Analytical Techniques: Question 8

Syllabus 22.1

Structured AS 7 marks

The infrared spectrum of a colourless liquid, compound Z, shows two separate medium-intensity absorptions at 3300 cm−13300\ \text{cm}^{-1} and 3380 cm−13380\ \text{cm}^{-1}, together with a C–H absorption in the range 28502850–2960 cm−12960\ \text{cm}^{-1}. There is no absorption anywhere in the range 16501650–1750 cm−11750\ \text{cm}^{-1}, and no absorption in the range 32003200–3600 cm−13600\ \text{cm}^{-1} other than the two peaks already stated.

You may use the following characteristic infrared absorption data:

Bond Functional group Wavenumber / cm⁻¹ Typical peak shape
N–H primary amine, −NH2-\text{NH}_2 3300–3500 two absorptions (symmetric and asymmetric N–H stretch)
N–H secondary amine, −NH−-\text{NH}- 3300–3500 one absorption
O–H alcohol (hydrogen bonded) 3200–3600 one broad absorption
C=O carbonyl (aldehyde, ketone, acid, ester, amide) 1650–1750 one strong, sharp absorption
C–H alkyl 2850–2960 one or more absorptions

(a) Identify the functional group present in compound Z, and explain how the number of absorptions in the 32003200–3600 cm−13600\ \text{cm}^{-1} region distinguishes it from both a secondary amine and an alcohol. [3]

(b) Explain why the absence of any absorption in the range 16501650–1750 cm−11750\ \text{cm}^{-1} rules out compound Z being a primary amide, R-CONH2\text{R-CONH}_2, even though an amide also contains N–H bonds. [2]

(c) A second compound, X, gives only one absorption in the 33003300–3500 cm−13500\ \text{cm}^{-1} region. Suggest why this single absorption alone is not, by itself, enough to decide whether X is a secondary amine or an alcohol, and state what further infrared evidence would help distinguish between them. [2]

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Worked solution

Part (a): Identifying compound Z from the N–H region

The data table shows that the number of separate absorptions in the 32003200–3600 cm−13600\ \text{cm}^{-1} region is diagnostic:

  • A primary amine, −NH2-\text{NH}_2, has two N–H bonds that vibrate independently (symmetric and asymmetric stretching), giving two separate absorptions in this region.
  • A secondary amine, −NH−-\text{NH}-, has only one N–H bond, giving one absorption.
  • An alcohol O–H bond also gives only one (typically broader) absorption.

Compound Z shows two separate medium-intensity absorptions, at 3300 cm−13300\ \text{cm}^{-1} and 3380 cm−13380\ \text{cm}^{-1}. This matches the symmetric and asymmetric N–H stretches of a primary amine, and rules out both a secondary amine and an alcohol, each of which would give only a single absorption here.

Compound Z contains a primary amine group, −NH2-\text{NH}_2.

Part (b): Ruling out a primary amide

A primary amide, R-CONH2\text{R-CONH}_2, also contains N–H bonds and so would also absorb in the 33003300–3500 cm−13500\ \text{cm}^{-1} region, but it additionally contains a carbonyl, C=O, group, which would produce a strong, sharp absorption somewhere in the 16501650–1750 cm−11750\ \text{cm}^{-1} range.

Since compound Z shows no absorption anywhere in 16501650–1750 cm−11750\ \text{cm}^{-1}, it cannot contain a C=O bond, and so it cannot be an amide, despite the N–H absorptions being consistent with one. The N–H absorptions alone must instead come from an amine.

Part (c): Why one N–H/O–H peak is ambiguous

A secondary amine gives exactly one N–H absorption in 33003300–3500 cm−13500\ \text{cm}^{-1}, and an alcohol gives exactly one O–H absorption in the overlapping range 32003200–3600 cm−13600\ \text{cm}^{-1}. Since these two ranges overlap and both functional groups give only a single peak, seeing just one absorption there is consistent with either possibility, the peak count that worked to identify a primary amine in part (a) cannot, on its own, distinguish a secondary amine from an alcohol.

To decide between them, further evidence is needed: for example, checking for a C–N absorption (distinct from the C–O absorption an alcohol would show), or carrying out a simple chemical test that responds differently to an amine and an alcohol.

Final answers

  • (a) Primary amine (−NH2-\text{NH}_2); two N–H absorptions (rather than one) distinguish it from a secondary amine and from an alcohol.
  • (b) No C=O absorption is present (1650–1750 cm⁻¹ is empty), so compound Z cannot be an amide even though it has N–H bonds.
  • (c) A secondary amine and an alcohol can both give a single peak in overlapping wavenumber ranges, so further evidence (e.g. a C–N absorption or a chemical test) is needed to distinguish them.