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Chemistryp-Block Elements
When 1 dm³ of CO₂ gas is passed over hot coke, the volume of gaseous mixture after complete reaction at STP becomes 1·4 dm³. The composition of the gaseous mixture at STP is :
Options
1
0·6 dm³ of CO, 0·8 dm³ of CO₂
2
0·8 dm³ of CO, 0·8 dm³ of CO₂
3
0·8 dm³ of CO, 0·6 dm³ of CO₂
4
0·6 dm³ of CO, 0·4 dm³ of CO₂
Correct Answer
Option 3 : 0·8 dm³ CO + 0·6 dm³ CO₂
Step-by-Step Solution
1

Reaction of CO₂ with hot coke (carbon):

CO₂(g) + C(s) → 2CO(g)

Note: C is solid — it does NOT contribute to gas volume!

2

Let x dm³ of CO₂ react:

CO₂ remaining = (1 − x) dm³

CO formed = 2x dm³ (2 moles CO per mole CO₂, by Avogadro's law)

Total volume = (1 − x) + 2x = 1 + x dm³

3

Apply given condition:

1 + x = 1·4 → x = 0·4 dm³

CO₂ remaining = 1 − 0·4 = 0·6 dm³

CO formed = 2 × 0·4 = 0·8 dm³

CO₂(g) + C(s) → 2CO(g)

x = 0·4 dm³ reacted → 0·8 dm³ CO formed

CO₂ remaining = 0·6 dm³ | CO formed = 0·8 dm³

Theory: Carbon and Its Oxides — p-Block Chemistry
1. Boudouard Reaction — CO₂ + C ⇌ 2CO

The reaction CO₂ + C → 2CO is called the Boudouard reaction. It is endothermic (ΔH > 0), so it proceeds forward at high temperatures. At low temperatures (~400°C), equilibrium favours CO₂. At high temperatures (~1000°C), equilibrium strongly favours CO. This reaction is industrially important in blast furnaces for iron production. Hot coke (carbon) reduces CO₂ to CO, which then reduces iron oxide (Fe₂O₃ → Fe). The reaction increases the number of moles of gas (1 mol CO₂ → 2 mol CO), so by Avogadro's law, volume increases at constant T and P.

2. Avogadro's Law and Gas Volume Calculations

Avogadro's law: at the same temperature and pressure, equal volumes of all gases contain equal numbers of molecules. Therefore, mole ratio = volume ratio for gases at same T and P. In this problem, CO₂(g) + C(s) → 2CO(g). At STP, 1 mole CO₂ occupies 22·4 L. If x dm³ of CO₂ reacts, it produces 2x dm³ of CO (volume doubles because 1 mol → 2 mol gas). Carbon is solid — it occupies no gas volume. Total gas volume = unreacted CO₂ + CO formed = (1−x) + 2x = 1+x.

3. Properties of Carbon Monoxide (CO)

📌 Colourless, odourless, highly toxic gas — binds Hb 200× stronger than O₂ (CO poisoning)

📌 Excellent reducing agent — reduces metal oxides at high temperature

📌 Burns with blue flame: 2CO + O₂ → 2CO₂

📌 Reacts with Cl₂ in presence of charcoal: CO + Cl₂ → COCl₂ (phosgene — war gas)

📌 Used in Mond process: Ni + 4CO → Ni(CO)₄ (nickel tetracarbonyl) — purification of nickel

📌 Bond order = 3 (triple bond: C≡O), similar to N₂

📌 Water gas: CO + H₂ (from C + H₂O at 1000°C)

📌 Producer gas: CO + N₂ (from C + air)

4. Properties of Carbon Dioxide (CO₂)

CO₂ is a linear molecule (O=C=O), non-polar despite having polar bonds (dipole moments cancel). It is a greenhouse gas — absorbs IR radiation from Earth's surface, contributing to global warming. Solid CO₂ is "dry ice" — sublimes at −78·5°C. CO₂ forms carbonic acid with water: CO₂ + H₂O ⇌ H₂CO₃ ⇌ H⁺ + HCO₃⁻ (acidic). Uses: fire extinguisher (CO₂ blankets fire, cuts off O₂), carbonation of beverages, refrigerant (dry ice), photosynthesis (plant food), supercritical CO₂ as solvent.

5. Allotropes of Carbon

📌 Diamond: sp³ hybridised, tetrahedral 3D network, hardest natural substance, non-conductor of electricity (no free electrons), high melting point

📌 Graphite: sp² hybridised, layered hexagonal structure, soft (layers slide), good conductor (delocalised π electrons), used as lubricant, electrode, pencil lead

📌 Fullerene (C₆₀): Buckminsterfullerene — soccer ball shape, 20 hexagons + 12 pentagons, sp² hybridised, discovered 1985 (Nobel Prize 1996)

📌 Carbon nanotubes: cylindrical graphite sheets, extremely strong, excellent conductors

📌 Graphene: single layer of graphite, 2D material, Nobel Prize 2010

6. Industrial Importance — Blast Furnace

Iron is extracted from iron ore (Fe₂O₃) in a blast furnace. Key reactions: (1) C + O₂ → CO₂ (combustion of coke at bottom, 2000°C). (2) CO₂ + C → 2CO (Boudouard reaction in the middle zone). (3) Fe₂O₃ + 3CO → 2Fe + 3CO₂ (reduction of iron ore at top). (4) CaCO₃ → CaO + CO₂ (limestone decomposes). (5) CaO + SiO₂ → CaSiO₃ (slag formation — removes silica impurity). The CO produced in the Boudouard reaction is the actual reducing agent that reduces Fe₂O₃ to Fe.

7. Mole Concept and Stoichiometry with Gases

At STP (Standard Temperature and Pressure — 0°C, 1 atm): 1 mole of any ideal gas occupies 22·4 L = 22·4 dm³. At NTP (Normal Temperature and Pressure — 25°C, 1 atm): 1 mole occupies 24·5 L. This difference (22·4 vs 24·5) is tested in NEET — always check which standard conditions are specified. Mole ratio from balanced equation directly equals volume ratio for gases (by Avogadro's law). Solids and liquids do not contribute to gas volumes in such calculations.

8. Greenhouse Effect and Global Warming

Greenhouse gases (CO₂, CH₄, N₂O, H₂O vapour, CFCs) absorb IR radiation re-emitted from Earth's surface and re-radiate it back, warming the atmosphere. CO₂ is the most significant anthropogenic (human-caused) greenhouse gas due to fossil fuel combustion. Global warming → climate change → melting glaciers, rising sea levels, extreme weather events. The sixth mass extinction is currently underway — largely due to human activities including habitat destruction, pollution, and climate change — a key biology topic in NEET 2026.

Frequently Asked Questions
1. Why does volume increase from 1 dm³ to 1·4 dm³?
The reaction CO₂(g) + C(s) → 2CO(g) converts 1 mole of gas into 2 moles of gas. By Avogadro's law, at constant T and P, volume is proportional to moles. So if x dm³ of CO₂ reacts, it produces 2x dm³ of CO. Net change in volume = 2x − x = +x. Starting from 1 dm³: final volume = 1 + x. Given 1 + x = 1·4, so x = 0·4 dm³ reacted. Volume increase = 0·4 dm³.
2. Why doesn't carbon (coke) contribute to gas volume?
Carbon (coke) is a solid in this reaction. Avogadro's law applies only to gases — "equal volumes of gases at same T and P contain equal moles." Solids have their own fixed volume determined by their crystal structure, not by the number of moles in the same way gases do. In gas stoichiometry, only gaseous reactants and products are counted in volume calculations. C(s) is consumed but contributes no gas volume.
3. Why is CO more toxic than CO₂?
CO binds to haemoglobin (Hb) to form carboxyhaemoglobin (HbCO) with an affinity ~200–250 times greater than O₂. Once CO occupies haem sites, O₂ cannot bind → tissues are deprived of O₂ → CO poisoning (symptoms: headache, dizziness, death). CO₂ is not toxic at normal concentrations (we exhale it). CO₂ at very high concentrations displaces O₂ causing suffocation, but it doesn't bind haemoglobin. CO is colourless and odourless — making it a "silent killer."
4. What is water gas and producer gas?
Water gas: C + H₂O(steam) →(1000°C) CO + H₂. Equal volumes of CO and H₂. Also called syngas. Used as fuel, in synthesis of methanol, in Fischer-Tropsch process. Producer gas: 2C + O₂ + 4N₂(air) → 2CO + 4N₂. Contains CO (~25%) + N₂ (~75%). Used as industrial fuel. Mixed with water gas to get a more efficient fuel. Both are produced by passing air/steam over hot coke.
5. What makes diamond hard but graphite soft?
Diamond: each carbon is sp³ hybridised, bonded to 4 other carbons in a 3D tetrahedral network. Every bond must be broken to move atoms — extremely strong covalent network → hardest substance. Graphite: sp² hybridised carbons form flat hexagonal layers. Within layers: strong covalent bonds. Between layers: weak van der Waals forces only. Layers slide over each other easily → soft, lubricant. The free π electrons (one per carbon) make graphite a good conductor — unlike diamond.
6. What is the Boudouard equilibrium?
CO₂(g) + C(s) ⇌ 2CO(g), ΔH = +172 kJ/mol (endothermic). At low temperature: equilibrium favours CO₂ (left). At high temperature: equilibrium favours CO (right — Le Chatelier: increasing T shifts endothermic reaction forward). Also, by Le Chatelier: higher pressure shifts equilibrium toward fewer moles of gas (left, toward CO₂). So high T + low P favours CO production. This reaction is critical in metallurgy wherever carbon-based reduction is used.
7. What is phosgene and how is it related to CO?
Phosgene (COCl₂ = carbonyl chloride) is prepared by: CO + Cl₂ →(charcoal catalyst) COCl₂. Phosgene is an extremely toxic gas — used as a chemical weapon in World War I. It reacts with water in lungs to form HCl and CO₂, causing pulmonary edema. In chemistry: phosgene is used to synthesise polycarbonates, isocyanates (for polyurethanes), and dyes. However, due to toxicity, safer alternatives (like triphosgene) are used in modern laboratory synthesis.
8. How is CO used in the Mond process?
The Mond process purifies nickel: Ni(impure) + 4CO →(50–60°C) Ni(CO)₄ (nickel tetracarbonyl, volatile). Ni(CO)₄ →(decomposition at 180°C) Ni(pure) + 4CO. CO is recycled. Ni(CO)₄ is a volatile liquid/gas that leaves impurities behind. Very high purity Ni is obtained this way. CO forms similar carbonyls with Fe, Cr, Mo, W. These metal carbonyls are important in organometallic chemistry and industrial catalysis.
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