Part 2 · Chapter 22

Environmental Chemistry

Chemistry where it matters most — the reactions in our air, water and soil that produce smog, acid rain and the ozone hole, and the green chemistry that can undo them

Fundamentals of Chemistry Prof. Mithun Mondal Reading time ≈ 45 min
i What you'll learn
  • What a pollutant is, and the layers of the atmosphere where pollution acts.
  • The major tropospheric pollutants — oxides of S, N and C, and particulates.
  • The difference between classical and photochemical smog.
  • The chemistry of the greenhouse effect, acid rain and ozone depletion.
  • How water quality is measured by BOD, and what drives eutrophication.
  • The aims and methods of green chemistry.
Section 22-1

Pollutants & the Atmosphere

Environmental chemistry studies the chemical species and reactions in our surroundings, and how human activity disturbs them. A pollutant is any substance present in a high enough concentration to harm living things or materials. Pollutants may be biodegradable (broken down by nature, like sewage) or non-biodegradable (persistent, like DDT and most plastics).

Two layers, two stories. The lower atmosphere — the troposphere (up to ~10 km) — is where we breathe and where smog and acid rain form. The stratosphere (10–50 km) holds the protective ozone layer. The same molecule, ozone, is a pollutant in the troposphere but a shield in the stratosphere — location is everything.
Section 22-2

Tropospheric Pollution

Most everyday air pollution is tropospheric, caused by gases and tiny particulates from burning fossil fuels. The chief gaseous offenders are the oxides of sulphur, nitrogen and carbon.

PollutantSourceHarm
\(\ce{SO2}\)burning sulphur-rich coal/oilrespiratory damage, acid rain
\(\ce{NO},\ \ce{NO2}\)high-temperature combustionphotochemical smog, acid rain
\(\ce{CO}\)incomplete combustionbinds haemoglobin (toxic)
\(\ce{CO2}\)complete combustiongreenhouse gas
Particulatessmoke, dust, fumeslung disease, reduced visibility
Why CO is deadly. Carbon monoxide binds haemoglobin some 200 times more strongly than oxygen, forming carboxyhaemoglobin and starving tissues of oxygen. It is odourless and colourless, which is exactly what makes it so dangerous.
Section 22-3

Smog: Two Kinds

"Smog" (smoke + fog) comes in two chemically opposite forms. Classical (London) smog is reducing, formed in cool, humid air from smoke and \(\ce{SO2}\). Photochemical (Los Angeles) smog is oxidising, formed in warm, sunny, dry air from nitrogen oxides and hydrocarbons.

FeatureClassical smogPhotochemical smog
Chemistryreducing (\(\ce{SO2}\), smoke)oxidising (\(\ce{NO2}\), \(\ce{O3}\), PAN)
Conditionscool, humidwarm, sunny, dry
Key products\(\ce{H2SO4}\) aerosolozone, peroxyacetyl nitrate
☀️
Photochemical smog — the trigger
\(\ce{NO2 ->[h\nu] NO + O}\); \(\ \ce{O + O2 -> O3}\)

Sunlight splits \(\ce{NO2}\); the freed oxygen atom makes ground-level ozone. Ozone and unburnt hydrocarbons then form eye-stinging PAN (peroxyacetyl nitrate). The result is a brown, irritating haze.

Section 22-4

The Greenhouse Effect & Global Warming

The greenhouse effect is natural and necessary — certain gases let sunlight in but trap the outgoing infrared, keeping Earth warm. The problem is its intensification: rising concentrations of these gases trap more heat, driving global warming.

greenhouse gases (CO₂, CH₄, O₃, CFCs) sunlight IR trapped & re-radiated
Greenhouse gases let light in but trap outgoing infrared
The main culprits. Carbon dioxide contributes the most overall, but molecule for molecule methane, ozone and CFCs are far more potent. Consequences include rising sea levels, shifting climate zones, and more extreme weather.
Section 22-5

Acid Rain

When \(\ce{SO2}\) and \(\ce{NO2}\) dissolve in atmospheric water and are oxidised, they form sulphuric and nitric acids. Rain with a pH below about \(5.6\) is acid rain.

🌧️
Acid-forming reactions
\(\ce{2SO2 + O2 + 2H2O -> 2H2SO4}\); \(\ \ce{4NO2 + O2 + 2H2O -> 4HNO3}\)

Acid rain corrodes marble and limestone buildings ("marble cancer": \(\ce{CaCO3 + H2SO4 -> CaSO4 + H2O + CO2}\)), acidifies lakes and kills fish, and leaches nutrients from soil.

Section 22-6

Stratospheric Ozone & Its Depletion

High in the stratosphere, ozone forms and breaks down in a natural cycle, absorbing harmful ultraviolet light as it does. Chlorofluorocarbons (CFCs) upset this balance: UV light frees chlorine atoms from them, and each chlorine atom destroys ozone catalytically — over and over.

Cl• ClO• + O₃ → ClO• + O₂ + O → Cl• + O₂
One chlorine radical destroys thousands of ozone molecules
🛡️
The catalytic chain
\(\ce{Cl. + O3 -> ClO. + O2}\); \(\ \ce{ClO. + O -> Cl. + O2}\)

The chlorine atom is regenerated, so it keeps going — a single \(\ce{Cl}\) can destroy thousands of \(\ce{O3}\) molecules. The thinning is worst over Antarctica (the "ozone hole"), and more UV-B at the surface raises skin cancer and cataract rates and harms phytoplankton.

Section 22-7

Water Pollution & BOD

Water is polluted by pathogens, organic waste, industrial chemicals and fertiliser run-off. A key measure of organic pollution is the biochemical oxygen demand (BOD) — the oxygen that micro-organisms need to break down the organic matter in a water sample.

💧
BOD as a quality index
Clean water: BOD < 5 ppm · Highly polluted: BOD > 17 ppm

A high BOD means lots of organic waste, so bacteria consume the dissolved oxygen — suffocating fish. Eutrophication is the related danger: fertiliser nutrients (\(\ce{N},\ \ce{P}\)) trigger algal blooms that, on decaying, strip the water of oxygen.

Section 22-8

Soil Pollution

Soil is polluted chiefly by pesticides, herbicides and industrial waste. The most persistent — like the insecticide DDT — are non-biodegradable, so they accumulate up the food chain in a process called biomagnification, reaching toxic levels in top predators.

Biomagnification in one line. A pollutant present in trace amounts in water becomes concentrated at each step of the food chain — water → plankton → small fish → large fish → bird — so the top predator can carry a dose millions of times higher than the surrounding water. This is why DDT thinned the eggshells of birds of prey.
Section 22-9

Green Chemistry

Green chemistry is the design of products and processes that prevent pollution rather than clean it up — using safer reagents, less energy, and producing less waste. The guiding idea is to maximise atom economy (more of the reactants ending up in the product) and avoid hazardous substances altogether.

ConventionalGreener alternative
Bleaching with \(\ce{Cl2}\)bleaching with \(\ce{H2O2}\)
Dry-cleaning with tetrachloroetheneliquid \(\ce{CO2}\) with a detergent
Toxic solvent reactionsreactions in water or solvent-free
Worked Examples

Putting It to Work

1 Classify the smog

Problem. A brown haze forms on a hot, sunny afternoon over a city full of traffic. Which smog is it, and is it oxidising or reducing?

Solution. Sun + vehicle \(\ce{NO_x}\) → ozone and PAN:

Working
\[ \textbf{photochemical smog},\ \text{oxidising} \]
2 Acid rain reaction

Problem. Write the reaction by which \(\ce{NO2}\) produces nitric acid in rain.

Solution. \(\ce{NO2}\) is oxidised and dissolves in water:

Working
\[ \ce{4NO2 + O2 + 2H2O -> 4HNO3} \]
3 Why CFCs deplete ozone

Problem. Explain why one chlorine atom from a CFC destroys many ozone molecules.

Solution. The chlorine is regenerated, so it acts catalytically:

Working
\[ \ce{Cl. + O3 -> ClO. + O2};\ \ce{ClO. + O -> Cl. + O2}\ (\text{chain}) \]
4 Interpret BOD

Problem. Sample A has a BOD of 3 ppm and sample B has 20 ppm. Which is cleaner, and why?

Solution. Lower BOD means less organic waste demanding oxygen:

Working
\[ \text{A (3 ppm) is cleaner};\quad \text{B (20 ppm) is highly polluted} \]
5 CO toxicity

Problem. Why is carbon monoxide far more dangerous than carbon dioxide at low concentration?

Solution. CO binds haemoglobin much more strongly than \(\ce{O2}\):

Working
\[ \ce{Hb + CO -> HbCO}\ \Rightarrow\ \text{blocks }\ce{O2}\text{ transport} \]
6 A green choice

Problem. Suggest a green-chemistry replacement for chlorine bleaching of paper, and state the benefit.

Solution. Hydrogen peroxide bleaches and decomposes to harmless products:

Working
\[ \ce{H2O2}\ \text{(by-products }\ce{H2O} + \ce{O2}\text{; no toxic chlorinated waste)} \]
Review

Chapter Summary

Pollutants

Biodegradable vs non-biodegradable; troposphere (smog, acid rain) vs stratosphere (ozone).

Air pollutants

Oxides of S, N, C and particulates; CO binds haemoglobin and is silently toxic.

Smog

Classical (reducing, \(\ce{SO2}\)) vs photochemical (oxidising, \(\ce{O3}\), PAN).

Global threats

Greenhouse warming, acid rain (\(\ce{H2SO4}/\ce{HNO3}\)), CFC-driven ozone depletion.

Water & soil

BOD measures organic pollution; eutrophication and biomagnification spread harm.

Green chemistry

Prevent pollution at source — safer reagents, atom economy, benign solvents.

Practice

Problems

For each item, first decide whether it concerns air, water, soil or green chemistry — then apply the relevant idea. Difficulty rises down the list.

  1. Define a pollutant and distinguish biodegradable from non-biodegradable, with one example of each.
  2. Name three gaseous tropospheric pollutants and their main sources.
  3. Explain why carbon monoxide is toxic even at low concentration.
  4. Compare classical and photochemical smog in chemistry and conditions.
  5. Write the reactions that initiate photochemical smog from \(\ce{NO2}\).
  6. What is the greenhouse effect, and name three greenhouse gases.
  7. Write the reactions forming sulphuric and nitric acid in acid rain.
  8. Explain, with reactions, how CFCs deplete stratospheric ozone.
  9. Define BOD and state typical values for clean and polluted water.
  10. What is eutrophication, and how do fertilisers cause it?
  11. Explain biomagnification using DDT as an example.
  12. State two principles of green chemistry and give one practical example.
Tip: almost every problem in this chapter is the same molecule doing harm in the wrong place or amount — \(\ce{CO2}\) is harmless to breathe but warms the planet; ozone shields us above yet poisons us below; nitrogen feeds crops but suffocates lakes. Ask "which species, in what amount, in which compartment?" and the harm — and its cure — becomes clear.