Purification of Organic Compounds: Crystallisation, Distillation, Chromatography

Chemistry · General Principles Of Organic Chemistry · NEET

Purification means separating a pure organic compound from its impurities. You pick the method based on the compound's physical properties: crystallisation for solids with different solubility, distillation for liquids with different boiling points, sublimation for solids that turn straight to vapour, and chromatography to separate very close mixtures. Memory hook: "Solid + solubility = crystallise, Liquid + boiling point = distil, Vapourises directly = sublime, Close mixture = chromatography."
Choosing a Purification MethodImpure compoundSOLIDLIQUIDCLOSE MIXTURESolubility -> CrystalliseVapourises -> SublimeBP far apart -> Simple distilSteam-volatile -> Steam distilColumn / TLC (adsorb)Paper (partition)
Decision tree for NEET: match the compound's physical property (solubility, boiling point, volatility, closeness of the mixture) to the right purification technique.

Your doubts, answered

What is crystallisation in organic chemistry?

Crystallisation purifies a solid using solubility. You dissolve the impure solid in a hot solvent where it dissolves a lot when hot but very little when cold. On cooling, the pure compound forms crystals and comes out, while soluble impurities stay dissolved in the liquid (called the mother liquor). It only works if the compound and impurity have different solubilities in the chosen solvent.

What is the difference between simple distillation and fractional distillation?

Simple distillation separates a liquid from a non-volatile impurity, OR two liquids whose boiling points are FAR apart (like chloroform 61C and aniline 184C). Fractional distillation is for liquids whose boiling points are CLOSE together (like the fractions in crude oil). It uses a fractionating column so the vapour condenses and re-evaporates many times, giving a cleaner separation.

Why is steam distillation used for compounds like aniline?

Steam distillation is for compounds that are steam-volatile (they evaporate with steam), immiscible with water, and would decompose if heated to their normal boiling point. Passing steam lets the compound distil over well below its own boiling point, so it does not burn or break down. Aniline, o-nitrophenol and essential oils are purified this way.

What is Rf value in chromatography?

Rf (retention factor) = distance moved by the compound divided by distance moved by the solvent front. It is always less than 1 and is a fixed value for a compound in a given solvent, so it helps identify the compound. A component that sticks less to the stationary phase moves further and has a higher Rf.

What is the difference between adsorption and partition chromatography?

Adsorption chromatography (column, TLC) works because components stick (adsorb) to a solid stationary phase by different amounts. Partition chromatography (paper) works because components distribute (partition) between a liquid stationary phase and a liquid mobile phase by different amounts. In paper chromatography the stationary phase is actually water trapped in the paper, so it is partition, not adsorption.

When is distillation under reduced pressure used?

It is used for liquids that decompose at or below their boiling point. Lowering the pressure lowers the boiling point, so the liquid distils at a lower temperature and does not break down. Example: glycerol is separated from spent-lye by distillation under reduced pressure.

⚠️ The NEET trap
Choosing Chromatography or Crystallisation to separate a 1:1 mixture of ortho- and para-nitrophenol.
The correct method is Steam distillation. o-Nitrophenol has intramolecular H-bonding (chelation) so it is steam-volatile and distils over; p-nitrophenol has intermolecular H-bonding, so it is non-volatile in steam and stays behind.
🧠 See two isomers that differ in volatility -> think STEAM distillation, not chromatography.

Real NEET questions

NEET 2017

The most suitable method of separation of a 1:1 mixture of ortho- and para-nitrophenols is:

A · Sublimation
B · Chromatography
C · Crystallisation
D · Steam distillation
Solution: o-Nitrophenol has intramolecular hydrogen bonding (chelation), making it steam-volatile, while p-nitrophenol has intermolecular hydrogen bonding and is non-volatile in steam. Steam distillation carries over the ortho isomer and leaves the para isomer behind. Answer (D).
NEET 2020

Paper chromatography is an example of:

A · Thin layer chromatography
B · Column chromatography
C · Adsorption chromatography
D · Partition chromatography
Solution: In paper chromatography the stationary phase is water held in the fibres of the paper, and the components partition (distribute) between this stationary water and the mobile solvent. So it is partition chromatography. Answer (D).
NEET 2025

Match List I (Mixture) with List II (Method of Separation). List I: A. CHCl3 + C6H5NH2, B. Crude oil in the petroleum industry, C. Glycerol from spent-lye, D. Aniline-water. List II: I. Distillation under reduced pressure, II. Steam distillation, III. Fractional distillation, IV. Simple distillation.

A · A-III, B-IV, C-I, D-II
B · A-III, B-IV, C-II, D-I
C · A-IV, B-III, C-I, D-II
D · A-IV, B-III, C-II, D-I
Solution: Chloroform and aniline have widely different boiling points -> simple distillation (A-IV). Crude oil fractions have close boiling points -> fractional distillation (B-III). Glycerol decomposes near its boiling point -> distillation under reduced pressure (C-I). Aniline is steam-volatile and immiscible with water -> steam distillation (D-II). Answer (C).

Solved General Principles Of Organic Chemistry NEET PYQs

Try the real previous-year questions from this chapter — each with the answer and a full solution.

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Frequently asked

How do I decide which purification method to use?

Look at the state and property. Solid with different solubility -> crystallisation. Solid that vapourises directly -> sublimation. Liquids with far-apart boiling points -> simple distillation. Liquids with close boiling points -> fractional distillation. Heat-sensitive liquid -> distillation under reduced pressure. Steam-volatile compound -> steam distillation. Very close mixture or tiny amounts -> chromatography.

Is sublimation the same as evaporation?

No. In sublimation a solid changes directly to vapour without becoming a liquid first, then re-forms as solid on cooling. Evaporation is a liquid changing to vapour. Camphor, naphthalene and benzoic acid are purified by sublimation.

What is the mother liquor in crystallisation?

The mother liquor is the leftover solution after the pure crystals have separated out. It holds the dissolved soluble impurities, which is why the crystals that form are purer.

Which method separated crude oil into fractions?

Fractional distillation. The many components of crude oil have close boiling points, so a fractionating column is used to separate them into fractions like petrol, kerosene and diesel.