note: Concentration is only 10 ppb

i.e 10 out of one billion molecules of air:
How pollutants are removed from
Troposphere ( Altitude band: 0 Km – 12Km )

1. Washing with rain

2. Chemical reactions: OH + CO → CO2 + H

3. Photolysis: NO2 + hʋ ( ≤ 420nm ) → NO + O

4. Dry deposition on surfaces

OH in the Troposphere removes
pollutants
 Removal of CH4

CH4 + OH → CH3 ( methyl ) + H2O

CH3 + O2 → CH3OO ( methyl peroxy )

CH3OO + NO → CH3O ( methoxy )+ NO2

CH3O + O2 → H2CO + OOH ( hydroperoxy )….(1)

Formaldehyde either reacts with OH or is photolysed

Photolysis removes H2CO:

H2CO + λ≤ 338nm → H + HCO

H + O2 → OOH…(2) HCO + O2 → OOH + CO…(3)

OH removes H2CO

H2CO + OH → H2O + HCO

HCO + O2 → OOH + CO

what happens to CO
What happens to CO ( where CO come from ):

CO + OH → H + CO2 H + O2 → OOH….(4)

CH4 degradation into CO2 produces 4OOH:

4OOH + 4NO → 4OH + 4NO2

Sum of all reactions with photolysis route:

CH4 + 5O2 + 5NO + 2OH + λ≤ 338nm →

CO2 + H2O + 5NO2 + 4OH

Think about this overall change !!

 NOx ( NO + NO2 ) in the troposphere

NO2 + λ≤420nm → NO + O
O + O2 + M → O3 + M

NO + OH → HONO NO2 + OH → HNO3

NO2 + OOH → HOONO2 NO2 + OOH → NO3 + OH

NO2 + NO3 → N2O5 N2O5 + H2O → 2HNO3

O
CH3-C-O-ONO2 PAN, Nox involved in oxidation of HC
 Sources of OH in the troposphere ( 0.05ppt )

1. O3, H2O, & radiation between 290 – 340nm

O3 + λ ( 290 – 340nm ) → O (1D ) + O2
O (1D ) + H2O → 2OH

2. HONO + hν → OH + NO

3. H2O2 + hν → 2OH

4. OOH + NO → OH + NO2
 Tropospheric Chemistry

`
 Ozone in the Atmosphere
►in the stratosphere decreasing
► in the troposphere increasing

Stratospheric ozone formation only

O2 + h  2O;  < 242 nm Altitude band 30-90 Km

O2 + O → O3* ( 105kJ/mol energy released, unstable )

O3 * + M → O3 + M* ( heating )
Sum: O + O2 + M → O3 + M* ( responsible for heating stratosphere )

Ozone is key absorber of photons with wavelengths of

290 to 310 nm.
Ozone formation and destruction in the stratosphere

Chapman Explanation:

1. O2 (g) + hʋ → O (g) + O (g)

2. O (g) + O2 (g) + M (g) → O3 (g) + M‡ (g)

3. O3 (g) + hʋ → O2 (g) + O (g)

4. O (g) + O3 (g) → 2O2 (g)

Reaction 4 is very slow and catalysts such as

Cl, NO, and Cl can catalyze it
 O + O2 → O3 exothermic

Adiabatic expansion
 Depletion of the Ozone layer
Stratospheric Chemistry

►CF2Cl2 + hν → CF2Cl + Cl: λ range 190 – 225nm

►Cl atom production maximum at altitude of 30 km

►Cl atom works as a catalyst and speeds up the reaction:

O + O3 → 2 O2 ( recall this reaction is very slow )

O3 + Cl → ClO
ClO + O → Cl + O2 Much faster, why ?

Sum: O + O 3 → 2 O2
► Cl atom speeds up the reaction
►recycles to destroy upto 100,000 ozone molecules
 Two more catalytic cycles for the destruction of Ozone

We discussed only Cl atom and NO catalytically destroying

ozone. There are many other species doing this job such
as
OH + O3 → OOH + O2
OOH + O → O2 + OH
Oxides of Sulfur, Nitrogen and Acid Rain

SO2(g) + O2 (g) /O3  SO3(g)

SO3(g)+H2O(l)H2SO4(aq)
 Oxides of Nitrogen, acid rain and photochemical smog

N2 + O2 2 NO

O2 + 2 NO 2 NO2 NO and NO2 are called NOx

Acid rain: NO2 + OH → HNO3

Note: CH3COOH, HCOOH, HCl, HNO3, and H2SO4

are responsible for all the acid rain

Note also that NO2 + hν ( λ < 393nm ) → NO + O

O + O2 + M → O3 + M*
These two are the main reactions responsible for the
formation of Ozone in the urban atmosphere
Global Warming
 Global Warming Gases: CH4, CO2, O3, N2O, CFC’s

Earth at 254 K is hanging in a cold universe at 3 K.

H2O vapors warm it and keep it close to 288 K.
Green house gases make it still warmer i.e above 288 K
 Waste Water Treatment

►Treatment of water for house hold

because microbes may be of great concern

►Treatment of water for specialized industrial application

because Ca & Mg ions may be of great concern

►Treatment of wastewater
because health of plants, animals, and people downstream of
rivers may be of concern
 Municipal Sewage Treatment
Sediments, grit, grease, oil, scum, pathogenic bacteria, viruses,
salts, algal nutrients, pesticides, un-reactive organic
compounds, wood chunks, heavy metals, floating objects

Municipal sewage is treated in three stages:

1. Primary waste treatment

2. Secondary waste treatment
3. Tertiary waste treatment ( rarely done )

Then the treated waste water is

discharged into rivers
 Waste water Treatment : primary

Screeing: grit, grease and scum removal

 It removes or reduces the size of trash and large solids.
 These solids are collected on screens and scraped off

Sand and grit removal

 Grit consists of fine sand, silt etc
 If not removed it chokes pipes etc
 Grit settles as waste water is allowed to flow slowly which is
then scraped mechanically from the bottom of the tank.
 Waste Treatment: Secondary

The following process takes place under natural conditions also.

We simply provide conditions for accelerated growth of bacteria
and confine the process to smaller space

Consider the Interaction between:

►Dissolved oxygen ( upto 8 mg / liter of water )
►Bacteria
►Organic compounds ( dissolved or suspended )

►Micro-organisms degrade organic matter in waste

water in the presence of oxygen.
Oxygen required for this purpose is called BOD
( biochemical oxygen demand )
►depletion of dissolved O2 in waste water may result

►Dissolved oxygen is replenished by thorough contact

with air
Activated
Sludge
Process
 Ozone as disinfectant
No possible production of toxic organochlorine compounds

ozone is more
destructive to
viruses than is
chlorine.

No production of toxic
organochlorine compounds
Initial Filtration –
Often the initial step is to filter the water through some course screens to remove
any fish, bugs, leaves, twigs, and debris.
Coagulation & Sedimentation –
Alum and lime are added to the water. These chemicals then bond with suspended
sediments, bacteria and fine particles present in the water to form a sticky floc,
which looks like white foam or suds on the water. Over time and as the water is
stirred slightly all the fine particulate matter is bonded to the floc, which eventually
becomes heavy and sinks to the bottom of the tank.
Disinfection –
This is the controlled addition of some germ-killing chemical, usually chlorine, to
the water. This treatment step can take place early, late or even repeatedly in the
water treatment process. Often it is a final step.
Aeration –
Taste and odor problems are often a result of the presence of dissolved gas such
as natural occurring hydrogen sulfide, or living organic material such as algae, or
decaying organic material, industrial waste or even residual chlorine. Forcing tiny
bubbles of air through the water facilitates the release of these gases from solution
reducing unpleasant odors and taste.
Municipal water purification Plant
OSMOSIS
At
WORK
Purification of water using reverse osmosis
 Treatment of water for industrial use

Considerations such as how much water is required, how

much and what quality of water is available, water recycling,
discharge standards are important

External which is simple filtration, sedimentation etc

Internal treatment:
Reaction of dissolved oxygen with hydrazine or sulfite
Chelating agent to remove Ca2+ and Mg2+
Addition of phosphate for removal of Calcium
Treatment with dispersant to inhibit scale
Addition of inhibiters to prevent corrosion
Adjustment of pH
Disinfection to prevent bacterial growth
 pH for ppt For lowering pH
Fe(II) → Fe (III) Mg2+and Ca2+ Al2(SO4)3
Mn(II)→ Mn (IV)
H2S, CH4, CH3SH, NH3

Killing microbes
Filtration Oxidants other than Cl2
& sedimentation can be used
Is used if water is from river
Note: Fresh water contains less salts (should be less than 500ppm )
Sea water contains large amounts of salts
Brackish water is in between fresh and see water
Water purification by reverse osmosis
 Common Disinfection Agents / procedures
1. Chlorine:
Cl2 + H2O → H+ + Cl- + HOCl

HOCl ↔ H+ + OCl-
2. Calcium Hypochlorite: Ca(OCl)2 is substituted for chlorine

3. NH2Cl ( monochloramine ) ,
NH2Cl2 ( dichloramine ),
and NCl3 ( Trichloramine ) are also used
4. Chlorine dioxide, ClO2
5. Ozone, O3

6. Disinfection by ultra-filtration with modern membranes

7. UV radiation

8. Boiling