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Section III · Topic guide

Working out a structure from spectra

Section III — Sciences · a free, hand-written guide with worked reasoning and adaptive practice that finds your weak spots.

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The short answer

Turn a molecular formula plus two or three spectral clues into a structure you have never seen before.

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Try the reasoning style

Section I · Humanities & Social SciencesIllustrative example

We treat forgetting as a failure — a lapse to be patched with reminders and records. Yet a mind that kept everything could not think; it would drown in the undifferentiated noise of every moment it had ever lived. To forget is not so much to lose information as to decide, mostly without our noticing, what was never worth keeping.

The author's argument relies most directly on which unstated assumption?

Pick an option to see how the tutor reasons to the answer — not just whether you were right.

How to reason to the answer

Not quite — the answer is B.

Work backwards from the conclusion: a mind that ‘kept everything’ supposedly ‘could not think.’ That only follows if thinking means leaving most of experience out — so B is the premise the argument quietly rests on. A raises reliability, which the passage never weighs; C contradicts ‘mostly without our noticing’; D smuggles in a claim about intellect the passage never makes. The question rewards finding the hidden premise, not recalling a fact.

Spectroscopy is a logic puzzle. Each instrument answers one question — mass spec, how heavy and which halogen; IR, which functional group; ¹H NMR, how the hydrogens sit — and each answer deletes structures.

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Bars are evenly spaced: read mass gaps off the m/z labels, not the axis. Molecular ion 78, twin at 80 a third its height — one Cl, leaving C₃H₇, so X is C₃H₇Cl.

Start with degrees of unsaturation

1

Take it off the formula

DoU = (2C + 2 + N − H − X)/2, X counting halogens, oxygen ignored.

2

Read what it licenses

Each degree buys one ring or one π bond; zero means a saturated open chain.

3

Spend it, then subtract

An IR band near 1700 cm⁻¹ spends one on C=O; if the formula bought only one, nothing is left — no ring, no alkene, whatever the options say.

What ¹H NMR gives you

1

Signals = environments

One per distinct hydrogen environment: the count measures symmetry.

2

Integration = ratio, never a headcount

3:2:3 is 3, 2, 3 in an eight-hydrogen molecule but 6, 4, 6 in a sixteen.

3

Splitting = n + 1 neighbours

n is the hydrogens on the adjacent carbons, never the signal's own.

Diagnostic signals worth carrying into the exam.
What you seeTechniqueWhat it points to
Very broad band, 2500–3300 cm⁻¹IRO–H of a carboxylic acid
Broad band, 3200–3600 cm⁻¹IRO–H of an alcohol
Sharper band(s), 3300–3500 cm⁻¹IRN–H (twin peaks = primary amine)
Strong band, 1670–1750 cm⁻¹IRC=O, a carbonyl of some kind
δ 0.9–1.7¹H NMRH on a carbon with no electronegative neighbour
δ 2.0–2.6¹H NMRH on the carbon next to a C=O
δ 3.3–4.2¹H NMRH on a carbon bonded to O or a halogen
δ 6.5–8.0¹H NMRH on an aromatic ring
δ 9.5–10.1¹H NMRthe H of an aldehyde, —CHO
δ 10–13, broad¹H NMRthe H of a carboxylic acid (position varies a lot)
Approximate ranges; electronegative neighbours drag signals downfield.

The deduction

An unknown liquid, C₄H₈O₂. IR: strong band at 1740 cm⁻¹, nothing broad from 2500 to 3600 cm⁻¹. ¹H NMR: δ 4.1 (2H, quartet), δ 2.0 (3H, singlet), δ 1.2 (3H, triplet).

The tallest peak is not the molecular ion

That is the base peak, usually a fragment (43 in Figure 1). The molecular ion is the heaviest peak that is not an isotope twin of a lighter one: 78, since 80 is its M+2.

Check yourself

An unknown liquid has molecular formula C₃H₆O. Its IR spectrum shows a strong band at 1715 cm⁻¹ and nothing at all in the 3200–3600 cm⁻¹ region. Its ¹H NMR spectrum is a single signal at δ 2.1. Which structure fits every one of those observations?

Key takeaways

  • Take degrees of unsaturation off the formula first; the spectra spend them.
  • Twin peaks two apart: ≈3:1 is one Cl, ≈1:1 is one Br.
  • Signals = environments, integration = ratio, splitting = n + 1.
  • You eliminate structures; you never build one.

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8 min read · Technique