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This chapter develops the reactions and mechanisms of the core homologous series of aliphatic organic chemistry. It covers the alkanes (distillation, cracking, combustion and free-radical substitution), the halogenoalkanes (nucleophilic substitution and elimination), the alkenes (electrophilic addition, Markownikoff's rule and addition polymerisation) and the alcohols (production, oxidation and dehydration).
5 sections~15 min reading time3 competenciesLevel Standard 3 · Advanced 2
basic level
AS-Level requires the reactions and the four mechanisms (free-radical substitution, nucleophilic substitution, elimination, electrophilic addition) for these four series.
higher level
The full A-Level uses these transformations in multi-step synthesis and combines them with the analytical and further organic topics.
Reading depth: In depth
Text size: Standard
Fractional distillation of crude oil
Initiation
Ultraviolet light homolytically splits the chlorine molecule into two radicals.
Propagation
Each step consumes one radical and makes another, sustaining the chain.
Give the mechanism for the reaction of methane with chlorine in ultraviolet light to form chloromethane.
UV light splits chlorine into radicals: Cl2 -> 2Cl(.).
Cl(.) + CH4 -> HCl + CH3(.); then CH3(.) + Cl2 -> CH3Cl + Cl(.).
Two radicals combine, e.g. CH3(.) + Cl(.) -> CH3Cl, removing radicals from the chain.
Result: Initiation (UV homolysis), a two-step propagation chain forming chloromethane, and termination by radical combination.
Typical mistakes
Active revision
Write the three types of step (initiation, propagation, termination) for the reaction of methane with chlorine in UV light, giving one termination step.
Active recall
Recall the key points — then reveal.
Sources: GCE AS and A level subject content for the sciences (Department for Education) · AQA A-level Chemistry 7405 specification (AQA)
Nucleophilic substitution by hydroxide
Nucleophilic substitution
Warm aqueous hydroxide converts a halogenoalkane to an alcohol by substitution.
State the conditions and product when 2-bromopropane reacts with (a) warm aqueous sodium hydroxide and (b) hot ethanolic sodium hydroxide.
OH- acts as a nucleophile in nucleophilic substitution, giving propan-2-ol.
OH- acts as a base in elimination, removing HBr to form propene.
The aqueous, ionising solvent favours the nucleophile (substitution); the hot ethanolic conditions favour the base (elimination).
Result: Warm aqueous NaOH gives propan-2-ol (substitution); hot ethanolic NaOH gives propene (elimination).
Typical mistakes
Active revision
Explain why 1-iodobutane is hydrolysed faster than 1-chlorobutane, and give the mechanism for the reaction of 1-bromopropane with aqueous sodium hydroxide.
Active recall
Recall the key points — then reveal.
Sources: AQA A-level Chemistry 7405 specification (AQA)
Electrophilic addition of HBr to propene (first step)
Markownikoff addition
The H adds to the carbon with more hydrogens, giving 2-bromopropane via the more stable secondary carbocation.
When HBr adds to propene, explain why 2-bromopropane is the major product rather than 1-bromopropane.
The H+ can add to either double-bond carbon, giving a secondary carbocation (positive on the middle carbon) or a primary one (positive on the end carbon).
The secondary carbocation is more stable, because two electron-releasing alkyl groups spread out the positive charge.
The reaction goes through the more stable secondary carbocation, so Br- adds to the middle carbon, giving 2-bromopropane.
Result: 2-bromopropane predominates because it forms via the more stable secondary carbocation (Markownikoff's rule).
Typical mistakes
Active revision
Predict the major product of the addition of HBr to but-1-ene and justify it using carbocation stability.
Active recall
Recall the key points — then reveal.
Sources: AQA A-level Chemistry 7405 specification (AQA)
Addition polymerisation of ethene
Addition polymerisation
Many ethene monomers add together; the repeat unit has the same atoms as the monomer with the double bond opened.
Chloroethene is CH2=CHCl. Draw the repeat unit of the polymer it forms (PVC) and name the polymer.
The C=C becomes a C-C single bond, with bonds continuing at each end through the brackets.
One carbon keeps its chlorine and hydrogen, the other keeps its two hydrogens, giving the repeat unit -CH2-CHCl-.
The polymer is poly(chloroethene), commonly PVC.
Result: The repeat unit is -(CH2-CHCl)- and the polymer is poly(chloroethene), PVC.
Typical mistakes
Active revision
Draw the repeat unit of the polymer formed from propene () and name it.
Active recall
Recall the key points — then reveal.
Sources: AQA A-level Chemistry 7405 specification (AQA)
Oxidation routes of the alcohols
Fermentation
Yeast enzymes convert glucose to ethanol and carbon dioxide at low temperature.
Dehydration
Concentrated acid removes water from an alcohol to form an alkene.
You have samples of propan-1-ol (primary) and 2-methylpropan-2-ol (tertiary). Describe a test using acidified potassium dichromate(VI) to distinguish them.
Add acidified potassium dichromate(VI) to each sample and warm gently.
Propan-1-ol is oxidised, so the dichromate turns from orange to green.
2-methylpropan-2-ol is not oxidised, so the dichromate stays orange.
Result: The primary alcohol turns the dichromate orange to green; the tertiary alcohol leaves it orange, distinguishing the two.
Typical mistakes
Active revision
Describe how you would obtain (a) ethanal and (b) ethanoic acid from ethanol, giving the reagent, conditions and colour change.
Active recall
Recall the key points — then reveal.
Sources: AQA A-level Chemistry 7405 specification (AQA)
References & sources
Department for Education