Alcohols and Oxidation

Classify alcohols and follow their oxidation to carbonyls and acids.

  • Define and explain Alcohols and Oxidation in your own words
  • Use key terms such as functional group accurately
  • Apply what you have learned to new examples and questions
  • Avoid the common mistakes learners make with this topic

This lesson focuses on Alcohols and Oxidation: classify alcohols and follow their oxidation to carbonyls and acids.

Definition: Alcohols and Oxidation

Classify alcohols and follow their oxidation to carbonyls and acids.

Key ideas

Alcohols oxidise in stages

Primary alcohols oxidise first to aldehydes and then to carboxylic acids: ethanol → ethanal → ethanoic acid, using acidified potassium dichromate. Gentle distillation collects the aldehyde; reflux drives oxidation all the way to the acid. Secondary alcohols stop at ketones, and tertiary alcohols resist oxidation — a difference used to classify unknown alcohols.

Synthesis is planned backwards

Planning a synthesis means working backwards from the target molecule, choosing reactions that build each functional group in turn. Each step must use conditions that do not destroy groups already present — for instance, oxidise an alcohol before introducing an alkene that the oxidiser would attack. Good routes are short, high-yielding and use cheap starting materials.

Key term — functional group: The atom or group of atoms responsible for a compound's characteristic reactions, e.g. –OH in alcohols.

Addition of HBr to propene

Hydrogen bromide adds to propene (CH₃CH=CH₂). Describe the mechanism and name the major product.

The C=C pi bond's electrons attack the H of H–Br, breaking the pi bond. H⁺ adds to the end carbon (C1), forming the more stable secondary carbocation on C2. Br⁻ then attacks the carbocation on C2. Overall: CH₃CH=CH₂ + HBr → CH₃CHBrCH₃ (Markownikoff addition).

Answer: Major product: 2-bromopropane, formed via the secondary carbocation (Markownikoff's rule).

Common mistakes
  • Oxidising a tertiary alcohol Tertiary alcohols have no hydrogen on the carbon bearing the –OH group, so they cannot be oxidised without breaking carbon–carbon bonds. Acidified dichromate stays orange with a tertiary alcohol — a classic test result.
  • Drawing curly arrows starting at atoms Curly arrows show electron pairs moving: they start at the electron source (a bond or lone pair) and point to where the electrons go. An arrow starting at an atom rather than the bond is meaningless.

Practice

Write the equation for the complete combustion of propane.
Alkane + O₂ → CO₂ + H₂O; balance it.

C₃H₈ + 5O₂ → 3CO₂ + 4H₂O.

Bromine water is added to ethene. Describe what you see and name the product.
What happens to the orange colour?

The orange bromine water decolourises; the product is 1,2-dibromoethane.

Explain why the addition of HBr to propene gives mainly 2-bromopropane.
Which carbocation is more stable?

H⁺ adds to C1, giving a secondary carbocation on C2, which is more stable than the primary alternative; Br⁻ then attacks C2 (Markownikoff's rule).

Acidified potassium dichromate is refluxed with ethanol. Name the final organic product and describe the colour change.
Reflux drives oxidation to completion.

Ethanoic acid; the orange dichromate turns green as it is reduced.

Quick check

Alcohols and Oxidation — quick check

Which of these best defines "functional group"?

The atom or group of atoms responsible for a compound's characteristic reactions, e.g. –OH in alcohols.

Plan a two-step synthesis of ethanoic acid from ethene.

Step 1: ethene + steam (phosphoric acid catalyst, heat, pressure) → ethanol. Step 2: reflux ethanol with acidified potassium dichromate → ethanoic acid.

Name the structural isomers of C₄H₁₀.

Butane (CH₃CH₂CH₂CH₃) and methylpropane (CH₃CH(CH₃)CH₃).
Key takeaways
  • Alcohols and Oxidation: classify alcohols and follow their oxidation to carbonyls and acids.
  • Alcohols oxidise in stages: Primary alcohols oxidise first to aldehydes and then to carboxylic acids: ethanol → ethanal → ethanoic acid, using acidified potassium dichromate.
  • electrophile: An electron-pair acceptor, attracted to electron-rich areas such as C=C double bonds.
  • Watch out for: oxidising a tertiary alcohol