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Organic Chemistry

Topic 20 of 34

The carbon bearing OH determines the oxidation product

Distillation removes an aldehyde; reflux keeps it with oxidant long enough to form an acid.

A-Level 9476 (2026-2027)

The carbon bearing OH determines the oxidation product

Distillation removes an aldehyde; reflux keeps it with oxidant long enough to form an acid.

Ethanol as the reference alcohol
TransformationReagents and conditionsRepresentative equation or product
Complete combustionOxygen and ignition.C2H5OH + 3O2 → 2CO2 + 3H2O.
Substitution to halogenoalkaneHX, with suitable heating; primary alcohol with HCl often needs an activating catalyst. PCl5 also replaces OH by Cl.C2H5OH + PCl5 → C2H5Cl + POCl3 + HCl.
Reaction with sodiumSodium with the alcohol; distinguish from water contamination.2C2H5OH + 2Na → 2C2H5ONa + H2.
Oxidation to aldehydeAcidified K2Cr2O7; heat and distil the aldehyde as it forms.CH3CH2OH + [O] → CH3CHO + H2O.
Oxidation to acidExcess acidified KMnO4 or K2Cr2O7; heat under reflux.CH3CH2OH + 2[O] → CH3COOH + H2O.
DehydrationConcentrated H3PO4 catalyst and heat.CH3CH2OH → CH2=CH2 + H2O.
Distinguish the three alcohol classes by mild oxidation
Alcohol classHydrogen on OH-bearing carbon?Usual oxidation result
Primary, RCH2OHTwo.Aldehyde, then carboxylic acid if oxidation continues.
Secondary, R2CHOHOne.Ketone; for example propan-2-ol → propanone.
Tertiary, R3COHNone.Resists these mild oxidation conditions; oxidising further would require carbon-carbon bond cleavage.

Acidified dichromate(VI) changes from orange to green as it is reduced; acidified manganate(VII) loses its purple colour as Mn2+ forms. The colour change indicates oxidation has occurred but does not alone distinguish a primary from a secondary alcohol. Identify the product using a carbonyl test and, where needed, an aldehyde-specific test.

Distillation allows a volatile aldehyde to leave the oxidising mixture, limiting further oxidation. Reflux condenses vapour back into the flask, allowing prolonged heating without losing volatile reactants. Neither term itself identifies a reagent: write both the oxidant and the apparatus condition.

Aldehydes reduce to primary alcohols and ketones to secondary alcohols using LiAlH4 in dry ether followed by aqueous work-up, or H2/Ni under suitable hydrogenation conditions. For example, CH3COCH3 + 2[H] → CH3CH(OH)CH3. The carbon skeleton is retained.