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Cracking methods, conditions and useful examples for hydrocarbons

Organic chemistryCarbon compounds as fuels

Flashcards

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Balance the cracking equation: dodecane to heptane and pentene.

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Balanced equation: C12H26 → C7H16 + C5H10.

Key concepts

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Definition and purpose of cracking

Cracking is the process that breaks long-chain hydrocarbons into shorter-chain hydrocarbons by cleaving C–C bonds. The purpose of cracking includes producing lighter fuels from heavy fractions and generating alkenes that serve as feedstock for polymers and other chemicals. Heavy fractions cause low fuel efficiency; cracking increases the proportion of petrol and alkenes, improving fuel value and industrial utility.

Catalytic cracking: method and conditions

Catalytic cracking uses a solid acid catalyst, commonly a zeolite, to lower activation energy and steer reaction pathways toward branched alkanes, cycloalkanes and aromatic compounds plus some alkenes. The catalyst surface promotes carbonium-ion mechanisms that favor stable carbocation intermediates and rearrangements. Typical conditions include temperatures around 450 °C, low to moderate pressure and a contact time short enough to limit excessive gas formation and coke deposition. Catalyst choice and temperature control influence product distribution: higher acidity and specific pore sizes favor gasoline-range molecules and some aromatics.

Steam (thermal) cracking: method and conditions

Steam cracking relies on very high temperatures to break C–C bonds by thermal homolytic cleavage, producing a large proportion of small alkenes. Typical conditions include temperatures from about 700 °C to 1200 °C, rapid heating and very short residence times to limit secondary reactions. Addition of steam lowers hydrocarbon partial pressure and reduces coke formation; steam itself does not react as a reagent in the main cracking step. Steam cracking of naphtha or ethane-rich feeds gives high yields of ethene and propene used as polymer feedstocks.

Balancing cracking equations: general approach

Balancing cracking equations requires conservation of carbon and hydrogen atoms between reactants and products. Cracking commonly converts one alkane into one smaller alkane and one alkene, or into two alkenes, etc. The approach involves counting carbon and hydrogen atoms on each side and adjusting product formulas or coefficients until totals match. Some cracking reactions also produce hydrogen gas; inclusion of H2 in the products ensures hydrogen balance in such cases.

Representative balanced cracking reactions

Example 1: Thermal cracking of decane to octane and ethene is written C10H22 → C8H18 + C2H4. Carbon count: 10 = 8 + 2. Hydrogen count: 22 = 18 + 4. Example 2: Catalytic cracking of dodecane to heptane and pentene is written C12H26 → C7H16 + C5H10. Carbon count: 12 = 7 + 5. Hydrogen count: 26 = 16 + 10. Example 3: Cracking of ethane to ethene and hydrogen is written C2H6 → C2H4 + H2. These equations demonstrate conservation of atoms and typical product types (alkanes, alkenes, H2).

Practical usefulness of cracking

Cracking increases the yield of petrol-range hydrocarbons from crude oil by converting heavy, less valuable fractions into lighter fuels. Cracking supplies alkenes such as ethene and propene, which serve as primary feedstocks for polymers (polyethene, polypropene) and other chemicals. Cracking also provides hydrogen as a by-product in some processes, which supports hydrogen-demanding industries (e.g., hydrogenation or synthesis processes).

Limiting factors and side reactions

Uncontrolled cracking leads to excessive gas formation, unwanted coke deposition on catalysts and reduced selectivity for desired products. Higher temperatures and longer residence times increase secondary cracking and aromatisation. Catalysts reduce required temperatures and increase selectivity but suffer deactivation by coke; periodic regeneration removes coke. Steam mitigates coke formation but requires energy input to produce and heat the steam.

Key notes

Important points to keep in mind

Catalytic cracking uses a solid acid catalyst (often zeolite) and moderate temperatures (~450 °C).

Steam cracking uses very high temperatures (700–1200 °C) with steam to suppress coke and favour alkenes.

Balance cracking equations by conserving carbon and hydrogen atoms on both sides.

Common product pairs include one alkane plus one alkene, or two smaller alkenes, sometimes with H2.

Cracking increases petrol yield and produces alkenes used as chemical feedstocks.

Coke formation deactivates catalysts; steam and catalyst regeneration reduce its impact.

Short residence time in steam cracking limits secondary reactions and improves alkene yield.

Catalysts alter reaction pathways and lower energy requirements but require periodic regeneration.

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