Modern analytical techniques (Topics 7 and 19)Infrared (IR) spectroscopy (Topic 7B)

Infrared (IR) spectroscopy (Topic 7B)

Linking molecular stretching to absorption patterns on an infrared spectrum.
3 min

Different functional groups present in an organic compound can be identified from their IR stretching peaks.

A basic outline of the main groups and their characteristics absorption frequencies in IR is as shown below:

A graph displaying transmittance percentage on the vertical axis and wavenumber in cm⁻¹ on the horizontal axis. The graph is divided into regions for single bonds, triple bonds, double bonds, and a fingerprint region. It lists specific bonds like O–H, N–H, C–H, C≡N, C≡C, C=O, and C=C, with a note about using a database to match spectra.

You will not be required to memorise this data.

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The presence of the bond stretching is easy to locate, though of limited use in distinguishing one organic compound from another.

A graph displaying transmittance percentage on the vertical axis and wavenumber in cm⁻¹ on the horizontal axis. The graph shows a dip in transmittance around the wavenumber range of 2850-3100 cm⁻¹, indicating the presence of C-H bonds in alkyl, alkene, and arene compounds.
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A strong, broad peak is characteristic of bond stretching in alcohols.

This notable peak is located just to the left of the landmark bond peak and is very popular in exam questions.

A graph showing transmittance percentage on the vertical axis and wavenumber in cm⁻¹ on the horizontal axis. The graph features a curve indicating transmittance levels, with notable dips corresponding to O–H bonds in alcohols and phenols between 3200 and 3600 cm⁻¹, and C–H bonds indicated.

Be careful as the bond, although a weaker signal, is located in the same region as a bond.

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The bond stretching, found in aldehydes, ketones, and other carbonyl-containing compounds is very easy to recognise as a strong narrow peak, almost in the middle of the spectrum around .

A graph showing transmittance percentage on the vertical axis and wavenumber in cm-1 on the horizontal axis. The graph features a dip indicating the presence of C=O functional groups in various organic compounds, with a specific range noted between 1630-1820 cm-1.

More details are required to fully identify the functional group.

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The spectrum for the carboxylic acid group contains a stretch at and the very broad and strong peak of the group in carboxylic acids from .

Its breadth is due to hydrogen bonding between carboxylic acid groups causing variation in the vibration.

A graph depicting transmittance percentage on the vertical axis and wavenumber in cm⁻¹ on the horizontal axis. The graph shows peaks and troughs indicating the presence of functional groups, specifically C=O in carboxylic acids between 1630-1820 cm⁻¹ and O-H in carboxylic acids between 2500-3300 cm⁻¹, with a broad peak. The C-H bond is also indicated on the graph.

The carboxylic acid peak overlaps the bond peak, which can often be seen just below the broad carboxylic acid peak.

If there was a narrow peak and a peak this would indicate an alcohol and a carbonyl were present, not a carboxylic acid.

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In amine’s, bond stretching appears as a characteristic peak in the IR spectrum, typically between .

This peak is often medium in intensity and can be either sharp or broad, depending on whether the amine is primary or secondary. It is significantly less intense than the of an alcohol, but is in the same region.

A graph showing the transmittance percentage of a primary amine as a function of wavenumber in cm⁻¹. The y-axis represents transmittance from 0% to 100%, while the x-axis displays wavenumbers ranging from 4000 to 500 cm⁻¹. Notable features include a dip in transmittance around 3000 cm⁻¹, indicating the presence of an amine functional group.
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Most exam questions present an infrared spectrum and ask for the identity of the compound, or some structural features, deducible from the data.

Using the supplied data sheet spectroscopy table is essential here but a good understanding of the key peaks below will speed up your analysis.

A graph displaying transmittance percentage on the vertical axis and wavenumber in cm⁻¹ on the horizontal axis. The graph shows several peaks and troughs, indicating the presence of functional groups such as O-H for alcohol/phenol and carboxylic acid, C-H for hydrocarbons, and C=O for carbonyl. Additional annotations highlight regions for ester, alcohol, and carboxylic acid.

IR spectra are most commonly assessed in combination with other techniques such as nuclear magnetic resonance (NMR) and mass spectrometry.

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The absence of particular peaks from a spectrum can also help to confirm the identity of a functional group.

A commonly tested scenario is analysis of an alcohol oxidation. This involves distinguishing unreacted alcohol, aldehydes, ketones, and/or carboxylic acids.

Here we need to look for the absence, or presence, of the carboxylic acid’s broad peak. Likewise, the absence or presence of an alcohol peak. This will give a definitive answer on the presence of a carboxylic acid or an unreacted alcohol.

Aldehydes and ketones require additional data to identify. The IR spectra could be combined with NMR, mass spectrometry or qualitative tests such as using the Tollens reagent.

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Question walkthrough

Combined spectroscopic analysis

Using mass spectrometry, IR spectrometry and elemental analysis in tandem