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Chapter 3 of 8

Cement Chemistry & Fuels

In the DSSSB AE Civil syllabus under Engineering Chemistry & Environmental Science · 2 parts

📑 Contents (20 sections)

Part 1 of 2

Cement — Manufacture, Composition, Types & Tests

Last reviewed 16 Sept 2026 · 11 min read

Portland cement

Cement is a finely ground hydraulic binder that sets and hardens by chemical reaction with water and remains stable under water. Joseph Aspdin patented Portland cement in 1824, naming it after its resemblance to Portland stone.

Raw materials

Material Examples Supplies
Calcareous Limestone, chalk, marl, shells Lime (CaO)
Argillaceous Clay, shale, slate Silica (SiO₂), alumina (Al₂O₃), iron oxide (Fe₂O₃)
Corrective materials Bauxite, iron ore, sand Adjust alumina, iron or silica
Gypsum (added to clinker during grinding) Calcium sulphate Retards setting — prevents flash set due to C₃A
Fuel Coal, petcoke, alternative fuels Heat

Manufacture

Processes

Wet process Dry process
Raw materials ground with water to form a slurry (about 35–40% water) Raw materials dried and ground to fine raw meal
High fuel consumption (evaporation of water) Lower fuel consumption — used by modern plants with preheaters and precalciners
Better homogenisation (older technology) Needs efficient blending; faster
Longer kilns Shorter kilns with suspension preheaters

Burning in the rotary kiln

The kiln is a long inclined steel cylinder lined with refractory bricks, rotating slowly; material moves down towards the hot end.

Zone Temperature (approx.) Reactions
Drying zone Up to about 100–200 °C Evaporation of free water
Preheating / calcination zone About 600–900 °C Dehydration of clay; calcination of limestone (CaCO₃ → CaO + CO₂)
Burning (clinkering) zone About 1400–1500 °C Lime combines with silica, alumina and iron oxide to form clinker compounds; partial fusion
Cooling zone Clinker cooled rapidly Rapid cooling improves quality (glassy phases, less free lime)

The clinker (dark nodules, a few mm to 25 mm) is cooled, stored and ground with about 3–5% gypsum (and other additions for blended cements) to a fine powder, then stored in silos and packed (commonly 50 kg bags) or dispatched in bulk.

Composition of cement

Oxide composition (typical ranges for OPC)

Oxide Approx. % Remarks
Lime (CaO) 60–67 Excess causes unsoundness (free lime); deficiency reduces strength
Silica (SiO₂) 17–25 Strength (forms silicates)
Alumina (Al₂O₃) 3–8 Quick setting; lowers clinkering temperature
Iron oxide (Fe₂O₃) 0.5–6 Colour, fluxing, contributes to C₄AF
Magnesia (MgO) 0.1–4 Excess causes unsoundness (limited by standards)
Sulphur trioxide (SO₃) 1–3 From gypsum — controls setting; excess causes unsoundness
Alkalis (Na₂O, K₂O) 0.2–1.3 Efflorescence, alkali–aggregate reaction

Bogue compounds

Compound Formula (cement notation) Approx. % in OPC Properties
Tricalcium silicate (alite) C₃S — 3CaO·SiO₂ 40–60 Hydrates rapidly — early strength (first 7–14 days); high heat of hydration (about 500 J/g)
Dicalcium silicate (belite) C₂S — 2CaO·SiO₂ 15–30 Hydrates slowly — later strength; low heat (about 260 J/g); better resistance to chemical attack
Tricalcium aluminate C₃A — 3CaO·Al₂O₃ 5–10 Reacts very fast — flash set (controlled by gypsum); highest heat (about 870 J/g); vulnerable to sulphate attack
Tetracalcium aluminoferrite (celite) C₄AF — 4CaO·Al₂O₃·Fe₂O₃ 8–12 Low strength contribution; gives grey colour; moderate heat
FormulaBogue's equations (percentages by mass; no free lime)

Part 2 of 2

Fuels, Lubricants & Polymers

Last reviewed 16 Sept 2026 · 12 min read

Fuels

A fuel is a combustible substance that releases heat energy on burning.

Classification

Origin Solid Liquid Gaseous
Primary (natural) Wood, peat, lignite, coal Crude petroleum Natural gas
Secondary (derived) Charcoal, coke, briquettes Petrol, diesel, kerosene, fuel oil, biodiesel, ethanol Producer gas, water gas, coal gas, LPG, biogas, hydrogen

Characteristics of a good fuel

High calorific value; moderate ignition temperature; low moisture and ash; low sulphur and non-polluting combustion products; controllable combustion; easy storage, transport and handling; low cost and availability.

Calorific value

Calorific value (CV) — heat liberated by complete combustion of unit mass (or volume) of fuel.

Term Meaning
Gross (higher) calorific value, HCV/GCV Heat released when combustion products are cooled to room temperature — water vapour condensed, latent heat recovered
Net (lower) calorific value, LCV/NCV Heat actually available when water vapour escapes — HCV minus latent heat of steam formed
FormulaCalorific value relations

Dulong's formula (HCV of coal from ultimate analysis, percentages):

Net calorific value:

(H in %; 587 kcal/kg ≈ latent heat of steam; 9 kg of water forms per kg of hydrogen.)

Bomb calorimeter (solids and liquids): (with corrections), where W = water mass, w = water equivalent of calorimeter, x = mass of fuel. Junkers gas calorimeter — for gaseous fuels.

1 kcal ≈ 4.187 kJ.

Solid fuels — coal

Formation and rank

Plant matter → peat → lignite (brown coal) → sub-bituminous → bituminous → anthracite (coalification with increasing pressure, temperature and time).

With increasing rank: carbon content and calorific value increase; moisture and volatile matter decrease; ignition becomes more difficult (anthracite burns with little smoke).

Analysis of coal

Analysis Determines Significance
Proximate analysis Moisture (at 105–110 °C), volatile matter (925 °C, covered crucible), ash (~700–750 °C, open), fixed carbon (by difference) Practical assessment: high moisture and ash reduce CV; high volatile matter → long smoky flame; high fixed carbon → higher CV
Ultimate analysis C, H, N, S, O (elemental) Calorific value calculation (Dulong), combustion air, pollution (S)

Carbonisation

Heating coal in absence of air:

  • Low-temperature carbonisation (~500–700 °C) — semi-coke, domestic fuel.
  • High-temperature carbonisation (~900–1200 °C) — metallurgical coke (strong, porous, low sulphur) for blast furnaces; by-products coal gas, tar, ammonia (Otto–Hoffman by-product ovens).

Liquid fuels

Petroleum refining

Crude oil is separated by fractional distillation into fractions (approximate boiling ranges): LPG gases → petrol (gasoline) → naphtha → kerosene → diesel → fuel oils → lubricating oils, waxes → bitumen (residue — used in road construction). Cracking (thermal/catalytic) breaks heavy fractions into lighter, more valuable ones; reforming improves octane.

Knocking, octane and cetane numbers

Concept Petrol (SI) engines Diesel (CI) engines
Knocking Premature auto-ignition of unburnt end gas → metallic knock, power loss, damage Long ignition delay → accumulated fuel burns suddenly (diesel knock)
Rating Octane number — % of iso-octane (ON = 100) in a mixture with n-heptane (ON = 0) that knocks like the fuel Cetane number — % of cetane (n-hexadecane) (CN = 100) in mixture with α-methylnaphthalene (CN = 0)
Good fuel High octane (branched chains, aromatics) High cetane (straight-chain paraffins)
Additives Anti-knock agents (earlier tetraethyl lead — phased out; now MTBE, ethanol) Cetane improvers
  • Straight-chain hydrocarbons have low octane but high cetane — so a good petrol is a poor diesel and vice versa.

Alternative liquid fuels

  • Biodiesel — methyl esters from vegetable oils/animal fats by transesterification; renewable, biodegradable, lower sulphur.
  • Ethanol — from sugarcane molasses, grains; blended with petrol (ethanol blending programmes increase blend ratios over time).
  • Power alcohol, methanol.

Gaseous fuels

Fuel Main constituents (approx.) Features / uses
Natural gas Mainly methane High CV; piped gas, power plants, fertilisers
CNG Compressed natural gas (methane) at high pressure Cleaner vehicle fuel
LPG Propane + butane (liquefied under pressure) Domestic cooking, industry; heavier than air (leaks settle low); odorant added
Biogas Methane (roughly 55–65%) + CO₂ Anaerobic digestion of cattle dung, sewage sludge, organic waste; manure by-product
Producer gas CO + N₂ (+ H₂) Air + steam over hot coke; low CV; furnaces
Water gas CO + H₂ Steam over red-hot coke; higher CV
Coal gas H₂, CH₄, CO Carbonisation by-product
Hydrogen H₂ Highest CV per unit mass, clean (water only); storage/safety challenges; green hydrogen from electrolysis using renewable power

Advantages of gaseous fuels: clean combustion, easy control, little excess air, no ash; disadvantages: storage and leakage hazards.

Combustion calculations

FormulaCombustion relations (by mass)
  • C + O₂ → CO₂ : 12 kg C needs 32 kg O₂ (→ 44 kg CO₂)
  • 2H₂ + O₂ → 2H₂O : 4 kg H₂ needs 32 kg O₂ (1 kg H needs 8 kg O₂; forms 9 kg H₂O)
  • S + O₂ → SO₂ : 32 kg S needs 32 kg O₂

Minimum O₂ per kg fuel (C, H, O, S as mass fractions) Air contains about 23% O₂ by mass (≈ 21% by volume):

Actual air includes excess air for complete combustion.

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