Interpret first-order spin–spin splitting and multiplicity

In CH₃CH₂Br, CH₃ is split by two equivalent CH₂ protons into a triplet; CH₂ is split by three CH₃ protons into a quartet.

  • GCE A-Level H3 Chemistry 9813-2027
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Learning objectives

  • Interpret first-order spin–spin splitting and multiplicity

Neighbours split one environment

In CH₃CH₂Br, CH₃ is split by two equivalent CH₂ protons into a triplet; CH₂ is split by three CH₃ protons into a quartet.

Use n+1 only for first-order coupling to n equivalent neighbouring protons under the supplied simple conditions.

Use splitting only after identifying which protons form one signal. Then count equivalent neighbouring protons in the simple first-order environment stated by the question.

Multiplicity and coupling

Spin–spin coupling splits a signal according to neighbouring nuclear spin states.

Singlet, doublet, triplet, quartet and septet describe line count; they do not state integration.

The n + 1 rule predicts line number, while Pascal's triangle predicts the relative line intensities for ideal first-order multiplets. Neither rule gives the signal's integral or chemical shift.

Read an ethyl pattern

A 3H triplet plus 2H quartet with matching coupling supports CH₃CH₂. Pascal intensities are 1:2:1 for a triplet and 1:3:3:1 for a quartet.

Equivalent protons do not split one another in this first-order treatment; labile-proton coupling may be absent through exchange.

Coupled partners share the same spacing, called the coupling constant. Matching spacing in a triplet and quartet is useful evidence that the two signals belong to the same ethyl fragment.

The simple rule can fail when neighbouring sets are non-equivalent or strongly coupled. Stay within the first-order cases supplied rather than forcing every complex multiplet into one n + 1 label.

Assign bromoethane

CH₃ has n = 2 neighbours, so n+1 = 3; CH₂ has n = 3, so four lines.

Combine with integrals 3H and 2H rather than assigning from multiplicity alone.

For bromoethane, show the reasoning in both directions: CH₃ sees two CH₂ neighbours and becomes a triplet; CH₂ sees three CH₃ neighbours and becomes a quartet.

Try this

Predict both multiplicities in CH₃CH₂Br.

Check your answer

A strong answer should include CH₃ triplet, CH₂ quartet and correct neighbour counts.

Recognise isopropyl

Supplied data: a 1H septet and a 6H doublet with the same coupling constant.

Use n + 1 to count the neighbours each multiplicity implies, then check that the two signals can be coupled to each other.

The isopropyl pattern is convincing only as a pair, with matching coupling.

Try this

Assign a ¹H septet and 6H doublet.

Check your answer

The 1H septet has six neighbours: a central CH next to two equivalent CH₃ groups. The 6H doublet has one neighbour: those two equivalent CH₃ groups, split by the CH. Matching J confirms they are coupled, giving an isopropyl group.

Transfer to propan-2-ol

Structure: propan-2-ol, (CH₃)₂CHOH.

Ignore coupling to OH for the carbon-bound signals, then say separately how the OH signal may appear.

Predict the carbon-bound signals first, then state separately that rapid O–H exchange may remove observable coupling. This keeps the structural rule and experimental limitation distinct.

Try this

Predict multiplicity and integration for the carbon-bound signals.

Check your answer

The two equivalent CH₃ groups give a 6H doublet, split by the one CH. The CH gives a 1H septet, split by six methyl protons. The OH is often a broad 1H singlet because rapid exchange removes its coupling.

Do not split a group by itself

The three equivalent protons within one CH₃ environment do not split one another.

Count equivalent neighbours on adjacent atoms in the stated first-order system.

Equivalent protons within one signal do not split one another in this treatment. A methyl group is a quartet only when it has three suitable neighbouring protons, not because it contains three protons itself.

Try this

Better reasoning: “A CH₃ group is always a quartet because it contains three protons.”

Check your answer

Multiplicity depends on neighbouring protons; an isolated CH₃ can be a singlet.

Combine n+1 with shift and area

After the check questions, interpret the ether splitting pattern without notes. Return later for a different isopropyl-ketone question.

Try this next: use TMS and δ.

A complete annotation gives integral, multiplicity, neighbour count and relative line intensities, then checks that the paired signals describe a chemically possible fragment.

Try this

Annotate the fixed ethyl spectrum with n, n+1, integral and Pascal ratio.

Check your answer

A strong answer should include all four features separately for triplet and quartet.

Interpret first-order spin–spin splitting and multiplicity scientific representation

Text lists each signal centre, line count, relative line intensities, integral and exact neighbouring group.

About 5 minutes

Key visual: Interpret first-order spin–spin splitting and multiplicity. A fixed stick spectrum with Pascal intensities and integrals makes first-order n+1 reasoning auditable.
Interpret first-order spin–spin splitting and multiplicity authored spectrumText lists each signal centre, line count, relative line intensities, integral and exact neighbouring group.relative intensity / %chemical shift, δ / ppm (high → low)503.4 quartet2H quartet1.7 triplet3H triplet3.9 septet1H septet1.1 doublet6H doubletBromoethane · CH₃CH₂BrIsopropyl group · (CH₃)₂CH–
Neighbour count and first-order multiplicity
FragmentSignalIntegralEquivalent neighbours, nn + 1 resultIdeal line ratio
CH₃CH₂BrCH₃3 H2triplet1:2:1
CH₃CH₂BrCH₂2 H3quartet1:3:3:1
(CH₃)₂CH–two CH₃ groups6 H1doublet1:1
(CH₃)₂CH–CH1 H6septet1:6:15:20:15:6:1

Text alternative: Text lists each signal centre, line count, relative line intensities, integral and exact neighbouring group.